Note: Descriptions are shown in the official language in which they were submitted.
CA 02295395 2000-O1-13
72932-193E
1
TITLE
PROPYLENE POLYMER COMPOSITTONS
This is a divisional application of Canadian Patent
Application No. 2,117,699 filed January 11, 1994.
FIELD OF THE INVENTION
The description part of this specification describes
several inventions relating to propylene polymer compositions
each comprising two kinds of propylene polymers and to
propylene polymer compositions each comprising a propylene
polymer and other olefin (co)polymer. It should be understood
that the expression "the present invention" or the like means
only one of these inventions.
The subject matter claimed in this divisional appli-
cation is restricted to sixth to twelvth propylene polymer
compositions described hereinunder.
BACKGROUND OF THE INVENTION
Propylene polymers have been conventionally molded
by various molding methods and the molded articles are applied
to extensive uses.
The propylene polymers are generally prepared using
a catalyst comprising a transition metal compound and an
organoaluminum compound, i. e., so-called Ziegler catalyst.
Propylene polymers prepared by the use of a
titanium catalyst containing a halogen-containing titanium
catalyst component among the Ziegler catalysts are excellent
in moldability and rigidity, but they have such problems that
they are poor in tensile elongation at break. Moreover, the
titanium catalyst causes a large amount of a catalyst residue
in the resulting polymer because of low polymerization
activities, and hence the molded article is sometimes colored
or deteriorated in sanitariness.
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On the other hand, propylene polymers prepared by the
use of a metallocene catalyst containing a transition metal
compound catalyst component such as zirconocene are
excellent in tensile elongation at break, but they have
such problems that they are poor in moldability and
rigidity (flexural modulus). As for the metallocene
catalyst, however, the amount of the catalyst residue is
small because of high polymerization activities, and the
molded article is never colored and is good in
sanitariness.
Though the characteristics required for the propylene
polymers vary depending on the molding methods or uses,
generally required are moldability, heat resistance,
mechanical strength, high tensile elongation at break,
impact resistance, etc. For satisfying these requirements,
researches on various compositions such as a composition
obtained by blending two or more kinds of propylene
polymers and a composition obtained by blending a propylene
polymer and other synthetic resin have been made.
2 0 For example, blending of two kinds of propylene
polymers which are different in the molecular weight has
been carried out in order to improve physical properties of
the propylene polymers prepared by the use of a titanium
catalyst. However, when two kinds of propylene polymers
produced by the use of a titanium catalyst are blended to
prepare a propylene polymer composition, the tensile
elongation at break of the resulting composition is
CA 02295395 2000-O1-13
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markedly lowered, though the moldability thereof is
improved.
Further, adding of a soft polymer to a propylene
polymer which is prepared by the use of a titanium catalyst
has been carried out in order to improve the tensile
elongation at break and the impact resistance of the
propylene polymer. The soft polymer used therefor is, for
example, an ethylene/propylene random copolymer prepared by
the use of a titanium catalyst or a vanadium catalyst.
However, even if the propylene polymer prepared by the use
of a titanium catalyst is blended with the
ethylene/propylene random copolymer prepared by the use of
a titanium catalyst or the like, the resulting composition
is not sufficiently improved in the tensile elongation at
break and the impact resistance.
As described above, the conventional propylene polymer
compositions are not always satisfactory in the properties
such as heat resistance, mechanical strength and tensile
elongation at break.
OBJECT OF THE INVENTION
The present invention has been accomplished in the
light of the foregoing prior art technique, and an object
of the present invention is to provide propylene polymer
2 5 compositions which are excellent in heat resistance,
mechanical strength, tensile elongation at break, etc. as
CA 02295395 2000-O1-13
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4
compared with the conventional propylene polymers or
propylene polymer compositions.
SUMMARY OF THE INVENTION
S The first propylene polymer composition of the
invention comprises:
(A1) a propylene polymer, in an amount of 10 to 90 $
by weight, which is characterized in that:
(1) the propylene polymer is obtained by polymerizing
propylene in the presence of an olefin polymerization
catalyst comprising:
(i) (a) a compound of a Group IVB transition
metal in the periodic table containing a ligand having a
cyclopentadienyl skeleton, and
1S (ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(c) a compound which reacts with the
transition metal compound (a) to form an ion pair,
2 0 (2) the propylene polymer has a melt flow rate (MFR),
as measured at 230 °C under a load of 2.16 kg, of 0.01 to
30 g/10 min, and
(3) the propylene polymer has a molecular weight
distribution (Mw/Mn), as measured by gel permeation
2 S chromatography (GPC), of 2 to 3; and
(A2) a propylene polymer, in an amount of 10 to 90 0
by weight, which is characterized in that:
CA 02295395 2000-O1-13
(1) the propylene polymer is obtained by polymerizing
propylene in the presence of an olefin polymerization
catalyst comprising:
(i) (a) a compound of a Group IVB transition
5 metal in the periodic table containing a ligand having a
cyclopentadienyl skeleton, and
(ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
1~ (c) a compound which reacts with the
transition metal compound (a) to form an ion pair,
(2) the propylene polymer has a melt flow rate (MFR),
as measured at 230 °C under a load of 2.16 kg, of 30 to
1,000 g/10 min, and
(3) the propylene polymer has a molecular weight
distribution (Mw/Mn), as measured by gel permeation
chromatography (GPC), of 2 to 4;
a ratio ((A2)/(A1)) of the MFR of said propylene
polymer (A2) to the MFR of said propylene polymer (A1)
2 0 being not less than 30.
Such propylene polymer composition is excellent in not
only heat resistance, rigidity and tensile elongation at
break but also moldability.
The second propylene polymer composition of the
2 5 invention comprises:
(A1) a propylene polymer, in an amount of 10 to 90
parts by weight, which is characterized in that:
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(1) the propylene polymer is obtained by polymerizing
propylene in the presence of an olefin polymerization
catalyst comprising:
(i) (a) a compound of a Group IVB transition
metal in the periodic table containing a ligand having a
cyclopentadienyl skeleton, and
(ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
1 0 (c) a compound which reacts with the
transition metal compound (a) to form an ion pair,
(2) the propylene polymer has a melt flow rate (MFR),
as measured at 230 °C under a load of 2.16 kg, of 0.01 to
30 g/10 min, and
(3) the propylene polymer has a molecular weight
distribution (Mw/Mn), as measured by gel permeation
chromatography (GPC), of 2 to 3;
(A2) a propylene polymer, in an amount of 10 to 90
parts by weight, which is characterized in that:
2 0 (1) the propylene polymer is obtained by polymerizing
propylene in the presence of an olefin polymerization
catalyst comprising:
(i) (a) a compound of a Group IVB transition
metal in the periodic table containing a ligand having a
2 5 cyclopentadienyl skeleton, and
(ii) at least one compound selected from the
group consisting of
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(b) an organoaluminum oxy-compound, and
(c) a compound which reacts with the
transition metal compound (a) to form an ion pair,
(2) the propylene polymer has a melt flow rate (MFR),
as measured at 230 °C under a load of 2.16 kg, of 30 to
1,000 g/10 min, and
(3) the propylene polymer has a molecular weight
distribution (Mw/Mn), as measured by gel permeation
chromatography (GPC), of 2 to 4; and
(B) a soft polymer in an amount of 3 to 30 parts by
weight;
a ratio ((A2)/(Al)) of the MFR of said propylene
polymer (A2) to the MFR of said propylene polymer (A1)
being not less than 30.
Such propylene polymer composition is excellent in not
only heat resistance, rigidity and tensile elongation at
break but also moldability and impact resistance.
The third propylene polymer composition of the
invention comprises:
2 0 (A3) a propylene polymer, in an amount of 10 to 90 $
by weight, which is characterized in that:
(1) the propylene polymer is obtained by polymerizing
propylene in the presence of an olefin polymerization
catalyst comprising:
2 5 (d) a solid titanium catalyst component, and
(e) an organometallic compound catalyst
component,
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(2) the propylene polymer has a melt flow rate (MFR),
as measured at 230 °C under a load of 2.16 kg, of 0.01 to
30 g/10 min, and
(3) the propylene polymer has a molecular weight
S distribution (Mw/Mn), as measured by gel permeation
chromatography (GPC), of 4 to 15; and
(A2) a propylene polymer, in an amount of 90 to 10 ~
by weight, which is characterized in that:
(1) the propylene polymer is obtained by polymerizing
propylene in the presence of an olefin polymerization
catalyst comprising:
(i) (a) a compound of a Group IVB transition
metal in the periodic table containing a ligand having a
cyclopentadienyl skeleton, and
(ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(c) a compound which reacts with the
transition metal compound (a) to form an ion pair,
2 0 (2) the propylene polymer has a melt flow rate (MFR),
as measured at 230 °C under a load of 2.16 kg, of 30 to
1,000 g/10 min, and
(3) the propylene polymer has a molecular weight
distribution (Mw/Mn), as measured by gel permeation
2 5 chromatography (GPC), of 2 to 4.
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Such propylene polymer composition is excellent in not
only heat resistance, rigidity and tensile elongation at
break but also moldability.
The fourth propylene polymer composition of the
invention comprises:
(A3) a propylene polymer, in an amount of 10 to 90
parts by weight, which is characterized in that:
(1) the propylene polymer is obtained by polymerizing
propylene in the presence of an olefin polymerization
catalyst comprising:
(d) a solid titanium catalyst component, and
(e) an organometallic compound catalyst
component,
(2) the propylene polymer has a melt flow rate (MFR),
as measured at 230 °C under a load of 2.16 kg, of 0.01 to
30 g/10 min, and
(3) the propylene polymer has a molecular weight
distribution (Mw/Mn), as measured by gel permeation
chromatography (GPC), of 4 to 15;
2 0 (A2) a propylene polymer, in an amount of 90 to 10
parts by weight, which is characterized in that:
(1) the propylene polymer is obtained by polymerizing
propylene in the presence of an olefin polymerization
catalyst comprising:
2 5 (i) (a) a compound of a Group IVB transition
metal in the periodic table containing a ligand having a
cyclopentadienyl skeleton, and
CA 02295395 2000-O1-13
(ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(c) a compound which reacts with the
5 transition metal compound (a) to form an ion pair,
(2) the propylene polymer has a melt flow rate (MFR),
as measured at 230 °C under a load of 2.16 kg, of 30 to
1,000 g/10 min, and
(3) the propylene polymer has a molecular weight
10 distribution (Mw/Mn), as measured by gel permeation
chromatography (GPC), of 2 to 4; and
(B) a soft polymer in an amount of 3 to 30 parts by
weight.
Such propylene polymer composition is excellent in not
1$ only heat resistance, rigidity and tensile elongation at
break but also moldability and impact resistance.
The fifth propylene polymer composition of the
invention comprises:
(A4) a propylene polymer, in an amount of 50 to 97 $
2 0 by weight, which is characterized in that:
(1) the propylene polymer is obtained by polymerizing
propylene in the presence of an olefin polymerization
catalyst comprising:
(d) a solid titanium catalyst component, and
2 5 (e) an organometallic compound catalyst
component,
CA 02295395 2000-O1-13
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(2) the propylene polymer has a melt flow rate (MFR),
as measured at 230 °C under a load of 2.16 kg, of 0.01 to
50 g/10 min,
(3) the propylene polymer has a molecular weight
distribution (Mw/Mn), as measured by gel permeation
chromatography (GPC), of 4 to 15, and
(4) the propylene polymer has a crystallinity, as
measured by X-ray diffractometry, of not less than 50
and
(C) an ethylene/olefin random copolymer, in an amount
of 3 to 50 $ by weight, which is characterized in that:
(1) the copolymer is obtained by copolymerizing
ethylene and at least one monomer selected from a-olefins
of 3 to 20 carbon atoms and polyenes of 5 to 20 carbon
1$ atoms in the presence of an olefin polymerization catalyst
comprising:
(i) (f) a compound of a Group IVB transition
metal in the periodic table containing a ligand having a
cyclopentadienyl skeleton,
2 0 (ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(g) a compound which reacts with the
transition metal compound (f) to form an ion pair,
2 5 (2) the copolymer contains constituent units derived
from ethylene in an amount of 20 to 80 o by mol, and
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(3) the copolymer has an intrinsic viscosity [~], as
measured in decalin at 135 °C, of 1.5 to 5 dl/g.
Such propylene polymer composition is excellent in not
only heat resistance, rigidity and tensile elongation at
S break but also impact resistance, particularly low-
temperature impact resistance.
The sixth propylene polymer composition of the
invention comprises:
(A5) a propylene homopolymer, in an amount of 5 to 95
~ by weight, which is obtained by polymerizing propylene in
the presence of an olefin polymerization catalyst
comprising:
(i) (h) a transition metal compound represented
by the following formula (I), and
(ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(i) a compound which reacts with the
transition metal compound (h) to form an ion pair; and
2 0 (A6) a propylene polymer, in an amount of 5 to 95 ~ by
weight, which contains constituent units derived from
propylene in an amount of not less than 90 $ by mol and is
different from the propylene homopolymer (A5);
CA 02295395 2000-O1-13
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X1 X2
M
R2 R2
R1
(I)
wherein M is a transition metal of Group IVa, Group Va or
Group VIa of the periodic table; R1 is a hydrocarbon group
of 2 to 6 carbon atoms; Rz is an aryl group of 6 to 16
carbon atoms which may be substituted with a halogen atom
or a hydrocarbon group of 1 to 20 carbon atoms; X1 and Xz
are each a hydrogen atom, a halogen atom, a hydrocarbon
group of 1 to 20 carbon atoms, a halogenated hydrocarbon
group of 1 to 20 carbon atoms, an oxygen-containing group
or a sulfur-containing group; Y is a divalent hydrocarbon
group of 1 to 20 carbon atoms, a divalent halogenated
hydrocarbon group of 1 to 20 carbon atoms, a divalent
silicon-containing group, a divalent germanium-containing
group, a divalent tin-containing group, -O-, -CO-, -S-, -
1 5 SO-, -SOZ-, -NR3-, -P (R3) -, -P (O) (R3) -, -BR3- or -A1R3- (R3
is a hydrogen atom, a halogen atom, a hydrocarbon group of
1 to 20 carbon atoms or a halogenated hydrocarbon group of
1 to 20 carbon atoms).
Such propylene polymer composition is excellent in not
2 0 only heat resistance, rigidity and tensile elongation at
break but also moldability.
The seventh propylene polymer composition of the
invention comprises:
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14
(A5) a propylene homopolymer, in an amount of 5 to 95
$ by weight, which is obtained by polymerizing propylene in
the presence of an olefin polymerization catalyst
comprising:
S (i) (h) a transition metal compound represented
by the above formula (I), and
(ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(i) a compound which reacts with the
transition metal compound (h) to form an ion pair; and
(D) an olefin elastomer, in an amount of 5 to 95 ~ by
weight, which is characterized in that:
(1) the elastomer is a polymer or copolymer of at
least one monomer selected from olefins of 2 to 20 carbon
atoms and polyenes of 5 to 20 carbon atoms,
(2) the elastomer contains constituent units derived
from ethylene, propylene, butene or 4-methyl-1-pentene in
an amount of less than 90 ~ by mol, and
2 0 (3) the elastomer has a glass transition temperature
(Tg) of not higher than 10 °C .
Such propylene polymer composition is excellent in not
only heat resistance, rigidity and tensile elongation at
break but also impact resistance.
2 5 The eighth propylene polymer composition of the
invention comprises:
CA 02295395 2000-O1-13
(A5) a propylene homopolymer, in an amount of 5 to 95
by weight, which is obtained by polymerizing propylene in
the presence of an olefin polymerization catalyst
comprising:
5 (i) (h) a transition metal compound represented
by the above formula (I), and
(ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
10 (i) a compound which reacts with the
transition metal compound (h) to form an ion pair; and
(E) an olefin polymer, in an amount of 5 to 95 ~ by
weight, which contains constituent units derived from one
monomer selected from the group consisting of ethylene,
15 butene and 4-methyl-1-pentene in an amount of not less than
90 $ by mol.
Such propylene polymer composition is excellent in
heat resistance, rigidity and tensile elongation at break.
The ninth propylene polymer composition of the
2 0 invention comprises:
(A5) a propylene homopolymer which is obtained by
polymerizing propylene in the presence of an olefin
polymerization catalyst comprising:
(i) (h) a transition metal compound represented
2 5 by the above formula (I), and
(ii) at least one compound selected from the
group consisting of
CA 02295395 2000-O1-13
16
(b) an organoaluminum oxy-compound, and
(i) a compound which reacts with the
transition metal compound (h) to form an ion pair;
(A6) a propylene polymer which contains constituent
units derived from propylene in an amount of not less than
90 ~ by mol and is different from the propylene homopolymer
(A5 ) : and
(D) an olefin elastomer which is characterized in
that:
(1) the elastomer is a polymer or copolymer of at
least one monomer selected from olefins of 2 to 20 carbon
atoms and polyenes of 5 to 20 carbon atoms,
(2) the elastomer contains constituent units derived
from ethylene, propylene, butene or 4-methyl-1-pentene in
an amount of less than 90 $ by mol, and
(3) the elastomer has a glass transition temperature
(Tg) of not higher than 10 °C;
said propylene polymer composition containing the
propylene homopolymer (AS) in an amount of 5 to 95 ~ by
2 0 weight, the propylene polymer (A6) in an amount of not more
than 95 ~ by weight and the olefin elastomer (D) in an
amount of not more than 95 o by weight.
Such propylene polymer composition is excellent in not
only heat resistance, rigidity and tensile elongation at
2 5 break but also moldability and impact resistance.
The tenth propylene polymer composition of the
invention comprises:
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1 7
(A5) a propylene homopolymer which is obtained by
polymerizing propylene in the presence of an olefin
polymerization catalyst comprising:
(i) (h) a transition metal compound represented
S by the above formula (I) , and
(ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(i) a compound which reacts with the
transition metal compound (h) to form an ion pair;
(A6) a propylene polymer which contains constituent
units derived from propylene in an amount of not less than
90 $ by mol and is different from the propylene homopolymer
(AS); and
1$ (E) an olefin polymer which contains constituent
units derived from one monomer selected from the group
consisting of ethylene, butene and 4-methyl-1-pentene in an
amount of not less than 90 ~ by mol;
said propylene polymer composition containing the
2 0 propylene homopolymer (A5) in an amount of 5 to 95 ~ by
weight, the propylene polymer (A6) in an amount of not more
than 95 $ by weight and the olefin polymer (E) in an amount
of not more than 95 o by weight.
Such propylene polymer composition is excellent in not
25 only heat resistance, rigidity and tensile elongation at
break but also moldability.
CA 02295395 2000-O1-13
1 g
The eleventh propylene polymer composition of the
invention comprises:
(A5) a propylene homopolymer which is obtained by
polymerizing propylene in the presence of an olefin
polymerization catalyst comprising:
(i) (h) a transition metal compound represented
by the above formula (I), and
(ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(i) a compound which reacts with the
transition metal compound (h) to form an ion pair;
(D) an olefin elastomer which is characterized in
that:
(1) the elastomer is a polymer or copolymer of at
least one monomer selected from olefins of 2 to 20 carbon
atoms and polyenes of 5 to 20 carbon atoms,
(2) the elastomer contains constituent units derived
from ethylene, propylene, butene or 4-methyl-1-pentene in
2 0 an amount of less than 90 ~ by mol, and
(3) the elastomer has a glass transition temperature
(Tg) of not higher than 10 °C; and
(E) an olefin polymer which contains constituent
units derived from one monomer selected from the group
2 5 consisting of ethylene, butene and 4-methyl-1-pentene in an
amount of not less than 90 ~ by mol;
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19
said propylene polymer composition containing the
propylene homopolymer (A5) in an amount of 5 to 95 $ by
weight, the olefin elastomer (D) in an amount of not more
than 95 ~ by weight and the olefin polymer (E) in an amount
of not more than 95 ~ by weight.
Such propylene polymer composition is excellent in not
only heat resistance, rigidity and tensile elongation at
break but also impact resistance.
The twelfth propylene polymer composition of the
invention comprises:
(A5) a propylene homopolymer which is obtained by
polymerizing propylene in the presence of an olefin
polymerization catalyst comprising:
(i) (h) a transition metal compound represented
by the above formula (I), and
(ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(i) a compound which reacts with the
2 0 transition metal compound (h) to form an ion pair;
(A6) a propylene polymer which contains constituent
units derived from propylene in an amount of not less than
90 ~ by mol and is different from the propylene homopolymer
(A5) ;
2 5 (D) an olefin elastomer which is characterized in
that:
CA 02295395 2000-O1-13
(1) the elastomer is a polymer or copolymer of at
least one monomer selected from olefins of 2 to 20 carbon
atoms and polyenes of 5 to 20 carbon atoms,
(2) the elastomer contains constituent units derived
5 from ethylene, propylene, butene or 4-methyl-1-pentene in
an amount of less than 90 ~ by mol, and
(3) the elastomer has a glass transition temperature
(Tg) of not higher than 10 °C; and
(E) an olefin polymer, which contains constituent
10 units derived from one monomer selected from the group
consisting of ethylene, butene and 4-methyl-1-pentene in an
amount of not less than 90 ~ by mol;
said propylene polymer composition containing the
propylene homopolymer (A5) in an amount of 5 to 95 ~ by
15 weight, the propylene polymer (A6) in an amount of not more
than 95 ~ by weight, the olefin elastomer (D) in an amount
of not more than 95 ~ by weight and the olefin polymer (E)
in an amount of not more than 95 ~ by weight.
Such propylene polymer composition is excellent in not
2 0 only heat resistance, rigidity and tensile elongation at
break but also moldability and impact resistance.
The thirteenth propylene polymer composition of the
invention comprises:
(A7) a propylene copolymer, in an amount of 5 to 95 ~
2 5 by weight, which is characterized in that:
(1) the propylene copolymer is obtained by
copolymerizing propylene and at least one a-olefin selected
CA 02295395 2000-O1-13
21
from ethylene and a-olefins of 4 to 20 carbon atoms in the
presence of an olefin polymerization catalyst comprising:
(i) (h) a transition metal compound represented
by the above formula (I), and
(ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(i) a compound which reacts with the
transition metal compound (h) to form an ion pair, and
(2) the propylene copolymer contains constituent
units derived from propylene in an amount of not less than
90 ~ by mol; and
(A6) a propylene polymer, in an amount of 5 to 95 ~ by
weight, which contains constituent units derived from
1$ propylene in an amount of not less than 90 ~ by mol and is
different from the propylene copolymer (A7).
Such propylene polymer composition is excellent in not
only heat resistance, rigidity and tensile elongation at
break but also moldability.
2 0 The fourteenth propylene polymer composition of the
invention comprises:
(A7) a propylene copolymer, in an amount of 5 to 95 $
by weight, which is characterized in that:
(1) the propylene copolymer is obtained by
2 5 copolymerizing propylene and at least one a-olefin selected
from ethylene and a-olefins of 4 to 20 carbon atoms in the
presence of an olefin polymerization catalyst comprising:
CA 02295395 2000-O1-13
22
(i) (h) a transition metal compound represented
by the above formula (I), and
(ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(i) a compound which reacts with the
transition metal compound (h) to form an ion pair, and
(2) the propylene copolymer contains constituent
units derived from propylene in an amount of not less than
90 ~ by mol; and
(D) an olefin elastomer, in an amount of 5 to 95 ~ by
weight, which is characterized in that:
(1) the elastomer is a polymer or copolymer of at
least one monomer selected from olefins of 2 to 20 carbon
atoms and polyenes of 5 to 20 carbon atoms,
(2) the elastomer contains constituent units derived
from ethylene, propylene, butene or 4-methyl-1-pentene in
an amount of less than 90 ~ by mol, and
(3) the elastomer has a glass transition temperature
(Tg) of not higher than 10 °C.
Such propylene polymer composition is excellent in not
only heat resistance, rigidity and tensile elongation at
break but also impact resistance.
The fifteenth propylene polymer composition of the
2 5 invention comprises:
(A7) a propylene copolymer, in an amount of 5 to 95 0
by weight, which is characterized in that:
CA 02295395 2000-O1-13
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(1) the propylene copolymer is obtained by
copolymerizing propylene and at least one oc-olefin selected
from ethylene and oc-olefins of 4 to 20 carbon atoms in the
presence of an olefin polymerization catalyst comprising:
$ (i) (h) a transition metal compound represented
by the above formula (I), and
(ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(i) a compound which reacts with the
transition metal compound (h) to form an ion pair, and
(2) the propylene copolymer contains constituent
units derived from propylene in an amount of not less than
90 ~ by mol; and
(E) an olefin polymer, in an amount of 5 to 95 ~ by
weight, which contains constituent units derived from one
monomer selected from the group consisting of ethylene,
butene and 4-methyl-1-pentene in an amount of not less than
90 ~ by mol.
2 0 Such propylene polymer composition is excellent in
heat resistance, rigidity and tensile elongation at break.
The sixteenth propylene polymer composition of the
invention comprises:
(A7) a propylene copolymer which is characterized in
2 5 that
(1) the propylene copolymer is obtained by
copolymerizing propylene and at least one oc-olefin selected
CA 02295395 2000-O1-13
24
from ethylene and oc-olefins of 4 to 20 carbon atoms in the
presence of an olefin polymerization catalyst comprising:
(i) (h) a transition metal compound represented
by the above formula (I), and
(ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(i) a compound which reacts with the
transition metal compound (h) to form an ion pair, and
(2) the propylene copolymer contains constituent
units derived from propylene in an amount of not less than
90 ~ by mol;
(A6) a propylene polymer which contains constituent
units derived from propylene in an amount of not less than
90 ~ by mol and is different from the propylene copolymer
(A7 ) ; and
(D) an olefin elastomer which is characterized in
that:
(1) the elastomer is a polymer or copolymer of at
2 0 least one monomer selected from olefins of 2 to 20 carbon
atoms and polyenes of 5 to 20 carbon atoms,
(2) the elastomer contains constituent units derived
from ethylene, propylene, butene or 4-methyl-1-pentene in
an amount of less than 90 $ by mol, and
2 S (3) the elastomer has a glass transition temperature
(Tg) of not higher than 10 °C;
CA 02295395 2000-O1-13
said propylene polymer composition containing the
propylene copolymer (A7) in an amount of 5 to 95 $ by
weight, the propylene polymer (A6) in an amount of not more
than 95 ~ by weight and the olefin elastomer (D) in an
5 amount of not more than 95 ~ by weight.
Such propylene polymer composition is excellent in not
only heat resistance, rigidity and tensile elongation at
break but also moldability and impact resistance.
The seventeenth propylene polymer composition of the
10 invention comprises:
(A7) a propylene copolymer which is characterized in
that:
(1) the propylene copolymer is obtained by
copolymerizing propylene and at least one a-olefin selected
15 from ethylene and a-olefins of 4 to 20 carbon atoms in the
presence of an olefin polymerization catalyst comprising:
(i) (h) a transition metal compound represented
by the above formula (I), and
(ii) at least one compound selected from the
2 0 group consisting of
(b) an organoaluminum oxy-compound, and
(i) a compound which reacts with the
transition metal compound (h) to form an ion pair, and
(2) the propylene copolymer contains constituent
2 5 units derived from propylene in an amount of not less than
90 ~ by mol;
CA 02295395 2000-O1-13
26
(A6) a propylene polymer which contains constituent
units derived from propylene in an amount of not less than
90 ~ by mol and is different from the propylene copolymer
(A7); and
$ (E) an olefin polymer which contains constituent
units derived from one monomer selected from the group
consisting of ethylene, butene and 4-methyl-1-pentene in an
amount of not less than 90 ~ by mol;
said propylene polymer composition containing the
1 0 propylene copolymer (A7) in an amount of 5 to 95 $ by
weight, the propylene polymer (A6) in an amount of not more
than 95 ~ by weight and the olefin polymer (E) in an amount
of not more than 95 o by weight.
Such propylene polymer composition is excellent in not
15 only heat resistance, rigidity and tensile elongation at
break but also moldability.
The eighteenth propylene polymer composition of the
invention comprises:
(A7) a propylene copolymer which is characterized in
2 0 that
(1) the propylene copolymer is obtained by
copolymerizing propylene and at least one oc-olefin selected
from ethylene and a-olefins of 4 to 20 carbon atoms in the
presence of olefins polymerization catalyst comprising:
2 5 (i) (h) a transition metal compound represented
by the above formula (I), and
CA 02295395 2000-O1-13
27
(ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(i) a compound which reacts with the
transition metal compound (h) to form an ion pair, and
(2) the propylene copolymer contains constituent
units derived from propylene in an amount of not less than
90 ~ by mol;
(D) an olefin elastomer which is characterized in
1 0 that
(1) the elastomer is a polymer or copolymer of at
least one monomer selected from olefins of 2 to 20 carbon
atoms and polyenes of 5 to 20 carbon atoms,
(2) the elastomer contains constituent units derived
from ethylene, propylene, butene or 4-methyl-1-pentene in
an amount of less than 90 ~ by mol, and
(3) the elastomer has a glass transition temperature
(Tg) of not higher than 10 °C; and
(E) an olefin polymer which contains constituent
2 0 units derived from one monomer selected from the group
consisting of ethylene, butene and 4-methyl-1-pentene in an
amount of not less than 90 ~ by mol;
said propylene polymer composition containing the
propylene copolymer (A7) in an amount of 5 to 95 ~ by
2 S weight, the olefin elastomer (D) in an amount of not more
than 95 ~ by weight and the olefin polymer (E) in an amount
of not more than 95 's by weight.
CA 02295395 2000-O1-13
28
Such propylene polymer composition is excellent in not
only heat resistance, rigidity and tensile elongation at
break but also impact resistance.
The nineteenth propylene polymer composition of the
S invention comprises:
(A7) a propylene copolymer which is characterized in
that
(1) the propylene copolymer is obtained by
copolymerizing propylene and at least one a.-olefin selected
from ethylene and oc-olefins of 4 to 20 carbon atoms in the
presence of an olefin polymerization catalyst comprising:
(i) (h) a transition metal compound represented
by the above formula (I), and
(ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(i) a compound which reacts with the
transition metal compound (h) to form an ion pair, and
(2) the propylene copolymer contains constituent
2 0 units derived from propylene in an amount of not less than
90 ~ by mol;
(A6) a propylene polymer which contains constituent
units derived from propylene in an amount of not less than
90 o by mol and is different from the propylene copolymer
(D) an olefin elastomer which is characterized in
that:
CA 02295395 2000-O1-13
29
(1) the elastomer is a polymer or copolymer of at
least one monomer selected from olefins of 2 to 20 carbon
atoms and polyenes of 5 to 20 carbon atoms,
(2) the elastomer contains constituent units derived
from ethylene, propylene, butene or 4-methyl-1-pentene in
an amount of less than 90 ~ by mol, and
(3) the elastomer has a glass transition temperature
(Tg) of not higher than 10 °C; and
(E) an olefin polymer which contains constituent
units derived from one monomer selected from the group
consisting of ethylene, butene and 4-methyl-1-pentene in an
amount of not less than 90 $ by mol;
said propylene polymer composition containing the
propylene copolymer (A7) in an amount of 5 to 95 ~ by
1$ weight, the propylene polymer (A6) in an amount of not more
than 95 ~ by weight, the olefin elastomer (D) in an amount
of not more than 95 ~ by weight and the olefin polymer (E)
in an amount of not more than 95 ~ by weight.
Such propylene polymer composition is excellent in not
2 0 only heat resistance, rigidity and tensile elongation at
break but also moldability and impact resistance.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a view illustrating steps of a process for
2 5 preparing an olefin polymerization catalyst which is used
far the preparation of the propylene polymer (A1) and the
propylene polymer (A2).
CA 02295395 2000-O1-13
Fig. 2 is a view illustrating steps of a process for
preparing an olefin polymerization catalyst which is used
for the preparation of the propylene polymer (A3) and the
propylene polymer (A4).
5 Fig. 3 is a view illustrating steps of a process for
preparing an olefin polymerization catalyst which is used
for the preparation of the ethylene/olefin random copolymer
(C) .
Fig. 4 is a view illustrating steps of a process for
10 preparing an olefin polymerization catalyst which is used
for the preparation of the propylene homopolymer (A5) and
the propylene copolymer (A7).
DETAILED DESCRIPTION OF THE INVENTION
15 The propylene polymer compositions according to the
present invention will be described in detail hereinafter.
The first propylene polymer composition
The first propylene polymer composition comprises:
(A1) a propylene polymer which is characterized in
2 0 that
the propylene polymer is obtained by polymerizing
propylene in the presence of an olefin polymerization
catalyst comprising:
(i) (a) a compound of a Group IVB transition
2 5 metal in the periodic table containing a ligand having a
cyclopentadienyl skeleton, and
CA 02295395 2000-O1-13
31
(ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(c) a compound which reacts with the
transition metal compound (a) to form an ion pair,
the propylene polymer has a melt flow rate (MFR), as
measured at 230 °C under a load of 2.16 kg, of 0.01 to 30
g/10 min, and
the propylene polymer has a molecular weight
distribution (Mw/Mn), as measured by gel permeation
chromatography (GPC), of 2 to 3; and
(A2) a propylene polymer which is characterized in
that:
the propylene polymer is obtained by polymerizing
propylene in the presence of an olefin polymerization
catalyst comprising:
(i) (a) a compound of a Group IVB transition
metal in the periodic table containing a ligand having a
cyclopentadienyl skeleton, and
2 0 (ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(c) a compound which reacts with the
transition metal compound (a) to form an ion pair,
2 5 the propylene polymer has a melt flow rate (MFR), as
measured at 230 °C under a load of 2.16 kg, of 30 to 1,000
g/10 min, and
CA 02295395 2000-O1-13
32
the propylene polymer has a molecular weight
distribution (Mw/Mn), as measured by GPC, of 2 to 4.
In this propylene polymer composition, the ratio
((A2)/(A1)) of the MFR of said propylene polymer (A2) to
the MFR of said propylene polymer (A1) is not less than 30.
The propylene polymer (A1) for constituting the first
propylene polymer composition is a propylene homopolymer or
a propylene copolymer obtained by the use of an olefin
polymerization catalyst comprising a transition metal
compound (a) and at least one compound selected from the
group consisting of an organoaluminum oxy-compound (b) and
a compound (C), all compounds being described later.
The propylene polymer (A1) is desired to have MFR, as
measured at 230 °C under a load of 2.16 kg, of 0.01 to 30
g/10 min, preferably 0.5 to 5.0 g/10 min, and Mw/Mn, as
measured by GPC, of 2 to 3.
Further, the propylene polymer (A1) is desired to have
an intrinsic viscosity [1~] of 1.3 to 5.0 dl/g, preferably
2 0 2.0 to 4.0 dl/g, a weight-average molecular weight of 12 x
10q to 100 x 109, preferably 20 x 104 to 70 x 109, and a
crystallinity, as measured by X-ray diffractometry, of not
less than 40 0, preferably not less than 50 ~.
The propylene polymer (A1) may contain constituent
2 5 units derived from other monomers than propylene, such as
ethylene and oc-olefins of 4 to 20 carbon atoms, e.g., 1-
butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene,
CA 02295395 2000-O1-13
33
1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-
octadecene and 1-eicosene, in an amount of not more than 10
by mol.
Pro~,Xlene polymer fA2)
The propylene polymer (A2) for constituting the first
propylene polymer composition is a propylene homopolymer or
a propylene copolymer obtained by the use of an olefin
polymerization catalyst comprising a transition metal
compound (a) and at least one compound selected from the
group consisting of an organoaluminum oxy-compound (b) and
a compound (C), all compounds being described later.
The propylene polymer (A2) is desired to have MFR, as
measured at 230 °C under a load of 2.16 kg, of 30 to 1,000
g/10 min, preferably 50 to 200 g/10 min, and Mw/Mn, as
measured by GPC, of 2 to 4.
Further, the propylene polymer (A2) is desired to have
an intrinsic viscosity ['~] of not less than 0.5 and less
than 1.3 dl/g, preferably not less than 0.8 and less than
1.3 dl/g, a weight-average molecular weight of 5 x 103 to
2 0 15 x 104, preferably 1 x 104 to 12 x 10q, and a
crystallinity, as measured by X-ray diffractometry, of not
less than 40 0, preferably not less than SO $.
The propylene polymer (A2) may contain constituent
units derived from other monomers than propylene, which are
2 5 exemplified for the propylene polymer (A1), in an amount of
not more than 5 ~ by mol.
CA 02295395 2000-O1-13
34
The first propylene polymer composition comprises the
propylene polymer (A1) and the propylene polymer (A2). In
this composition, it is desired that the propylene polymer
(A1) is contained in an amount of 10 to 90 $ by weight,
preferably 30 to 70 ~ by weight; and the propylene polymer
(A2) is contained in an amount of 10 to 90 ~ by weight,
preferably 30 to 70 ~ by weight. A ratio ((A2)/(A1)] of
the MFR of the propylene polymer (A2) to the MFR of the
propylene polymer (A1) is not less than 30, preferably in
the range of 40 to 300, more preferably 50 to 100.
The first propylene polymer composition is desired to
have MFR, as measured at 230 °C under a load of 2.16 kg, of
1 to 100 g/10 min, preferably 5 to 50 g/10 min. In this
composition, Mw/Mn of all the propylene components for
constituting the composition is desirably in the range of 4
to 15.
The density of the first propylene polymer composition
is desired to be in the range of 0.89 to 0.92 g/cm3,
preferably 0.90 to 0.92 g/cm3.
2 0 The heat distortion temperature (HDT) thereof is
desired to be not lower than 95 °C, preferably in the range
of 100 to 140 °C.
The flexural modulus (FM) thereof is desired to be in
the range of 12,000 to 19,000 kg/cm2, preferably 14,000 to
2 5 18, 000 kg/cmz .
CA 02295395 2000-O1-13
The Izod impact strength (IZ) thereof at 23 °C is
desired to be in the range of 2 to 4 kg~cm/cm, preferably 2
to 3 kg~cm/cm.
The tensile elongation at break (EL) thereof is
S desired to be in the range of 100 to 500 ~, preferably 200
to 400
The first propylene polymer composition may contain
additives, if necessary, such as weathering stabilizer,
heat stabilizer, antistatic agent, anti-slip agent, anti-
10 blocking agent, anti-fogging agent, lubricant, pigment,
dye, nucleating agent, plasticizer, anti-aging agent,
hydrochloric acid absorber and antioxidant, with the
proviso that the object of the invention is not marred.
The first propylene polymer composition can be
1$ prepared by conventionally known processes, for example, by
the following ones.
(1) A process comprising mechanically blending the
propylene polymer (A1), the propylene polymer (A2) and, if
desired, other components by means of an extruder, a
2 0 kneader, etc .
(2) A process comprising dissolving the propylene
polymer (A1), the propylene polymer (A2) and, if desired,
other components in an appropriate good solvent (e. g.,
hydrocarbon solvents such as hexane, heptane, decane,
2 5 cyclohexane, benzene, toluene and xylene), and removing the
solvent.
CA 02295395 2000-O1-13
36
(3) A process comprising individually dissolving the
propylene polymer (A1), the propylene polymer (A2) and, if
desired, other components in appropriate good solvents
respectively to give solutions, then mixing the solutions,
and removing the solvent.
(4) A process comprising conducting the above
processes (1) to (3) in combination.
(5) A process comprising conducting the
polymerization in two or more steps having different
reaction conditions, in the first step of which the
propylene polymer (A1) is prepared, and in another step of
which the propylene polymer (A2) is prepared;
alternatively, comprising using plural polymerizers, in one
polymerizer of which the propylene polymer (A1) is
prepared, and in another polymerizer of which the propylene
polymer (A2) is prepared.
The first propylene polymer composition as mentioned
above is excellent in not only heat resistance, rigidity
and tensile elongation at break but also moldability.
2 0 Further, since the amount of the catalyst residue in the
polymer composition is small, the article molded from the
composition is never colored and is good in sanitariness.
Next, the olefin polymerization catalyst used in the
preparation of the propylene polymer (A1) and the propylene
2 S polymer (A2) and the process for preparing the propylene
polymer (A1) and the propylene polymer (A2) are described.
CA 02295395 2000-O1-13
37
The propylene polymer (A1) and the propylene polymer
(A2) can be prepared by polymerizing propylene in the
presence of an olefin polymerization catalyst [olefin
polymerization catalyst (1)] comprising:
S (i) (a) a compound of a Group IVB transition
metal in the periodic table containing a ligand having a
cyclopentadienyl skeleton, and
(ii) at least one compound selected from the
group consisting of
(b) an organloaluminum oxy-compound, and
(c) a compound which reacts with the
transition metal compound (a) to form an ion pair.
Fig. 1 illustrates steps of a process for preparing
the olefin polymerization catalyst which is used for the
preparation of the propylene polymer (A1) and the propylene
polymer (A2).
Examples of the compound (a) of the Group IVB
transition metal of. the periodic table which contains a
ligand having a cyclopentadienyl skeleton include the
2 0 transition metal compound represented by the following
formula (Ia) and the transition metal compound represented
by the following formula (I).
MLx ...(Ia)
wherein M is a transition metal atom selected from the
2 S group consisting of titanium, zirconium, hafnium, vanadium,
niobium, tantalum and chromium, preferably titanium,
CA 02295395 2000-O1-13
38
zirconium or hafnium, and x is a valence of the transition
metal atom.
L is a ligand coordinating to the transition metal, at
least one of L is a ligand having a cyclopentadienyl
skeleton, and preferably at least two of L are ligands
having a cyclopentadienyl skeleton.
The ligands having a cyclopentadienyl skeleton are,
for example, cyclopentadienyl group, indenyl group,
4,5,6,7-tetrahydroindenyl group, 4,5,6,6a-
tetrahydropentarenyl group; 7,8-dihydro-3H.6H-as-indacenyl
group and fluorenyl group. These groups as exemplified
above may be substituted with an alkyl group, an aryl
group, an aralkyl group, a trialkylsilyl group, a halogen
atom, an alkoxy group, an aryloxy group, a linear alkylene
group or a cyclic alkylene group. Further, these groups
having a cyclopentadienyl skeleton may form ring condensate
with benzene ring, naphthalene ring, acenaphthene ring or
indene ring.
Of the ligands coordinating with the transition metal
2 0 atom, preferred is a ligand having an indenyl skeleton, and
particularly preferred is ligand having a substituted
indenyl skeleton.
When the transition metal compound represented by the
above general formula (Ia) contains 2 or more ligands each
2 $ having a cyclopentadienyl skeleton, the two ligands out of
them may be linked together through
an alkylene group such as ethylene or propylene;
CA 02295395 2000-O1-13
39
a substituted alkylene group such as 1,2-
di(methyl)ethylene;
a cycloalkylene group such as 1,4-cyclohexylene or
1,3-cyclopentylene;
a substituted alkylidene group such as isopropylidene
or diphenylmethylene;
a silylene group;
a substituted silylene group such as dimethylsilylene,
diphenylsilylene or methylphenylsilylene;
a germyl group;
-P (Ra) -, -P (0) (Rb) -, S02N- (Rc) - or Sn (Rd2 ) - [wherein
each of Ra, Rc and Rd2 is an alkyl group, and Rb is an aryl
group].
Of these, particularly preferred is ligand linked
together through a substituted silylene group such as
dimethylsilylene group, diphenylsilylene group or
methylphenylsilylene group.
Example the ligands L other than those having a
cyclopentadienyl skeleton may include
2 0 a hydrocarbon group of 1-10 carbon atoms such as an
alkyl group (e. g. methyl group, ethyl group, propyl group,
isopropyl group, butyl group, propyl group, pentyl group or
neopentyl group), a cycloalkyl group (e. g. cyclopentyl
group or cyclohexyl group), an aryl group (e. g. phenyl
2 5 group, tolyl group or mesityl group) and an aralkyl group
(e. g. benzyl or neophyl),
CA 02295395 2000-O1-13
an alkoxy group of 1-10 carbon atoms such as methoxy
group, ethoxy group, propoxy group or butoxy group,
an aryloxy group of 6-10 carbon atoms such as phenoxy
group,
S a ligand represented by -OS02Re or -CH2SiReg (wherein
Re is a hydrocarbon group of 1-10 carbon atoms) such as
mesitylsulfonate, phenylsulfonate, benzylsulfonate,
methylsulfonate, p-toluenesulfonate or
trifluoromethanesulfonate, .
10 a halogen atom such as fluorine, chlorine, bromine or
iodine, and
hydrogen atom.
When the transition metal compound contains 2 or more
ligands other than those having a cyclopentadienyl
1S skeleton, each ligand may be the same or different.
When the valence of the transition metal atom is, for
example, 4, the transition metal compound represented by
the above formula (Ia) is represented by the following
formula (Ib) in more detail.
R4kRS(R6mR~nM ... (Ib)
wherein M represents the above mentioned transition metal
atom, R4 represents a ligand having a cyclopentadienyl
skeleton as in the above formula (Ia), R5, R6 and R~ each
represent a ligand having a cyclopentadienyl skeleton or a
2 S ligand L other than those having a cyclopentadienyl
skeleton, k is an integer of 1 or more, and k+l+m+n=4.
CA 02295395 2000-O1-13
41
In the present invention, there is used preferably a
transition metal compound having the above-mentioned
formula ( Ib) in which at least two of R4, R5, R6 and R~ are
the substituted indenyl groups. In this case, these groups
S are prefereably linked together through a group as in the
above formula (Ia).
Exemplified below are the transition metal compounds
wherein M is zirconium.
rac-ethylene-bis{1-(2-methylindenyl)}zirconium
dichloride,
rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
dichloride,
rac-dimethylsilylene-bis{1-(2-methylindenyl))zirconium
dihydride,
rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
difluoride,
rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
dibromide,
rac-dimethylsilylene-bis{1-(2-methylindenyl)}'zirconium
2 0 diiodide,
rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
dimethoxide,
rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
di-n-butoxide,
2 5 rac-dimethylsilylene-bis(1-(2-methylindenyl)}zirconium
diphenoxide,
CA 02295395 2000-O1-13
42
rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
di-t-butoxide,
rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
dimethyl,
rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
dineopentyl,
rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
ditrimethylsilylmethyl,
rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
ditosylate,
rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
dimesilate,
rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
di(mesitylsulfonate),
1$ rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
di(phenylsulfonate),
rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
di(benzylsulfonate),
rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
2 0 di(trifluoromethanesulfonate),
rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
monochloride monohydride,
rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
monochloride monofluoride,
2 5 rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
monochloride monobromide,
CA 02295395 2000-O1-13
43
rac-dimethylsilylene-bis(1-(2-methylindenyl)}zirconium
monochloride monoiodide,
rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
monochloride monomethoxide,
rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
monochloride mono-n-butoxide,
rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
monochloride monophenoxide,
rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
monochloride mono-t-butoxide,
rac-dimethylsilylene-bis(1-(2-methylindenyl)}zirconium
monochloride monomethyl,
rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
monochloride mononeopentyl,
1$ rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
monochloride monotrimethylsilylmethyl,
rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
monochloride monotosylate,
rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
2 0 monochloride monomesilate,
rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
monochloride mono(mesitylsulfonate),
rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
monochloride mono(phenylsulfonate),
2 5 rac-dimethylsilylene-bis(1-(2-methylindenyl)}zirconium
monochloride mono(benzylsulfonate),
CA 02295395 2000-O1-13
44
rac-dimethylsilylene-bis{1-(2-methylindenyl)}zirconium
monochloride mono(trifluoromethanesulfonate),
rac-diphenylsilylene-bis{1-(2-methylindenyl)}zirconium
dichloride,
$ rac-methylphenylsilylene-bis{1-(2-
methylindenyl)}zirconium dichloride,
rac-silylene-bis{1-(2-methylindenyl)}zirconium
dichloride,
rac-dimethylgermylene-bis{1-(2-
methylindenyl)}zirconium dichloride,
rac-phenylphosphinylene-bis{1-(2-
methylindenyl)}zirconium dichloride,
rac-ethylene-bis{1-(2,4-dimethylindenyl)}zirconium
dichloride,
rac-ethylene-bis{1-(2-methyl, 9-
isopropylindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2,4-
dimethylindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-methyl, 4-
2 0 ethylindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-{2-methyl, 4-n-
propylindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-methyl,
isopropylindenyl)}zirconium dichloride,
2 5 rac-dimethylsilylene-bis{1-(2-methyl, 4-n-
butylindenyl)}zirconium dichloride,
CA 02295395 2000-O1-13
rac-dimethylsilylene-bis{1-(2-methyl, 4-i-
butylindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-methyl, 4-t-
butylindenyl)}zirconium dichloride,
5 rac-dimethylsilylene-bis{1-(2-methyl, 4-
trimethylsilylindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-ethyl, 4-
isopropylindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-n-propyl, 4-
10 isopropylindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-i-propyl, 4-
isopropylindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-n-butyl, 4-
isopropylindenyl)}zirconium dichloride,
15 rac-dimethylsilylene-bis{1-(2-i-butyl, 4-
isopropylindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-t-butyl, 4-
isopropylindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-trimethylsilyl, 4-
2 0 isopropylindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-phenyl, 4-
isopropylindenyl)}zirconium dichloride,
rac-diphenylsilylene-bis{1-(2,4-
dimethylindenyl)}zirconium dichloride,
2 S rac-diphenylsilylene-bis{1-(2-methyl, 4-
isopropylindenyl)}zirconium dichloride,
CA 02295395 2000-O1-13
46
rac-methylphenylsilylene-bis{1-(2,4-
dimethylindenyl)}zirconium dichloride,
rac-methylphenylsilylene-bis(1-(2-methyl, 4-
isopropylindenyl)}zirconium dichloride,
S rac-ethylene-bis{1-(2,5-dimethylindenyl)}zirconium
dichloride,
rac-ethylene-bis{1-(2-methyl, 5-
isopropylindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2,5-
dimethylindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-methyl, 5-
isopropylindenyl)}zirconium dichloride,
rac-diphenylsilylene-bis{1-(2,5-
dimethylindenyl)}zirconium dichloride,
rac-diphenylsilylene-bis{1-(2-methyl, 5-
isopropylindenyl)}zirconium dichloride,
rac-methylphenylsilylene-bis{1-(2,5-
dimethylindenyl)}zirconium dichloride,
rac-methylphenylsilylene-bis{1-(2-methyl, 5-
2 0 isopropylindenyl)}zirconium dichloride,
rac-ethylene-bis{1-(2,6-dimethylindenyl)}zirconium
dichloride,
rac-ethylene-bis{1-(2-methyl, 6-
isopropylindenyl))zirconium dichloride,
2 $ rac-dimethylsilylene-bis{1-(2,6-
dimethylindenyl)}zirconium dichloride,
CA 02295395 2000-O1-13
47
rac-dimethylsilylene-bis{1-(2-methyl, 6-
isopropylindenyl)}zirconium dichloride,
rac-diphenylsilylene-bis{1-(2,6-
dimethylindenyl)}zirconium dichloride,
rac-diphenylsilylene-bis{1-(2-methyl, 6-
isopropylindenyl) }zirconium dichloride,
rac-methylphenylsilylene-bis{1-(2,6-
dimethylindenyl)}zirconium dichloride,
rac-methylphenylsilylene-bis{1-(2-methyl, 6-
isopropylindenyl)}zirconium dichloride,
rac-ethylene-bis{1-(2,4,5-trimethylindenyl)}zirconium
dichloride,
rac-ethylene-bis{1-(2-isopropyl-4,5-
dimethylindenyl)}zirconium dichloride,
1$ rac-dimethylsilylene-bis{1-(2,4,5-
trimethylindenyl)}zirconium dichloride,
rac-diphenylsilylene-bis{1-(2,4,5-
trimethylindenyl)}zirconium dichloride,
rac-methylphenylsilylene-bis{1-(2,4,5-
2 0 trimethylindenyl)}zirconium dichloride,
rac-ethylene-bis{1-(2,5,6-trimethylindenyl)}zirconium
dichloride,
rac-dimethylsilylene-bis{1-(2,5,6-
trimethylindenyl)}zirconium dichloride,
2 S rac-diphenylsilylene-.bis{1-(2,5,6-
trimethylindenyl)}zirconium dichloride,
CA 02295395 2000-O1-13
48
rac-methylphenylsilylene-bis{1-(2,5,6-
trimethylindenyl)}zirconium dichloride,
rac-ethylene-bis{1-(2-methyl-5-t-
butylindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-methyl-5-t-
butylindenyl)}zirconium dichloride,
rac-diphenylsilylene-bis{1-(2-methyl-5-t-
butylindenyl)}zirconium dichloride,
rac-methylphenylsilylene-bis{1-(2-methyl-5-t-
butylindenyl)}zirconium dichloride,
rac-ethylene-bis{1-(2-methyl-6-t-
butylindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-methyl-6-t-
butylindenyl)}zirconium dichloride,
rac-diphenylsilylene-bis{1-(2-methyl-6-t-
butylindenyl)}zirconium dichloride,
rac-methylphenylsilylene-bis{1-(2-methyl-6-t-
butylindenyl)}zirconium dichloride,
rac-ethylene-bis{1-(2-methyl-5,6-di-t-
2 ~ butylindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-methyl-5,6-di-t-
butylindenyl)}zirconium dichloride,
rac-diphenylsilylene-bis{1-(2-methyl-5,6-di-t-
butylindenyl)}zirconium dichloride,
2 S rac-methylphenylsilylene-bis{1-(2-methyl-5,6-di-t-
butylindenyl)}zirconium dichloride,
CA 02295395 2000-O1-13
49
rac-ethylene-bis{1-(2-methyl-5-
trimethylsilylindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-methyl-5-
trimethylsilylindenyl)}zirconium dichloride,
S rac-diphenylsilylene-bis{1-(2-methyl-5-
trimethylsilylindenyl)}zirconium dichloride,
rac-methylphenylsilylene-bis{1-(2-methyl-5-
trimethylsilylindenyl)}zirconium dichloride,
rac-ethylene-bis(1-(2-methyl-6-
trimethylsilylindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-methyl-6-
trimethylsilylindenyl)}zirconium dichloride,
rac-diphenylsilylene-bis{1-(2-methyl-6-
trimethylsilylindenyl)}zirconium dichloride,
rac-methylphenylsilylene-bis(1-(2-methyl-6-
trimethylsilylindenyl)}zirconium dichloride,
rac-ethylene-bis{1-(2-methyl-5,6-
bistrimethylsilylindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-methyl-5,6-
2 ~ bistrimethylsilylindenyl)}zirconium dichloride,
rac-diphenylsilylene-bis{1-(2-methyl-5,6-
bistrimethylsilylindenyl)}zirconium dichloride,
rac-methylphenylsilylene-bis{1-(2-methyl-5,6-
bistrimethylsilylindenyl)}zirconium dichloride,
2 5 rac-ethylene-bis(1-(2-methyl-5,6-
bistriphenylsilylindenyl)}zirconium dichloride,
CA 02295395 2000-O1-13
rac-dimethylsilylene-bis{1-(2-methyl-5,6-
bistriphenylsilylindenyl)}zirconium dichloride,
rac-ethylene-bis{1-(2-methyl-4-
methoxyindenyl)}zirconium dichloride,
5 rac-dimethylsilylene-bis{1-(2-methyl-4-
methoxyindenyl)}zirconium dichloride,
rac-diphenylsilylene-bis{1-(2-methyl-4-
methoxyindenyl)}zirconium dichloride,
rac-methylphenylsilylene-bis{1-(2-methyl-4-
10 methoxyindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-methyl-5-
methoxyindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-methyl-6-
methoxyindenyl)}zirconium dichloride,
15 rac-ethylene-bis{1-(2-methyl-5,6-
dimethoxyindenyl)}zirconium dichloride,
ethylene-bis{1-(2-methyl-4,5,6,7-
tetrahydroindenyl)}zirconium dichloride,
dimethylsilylene-bis{1-(4,5,6,7-
2 0 tetrahydroindenyl)}zirconium dichloride,
dimethylsilylene-bis{1-(2-methyl-4,5,6,7-
tetrahydroindenyl)}zirconium dichloride,
dimethylsilylene-bis{1-(2-
methylcyclopentadienyl)}zirconium dichloride,
2 5 dimethylsilylene-bis{1-(3-
methylcyclopentadienyl)}zirconium dichloride,
CA 02295395 2000-O1-13
51
dimethylsilylene-bis{1-(4-
methylcyclopentadienyl)}zirconium dichloride,
dimethylsilylene-bis{1-(5-
methylcyclopentadienyl)}zirconium dichloride,
S dimethylsilylene-bis(1-(2,4-
dimethylcyclopentadienyl)}zirconium dichloride,
dimethylsilylene-bis{1-(2,5-
dimethylcyclopentadienyl))zirconium dichloride,
dimethylsilylene-bis(1,-(2,4,5-
trimethylcyclopentadienyl)}zirconium dichloride,
MeZ
dimethylsilylene-
Si
bis (benzo [e] indenyl)
zirconium dichloride
dc~ a
b zrCl2
1 2 Me2
dimethylsilylene-bis(1,2-
Si dihydroacenaphthylo[4,5-
~4
b]cyclopentadienyl)
:' ~ zirconium dichloride
,,'zrCly
Me2
dimethylsilylene-bis(7,8-
Si 5 6 dihydro-3H,6H-3-as-
4
indathenyl)zirconium
dichloride
2. ~~ 8
~ZrCl2 1
CA 02295395 2000-O1-13
52
a d c
n dimethylsilylene-
bis (benzo[f] indenyl)
gvh
zirconium dichloride
Me2Si ZrCl2
Ph
dimethylsilylene-bis{1-
Me (toluo[4,3-f]-2-methyl-4-
v v ~.,,, phenylindenyl) } zirconium
Me
Mezsi , zrCl2 dichloride
Me
Me
Ph
ne0-C5H11 dimethylsilylene-bis { 1-
Me (benzo [f ] -2-methyl-4-
neopentylindenyl)zirconium
dichloride
Me2Si 2rC12
Me
neo-C5H11
There may also be used the compounds obtained by
substituting titanium, hafnium, vanadium, niobium, tantalum
or chromium for zirconium in the above-exemplified
zirconium compounds.
Of the transition metal compounds represented by the
aforesaid formula (Ia), preferred are those having
zirconium as the central metal atom and having at least two
ligands containing an indenyl skeleton.
CA 02295395 2000-O1-13
S3
In the present invention, transition metal compounds
preferably used as the transition metal compound (a) are
those represented by the following formula (I):
X1 X2
M
R2
Ri
S Y ~I~
wherein M is a transition metal atom of Group IVa, Group Va
and Group VIa of the periodic table. Examples the
transition metal atoms include titanium, zirconium,
hafnium, vanadium, niobium, tantalum, chromium, molybdenum
and tungsten. Of these, preferred are titanium, zirconium
and hafnium, and particularly preferred is zirconium.
R1 is a hydrocarbon group of 2 to 6 carbon atoms.
Examples of the hydrocarbon groups include an alkyl group
1S such as ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-
butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl and
cyclohexyl; and an alkenyl group such as vinyl and
propenyl.
Of these, preferred are alkyl groups whose carbon
2 0 bonded to the indenyl group is primary carbon, more
preferred are alkyl groups of 2 to 4 carbon atoms whose
carbon bonded to the indenyl group is primary carbon, and
particularly preferred is ethyl.
CA 02295395 2000-O1-13
I
54
Rz is an aryl group of 6 to 16 carbon atoms. Examples
of the aryl groups include phenyl, oc-naphthyl, ~3-naphthyl,
anthracenyl, phenanthryl, pyrenyl, acenaphthyl, phenarenyl,
aceanthryrenyl, tetrahydronaphthyl and indanyl. Of these,
preferred are phenyl, naphthyl, anthracenyl and
phenanthryl.
These aryl groups may be substituted with:
halogen atoms, such as fluorine, chlorine, bromine and
iodine;
hydrocarbon groups of 1 to 20 carbon atoms, such as
alkyl groups (e. g., methyl, ethyl, propyl, butyl, hexyl
cyclohexyl, octyl, nonyl, dodecyl, icosyl, norbornyl and
adamantyl), alkenyl groups (e.g., vinyl, propenyl and
cyclohexenyl), arylalkyl groups (e. g., benzyl, phenylethyl
and phenylpropyl) and aryl groups (e. g., phenyl, tolyl,
dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl,
biphenyl, naphthyl, methylnaphthyl, anthracenyl and
phenanthryl); and
organosilyl groups, such as trimethylsilyl,
2 0 triethylsilyl and triphenylsilyl.
X1 and Xz are each a hydrogen atom, a halogen atom, a
hydrocarbon group of 1 to 20 carbon atoms, a halogenated
hydrocarbon group of 1 to 20 carbon atoms, an oxygen-
containing group or a sulfur-containing group. As the
2 S halogen atom and the hydrocarbon group of 1 to 20 carbon
atoms, the aforesaid atoms and groups can be exemplified.
As the halogenated hydrocarbon group of 1 to 20 carbon
CA 02295395 2000-O1-13
atoms, groups obtained by substituting the aforesaid
hydrocarbon groups with halogen atoms can be exemplified.
Examples of the oxygen-containing groups include
hydroxy group; alkoxy groups such as methoxy, ethoxy,
5 propoxy and butoxy; aryloxy groups such as phenoxy,
methylphenoxy, dimethylphenoxy and naphthoxy; and
arylalkoxy groups such as phenylmethoxy and phenylethoxy.
Examples of the sulfur-containing groups include
substituents obtained by substituting sulfur for oxygen in
10 the above-mentioned oxygen-containing groups; sulfonate
groups such as methylsulfonate, trifluoromethanesulfonate,
phenylsulfonate, benzylsulfonate, p-toluenesulfonate,
trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-
chlorobenzenesulfonate and pentafluorobenzenesulfonate; and
15 sulfinate groups such as methylsulfinate, phenylsulfinate,
benzenesulfonate, p-toluenesulfinate,
trimehtylbenzenesulfinate and pentafluorobenzenesulfinate.
Of these, preferred are halogen atoms and hydrocarbon
groups of 1 to 20 carbon atoms.
2 0 Y is a divalent hydrocarbon group of 1 to 20 carbon
atoms, a divalent halogenated hydrocarbon group of 1 to 20
carbon atoms, a divalent silicon-containing group, a
divalent germanium-containing group, a divalent tin-
containing group, -O-, -CO-, -S-, -SO-, -S02-, -NR3-, -
2 5 P (R3) -, -P (0) (R3) -, -BR3- or -A1R3- (R3 is a hydrogen atom,
a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms
CA 02295395 2000-O1-13
56
or a halogenated hydrocarbon group of 1 to 20 carbon
atoms). More specifically, there can be mentioned:
divalent hydrocarbon groups of 1 to 20 carbon atoms,
such as alkylene groups, e.g., methylene,
dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene,
1,3-trimethylene, 1,4-tetramethylene and 1,2-cyclohexylene,
1,4-cyclohexylene, and arylalkylene groups, e.g.,
diphenylmethylene and diphenyl-1,2-ethylene;
halogenated hydrocarbon groups obtained by
halogenating the above-mentioned divalent hydrocarbon
groups of 1 to 20 carbon atoms, such as chloromethylene;
divalent silicon-containing groups, such as
alkylsilylene, alkylarylsilylene and arylsilylene groups,
e.g., methylsilylene, dimethylsilylene, diethylsilylene,
di(n-propyl)silylene, di(i-propyl)silylene,
di(cyclohexyl)silylene, methylphenylsilylene,
diphenylsilylene, di(p-tolyl)silylene and di(p-
chlorophenyl)silylene, and alkyldisilyl, alkylaryldisilyl
and aryldisilyl groups, e.g., tetramethyl-1,2-disilyl and
2 0 tetraphenyl-1,2-disilyl;
divalent germanium-containing groups obtained by
substituting germanium for silicon in the above-mentioned
divalent silicon-containing groups; and
divalent tin-containing groups obtained by
2 5 substituting tin for silicon in the above-mentioned
divalent silicon-containing groups.
CA 02295395 2000-O1-13
57
R3 is the same halogen atom, the same hydrocarbon
group of 1 to 20 carbon atoms or the same halogenated
hydrocarbon group of 1 to 20 carbon atoms as described
above.
Of these, preferred are divalent silicon-containing
groups, divalent germanium-containing groups and divalent
tin-containing groups; more preferred are divalent silicon-
containing groups; and most preferred are alkylsilylene,
alkylarylsilylene and arylsilylene.
Exemplified below are the transition metal compounds
represented by the above formula (I).
rac-dimethylsilylene-bis{1-(2-ethyl-4-
phenylindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-ethyl-4-(a-
naphthyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-ethyl-4-(~-
naphthyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis(1-(2-ethyl-4-(2-methyl-1-
naphthyl)indenyl)}zirconium dichloride,
2 0 rac-dimethylsilylene-bis{1-(2-ethyl-4-(5-
acenaphthyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-ethyl-4-(9-
anthracenyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis(1-(2-ethyl-4-(9-
2 5 phenantoryl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-ethyl-4-(0-
methylphenyl)indenyl)}zirconium dichloride,
CA 02295395 2000-O1-13
58
rac-dimethylsilylene-bis{1-(2-ethyl-4-(m-
methylphenyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-ethyl-4-(p-
methylphenyl)indenyl)}zirconium dichloride,
S rac-dimethylsilylene-bis{1-(2-ethyl-4-(2,3-
dimethylphenyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-ethyl-4-(2,4-
dimethylphenyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-ethyl-4-(2,5-
dimethylphenyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-ethyl-4-(2,4,6-
trimethylphenyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-ethyl-4-(0-
chlorophenyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-ethyl-4-(m-
chlorophenyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-ethyl-4-(p-
chlorophenyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-ethyl-4-(2,3-
2 ~ dichlorophenyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-ethyl-4-(2,6-
dichlorophenyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-ethyl-4-(3,5-
dichlorophenyl)indenyl)}zirconium dichloride,
2 5 rac-dimethylsilylene-bis{1-(2-ethyl-4-(2-
bromophenyl)indenyl)}zirconium dichloride,
CA 02295395 2000-O1-13
59
rac-dimethylsilylene-bis{1-(2-ethyl-4-(3-
bromophenyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-ethyl-4-(4-
bromophenyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-ethyl-4-(4-
biphenylyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-ethyl-4-(4-
trimethylsilylphenyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-n-propyl-4-
phenylindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-n-propyl-4-(a-
naphthyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-n-propyl-4-(~-
naphthyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-n-propyl-4-(2-methyl-1-
naphthyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-n-propyl-4-(5-
acenaphthyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-n-propyl-4-(9-
2 0 anthracenyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-n-propyl-4-(9-
phenantoryl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-i-propyl-4-
phenylindenyl)}zirconium dichloride,
2 S rac-dimethylsilylene-bis{1-(2-i-propyl-4-(a-
naphthyl)indenyl)}zirconium dichloride,
CA 02295395 2000-O1-13
rac-dimethylsilylene-bis{1-(2-i-propyl-4-(~-
naphthyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-i-propyl-4-(2-methyl-1-
naphthyl)indenyl)}zirconium dichloride,
5 rac-dimethylsilylene-bis{1-(2-i-propyl-4-(S-
acenaphthyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-i-propyl-4-(9-
anthracenyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-i-propyl-4-(9-
10 phenantoryl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-s-butyl-4-
phenylindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-s-butyl-4-(a-
naphthyl)indenyl)}zirconium dichloride,
15 rac-dimethylsilylene-bis{1-(2-s-butyl-4-(~-
naphthyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-s-butyl-4-(8-methyl-9-
naphthyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-s-butyl-4-(5-
2 0 acenaphthyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-s-butyl-4-(9-
anthracenyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-s-butyl-4-(9-
phenantoryl)indenyl)}zirconium dichloride,
2 S rac-dimethylsilylene-bis{1-(2-n-pentyl-4-
phenylindenyl)}zirconium dichloride,
CA 02295395 2000-O1-13
61
rac-dimethylsilylene-bis{1-(2-n-pentyl-4-(a-
naphthyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-n-butyl-4-
phenylindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-n-butyl-4-(a-
naphthyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-n-butyl-4-(~-
naphthyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-n-butyl-4-(2-methyl-1-
naphthyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-n-butyl-4-(S-
acenaphthyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-n-butyl-4-(9-
anthracenyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-n-butyl-4-(9-
phenantoryl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-i-butyl-4-
phenylindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-i-butyl-4-(a-
2 0 naphthyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-i-butyl-4-(~-
naphthyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-i-butyl-4-(2-methyl-1-
naphthyl)indenyl)}zirconium dichloride,
2 $ rac-dimethylsilylene-bis{1-(2-i-butyl-4-(5-
acenaphthyl)indenyl)}zirconium dichloride,
CA 02295395 2000-O1-13
62
rac-dimethylsilylene-bis{1-(2-i-butyl-4-(9-
anthracenyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-i-butyl-4-(9-
phenantoryl)indenyl)}zirconium dichloride,
S rac-dimethylsilylene-bis{1-(2-neopentyl-4-
phenylindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-neopentyl-4-(a-
naphthyl)indenyl)}zirconium dichloride,
rac-dimethylsilylene-b,is{1-(2-n-hexyl-4-
phenylindenyl)}zirconium dichloride,
rac-dimethylsilylene-bis{1-(2-n-hexyl-4-(a-
naphthyl)indenyl)}zirconium dichloride,
rac-methylphenylsilylene-bis{1-(2-ethyl-4-
phenylindenyl)}zirconium dichloride,
1S rac-methylphenylsilylene-bis{1-(2-ethyl-4-(a-
naphthyl)indenyl)}zirconium dichloride,
rac-methylphenylsilylene-bis{1-(2-ethyl-4-(9-
anthracenyl)indenyl)}zirconium dichloride,
rac-methylphenylsilylene-bis{1-(2-ethyl-4-(9-
2 0 phenantoryl)indenyl)}zirconium dichloride,
rac-diphenylsilylene-bis{1-(2-ethyl-4-
phenylindenyl)}zirconium dichloride,
rac-diphenylsilylene-bis{1-(2-ethyl-4-(a-
naphthyl)indenyl)}zirconium dichloride,
2 S rac-diphenylsilylene-bis{1-(2-ethyl-4-(9-
anthracenyl)indenyl)}zirconium dichloride,
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rac-diphenylsilylene-bis{1-(2-ethyl-4-(9-
phenantoryl)indenyl)}zirconium dichloride,
rac-diphenylsilylene-bis{1-(2-ethyl-4-(4-
biphenyl)indenyl)}zirconium dichloride,
rac-methylene-bis{1-(2-ethyl-4-
phenylindenyl)}zirconium dichloride,
rac-methylene-bis{1-(2-ethyl-4-(a-
naphthyl)indenyl)}zirconium dichloride,
rac-ethylene-bis{1-(2-ethyl-4-phenylindenyl))zirconium
1~ dichloride,
rac-ethylene-bis{1-(2-ethyl-4-(a-
naphthyl)indenyl)}zirconium dichloride,
rac-ethylene-bis{1-(2-n-propyl-4-(a-
naphthyl)indenyl)}zirconium dichloride,
rac-dimethylgermyl-bis{1-(2-ethyl-4-
phenylindenyl)}zirconium dichloride,
rac-dimethylgermyl-bis{1-(2-ethyl-4-(a-
naphthyl)indenyl)}zirconium dichloride, and
rac-dimethylgermyl-bis{1-(2-n-propyl-4-
2 0 phenylindenyl)}zirconium dichloride.
There may also be used the transition metal compounds
obtained by substituting titanium metal, hafnium metal,
vanadium metal, niobium metal, tantalum metal, chromium
metal, molybdenum metal or tungsten metal for zirconium
2 $ metal in the above-exemplified compounds.
The transition metal compounds represented by the
above formula (I) can be prepared in accordance with the
CA 02295395 2000-O1-13
64
S
methods described in Journal of Organometallic Chem. 288
(1985), pages 63 to 67, European Patent Publication No.
0,320,762 specification and Examples thereof, for instance,
by the following manner.
Z-Y-Z
2H2Ra + 2-butyl-Li -~ 2HRaLi
2-butyl-Li
HRa-Y-RaH
MClq
LiRa-Y-RaLi
Ra C1 Ra X1
/ \ / XlLi / \ /
I S Y M --> Y M
\ / \ \ / \
Ra C1 Ra C1
Ra X1
2 0 x2Li / \ /
Y M
\ / \
Ra X2
wherein, Z represents C1, Br, I or o-tosyl group, and
R2
~ R
H2Ra represents H H ,
CA 02295395 2000-O1-13
Though the transition metal compounds represented by
the aformentioned formula (Ij are usually used in the form
of racemic modification, R-type or S-type may also be used.
These transition metal compounds may be used singly or
5 in combination of two or more kinds. Further, they may be
diluted in hydrocarbon or halogenated hydrocarbon.
The organoaluminum oxy-compound which forms the olefin
polymerization catalyst (1) for polymerization of the
propylene polymer (A1) and the propylene polymer (2) may be
10 a known benzene-soluble aluminoxane or the benzene-
insoluble organoaluminum oxy-compound having been disclosed
in JP-A-2-78687/1990.
The above-mentioned known aluminoxane may be prepared,
for example, by the following procedures:
15 (1) a procedure for recovering an aluminoxane as its
hydrocarbon solution which comprises adding an
organoaluminum compound such as trialkylaluminum to a
suspension in a hydrocarbon medium of a compound containing
adsorbed water, or a salt containing water of
2 0 crystallization such as magnesium chloride hydrate, copper
sulfate hydrate, aluminum sulfate hydrate, nickel sulfate
hydrate and cerium chloride hydrate, and reacting the
organoaluminum compound;
(2) a procedure for recovering an aluminoxane as its
2 S hydrocarbon solution which comprises reacting water, ice or
steam directly with an organoaluminum compound such as
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trialkylaluminum in a solvent such as benzene, toluene,
ethyl ether and tetrahydrofuran; and
(3) a procedure for recovering an aluminoxane which
comprises reacting an organotinoxide such as
$ dimethyltinoxide and dibutyltinoxide with an organoaluminum
compound such as trialkylaluminum in a solvent such as
decane, benzene or toluene.
Moreover, the aluminoxane may contain a small amount
of an organometal component,. Furthermore, the solvent or
1~ unreacted organoaluminum compound may be removed from the
above-mentioned recovered aluminoxane-containing solution,
by distillation, and the aluminoxane may be redissolved in
a solvent.
Concrete examples of the organoaluminum compound used
15 for the preparation of the aluminoxane include
trialkylaluminum such as trimethylaluminum,
triethylaluminum, tripropylaluminum, triisopropylaluminum,
tri-n-butylaluminum, triisobutylaluminum, tri-sec-
butylaluminum, tri-tert-butylaluminum, tripentylaluminum,
2 0 trihexylaluminum, trioctylaluminum and tridecylaluminum;
tricycloalkylaluminums such as tricyclohexylaluminum
and tricyclooctylaluminum;
dialkylaluminum halides such as dimethylaluminum
chloride, diethylaluminum chloride, diethylaluminum bromide
2 5 and diisobutylaluminum chloride;
dialkylaluminum hydrides such as diethylaluminum
hydride and diisobutylaluminum hydride;
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dialkylaluminum alkoxides such as dimethylaluminum
methoxide and diethylaluminum ethoxide: and
dialkylaluminum aryloxides such as diethylaluminum
phenoxide.
Of these compounds, trialkylaluminum and tricyclo-
alkylaluminum are preferable, and trimethylaluminum is
particularly preferable.
Furthermore, there may also be used as the
organoaluminum compound isoprenylaluminum represented by
the general formula
(i-C4H9) xAly (CSHlp) z
wherein x, y and z are each a positive number, and z >_ 2x.
The organoaluminum compounds mentioned above may be
used either singly or in combination.
Solvents used for the solutions of the aluminoxane
include aromatic hydrocarbons such as benzene, toluene,
xylene, cumene and cymene; aliphatic hydrocarbons such as
pentane, hexane, heptane, octane, decane, dodecane,
hexadecane and octadecane; alicyclic hydrocarbons such as
2 0 cyclopentane, cyclohexane, cyclooctane and
methylcyclopentane; petroleum fractions such as gasoline,
kerosene and gas oil; and halogenated compounds derived
from the above-mentioned aromatic hydrocarbons, aliphatic
hydrocarbons and alicyclic hydrocarbons, especially
2 5 chlorinated and brominated hydrocarbons. In addition,
there may also be used ethers such as ethyl ether and
tetrahydrofuran. Of these solvents as exemplified above,
CA 02295395 2000-O1-13
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aromatic hydrocarbons or aliphatic hydrocarbons are
particularly preferred.
As the compound (c) which reacts with the aforesaid
transition metal compound (a) to form an ion pair and which
S is used for forming the olefin polymerization catalyst (1)
employable for the preparation of the propylene polymer
(A1) and the propylene polymer (A2), there can be mentioned
Lewis acid, ionic compounds and carborane compounds
described in JP-A-1-501950/,1989, JP-A-1-502036/1989, JP-A-
3-179005/1992, JP-A-3-179006/1992, JP-A-3-207703/1992 and
JP-A-3-207704/1992, and U.S. Patent Application No. 547718
(now USP 5, 321, 106).
Examples of the Lewis acid include triphenylboron,
tris(4-fluorophenyl)boron, tris(p-tolyl)boron, tris(o-
tolyl)boron, tris(3,5-dimethylphenyl)boron,
tris (pentafluorophenyl) boron, MgCl2, A1203 and Si02-A1203.
Examples of the ionic compounds include
triphenylcarbeniumtetrakis(pentafluorophenyl)borate, tri-n-
butylammoniumtetrakis(pentafluorophenyl)borate, N,N-
2 0 dimethylaniliniumtetrakis(pentafluorophenyl)borate and
ferroceniumtetra(pentafluorophenyl)borate.
Examples of the carborane compounds include
dodecaborane, 1-carbaundacaborane, bis-n-butylammonium(1-
carbedodeca)borate, tri-n-butylammonium(7,8-
2 5 dicarbaundeca)borate and tri-n-
butylammonium(tridecahydride-7-carbaundeca)borate..
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The compound (c) which reacts with the transition
metal compound (a) to form an ion pair can be used in
combination of two or more kinds.
The olefin polymerization catalyst (1) used for
S preparing the propylene polymer (A1) and the propylene
polymer (A2) is formed from the transition metal compound
(a) and at least one compound selected from the
organoaluminum oxy-compound (b) and the compound (c).
However, the catalyst (1) may further contain an
1 0 organoaluminum compound (j), if necessary, together with
the above components.
The organoaluminum compound (j) is, for example, an
organoaluminum compound represented by the following
formula (II)
1 5 R9~A1X3_n ( I I )
wherein R9 is a hydrocarbon group of 1 to 12 carbon atoms,
X is a halogen atom, and n is 1 to 3.
In the above formula (II), R9 is a hydrocarbon group
of 1 to 12 carbon atoms, for example, an alkyl group, a
2 0 cycloalkyl group or an aryl group. Examples of those
groups include methyl, ethyl, n-propyl, isopropyl,
isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl,
phenyl and tolyl.
Particular examples of such organoaluminum compounds
2 S ( j ) include
trialkylaluminums, such as trimethylaluminum,
triethylaluminum, triisopropylaluminum,
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triisobutylaluminum, trioctylaluminum, tri(2-
ethylhexyl)aluminum and tridecylaluminum;
alkenylaluminums, such as isoprenylaluminum;
dialkylaluminum halides, such as dimethylaluminum
5 chloride, diethylaluminum chloride, diisopropylaluminum
chloride, diisobutylaluminum chloride and dimethylaluminum
bromide;
alkylaluminum sesquihalides, such as methylaluminum
sesquichloride, ethylaluminum sesquichloride,
10 isopropylaluminum sesquichhoride, butylaluminum
sesquichloride and ethylaluminum sesquibromide;
alkylaluminum dihalides, such as methylaluminum
dichloride, ethylaluminum dichloride, isopropylaluminum
dichloride and ethylaluminum dibromide; and
15 alkylaluminum hydrides, such as diethylaluminum
hydride and diisobutylaluminum hydride.
Also employable as the organoaluminum compound (j) is
a compound represented by the following formula (III):
R9nA1L3_~ ( I I I )
2 0 wherein R9 is the same as above, L is -OR1° group, -OSiR113
group, -OAlRizz group, -NRl3z group, -SiRlq3 group or -
N (R15) A1R16z group; n is 1 or 2; R1°, R11, Riz and R16 are
each methyl, ethyl, isopropyl, isobutyl, cyclohexyl, phenyl
or the like: R13 is a hydrogen atom, methyl, ethyl,
2 5 isopropyl, phenyl, trimethylsilyl or the like; and R14 and
R15 are each methyl, ethyl or the like.
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71
Of such organoaluminum compounds, preferred are
compounds represented by the formula R9nA1 (OA1R1°2) s-r,~ for
example, Et2AlOAlEt2, and (iso-Bu)2AlOA1(iso-Bu)2.
Of the organoaluminum compounds represented by the
above formulas (II) and (III), preferred are compounds
represented by the formula R9nAl, and particularly
preferred are compounds of the formula R9nA1 wherein R9 is
an isoalkyl group.
The olefin polymerization catalyst (1) used for
1~ preparing the propylene polymer (A1) and the propylene
polymer (A2) can be prepared by mixing the transition metal
compound (a) [component (a)] and the organoaluminum oxy-
compound (b) [component (b)] (or the compound (c) which
reacts with the transition metal compound (a) to form an
ion pair, [component (c)]), and if desired, the
organoaluminum compound (j) [component (j)] in an inert
hydrocarbon solvent or an olefin solvent.
Examples of the inert hydrocarbon solvents used for
preparing the olefin polymerization catalyst (1) include:
2 0 aliphatic hydrocarbons, such as propane, butane,
pentane, hexane, heptane, octane, decane, dodecane and
kerosine;
alicyclic hydrocarbons, such as cyclopentane,
cyclohexane and methylcyclopentane;
2 5 aromatic hydrocarbons, such as benzene, toluene and
xylene;
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halogenated hydrocarbons, such as ethylene chloride,
chlorobenzene and dichloromethane; and
mixtures of the above hydrocarbons.
In the preparation of the olefin polymerization
catalyst (1), each components may be mixed in an optional
order, but preferably they are mixed in the following
manner:
the component (b) [or the component (c)] is mixed with
the component (a); ,
the component (b) is mixed with the component (j), and
the resulting mixture is then mixed with the component (a);
the component (a) is mixed with the component (b) [or
the component (c)], and the resulting mixture is then mixed
with the component (j); or
the component (a) is mixed with the component (j), and
the resulting mixture is then mixed with the component (b)
[or the component (c) ] .
In the mixing of each components, an atomic ratio
(A1/transition metal) of the aluminum in the component (b)
2 0 to the transition metal in the component (a) is in the
range of usually 10 to 10,000, preferably 20 to 5,000; and
a concentration of the component (a) is in the range of
about 10'8 to 10'1 mol/1-solvent, preferably 10'~ to 5 x 10-Z
mol/1-solvent.
2 5 When the component (c) is used, a molar ratio
[component (a)/component (c)] of the component (a) to the
component (c) is in the range of usually 0.01 to 10,
CA 02295395 2000-O1-13
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preferably 0.1 to 5; and a concentration of the component
(a) is in the range of about 10-8 to 10-1 mol/1-solvent,
preferably 10'~ to 5 x 10-2 mol/1-solvent .
When the component (j) is used, an atomic ratio
S (A1~/Alb) of the aluminum atom (A1~) in the component (j) to
the aluminum atom (Alb) in the component (b) is in the
range of usually 0.02 to 20, preferably 0.2 to 10.
The above-mentioned catalyst components may be mixed
in a polymerizer. Otherwise, a mixture of the components
beforehand prepared may be fed to a polymerizer.
If the components are beforehand mixed, the mixing
temperature is in the range of usually -50 to 150 °C,
preferably -20 to 120 °C; and the contact time is in the
range of 1 to 1,000 minutes, preferably 5 to 600 minutes.
The mixing temperature may be varied while the components
are mixed and contacted with each other.
The olefin polymerization catalyst (1) may be an
olefin polymerization solid catalyst in which at least one
of the component (a), the component (b) [or the component
2 0 (c)] and the component (j) is supported on an inorganic or
organic carrier of granular or particulate solid.
The inorganic carrier is preferably a porous oxide,
for example, Si02 or A1203.
Examples of the granular or particulate solid organic
2 5 compounds include polymers or copolymers produced mainly
from oc-olefins such as ethylene, propylene and 1-butene or
styrene.
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The olefin polymerization catalyst (1) may be a
prepolymerized catalyst for olefin polymerization formed
from the particulate carrier, the component (a), the
component (b) [or the component (c)] and an olefin polymer
$ produced by the prepolymerization, and if desired, the
component (j).
The olefin used for the prepolymerization includes
propylene, ethylene and 1-butene. Further, a mixture of
these olefins and other olefin may also be employed.
In addition to the above components, the olefin
polymerization catalyst (1) may contain other components
which are useful for the olefin polymerization, for
example, water as a catalyst component.
The propylene polymer (A1) and the propylene polymer
(A2) can be prepared by polymerizing propylene in the
presence of the olefin polymerization catalyst (1). In the
polymerization of propylene, monomers such as ethylene and
a-olefins of 4 to 20 carbon atoms (e.g., 1-butene, 1-
pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene,
2 0 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and
1-eicosene) may be used in amounts of not more than 0.1
mol.
The polymerization may be carried out by either a
liquid phase polymerization process such as a suspension
2 5 polymerization process and a solution polymerization
process, or a gas phase polymerization process.
CA 02295395 2000-O1-13
In the liquid phase polymerization process, the same
inert hydrocarbon solvent as used in the preparation of the
catalyst described before can be used, or propylene can be
also used as a solvent.
5 In the suspension polymerization process, the
temperature for polymerizing propylene is in the range of
usually -50 to 100 °C, preferably 0 to 90 °C. In the
solution polymerization process, the polymerization
temperature is in the range of usually 0 to 250 °C,
10 preferably 20 to 200 °C. In the gas phase polymerization
process, the polymerization temperature is in the range of
usually 0 to 120 °C, preferably 20 to 100 °c. The
polymerization pressure is in the range of usually
atmospheric pressure to 100 kg/cmz, preferably atmospheric
15 pressure to 50 kg/cm2. The polymerization reaction may be
carried out either batchwise, semi-continuously or
continuously. Further, it is also possible to conduct the
polymerization in two or more steps having different
reaction conditions.
2 ~ The molecular weight of the resulting propylene
polymer can be regulated by allowing hydrogen to exist in
the polymerization system or by varying the polymerization
temperature and the polymerization pressure.
The second ~,py1_ene ~ymer composition
2 S The second propylene polymer composition comprises:
(A1) a propylene polymer which is characterized in
that:
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76
the propylene polymer is prepared by the use of an
olefin polymerization catalyst comprising:
(i) (a) a transition metal compound, and
(ii) at least one compound selected from the
S group consisting of
(b) an organoaluminum oxy-compound, and
(c) a compound which reacts with the
transition metal compound (a) to form an ion pair,
the propylene polymer,has a melt flow rate (MFR), as
measured at 230 °C under a load of 2.16 kg, of 0.01 to 30
g/10 min, and
the propylene polymer has a molecular weight
distribution (Mw/Mn), as measured by GPC, of 2 to 3;
(A2) a propylene polymer which is characterized in
1 5 that
the propylene polymer is prepared by the use of an
olefin polymerization catalyst comprising:
(i) (a) a transition metal compound, and
(ii) at least one compound selected from the
2 0 group consisting of
(b) an organoaluminum oxy-compound, and
(c) a compound which reacts with the
transition metal compound (a) to form an ion pair,
the propylene polymer has a melt flow rate (MFR), as
2 5 measured at 230 °C under a load of 2.16 kg, of 30 to 1,000
g/10 min, and
CA 02295395 2000-O1-13
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77
the propylene polymer has a molecular weight
distribution (Mw/Mn), as measured by GPC, of 2 to 4; and
(B) a soft polymer.
In this propylene polymer composition, the ratio
((A2)/(A1)) of the MFR of said propylene polymer (A2) to
the MFR of said propylene polymer (A1) is not less than 30.
Propylene golvmer (A1)
The propylene polymer (A1) for constituting the second
propylene polymer composition is identical with the
propylene polymer (A1) for~constituting the first propylene
polymer composition.
~,~Opvlene polymer (A21
The propylene polymer (A2) for constituting the second
propylene polymer composition is identical with the
propylene polymer (A2) for constituting the first propylene
polymer composition.
The soft polymer (B) for constituting the second
propylene polymer composition is a (co)polymer of an oc-
2 0 olefin of 2 to 20 carbon atoms, and desirably has MFR, as
measured at 190 °C under a load of 2.16 kg, of 0.01 to 100
g/10 min, preferably 0.05 to 50 g/10 min. This soft
polymer (B) has a crystallinity, as measured by X-ray
diffractometry, of less than 30 ~, and desirably is
2 S amorphous.
Examples of the Oc-olefins of 2 to 20 carbon atoms
include ethylene, propylene, 1-butene, 1-pentene, 1-hexene,
CA 02295395 2000-O1-13
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78
4-methyl-1-pentene, 1-octene, 1-decene and mixtures
thereof. Of these, particularly preferred are a-olefins of
1 to 10 carbon atoms.
The soft polymer (B) is preferably a copolymer of
ethylene and an oc-olefin, and the Oc-olefin is for example
an oc-olefin of 3 to 20 carbon atoms, preferably an oc-
olefin of 3 to 6 carbon atoms, particularly preferably
propylene.
The soft polymer (B) may contain other constituent
units than the constituent units derived from ot-olefins,
such as those derived from diene compounds, with the
proviso that the characteristics thereof are not marred.
Examples of the constituent units which are allowed to
be contained in the soft polymer (B) include constituent
1 S units derived from:
chain non-conjugated dienes, such as 1,4-hexadiene,
1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-
heptadiene and 7-methyl-1,6-octadiene;
cyclic non-conjugated dimes, such as cyclohexadiene,
2 0 dicyclopentadiene, methyltetrahydroindene, 5-
vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylPne-2-
norbornene, 5-isopropylidene-2-norbornene and 6-
chloromethyl-5-isopropenyl-2-norbornene; and
diene compounds, such as 2,3-diisopropylidene-5-
2 S norbornene, 2-ethylidene-3-isopropylidene-5-norbornene and
2-propenyl-2,2-norbornadiene.
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79
These diene components can be used singly or in
combination. A content of the diene component is usually
not more than 10 ~ by mol, preferably 0 to 5 ~ by mol.
The soft polymer (B) is, for example, a copolymer
S containing constituent units derived from ethylene in an
amount of 0 to 95 ~ by mol, preferably 30 to 92 ~ by mol,
more preferably 40 to 90 $ by mol, constituent units
derived from an a-olefin of 3 to 20 carbon atoms in an
amount of 1 to 100 ~ by mol;, preferably 4 to 70 ~ by mol,
l~ more preferably 8 to 60 ~ by mol, and constituent units
derived from the diene component in an amount of 0 to 10 ~
by mol, preferably 0 to 5 ~ by mol, more preferably 0 to 3
by mol.
Such soft polymer (B) as mentioned above can be
15 prepared by conventionally known processes using a titanium
catalyst, a vanadium catalyst, a zirconium catalysts, etc.
ProRylene polymer ~ompos;t;nn
The second propylene polymer composition comprises the
propylene polymer (A1), the propylene polymer (A2) and the
2 0 soft polymer (B). In this composition, it is desired that
the propylene polymer (A1) is contained in an amount of 10
to 90 parts by weight, preferably 30 to 70 parts by weight;
the propylene polymer (A2) is contained in an amount of 10
to 90 parts by weight, preferably 30 to 70 parts by weight;
2 $ and the soft polymer (B) is contained in an amount of 3 to
30 parts by weight, preferably 10 to 25 parts by weight. A
ratio ((A2)/(A1)] of the MFR of the propylene polymer (A2)
CA 02295395 2000-O1-13
to the MFR of the propylene polymer (A1) is not less than
30, preferably in the range of 40 to 300, more preferably
50 to 100.
The second propylene polymer composition is desired to
S have MFR, as measured at 230 °C under a load of 2.16 kg, of
1 to 100 g/10 min, preferably 5 to 50 g/10 min. In this
composition, Mw/Mn of all the propylene components for
constituting the composition is desirably in the range of 4
to 15.
10 The densit of the second
Y propylene polymer
composition is desired to be in the range of 0.88 to 0.92
g/cm3, preferably 0.89 to 0.92 g/cm3.
The heat distortion temperature (HDT) thereof is
desired to be not lower than 80 °C, preferably in the range
1 S of 90 to 140 °C .
The flexural modulus (FM) thereof is desired to be in
the range of 8,500 to 18,000 kg/cm2, preferably 9,000 to
15,000 kg/cm2.
The Izod impact strength (IZ) thereof at 23 °C is
2 0 desired to be in the range of 10 to 50 kg~cm/cm, preferably
10 to 40 kg~cm/cm.
The tensile elongation at break (EL) thereof is
desired to be in the range of 200 to 1,000 ~, preferably
300 to 1,000 g.
2S The second propylene polymer composition may contain,
if necessary, additives which may be added to the first
CA 02295395 2000-O1-13
g l
propylene polymer composition, with the proviso that the
object of the invention is not marred.
The second propylene polymer composition can be
prepared by known processes. For example, the composition
can be prepared in accordance with the processes (1) to (5)
described for the first propylene polymer composition,
using the propylene polymer (A1), the propylene polymer
(A2), the soft polymer (B) and if desired other components
Which may be optionally added.
The second propylene polymer composition may be
prepared by forming a composition of the propylene polymer
(A1) and the propylene polymer (A2), which has been
beforehand prepared in the following manner, and then
blending the resulting composition with the soft polymer
(B) in accordance with the aforesaid processes.
The composition of the propylene polymer (A1) and the
propylene polymer (A2) can be produced by a process
comprising conducting the polymerization in two or more
steps having different reaction conditions, in one step of
2 0 which the propylene polymer (A1) is prepared and in another
step of which the propylene polymer (A2) is prepared, or a
process comprising using plural polymerizers, in one
polymerizer of which the propylene polymer (A1) is prepared
and in another polymerizer of which the propylene polymer
2 5 (A2) is prepared.
The second propylene polymer composition as mentioned
above is excellent in not only heat resistance, rigidity
CA 02295395 2000-O1-13
82
and tensile elongation at break but also moldability and
impact resistance. Further, since the amount of the
catalyst residue in the polymer composition is small, the
article molded from the composition is never colored and is
good in sanitariness.
The third p~ppPnP _p~,ymer composition
The third propylene polymer composition comprises:
(A3) a propylene polymer which is prepared by the use
of an olefin polymerization catalyst comprising (d) a solid
titanium catalyst component and (e) an organometallic
compound catalyst component, said components (d) and (e)
being described later, and which has a melt flow rate
(MFR), as measured at 230 °C under a load of 2.16 kg, of
0.01 to 30 g/10 min, and a molecular weight distribution
(Mw/Mn), as measured by GPC, of 4 to 15; and
(A2) a propylene polymer which is characterized in
that:
the propylene polymer is prepared by the use of an
olefin polymerization catalyst comprising:
2 0 (i) (a) a transition metal compound, and
(ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(c) a compound which reacts with the
2 5 transition metal compound (a) to form an ion pair,
CA 02295395 2000-O1-13
83
the propylene polymer has a melt flow rate (MFR), as
measured at 230 °C under a load of 2.16 kg, of 30 to 1,000
g/10 min, and
the propylene polymer has a molecular weight
S distribution (Mw/Mn), as measured by GPC, of 2 to 4.
Propylene polymer (A31
The propylene polymer (A3) for constituting the third
propylene polymer composition is a propylene homopolymer or
a propylene copolymer obtained by the use of an olefin
polymerization catalyst comprising a solid titanium
catalyst component (d) and an organometallic compound
catalyst component (e), both components being described
later.
The propylene polymer (A3) is desired to have MFR, as
measured at 230 °C under a load of 2.16 kg, of 0.01 to 30
g/10 min, preferably 0.5 to 5 g/10 min, and Mw/Mn, as
measured by GPC, of 4 to 15, preferably 4 to 8.
Further, the propylene polymer (A3) is desired to have
an intrinsic viscosity [~] of 1.7 to 5.0 dl/g, preferably
2 0 2.2 to 3.5 dl/g, a weight-average molecular weight of 15 x
104 to 100 x 104, preferably 25 x 104 to 50 x 104, a
crystallinity, as measured by X-ray diffractometry, of not
less than 55 ~, preferably not less than 60 ~, and a
boiling heptane extraction residue proportion (I.I.) of not
2 5 less than 90 $, preferably not less than 93 ~.
The propylene polymer (A3) may contain constituent
units derived from monomers other than propylene, which are
CA 02295395 2000-O1-13
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exemplified for the propylene polymer (A1), in an amount of
not more than 5 ~ by mol.
Propylene polvmer lA2)
The propylene polymer (A2) for constituting the third
propylene polymer composition is identical with the
propylene polymer (A2) for constituting the above-mentioned
first propylene polymer composition.
propylene po~ymer composifiinn
The third propylene polymer composition comprises the
propylene polymer (A3) and the propylene polymer (A2). In
this composition, it is desired that the propylene polymer
(A3) is contained in an amount of 10 to 90 ~ by weight,
preferably 30 to 70 ~ by weight; and the propylene polymer
(A2) is contained in an amount of 10 to 90 ~ by weight,
preferably 30 to 70 ~ by weight. A ratio ((A2)/(A3)] of
the MFR of the propylene polymer (A2) to the MFR of the
propylene polymer (A3) is not less than 30, preferably in
the range of 40 to 100.
The third propylene polymer composition is desired to
2 0 have MFR, as measured at 230 °C under a load of 2.16 kg, of
1 to 100 g/10 min, preferably 5 to 50 g/10 min. In this
composition, Mw/Mn of all the propylene components for
constituting the composition is desirably in the range of 5
to 15.
2 5 The density of the third propylene polymer composition
is desired to be in the range of 0.89 to 0.92 g/cm3,
preferably 0.90 to 0.92 g/cm3.
CA 02295395 2000-O1-13
The heat distortion temperature (HDT) thereof is
desired to be not lower than 100 °C, preferably in the
range of 110 to 150 °C.
The flexural modulus (FM) thereof is desired to be in
5 the range of 14,000 to 21,000 kg/cm2, preferably 16,000 to
20,000 kg/cm2.
The Izod impact strength (IZ) thereof at 23 °C is
desired to be in the range of 2 to 4 kg-cm/cm, preferably 2
to 3 kg~cm/cm.
1 0 The tensile elongation-at break (EL) thereof is
desired to be in the range of 100 to 500 ~, preferably 200
to 400
The third propylene polymer composition may contain,
if necessary, additives which may be added to the first
1$ propylene polymer composition, with the proviso that the
object of the invention is not marred.
The third propylene polymer composition can be
prepared by known processes. For example, the composition
can be prepared in accordance with the processes (1) to (4)
2 0 described for the first propylene polymer composition,
using the propylene polymer (A3), the propylene polymer
(A2) and if desired other components which may be
optionally added.
The third propylene polymer composition as mentioned
2 S above is excellent in not only heat resistance, rigidity
and tensile elongation at break but also moldability.
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Next, the olefin polymerization catalyst used for
preparing the propylene polymer (A3) and the process for
preparing the propylene polymer (A3) are described.
The propylene polymer (A3) can be prepared by
polymerizing propylene in the presence of an olefin
polymerization catalyst [olefin polymerization catalyst
(2)] comprising:
(d) a solid titanium catalyst component, and
(e) an organometallic,compound catalyst component.
Fig. 2 illustrates steps of a process for preparing
the olefin polymerization catalyst which is used for the
preparation of the propylene polymer (A3).
As the solid titanium catalyst component (d), solid
titanium catalyst components containing titanium, magnesium
and halogen, and, if desired, an electron donor (k), can be
used.
The solid titanium catalyst component (d) can be
prepared by, for example, bringing a titanium compound, a
magnesium compound and an optional electron donor (k) into
2 0 contact with each other.
The titanium compounds used in the preparation of the
solid titanium catalyst component (d) include, for example,
tetravalent titanium compounds or trivalent titanium
compounds.
2 5 The tetravalent titanium compounds include compounds
represented by the following formula:
Ti (OR) QX4_g
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g7
wherein R is a hydrocarbon group, X is a halogen atom, and
g is a number satisfying the condition of 0 _< g <_ 4.
Of these compounds, preferred are titanium
tetrahalides, and particularly preferred is titanium
tetrachloride. These titanium compounds may be used singly
or in combination. Further, they may be diluted in
hydrocarbon compounds or halogenated hydrocarbon compounds.
The trivalent titanium compoun is, for example,
titanium trichloride.
The magnesium compound used for preparing the solid
titanium catalyst component (d) includes a magnesium
compound having reduction properties and a magnesium
compound having no reduction properties.
The magnesium compounds having reduction properties
include organo-magnesium compounds represented by the
following general formula:
XnMgR2_n
wherein n is a number satisfying the condition of 0 5 n <
2, R is hydrogen, an alkyl group of 1 to 20 carbon atoms,
2 0 aryl group or cycloalkyl group (when n is 0, two of R are
the same or different), and a hydrocarbon group.
Concrete examples of the magnesium compound having
reduction properties include dialkylmagnesium compounds,
alkylmagnesium halides, alkylmagnesium alkoxides and
butylmagnsium hydride.
Concrete examples of the magnesium compound having no
reduction properties include magnesium halide such as
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8g
magnesium chloride, magnesium bromide, magnesium iodide and
magnesium fluoride; alkoxymagnesium halide;
aryloxymagnesium halide; alkoxymagnesium; aryloxymagnesium;
and manesium carboxylate. Further, magnesium metal or
S hydrogenated magnesium may alsa be used.
These magnesium compounds having no reduction
properties may be those derived from the above-mentioned
magnesium compounds having reduction properties or those
derived during the catalyst~component preparation stage.
1~ In order to derive the magnesium compound having no
reduction properties from the magnesium compound having
reduction properties, the magnesium compound having
reduction properties is brought into contact with a
polysiloxane compound, a halogen-containing silane
i5 compound, a halogen-containing aluminum compound, an ester,
an alcohol, halogen-containing compound or a compound
having an OH-group or an active carbon-oxygen bond.
The magnesium compounds may be used singly or in
combination of two or more kinds, an in any of liquid state
2 0 or solid state. When the magnesium compound is solid, the
compound can be brought into liquid state by using the
electron donors as same as those described in later, such
as alcohols, carboxylic acids, aldehydes, amins or metal
acid esters.
2 5 In the preparation of the solid titanium catalyst
component (d), an electron donor (k) is preferably used.
Examples of the electron donor (k) include:
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oxygen-containing electron donors such as alcohols,
phenols, ketones, aldehydes, carboxylic acids, organic acid
halides, esters of organic acids or inorganic acids,
ethers, diethers, acid amides, acid anhydrides and
alkoxysilanes, and
nitrogen-containing donors such as an ammonia, amines,
nitriles, pyridines and isocyanates.
The solid titanium catalyst component (d) is prepared
by bringing the aforementioned titanium compound, magnesium
compound and the optional electron donor (k) into contact
with each other.
Though the processes for preparing the solid titanium
catalyst component (dy are no way limited, examples of such
processes by using the tetravalent titanium compound are
briefly described below.
(1) A process comprising bringing a solution
consisting of a magnesium compound, an electron donor (k)
and a hydrocarbon solvent into contact with an
organometallic compound, after or simultaneously with
2 0 precipitating a solid by bringing the solution into contact
with a titanium compound.
(2) A process comprising bringing a complex composed
of a magnesium compound and an electron donor (k) into
contact with an organometallic compound, and then bringing
2 5 the reaction~product into contact with a titanium compound.
(3) A process comprising bringing a product obtained
by the contact of an inorganic carrier and an organic
CA 02295395 2000-O1-13
magnesium compound into contact with a titanium compound.
In this case, the above product may be beforehand brought
into contact with a halogen-containing compound, an
electron donor (k) and/or an organometallic compound.
5 (4) A process comprising obtaining an inorganic or
organic carrier on which a magnesium compound is supported
from a mixture of an inorganic or organic carrier and a
solution containing a magnesium compound and an electron
donor (k) (and further a hydrocarbon solvent in some
10 cases), and then bringing the obtained carrier into contact
with a titanium compound.
(5) A process comprising bringing a solution
containing a magnesium compound, a titanium compound and an
electron donor (k) (and further a hydrocarbon solvent in
15 some cases) into contact with an inorganic or organic
carrier to obtain a solid titanium catalyst component on
which magnesium and titanium are supported.
(6) A process comprising bringing a liquid organic
magnesium compound into contact with a halogen-containing
2 0 titanium compound.
(7) A process comprising bringing a liquid organic
magnesium compound into contact with a halogen-containing
compound, and then bringing the product thus obtained into
contact with a titanium compound.
2 5 (8) A process comprising bringing an alkoxy group-
containing magnesium compound into contact with a halogen-
containing titanium compound.
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(9) A process comprising bringing a complex composed
of an alkoxy group-containing magnesium compound and an
electron donor (k) into contact with a titanium compound.
(10) A process comprising bringing a complex composed
of an alkoxy group-containing magnesium compound and an
electron donor (k) into contact with an organometallic
compound, and then bringing the product thus obtained into
contact with a titanium compound.
(11) A process comprising bringing a magnesium
compound, an electron donor (k) and a titanium compound
into contact with each other in an optional order. In this
reaction, each components may be pretreated with an
electron donor (k) and/or a reaction assistant such as an
organometallic compound or a halogen-containing silicon
compound. In this case, an electron donor is preferably
used at least one time
(12) A process comprising bringing a liquid magnesium
compound not having reducing ability into contact with a
liquid titanium compound, if necessary in the presence of
2 0 an electron donor (k), to precipitate a solid
magnesium/titanium complex compound.
(13) A process comprising further bringing the
reaction product obtained in the above process (12) into
contact with an titanium compound.
2 5 (14) A process comprising further bringing the
reaction product obtained in the above process (11) or (12)
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into contact with an electron donor (k) and a titanium
compound.
(15) A process comprising pulverizing a magnesium
compound and a titanium compound (and if necessary an
S electron donor (k)) to obtain a solid product, and treating
the solid product with either halogen, a halogen compound
or aromatic hydrocarbon. This process may include a step
of pulverizing only a magnesium compound, a step of
pulverizing a complex compound composed of a magnesium
compound and an electron donor (k), or a step of
pulverizing a magnesium compound and a titanium compound.
Further, after the pulverization, the solid product may be
subjected to a pretreatment with a reaction assistant and
then subjected to a treatment with halogen or the like.
Examples of the reaction assistants include an
organometallic compound and a halogen-containing silicon
compound.
(16) A process comprising pulverizing a magnesium
compound, and then bringing the pulverized magnesium
2 0 compound into contact with a titanium compound. In this
case, an electron donor (k) or a reaction assistant may be
used in the pulverization stage and/or the contacting
reaction stage.
(17) A process comprising treating the compound
2 5 obtained in any of the above processes (11) to (16) with
halogen, a halogen compound or aromatic hydrocarbon.
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(18) A process comprising bringing the reaction
product obtained by the contact of a metal oxide, an
organic magnesium compound and a halogen-containing
compound into contact with a titanium compound and if
S necessary an electron donor (k).
(19) A process comprising bringing a magnesium
compound such as a magnesium salt of organic acid,
alkoxymagnesium or aryloxymagnesium into contact with a
titanium compound and/or halogen-containing hydrocarbon and
if necessary an electron donor (k).
(20) A process comprising bringing a hydrocarbon
solution containing at least a magnesium compound and
alkoxytitanium into contact with a titanium compound and/or
an electron donor (k). In this case, a halogen-containing
compound such as a halogen-containing silicon compound may
be further brought into contact therewith, if necessary.
(21) A process comprising bringing a liquid magnesium
compound not having reducing ability into contact with an
organometallic compound so as to precipitate a solid
2 0 magnesium/metal (aluminum) complex compound, and then
bringing the resulting compound into contact with an
electron donor (k) and a titanium compound.
The preparation of the solid titanium catalyst
component (d) is conducted at a temperature of usually -70
2 S to 200 °C, preferably -50 to 150 °C .
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94
The solid titanium catalyst component (d) thus
obtained contains titanium, magnesium, halogen and an
optional electron donor.
In the solid titanium catalyst component (d), a ratio
S of halogen/titanium (atomic ratio) is about 2 to 200,
preferably about 4 to 90, a ratio of magnesium/titanium
(atomic ratio) is 1 to 100, preferably 2 to 50.
Further, the electron donor (k) is containined in a
ratio of electron donor (k)/titanium (molar ratio) being
about 0.01 to 100, preferably about 0.05 to 50.
Regarding the processes for preparation of the solid
titanium catalyst component (d), details thereof are
described in the following publications;
JP-B-46-34092/1971, JP-B-53-46799/1978, JP-B-60-
1~ 3323/1985, JP-B-63-54289/1988, JP-A-1-261404/1989, JP-A-1-
261407/1989, JP-B-47-41676/1972, JP-B-47-46269/1972, JP-B-
19794/1973, JP-A-60-262803/1985, JP-A-59-147004/1984, JP-A-
59-149911/1984, JP-A-1-201308/1989, JP-A-61-151211/1986,
JP-A-53-58495/1978, JP-A-53-87990/1978, JP-A-59-
2 0 206413/1984, JP-A-58-206613/1983, JP-A-58-125706/1983, JP-
A-63-68606/1988, JP-A-63-69806/1988, JP-A-60-81210/1985,
JP-A-61-40306/1986, JP-A-51-281189/1976, JP-A-50-
126590/1975, JP-A-51-92885/1976, JP-B-57-45244/1982, JP-B-
57-26613/1982, JP-B-61-5483/1986, JP-A-56-811/1981, JP-B-
2 S 60-37804/1985, JP-B-59-50246/1984, JP-A-58-83006/1983, JP-
A-48-16986/1973, JP-A-49-65999/1974, JP-A-49-86482/1974,
JP-B-56-39767/1981, JP-B-56-32322/1981, JP-A-55-29591/1980,
CA 02295395 2000-O1-13
JP-A-53-146292/1978, JP-A-57-63310/1982, JP-A-57-
63311/1982, JP-A-57-63312/1982, JP-A-62-273206/1987, JP-A-
63-69804/1988, JP-A-61-21109/1986, JP-A-63-264607/1988, JP-
A-60-23404/1985, JP-A-60-44507/1985, JP-A-60-158204/1985,
5 JP-A-61-55104/1986, JP-A-2-28201/1990, JP-A-58-196210/1983,
JP-A-64-54005/1989, JP-A-59-149905/1984, JP-A-61-
145206/1986, JP-A-63-302/1988, JP-A-63-225605/1988, JP-A-
64-69610, JP-A-1-168707/1989, JP-A-62-104810/1987, JP-A-62-
104811/1987, JP-A-62-104812,/1987 and JP-A-62-104813/1987.
10 In the present invention, conventional titanium
trichloride type catalyst component may also be used as the
solid titanium catalyst component (d).
The above mentioned titanium trichloride is
exemplified as the titanium trichloride type catalyst
15 component. The titanium trichloride is used together with
the aforementioned electron donor (k) and/or the
tetravalent titanium compound, or after the contact with
them.
Regarding the processes for preparation of the
2 0 titanium trichloride type catalyst component, details
thereof are described in the following publications;
JP-A-63-17274/1988, JP-A-64-38409/1989, JP-A-56-
34711/1981, JP-A-61-287904/1986, JP-A-63-75007/1988, JP-A-
63-83106/1988, JP-A-59-13630/1984, JP-A-63-108008/1988, JP-
2 5 A-63-27508/1988, JP-A-57-70110/1982, JP-A-58-219207/1983,
JP-A-1-144405/1989 and JP-A-1-292011/1989.
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Embodiment of the titanium trichloride type catalyst
component includes titanium trichloride. As the titanium
trichloride, there can be preferably used a titanium
trichloride which is obtained by, for example, reducing the
tetravalent titanium by contacting with hydrogen, metal
such as magnesium metal, aluminum metal or titanium metal,
or an organic metal compound such as organomagnesium
compound, organoaluminum compound or organozinc compound.
The titanium trichloride is~used together with the
aforementioned electron donor (k) and/or the tetravalent
titanium compound, or after the contact with them.
Examples of the organometallic compound catalyst
component (e) which forms the olefin polymerization
catalyst (2) used in the polymerization of the propylene
polymer (A3) include (e-1) an organoaluminum compound, (e-
2) a complex alkyl compound of aluminum with Group I metal
of the periodic table and (e-3) a organometallic compound
of Group II metal of the periodic table.
Examples of the organoaluminum compound (e-1) are the
2 0 same as those described as the organoaluminum (j).
Examples of the complex alkyl compound of aluminum
with Group I metals of the periodic table (e-2) are
represented by the following general formula;
MlAlRjq
2 5 wherein M1 is Li, Na or K and R7 is a hydrocarbon group of
1 to 15 carbon atoms.
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Examples of the organometallic compound of Group II
metal of the periodic table (e-3) are represented by the
following general formula;
RkRlM2
wherein Rk and R1 are hydrocarbon group of 1 to 15 carbon
atoms or halogen, and they being the same or different with
a proviso that excluding the case where the each of them is
halogen, and M2 is Mg, Zn or Cd.
These compounds may be used in combination of 2 or
more kinds.
In the preparation of the propylene polymer (A3), the
aforesaid organoaluminum oxy-compound (b) can be also
employed.
The propylene polymer (A3) can be prepared by
polymerizing propylene in the presence of the olefin
polymerization catalyst (2) formed from the solid titanium
catalyst component (d) and the organometallic compound
catalyst component (e).
The olefin polymerization catalyst (2) may be a
2 0 prepolymerized catalyst obtained by prepolymerizing the
catalyst comprising the solid titanium catalyst component
(d) and the organometallic compound catalyst component (e)
with an olefin.
Examples of the olefins used for the prepolymerization
include a-olefins of 2 to 20 carbon atoms. Of these,
propylene is preferred.
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In the prepolymerization, the same electron donor as
the aforementioned electron donor (k) or the following
electron donor (1) may be used if necessary, in addition to
the catalyst component (d) and the catalyst component (e).
The electron donor (1) is, for example, an
organosilicon compound represented by the following
formula:
RnSl (0R~ ) 4_~
wherein R and R' are each a hydrocarbon group, and 0 < n <
1~ 4.
The organosilicon compound represented by the above
formula includes the following compounds.
These organosilicon compounds may be used in
combination of two of more kinds.
Also employable as the electron donor (1) are:
nitrogen-containing electron donors, such as 2,6-
substituted piperidines, 2,5-substituted piperidines,
substituted methylenediamines and substituted
imidazolidines;
2 0 phosphorus-containing electron donors, such as
phosphites; and
oxygen-containing electron donors, such as 2,6-
substituted tetrahydropyrans and 2,5-substituted
tetrahydropyrans.
2 5 In the prepolymerization, the olefin is desirably
polymerized in an amount of usually 0.01 to 2,000 g,
preferably 0.03 to 1,000 g, particularly preferably 0.05 to
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200 g, per 1 g of the solid titanium catalyst component
(d) .
The prepolymerized catalyst prepared as above is
usually obtained in the form of a suspension. In the
S subsequent polymerization step, such prepolymerized
catalyst may be used in the form of the suspension.
Otherwise, the prepolymerized catalyst produced may be
separated from the suspension before use.
When the prepolymerized catalyst is used for the
polymerization to prepare the propylene polymer (A3), the
organometallic compound catalyst component (e) is
preferably used in combination with the prepolymerized
catalyst.
The propylene polymer (A3) can be prepared by
polymerizing propylene in the presence of the olefin
polymerization catalyst (2). In the polymerization of
propylene, ethylene and monomers which are exemplified for
the propylene polymer (A1) and the propylene polymer (A2),
such as oc-olefins of 4 to 20 carbon atoms, may be used in
2 ~ amounts of not more than 0.1 mol per 1 mol of propylene.
The propylene polymer (A3) may be prepared by either a
liquid phase polymerization process such as a solution
polymerization process and a suspension polymerization
process, or a gas phase polymerization process.
2 5 When the polymerization is conducted in the reaction
form of suspension polymerization, polyene compounds and
olefins which are liquid at reaction temperatures and/or
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the same inert solvents as used for the aforementioned
prepolymerization can be used as the reaction solvent.
The olefin polymerization catalyst (2) used for the
polymerization is generally used in the following amount,
S though the amount varies depending upon the kind.
The solid titanium catalyst component (d) (including
the prepolymerized catalyst) is used in an amount of
usually about 0.001 to 100 mmol, preferably about 0.005 to
20 mmol, in terms of the titanium atom in the solid
titanium catalyst component (d) or the prepolymerized
catalyst, based on 1 liter of the polymerization volume.
The organometallic compound catalyst component (e) is
used in such an amount that the amount of the metal atom in
said catalyst component (e) is in the range of usually
about 1 to 2,000 mol, preferably about 5 to 500 mol, based
on 1 mol of the titanium atom in the solid titanium
catalyst component (d) or the prepolymerized catalyst.
The electron donors (k) and (1) may be also employed
in addition to the catalyst component (d) and the catalyst
2 0 component (e). When the electron donor is used, the amount
of the electron donor is in the range of usually about
0.001 to 10 mol, preferably 0.01 to 5 mol, based on 1 mol
of the metal atom in the organometallic compound catalyst
component (e).
2 5 The olefin polymerization catalyst (2) may contain
other components than the above-mentioned components, which
are useful for the olefin polymerization.
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1~1
The molecular weight of the resulting polymer may be
regulated if hydrogen is used in the polymerization, and
thereby a polymer having a high melt flow rate can be
obtained.
S The polymerization is generally carried out under the
following conditions. The polymerization temperature is in
the range of about -40 to 300 °C, preferably about -20 to
150 °C, and the polymerization pressure is in the range of
atmospheric pressure to 100- kg/cm2, preferably about 2 to
50 kg/cm2.
The polymerization can be carried out either
batchwise, semi-continuously or continuously. Further, the
polymerization can be conducted in two or more steps, and
in this case, the reaction conditions rnay be the same as or
1S different from each other.
The fourth propylene pohymer composition
The fourth propylene polymer composition comprises:
(A3) a propylene polymer which is prepared by the use
of an olefin polymerization catalyst comprising the solid
2 0 titanium catalyst component (d) and the organometallic
compound catalyst component (e), and which has MFR, as
measured at 230 °C under a load of 2.16 kg, of 0.01 to 30
g/10 min, and a molecular weight distribution (Mw/Mn), as
measured by GPC, of 4 to 15;
2 S (A2) a propylene polymer which is characterized in
that:
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the propylene polymer is prepared by the use of an
olefin polymerization catalyst comprising:
(i) (a) a transition metal compound, and
(ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(c) a compound which reacts with the
transition metal compound (a) to form an ion pair,
the propylene polymer:has MFR, as measured at 230 °C
under a load of 2.16 kg, of 30 to 1,000 g/10 min, and
the propylene polymer has a molecular weight
distribution (Mw/Mn), as measured by GPC, of 2 to 4; and
(B) a soft polymer.
Propylene oolvmer (A3)
1S The propylene polymer (A3) for constituting the fourth
propylene polymer composition is identical with the
propylene polymer (A3) for constituting the above-mentioned
third propylene polymer composition.
Propylene .polymer (A2)
2 0 The propylene polymer (A2) for constituting the fourth
propylene polymer composition is identical with the
propylene polymer (A2) for constituting the above-mentioned
first propylene polymer composition.
loft polymer (B)
2 S The soft polymer (B) for constituting the fourth
propylene polymer composition is identical with the soft
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polymer (B) for constituting the above-mentioned second
propylene polymer composition.
Propylene _polymer composstinn
The fourth propylene polymer composition comprises the
S propylene polymer (A3), the propylene polymer (A2) and the
soft polymer (B). In this composition, it is desired that
the propylene polymer (A3) is contained in an amount of 10
to 90 parts by weight, preferably 30 to 70 parts by weight;
the propylene polymer (A2) is contained in an amount of 10
to 90 parts by weight, preferably 30 to 70 parts by weight;
and the soft polymer (B) is contained in an amount of 3 to
30 parts by weight, preferably 10 to 25 parts by weight. A
ratio ((A2)/(A3)] of the MFR of the propylene polymer (A2)
to the MFR of the propylene polymer (A3) is not less than
30, preferably in the range of 40 to 100.
The fourth propylene polymer composition is desired to
have MFR, as measured at 230 °C under a load of 2.16 kg, of
1 to 100 g/10 min, preferably 5 to 50 g/10 min. In this
composition, Mw/Mn of all the propylene components for
2 0 constituting the composition is desirably in the range of 5
to 15.
The density of the fourth propylene polymer
composition is desired to be in the range of 0.88 to 0.92
g/cm3, preferably 0.89 to 0.92 g/cm3.
2 5 The heat distortion temperature (HDT) thereof is
desired to be not lower than 85 °C, preferably in the range
of 95 to 140 °C.
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The flexural modulus (FM) thereof is desired to be in
the range of 8,500 to 18,000 kg/cm2, preferably 9,000 to
15, 000 kg/cm2 .
The Izod impact strength (IZ) thereof at 23 °C is
desired to be in the range of 10 to 50 kg~cm/cm, preferably
to 40 kg~cm/cm.
The tensile elongation at break (EL) thereof is
desired to be in the range of 200 to 1,000 ~, preferably
300 to 500 ~.
10 The fourth propylene polymer composition may contain
the aforesaid additives, if necessary, with the proviso
that the object of the invention is not marred.
The fourth propylene polymer composition can be
prepared by known processes. For example, the composition
can be prepared in accordance with the processes (1) to (4)
described for the first propylene polymer composition,
using the propylene polymer (A3), the propylene polymer
(A2), the soft polymer (B) and if desired other components
which may be optionally added.
2 0 The fifth propylene polymer com~oos~r;nn
The fifth propylene polymer composition according to
the invention comprises:
(A4) a propylene polymer which is prepared by the use
of a catalyst comprising (d) the solid titanium catalyst
2 5 component and (e) the organometallic compound catalyst
component, and which has MFR, as measured at 230 °C under a
load of 2.16 kg, of 0.01 to 50 g/10 min, a molecular weight
CA 02295395 2000-O1-13
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distribution (Mw/Mn), as measured by GPC, of 4 to 15 and a
crystallinity, as measured by X-ray diffractometry, of not
less than 50 ~; and
(C) an ethylene/olefin random copolymer which is
S characterized in that:
the copolymer is prepared by the use of a catalyst
comprising:
(i) (f) a transition metal compound containing a
ligand having a cyclopentad.ienyl skeleton,
(ii) at least one compound selected from the
groups consisting of
(b) an organoaluminum oxy-compound, and
(g) a compound which reacts with the
transition metal compound (f) to form an ion pair,
the copolymer contains constituent units derived from
ethylene in an amount of 20 to 80 $ by mol, and
the copolymer has an intrinsic viscosity [~], as
measured in decalin at 135 °C, of 1.5 to 5 dl/g.
2 0 The propylene polymer (A4) is a propylene homopolymer
or a propylene copolymer, and desirably has MFR, as
measured at 230 °C under a load of 2.16 kg, of 0.01 to 50
g/10 min, preferably 1 to 30 g/10 min. The molecular
weight distribution (Mw/Mn) of this propylene polymer, as
2 5 measured by GPC, is desired to be in the range of 4 to 15,
preferably 4 to 8. Further, this propylene polymer is
desired to have a crystallinity, as measured by X-ray
CA 02295395 2000-O1-13
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diffractometry, of not less than 50 0, more preferably not
less than 60 ~, and to be highly crystalline.
The propylene polymer (A4) is desired to have an
intrinsic viscosity [~], as measured in decalin at 135 °C,
S of 1.3 to 5.0 dl/g, preferably 1.4 to 3.0 dl/g, a weight-
average molecular weight of 12 x 104 to 100 x 10q,
preferably 13 x 10q to 40 x 10q, and a boiling heptane
extraction residue proportion (I.I.) of not less than 90
preferably not less than 93
The propylene polymer (A4) may contain constituent
units derived ethylene and a-olefins of 4 to 20 carbon
atoms in an amount of not more than 5 $ by mol.
Examples of the a-olefins of 4 to 20 carbon atoms
include 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene,
1S 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene,
4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-
pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-
decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-
octadecene and 1-eicosene.
2 0 Ethylene/olefin random copolymer lC)
The ethylene/olefin random copolymer (C) contains
constituent units derived from ethylene in an amount of 20
to 80 $ by mol, preferably 30 to 60 ~ by mol, and contains
constituent units derived from at least one monomer
2 S (olefin) selected from a-olefins of 3 to 20 carbon atoms
and polyenes of 5 to 20 carbon atoms in an amount of 80 to
~ by mol, preferably 70 to 40 ~ by mol.
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Examples of the a-olefins of 3 to 20 carbon atoms
include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-
1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,
1-hexadecene and 1-octadecene. Of these, propylene is
S preferred. These a-olefins may be used singly or in
combination of two or more.
The polyene of 5 to 20 carbon atoms is, for example, a
conjugated or non-conjugated polyene having two or more
olefinic double bonds.
Examples of such polyenes include:
chain polyene compounds, such as 1,3-pentadiene, 1,4-
pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 4-
methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 6-methyl-1,6-
octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene,
6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 6-methyl-
1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-
nonadiene, 7-ethyl-1,6-nonadiene, 6-methyl-1,6-decadiene,
7-methyl-1,6-decadiene, 6-methyl-1,6-undecadiene, 1,7-
octadiene, 1,9-decadiene, 2,4,6-octatriene, 1,3,7-
2 0 octatriene, 1,5,9-decatriene and divinylbenzene; and
cyclic polyene compounds, such as 1,3-cyclopentadiene,
1,3-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-
cycloheptadiene, dicyclopentadiene, dicyclohexadiene, 5-
ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-
2 S isopropylidene-2-norbornene, methylhydroindene, 2,3-
diisopropylidene-5-norbornene, 2-ethylidene-3-
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isopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-
5-norbornene and 2-propenyl-2,5-norbornadiene.
The ethylene/olefin random copolymer (C) has an
intrinsic viscosity [~], as measured in decalin at 135 °C,
of 1.5 to 5 dl/g, preferably 2.0 to 4.0 dl/g.
The ethylene/olefin random copolymer (C) desirably has
a molecular weight distribution (Mw/Mn), as measured by
GPC, of not more than 3.0, preferably 2.0 to 2.5.
Further, the ethylene/olefin random copolymer (C) is
desired to have a glass transition temperature (Tg) of not
higher than -40 °C, preferably not higher than -50 °C.
The ethylene/olefin random copolymer (C) is desired to
be lowly crystalline or amorphous, and to have a
crystallinity, as measured by X-ray diffractometry, of not
more than 30 ~, preferably 0 to 10 ~.
Propy ne polymer composition
The fifth propylene polymer composition comprises the
propylene polymer (A9) and the ethylene/olefin random
copolymer (C). In this composition, it is desired that the
2 0 propylene polymer (A4) is contained in an amount of 50 to
97 ~ by weight, preferably 70 to 90 ~ by weight; and the
ethylene/olefin random copolymer (C) is contained in an
amount of 3 to 50 ~ by weight, preferably 10 to 30 o by
weight.
2 S The fifth propylene polymer composition is desired to
have MFR, as measured at 230 °C under a load of 2.16 kg, of
0.01 to 100 g/10 min, preferably 1 to 50 g/10 min. In this
CA 02295395 2000-O1-13
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composition, Mw/Mn of all the propylene components for
constituting the composition is desirably in the range of 4
to 15.
The density of the fifth propylene polymer composition
S is desired to be in the range of 0.88 to 0.92 g/cm3,
preferably 0.89 to 0.92 g/cm3.
The flexural modulus (FM) thereof is desired to be in
the range of 8,000 to 17,000 kg/cm2, preferably 9,000 to
15, 000 kg/cmz . ,
The Izod impact strength (IZ) thereof at 23 °C is
desired to be in the range of 10 to 50 kg~cm/cm, preferably
10 to 40 kg~cm/cm, and at -30 °C in the range of 5 to 15
kg~cm/cm, preferably 7 to 15 kg~cm/cm.
The tensile elongation at break (EL) thereof is
desired to be in the range of 200 to 500 ~, preferably 250
to 450
The heat distortion temperature (HDT) thereof is
desired to be not lower than 80 °C, preferably in the range
of 90 to 110 °C.
2 0 The fifth propylene polymer composition may contain,
if necessary, additives which may be added to the first
propylene polymer composition, with the proviso that the
object of the invention is not marred.
The fifth propylene polymer composition can be
2 5 prepared by known processes. For example, the composition
can be prepared in accordance with the processes (1) to (4)
described for the first propylene polymer composition,
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using the propylene polymer (A4) and the ethylene/olefin
random copolymer (C).
Such fifth propylene polymer composition is excellent
in not only heat resistance and rigidity but also
mechanical strength such as flexural strength and impact
resistance.
The fifth propylene polymer composition is excellent
especially in the low-temperature impact resistance as
compared with a propylene polymer composition comprising a
propylene polymer and an ethylene/olefin random copolymer
prepared by the use of a conventional titanium catalyst.
The fifth propylene polymer composition can be
favorably used for structural materials such as those of
automobiles and electrical appliances.
Next, the catalyst used for the preparation of the
propylene polymer (A4), the process for preparing said
catalyst, the catalyst used for the preparation of the
ethylene/olefin random copolymer and the process for
preparing said catalyst are described.
2 0 The propylene polymer (4) is obtained by polymerizing
propylene in the presence of an olefin polymerization
catalyst comprising the solid titanium catalyst component
(d) and the organometallic compound catalyst component (e),
said catalyst being the same as the olefin polymerization
2 5 catalyst (2) which is used for the preparation of the
propylene polymer (A3).
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In the polymerization of propylene, other monomers
than propylene, such as ethylene and the aforesaid a-
olefins of 4 to 20 carbon atoms, may be used in the amounts
of not more than 0.1 mol based on 1 mol of propylene.
The propylene polymer (A4) can be prepared by either a
liquid phase polymerization process such as a solution
polymerization process and a suspension polymerization
process, or a gas phase polymerization process.
When the polymerization is conducted in the reaction
1~ form of the suspension polymerization, polyene compounds
and olefins which are liquid at reaction temperatures
and/or the same inert solvents as used for the preparation
of the olefin polymerization catalyst (1) can be used as
the reaction solvent.
The olefin polymerization catalyst used for the
polymerization is generally used in the following amount,
though the amount varies depending upon the kind.
The solid titanium catalyst component (d) (including
the prepolymerized catalyst) is used in an amount of
2 0 usually about 0.001 to 100 mmol, preferably about 0.005 to
mmol, in terms of the titanium atom in the solid
titanium catalyst component (d) or the prepolymerized
catalyst, based on 1 liter of the polymerization volume.
The organometallic compound catalyst component (e) is
2 5 used in such an amount that the amount of the metal atom in
said catalyst component (e) is in the range of usually
about 1 to 2,000 mol, preferably about 5 to 500 mol, based
CA 02295395 2000-O1-13
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on 1 mol of the titanium atom in the solid titanium
catalyst component (d) or the prepolymerized catalyst.
The same electron donors as the aforesaid electron
donors (k) and (1) may be also employed in addition to the
catalyst component (d) and the catalyst component (e).
When the electron donor is used, the amount of the electron
donor is in the range of usually about 0.001 to 10 mol,
preferably 0.01 to 5 mol, based on 1 mol of the metal atom
in the organometallic compound catalyst component (e).
The olefin polymerization catalyst used for preparing
the propylene polymer (A4) may contain other components
than the above-mentioned components, which are useful for
the olefin polymerization.
The molecular weight of the resulting polymer can be
regulated if hydrogen is used in the polymerization,
whereby a polymer having a high melt flow rate can be
obtained.
The polymerization is generally carried out under the
following conditions. The polymerization temperature is in
2 0 the range of about -40 to 300 °C, preferably about -20 to
150 °C, and the polymerization pressure is in the range of
atmospheric pressure to 100 kg/cmz, preferably about 2 to
50 kg/cm2.
The polymerization can be carried out either
2 S batchwise, semi-continuously or continuously. Further, the
polymerization can be conducted in two or more steps, and
CA 02295395 2000-O1-13
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in this case, the reaction conditions may be the same as or
different from each other.
The ethylene/olefin random copolymer (C) is obtained
by copolymerizing ethylene and at least one monomer
S (olefin) selected from an a-olefin of 3 to 20 carbon atoms
and a polyene of 5 to 20 carbon atoms in the presence of an
olefin polymerization catalyst [olefin polymerization
catalyst (3)] comprising:
(i) (f) a transition metal compound containing a
ligand having a cyclopentadienyl skeleton, and
(ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(g) a compound which reacts with the
transition metal compound (f) to form an ion pair.
Fig. 3 illustrates steps of a process for preparing
the olefin polymerization catalyst which is used for the
preparation of the ethylene/olefin random copolymer (C).
Examples of the transition metal compound (f) having a
2 0 cyclopentadienyl skeleton include the transition metal
compound (h) represented by the aforementioned formula (I)
and the compound represented by the following formula (Ic).
MLx ...(Ic)
wherein M is a transition metal atom selected from the
2 5 group consisting of zirconium, titanium, hafnium, vanadium,
niobium, tantalum and chromium, L is a ligand coordinating
to the transition metal, at least one of L is a ligand
CA 02295395 2000-O1-13
114
having a cyclopentadienyl skeleton, and L other than the
ligand having a cyclopentadienyl skeleton is a hydrocarbon
group of 1-12 carbon atoms, an alkoxy group, an aryloxy
group, a trialkylsilyl group, S03R group (provided that R
is a hydrocarbon group of 1-8 carbon atoms which may have
such a substituent as halogen), halogen atom or hydrogen
atom, and x is a valence of the transition metal atom.
The ligands having a cyclopentadienyl skeleton are,
for example, cyclopentadienyl group, alkyl-substituted
cyclopentadienyl groups such as methylcyclopentadienyl,
dimethylcyclopentadienyl, trimethylcyclopentadienyl,
tetramethylcyclopentadienyl, pentamethylcyclopentadienyl,
ethylcyclopentadienyl, methylethylcyclopentadienyl,
propylcyclopentadienyl, methylpropylcyclopentadienyl,
1$ butylcyclopentadienyl, methylbutylcyclopentadienyl and
hexylpentadienyl, or indenyl group, 4,5,6,7-
tetrahydroindenyl group and fluorenyl group. These groups
as exemplified above may be substituted with a halogen atom
or trialkylsilyl group.
2 0 Of the ligands coordinating with the transition metal
atom, particularly preferred is an alkyl-substituted
cyclopentadienyl group.
When the compound represented by the formula (Ic)
contains 2 or more ligands each having a cyclopentadienyl
2 5 skeleton, the two ligands out of those having a
cyclopentadienyl skeleton may be linked together through an
alkylene group such as ethylene or propylene, a substituted
CA 02295395 2000-O1-13
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alkylene group such as isopropylidene or diphenylmethylene,
a silylene group or a substituted silylene group such as
dimethylsilylene, diphenylsilylene or methylphenylsilylene.
The ligands L other than those having a
cyclopentadienyl skeleton may include those mentioned
below.
The hydrocarbon group of 1-12 carbon atoms includes
such group as alkyl, cycloalkyl, aryl or aralkyl, and more
particularly,
the alkyl group includes methyl, ethyl, propyl,
isopropyl or butyl;
the cycloalkyl group includes cyclopentlyl or
cyclohexyl;
the aryl group includes phenyl or tolyl; and
the aralkyl group includes benzyl or neophyl.
Further, the alkoxy group includes methoxy, ethoxy or
butoxy;
aryloxy group includes phenoxy;
the halogen includes fluorine, chlorine, bromine or
2 0 iodine; and
the ligand represented by S03R includes p-
toluenesulfonate, methanesulfonate or
trifluoromethanesulfonate.
When the valence of the transition metal atom is, for
2 S example, 4, the transition metal compound is represented by
the following formula (Id) in more detail.
R2kR31R4mR5nM ... (Id)
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wherein M represents the aforementioned transition metal
atom, R2 represents a group (ligand) having a
cyclopentadienyl skeleton, R3, R4 and RS each represent a
group having a cyclopentadienyl skeleton, alkyl group,
S cycloalkyl group, aryl group, aralkyl group, alkoxyl group,
aryloxy group, trialkylsilyl group, S03R group, halogen
atom or hydrogen atom, k is an integer of 1 or more, and
k+1+m+n=4.
In the present invention, there is used preferably a
metallocene compound having the above-mentioned formula
(Id) in which at least two of R2, R3, R4 and RS are the
groups (ligands) having a cyclopentadienyl skeleton, for
example, R2 and R3 are the groups (ligands) having a
cyclopentadienyl. In this case, the groups having a
cyclopentadienyl skeleton mentioned above may be linked
together through an alkylene group such as ethylene or
propylene, a substituted alkylene group such as
isopropylene or diphenylmethylene, a silylene group or a
substituted silylene group such as dimethylsilylene,
2 0 diphenylsilylene or methylphenylsilylene. Further, R4 and
R5 are each a group having a cyclopentadienyl skeleton,
alkyl group, cycloalkyl group, aryl group, arlakyl group,
alkoxyl group, aryloxy group, trialkylsilyl group, S03R
group, halogen atom or hydrogen atom.
2 $ Exemplified below are the transition metal compounds
wherein M is zirconium.
Bis(indenyl)zirconium dichloride,
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Bis(indenyl)zirconium dibromide,
Bis(indenyul)zirconium bis(p-toluenesulfonate),
Bis(4,5,6,7-tetrahydroindenyl)zirconium dichloride,
Bis(fluorenyl)zirconium dichloride,
Ethylenebis(indenyl)zirconium dichloride,
Ethylenebis(indenyl)zirconium dibromide,
Ethylenebis(indenyl)dimethylzirconium,
Ethylenebis(indenyl)diphenylzirconium,
Ethylenebis(indenyl)me.thylzirconium monochloride,
Ethylenebis(indenyl)zirconium bis(methanesulfonate),
Ethylenebis(indenyl)zirconium bis(p-toluenesulfonate),
Ethylenebis(indenyl)zirconium
bis(trifluoromethanesulfonate),
Ethylenebis(4,5,6,7-tetrahydroindenyl)zirconium
dichloride,
Isopropylidene(cyclopentadienyl-fluorenyl)zirconium
dichloride,
Isopropylidene(cyclopentadienyl-
methylcyclopentadienyl)zirconium dichloride,
2 0 Dimethylsilylenebis(cyclopentadienyl)zirconium
dichloride,
Dimethylsilylenebis(methylcyclopentadienyl)zirconium
dichloride,
Dimethylsilylenebis(dimethylcyclopentadienyl)zirconium
2 S dichloride,
Dimethylsilylenebis(trimethylcyclopentadienyl)
zirconium dichloride,
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Dimethylsilylenebis(indenyl)zirconium dichloride,
Dimethylsilylenebis(2-methylindenyl)zirconium
dichloride,
Dimethylsilylenebis(2-methyl, 4-
isopropylindenyl)zirconium dichloride,
Dimethylsilylenebis(indenyl)zirconium
bis(trifluoromethane-sulfonate),
Dimethylsilylenebis(4,5,6,7-
tetrahydroindenyl)zirconium dichloride,
Dimethylsilylene(cyclopentadienyl-fluorenyl)zirconium
dichloride,
Diphenylsilylenebis(indenyl)zirconium dichloride,
Diphenylsilylenebis(2-methyl, 4-
isopropylindenyl)zirconium dichloride,
1S
Methylphenylsilylenebis(indenyl)zirconium dichloride,
Bis(cyclopentadienyl)zirconium dichloride,
Bis(cyclopentadienyl)zirconium dibromide,
Bis(cyclopentadienyl)methylzirconium monochloride,
2 0 Bis(cyclopentadienyl)ethylzirconium monochloride,
Bis(cyclopentadienyl)cyclohexylzirconium monochloride,
Bis(cyclopentadienyl)phenylzirconium monochloride,
Bis(cyclopentadienyl)benzylzirconium monoc~~loride,
Bis(cyclopentadienyl)zirconium monochloride
2 S monohydride,
Bis(cyclopentadienyl)methylzirconium monohydride,
Bis(cyclopentadienyl)dimethylzirconium,
i
J
CA 02295395 2000-O1-13
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Bis(cyclopentadienyl)diphenylzirconium,
Bis(cyclopentadienyl)dibenzylzirconium,
Bis(cyclopentadienyl)zirconium methoxychloride,
Bis(cyclopentadienyl)zirconium ethoxychloride,
S Bis(cyclopentadienyl)zirconium bis(methanesulfonate),
Bis(cyclopentadienyl)zirconium bis(p-
toluenesulfonate),
Bis(cyclopentadienyl)zirconium
bis(trifluoromethanesulfonate),
1~ Bis(methylcyclopentadienyl)zirconium dichloride,
Bis(dimethylcyclopentadienyl)zirconium dichloride,
Bis(dimethylcyclopentadienyl)zirconium ethoxychloride,
Bis(dimethylcyclopentadienyl)zirconium
bis(trifluoromethanesulfonate),
15 Bis(ethylcyclopentadienyl)zirconium dichloride,
Bis(methylethylcyclopentadienyl)zirconium dichloride,
Bis(propylcyclopentadienyl)zirconium dichloride,
Bis(methylpropylcyclopentadienyl)zirconium dichloride,
Bis(butylcyclopentadienyl)zirconium dichloride,
2 0 Bis(methylbutylcyclopentadienyl)zirconium dichloride,
Bis(methylbutylcyclopentadienyl)zirconium
bis(methanesulfonate),
Bis(trimethylcyclopentadienyl)zirconium dichloride,
Bis(tetramethylcyclopentadienyl)zirconium dichloride,
2 S Bis(pentamethylcyclopentadienyl)zirconium dichloride,
Bis(hexylcyclopentadienyl)zirconium dichloride, and
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Bis(trimethylsilylcyclopetnadienyl)zirconium
dichloride.
In the compounds exemplified above, the di-substituted
cyclopentadienyl ring includes 1,2- and 1,3-substituted
S compounds, and the tri-substituted cyclopentadienyl ring
includes 1,2,3- and 1,2,4-substituted compounds. Further,
the alkyl group such as propyl or butyl includes isomer
such as n-, i-, sec-, tert-compounds,
In the present invention, the above-exemplified
zirconium compounds in which the zirconium has been
replaced by titanium, hafnium, vanadium, niobium, tantalum
or chromium can also be used as the transition metal
compounds.
Of the above-exemplified transition metal compounds,
1S preferably used are the zirconocene compounds which have
zirconium as the central metal atom and have at least two
ligands containing a cyclopentadienyl skeleton.
In the present invention, the transition metal
compound represented by the aforementioned formula (I) is
2 0 particularly preferably used as the transition metal
compound (f).
The transition metal compounds may be used singly or
in combination of two or more kinds. These compounds may
be used by diluting them with hydrocarbons or halogenated
2 S hydrocarbons.
The transition metal compound (f) may be supported on
a particulate carrier. As the carrier, the same
CA 02295395 2000-O1-13
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particulate carrier as used in the preparation of the
olefin polymerization catalyst (2) can be mentioned.
The organoaluminum oxy-compound (b) is identical with
the aforesaid organoaluminum oxy-compound, and this
organoaluminum oxy-compound (b) can be used by supporting
it on the above-mentioned carrier.
The compound (g) which reacts with the transition
metal compound (f) to form an ion pair is identical with
the aforesaid compound (c),~and this compound (g) can be
used by supporting it on the above-mentioned carrier.
The olefin polymerization catalyst (3) used for
preparing the ethylene/olefin random copolymer (C) can be
prepared by mixing the transition metal compound (f)
[component (f)] and the organoaluminum oxy-compound (b)
[component (b)) (or the compound (g) which reacts with the
transition metal compound (f) to form an ion pair,
[component (g)]), and if desired, the organometallic
compound (e) [component (e)] in an inert hydrocarbon
solvent or an olefin solvent.
2 0 As the inert hydrocarbon solvent used for the olefin
polymerization catalyst (3), the same inert hydrocarbon
solvent as used for preparing the olefin polymerization
catalyst (1) can be mentioned.
In the preparation of the olefin polymerization
2 S catalyst (3), each components may be mixed in an optional
order, but preferably they are mixed in the following
manner:
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the component (b) [or the component (g)] is mixed with
the component (f);
the component (b) is mixed with the component (e), and
the resulting mixture is then mixed with the component (f);
the component (f) is mixed with the component (b) [or
the component (g)], and the resulting mixture is then mixed
with the component (e); or
the component (f) is mixed with the component (e), and
the resulting mixture is then mixed with the component (b)
[or the component (g)].
In the mixing of each components, an atomic ratio
(A1/transition metal) of the aluminum in the component (b)
to the transition metal in the component (f) is in the
range of usually 10 to 10,000, preferably 20 to 5,000; and
a concentration of the component (f) is in the range of
about 10'8 to 10'1 mol/1-solvent, preferably 10-7 to S x 10'z
mol/1-solvent.
When the component (g) is used, a molar ratio
[component (f)/component (g)] of the component (f) to the
2 0 component (g) is in the range of usually 0.01 to 10,
preferably 0.1 to 5; and a concentration of the component
(f) is in the range of about 10'8 to 10'1 mol/1-solvent,
preferably 10'~ to 5 x 10'2 mol/1-solvent.
when the component (e) is used, an atomic ratio (M/A1)
of the metal atom (M) in the component (e) to the aluminum
atom (A1) in the component (b) is in the range of usually
0.02 to 20, preferably 0.2 to 10.
CA 02295395 2000-O1-13
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The above-mentioned components may be mixed in a
polymerizer. Otherwise, a mixture of the components
beforehand prepared may be fed to a polymerizer.
If the components are beforehand mixed, the mixing
temperature is in the range of usually -50 to 150 °C,
preferably -20 to 120 °C: and the contact time is in the
range of 1 to 1,000 minutes, preferably 5 to 600 minutes.
The mixing temperature may be varied while the components
are mixed and contacted with each other.
The olefin polymerization catalyst (3) may be an
olefin polymerization solid catalyst in which at least one
of the component (f), the component (b) [or the component
(g)) and the component (e) is supported on an inorganic or
organic carrier of granular or particulate solid.
As the particulate carrier, those used for the
preparation of the aforesaid olefin polymerization catalyst
( 2 ) can be employed.
The olefin polymerization catalyst (3) may be a
prepolymerized catalyst formed from the particulate
2 0 carrier, the component (f), the component (b) [or the
component (g)] and an olefin polymer produced by the
prepolymerization, and if desired, the component (e).
The olefin used for the prepolymerization includes
olefins such as propylene, ethylene and 1-butene, but a
2 S mixture of these olefins and other olefin may also be
employed.
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124
In addition to the above components, the olefin
polymerization catalyst (3) may contain other components
which are useful for the olefin polymerization, for
example, water as a catalyst component.
S The ethylene/olefin random copolymer (C) can be
prepared by copolymerizing ethylene and at least one
monomer (olefin) selected from oc-olefins of 3 to 20 carbon
atoms and polyenes of 5 to 20 carbon atoms in the presence
of the olefin polymerization catalyst (3). In the
copolymerization, ethylene and the olefin are used in such
amounts that the resulting ethylene/olefin random copolymer
(C) has the aforementioned composition.
The copolymerization to prepare the ethylene/olefin
random copolymer (C) may be carried out in the presence of
1$ a hydrocarbon medium.
Examples of the hydrocarbon media include hydrocarbons
which are used for preparing the organoaluminum oxy-
compound (b).
Of such hydrocarbons, preferably used are hexane,
2 0 methylpentane, methylcyclopentane, heptane, octane,
cyclohexane, etc. Also employable as the hydrocarbon
medium is an Oc-olefin which is liquid under the
copolymerization conditions.
The polymerization of ethylene and an olefin is
2 5 carried out under the conditions of a temperature of
usually -20 to 200 °C, preferably 0 to 180 °C, particularly
preferably 20 to 160 °C, and a pressure of usually
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atmospheric pressure to 100 kg/cmz, preferably atmospheric
pressure to 50 kg/cm2, particularly preferably atmospheric
pressure to 30 kg/cm2.
The molecular weight of the resulting copolymer can be
regulated by varying the polymerization conditions such as
a polymerization temperature or by controlling the amount
of hydrogen (molecular weight regulator) used.
In the present invention, the molecular weight is
regulated so that the resulting copolymer has MFR of the
aforesaid value.
The copolymerization may be carried out by a solution
polymerization process, a suspension polymerization
process, etc. In this invention, a solution polymerization
process is preferably used. Though the polymerization
reaction may be carried out either batchwise, semi-
continuously or continuously, it is preferably carried out
continuously. Further, it is also possible to conduct the
polymerization in two or more steps having different
reaction conditions.
2 ~ The polymer obtained immediately after the
polymerization can be recovered by conventionally known
separation and recovery methods.
In the case of the solution polymerization, it is
preferred to solidify the polymer by directly evaporating
2 S the solvent, or to solidify the polymer by evaporating the
solvent from the concentrated phase after phase separation.
The sixth p roQvlene p~ymer composition
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The sixth propylene polymer composition comprises:
(AS) a propylene homopolymer which is obtained by
polymerizing propylene in the presence of an olefin
polymerization catalyst comprising:
S (i) (h) a transition metal compound represented
by the aforesaid formula (I), and
(ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(i) a compound which reacts with the
transition metal compound (h) to form an ion pair; and
(A6) a propylene polymer which contains constituent
units derived from propylene in an amount of not less than
90 ~ by mol and is different from the propylene homopolymer
1 5 (A5) .
Propylene homopolymer lA5)
The propylene homopolymer (A5) for constituting the
sixth propylene polymer composition is a homopolymer of
propylene which is prepared by the use of an olefin
2 0 polymerization catalyst comprising a transition metal
compound (h) represented by the aforesaid formula (I) and
at least one compound selected from the organoaluminum oxy-
compound (b) and the compound (i).
The propylene homopolymer (A5) is desired to have MFR,
2 $ as measured at 230 °C under a load of 2.16 kg, of 0.01 to
1,000 g/10 min, preferably 0.5 to 200 g/10 min, and Mw/Mn,
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as measured by GPC, of 1.5 to 3.5, preferably 2.0 to 3.0,
more preferably 2.0 to 2.5.
Further, the propylene homopolymer (A5) is desired to
have an intrinsic viscosity [~], as measured in decalin at
S 135 °C, of 0.1 to 20 dl/g, preferably 0.5 to 10 dl/g, more
preferably 1 to 5 dl/g, and a weight-average molecular
weight of 1 x 103 to 500 x 104, preferably 1 x 104 to 100 x
104
The crystallinity of the propylene homopolymer (A5),
as measured by X-ray diffractometry, is desired to be not
less than 40 ~, preferably not less than 50 $, and the
boiling heptane extraction residue proportion (I. I.)
thereof is desired to be not less than 90 ~, preferably not
less than 93 ~.
~S The triad tacticity (mm fraction) of the propylene
homopolymer (A5) is desired to be not less than 99.0 ~,
preferably not less than 99.2 ~, more preferably not less
than 99.5 ~.
The proportion of the irregularly positioned units
2 0 (inversely inserted units) based on the 2,1-insertion of
the propylene monomer is desired to be not more than 0.5 g,
preferably not more than 0.18 $, more preferably not more
than 0.15 $.
The proportion of the irregularly positioned units
2 5 based on the 1,3-insertion of the propylene monomer is
desired to be less than the detected lower limit by the
i3C_NMR measurement (less than 0.03 0) .
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The triad tacticity (mm fraction), the proportion of
the irregularly positioned units based on the 2,1-insertion
of the propylene monomer, and the proportion of the
irregularly positioned units based on the 1,3-insertion of
S the propylene monomer, of the above-mentioned propylene
homopolymer and the later-described propylene copolymer are
determined in the following manner.
[Triad tacticity (mm fraction))
The triad tacticity (mm fraction) of the propylene
copolymer is defined, when a sequence of optional three
propylene units with head-to-tail bonds in the polymer
chain is expressed by a planar zigzag structure, as a
proportion of such propylene unit sequences that the
direction of methyl branches thereof are the same as each
other, and determined by the 13C-NMR spectrum using the
following equation:
PPP (mm)
Triad tacticity (%) - x 100
2 ~ PPP (mm) + PPP (mr) + PPP (rr)
wherein PPP (mm) , PPP (mr) and PPP (rr) denote absorption
intensities originating from the methyl group of the second
unit in the 3-propylene unit sequences with head-to-tail
bonds represented by the following formulas, respectively:
CH3 CH3 CH3
I I I
PPP (mm) . - (CH-CH2) - (CH-CH2) - (CH-CH2) -
CH3 CH3
I I
PPP ( mr ) . - ( CH-CH2 ) - ( CH-CH2 ) - ( CH-CH2 ) -
I
CHg
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CH3 CH3
I I
PPP (rr) . - (CH-CH2) - (CH-CH2) - (CH-CH2) -
$ CH3
The 13C-NMR spectrum was measured in the following
manner. A sample was completely dissolved in a mixed
solvent containing about 0.5 ml of hexachlorobutadiene, o-
dichlorobenzene or 1,2,4-trichlorobenzene and about 0.05 ml
of.deuterated benzene (i.e., lock solvent) in a NMR sample
tube (diameter: 5 mm), and then subjected to a proton
perfect decoupling method at 120 °C to measure the 13C-NMR
spectrum. The measurement is conducted under the
conditions of a flip angle of 45° and a pulse interval of
1S not less than 3.4 T1 (T1 is a maximum value with respect to
a spin-lattice relaxation time of the methyl group). As
for the propylene, the spin-lattice relaxation time of the
methyl group is longer than that of the methylene group and
that of the methine group, and hence the magnetization
2 0 recovery of all carbons in the sample under these
conditions is not less than 99 ~. With respect to the
chemical shift, the methyl group of the third unit in the
5-propylene unit sequence with head-to-tail bonds is set to
21.593 ppm, and the chemical shift of other carbon peak is
2 5 determined by using this value as a reference.
The peak region is classified into the first region
(21.1 - 21.9 ppm), the second region (20.3 - 21.0 ppm) and
the third region (19.5 - 20.3 ppm).
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In the first region, the methyl group of the second
unit in the 3-propylene unit sequence represented by
PPP (mm) resonates .
In the second region, the methyl group of the second
S unit in the 3-propylene unit sequence represented by
PPP(mr) and the methyl group (PPE-methyl group) of a
propylene unit whose adjacent units are a propylene unit
and an ethylene unit resonate.
In the third region, the methyl group of the second
unit in the 3-propylene unit sequence represented by
PPP(rr) and the methyl group (EPE-methyl group) of a
propylene unit whose adjacent units are ethylene units
resonate.
The propylene copolymer has, as partial structures
containing an irregularly positioned unit, the following
structures (i) , (ii) and (iii)
Structure (i)
A B C
2 0 CH3 CH3 CHg CH3 CH3 CH3
I I I I
- (CH2-CH) - (CH2-CH) - (CH2-CH) - (CH-CH2 ) - (CH2-CH) - (CH2-CH) -
2S
Structure (ii)
D E D
CH3 CH3 CH3 CH3 CH3
I I I I
- (CH2-CH) - (CH2-CH) - (CH2-CH2) - (CH-CH2) - (CHZ-CH) - (CH2-CH) -
3 0 Structure (iii)
E' D'
CH3 CH3 CH3 CH3 CH3
I I I I I
3 S - (CH2-CH) - (CH2-CH) - (CH2-CH2) n- (CH-CH2) - (CH2-CH) - (CH2-CH) -
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(n _> 2)
Of the peaks originating from these structures (i),
(ii) and (iii), the peaks based on the carbon A and the
carbon B do not appear in the first to third regions,
because the carbon A and the carbon B resonate at 17.3 ppm
and 17.0 ppm, respectively. Further, the carbon A and the
carbon B have no concern with the 3-propylene unit sequence
with head-to-tail bonds, so that it is unnecessary to take
those carbons into account in the calculation of the triad
tacticity.
The peak based on the carbon C, the peak based on the
carbon D and the peak based on the carbon D' appear in the
second region, and the peak based on the carbon E and the
peak based on the carbon E' appear in the third region.
Accordingly, of the peaks which appear in the first to
third regions, the peaks which are not based on the 3-
propylene unit sequence with heat-to-tail bonds are those
based on the PPE-methyl group (resonance in the vicinity of
2 0 20.7 ppm), the EPE-methyl group (resonance in the vicinity
of 19.8 ppm), the carbon C, the carbon D, the carbon D',
the carbon E and the carbon E'
The peak area based on the PPE-methyl group can be
determined from the peak area of the PPE-methine group
2 5 (resonance in the vicinity of 30.6 ppm); and the peak area
based on the EPE-methyl group can be determined from the
peak area of the EPE methine group (resonance in the
vicinity of 32.9 ppm). The peak area based on the carbon C
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can be determined from the peak area of the adjacent
methine group (resonance in the vicinity of 31.3 ppm); the
peak area based on the carbon D can be determined from 1/2
as much as the sum of the peak areas of the peaks based on
S the oc~3 methylene carbons of the above structure (ii)
(resonance in the vicinity of the 34.3 ppm and in the
vicinity of 34.5 ppm); the peak area based on the carbon D'
can be determined from the peak area based on the methine
group adjacent to the methyl group (resonance in the
vicinity of 33.3 ppm) of the carbon E' of the above
structure (iii); the peak area based on the carbon E can be
determined from the peak area of the adjacent methine
carbon (resonance in the vicinity of 33.7 ppm); and the
peak area based on the carbon E' can be determined from the
1S peak area of the adjacent methine carbon (resonance in the
vicinity of 33.3 ppm).
Accordingly, by subtracting these peak areas from the
total peak areas of the second and third regions, the peak
areas originating from the 3-propylene unit sequences
2 0 (PPP(mr) and PPP(rr)) consisting of head-to-tail bonds can
be obtained.
Thus, the peak areas of PPP (mm) , PPP (mr) and PPP (rr)
can be determined, and hence the triad tacticity (mm
fraction) of the propylene unit sequences consisting of the
2 S head-to-tail bonds can be calculated by the above-mentioned
equation.
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The triad tacticity (mm fraction) of the propylene
homopolymer is defined, when a sequence of optional three
propylene units with head-to-tail bonds in the polymer
chain is expressed by a planar zigzag structure, as a
proportion of such propylene unit sequences that the
direction of methyl groups thereof are the same as each
other, and determined by the 13C-NMR spectrum using the
following equation:
Triad tacticity (o) - PPPImm)
E ICH3
wherein PPP(mm) has the same meaning as defined above, and
EICH3 denotes the total peak areas based on all of the
methyl groups.
With respect to the chemical shift, the methyl group
of the third unit in the 5-propylene unit sequence with
heat-to-tail bonds is set to 21.593 ppm, and the chemical
shift of other carbon peak is determined by using this
2 0 value as a standard.
In accordance with the standard, the peak based on the
methyl group of the second unit in the 3-propylene unit
sequence represented by PPP(mm) appears within the range of
21.1 to 21.9 ppm; the peak based on the methyl group of the
2 5 second unit in the 3-propylene unit sequence represented by
PPP(mr) appears within the range of 20.3 to 21.0 ppm; and
the peak based on the methyl group of the second unit in
the 3-propylene unit sequence represented by PPP(rr)
appears within the range of 19.5 to 20.3 ppm.
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The propylene homopolymer has such a partial structure
containing the irregularly positioned unit based on the
2,1-insertion as represented by the aforesaid structure (i)
in a small amount, in addition to the regular structure in
S which the propylene units are bonding with head-to-tail.
In the irregular structure represented by the
structure (i), the aforementioned definition of PPP(mm) is
not applied to the carbon A, the carbon B and the carbon C.
However, the carbon A and the carbon B resonate in the
region of 16.5 to 17.5 ppm; and the carbon C resonates in
the vicinity of 20.7 ppm (the region of PPP(mr)).
(However, not only the peaks of these methyl groups but
also the peaks of the adjacent methylene and methine groups
must be confirmed in the case of identifying the partial
structure containing an irregularly positioned unit.)
Therefore, the carbon A, the carbon B and the carbon C are
not included in the region of PPP(mm).
Accordingly, the triad tacticity (mm fraction) of the
propylene homopolymer can be determined from the above
2 0 equation.
[Proportion of the irregularly positioned unit based
on the 2,1-insertion of the propylene monomer]
In the polymerization, the 1,2-insertion of the
propylene monomer often takes place (i.e., the methylene
2 S side is bonded to the catalyst), but the 2,1-insertion
thereof sometimes takes place. Therefore, the propylene
copolymer has such irregularly positioned units based on
CA 02295395 2000-O1-13
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the 2,1-insertion as represented by the aforesaid
structures (i), (ii) and (iii). The proportion of the
irregularly positioned units based on the 2,1-insertion was
calculated by the following formula using the 13C-NMR.
Proportion of irregularly positioned unit based on 2,1-
insertion
(O.SIa~(structure (i), (iii)) + 0.25Iaa(structure (ii))} x 100
-
Iaa+Ia~ (structure(i),(iii))+0.5(IaY+Iaa(structure(ii)+Ia8)
Naming of the peaks was made in accordance with a
method by Carman, et al. (Rubber Chem. Technol., 44 (1971),
781). Ian denotes a peak area of the a~ peak.
The propylene homopolymer has such an irregularly
positioned unit based on the 2,1-insertion as represented
by the aforesaid structure (i). The proportion of the
irregularly positioned units based on the 2,1-insertion was
calculated by the following formula using the 13C-NMR.
Proportion of irregularly positioned unit based on 2,1-
insertion
2 $ 0.5(area based on methyl group resonating in the region of
- 16.5~17.5ppm}
EICH3
3 0 wherein EICH3 has the same meaning as defined above.
[Proportion of the irregularly positioned unit based
on the 1,3-insertion of the propylene monomer]
In the propylene copolymer, the amount of the three
sequences based on the 1,3-insertion of propylene was
CA 02295395 2000-O1-13
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determined by the ~3y peak (resonance in the vicinity of
27.4 ppm) .
In the propylene homopolymer, the amount of the three
sequences based on the 1,3-insertion of propylene was
S determined by the a8 peak (resonance in the vicinity of
37.1 ppm) and the ~iy peak (resonance in the vicinity of
27.4 ppm) .
Propylene polymer (A61
The propylene polymer (A6) is a propylene homopolymer
or a propylene copolymer containing constituent units
derived from propylene in an amount of not less than 90 ~
by mol.
The propylene polymer (A6) is desired to have MFR, as
measured at 230 °C under a load of 2.16 kg, of 0.01 to
1,000 g/10 min, preferably 0.5 to 200 g/10 min. The
molecular weight distribution (Mw/Mn) of this propylene
polymer, as measured by GPC, is desired to be in the range
of 1.5 to 15, preferably 2.0 to 8Ø
Further, the propylene polymer (A6) is desired to have
2 0 a crystallinity, as measured by X-ray diffractometry, of
not less than 40 0, more preferably not less than 50 ~.
The propylene polymer (A6) is desired to have an
intrinsic viscosity ['~], as measured in decalin at 135 °C,
of 0.1 to 20 dl/g, preferably 0.5 to 10 dl/g, and a weight-
2 5 average molecular weight of 1 x 103 to 500 x 104,
preferably 1 x 104 to 100 x 109.
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The propylene polymer (A6) may contain constituent
units derived from ethylene and the same a-olefins of 4 to
20 carbon atoms as exemplified for the propylene polymer
(A4) in the amounts of not more than 10
The propylene polymer (A6) can be prepared by the use
of the olefin polymerization catalyst which is used for
preparing the propylene polymer (A1), the olefin
polymerization catalyst (2) which is used for preparing the
propylene polymer (A3), the olefin polymerization catalyst
(3) which is used for preparing the ethylene/a-olefin
random copolymer (C), or an olefin polymerization catalyst
(4) (described later) which is used for preparing the
propylene polymer (A5). Among these olefin polymerization
catalysts, preferably used are the olefin polymerization
catalyst (1), the olefin polymerization catalyst (3) and
the olefin polymerization catalyst (4), and of these,
particularly preferably used is the olefin polymerization
catalyst (4).
Propylene polymer composition
2 0 The sixth propylene polymer composition comprises the
propylene homopolymer (A5) and the propylene polymer (A6)
which is different from the propylene homopolymer (A5). In
this composition, it is desired that the propylene
homopolymer (A5) is contained in an amount of 5 to 95 $ by
2 S weight, preferably 15 to 85 $ by weight, more preferably 30
to 70 $ by weight; and the propylene polymer (A6) is
CA 02295395 2000-O1-13
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contained in an amount of 5 to 95 $ by weight, preferably
15 to 85 ~ by weight, more preferably 30 to 70 $ by weight.
In the sixth propylene polymer composition, when the
intrinsic viscosity (['~]AS) of the propylene homopolymer
(A5) and the intrinsic viscosity ( ['r~]A6) of the propylene
polymer (A6) has a relation of ['~]AS >_ ['r]]A6, it is desired
that [~]AS is in the range of 1 to 10 dl/g, preferably 2 to
5 dl/g; [~]A6 is in the range of 0.2 to 1.5 dl/g,
preferably 0.3 to 1.0 dl/g; and ( ['r~]AS/ ['t~]A6) is in the
range of 3 to 30, preferably 4 to 20.
When the intrinsic viscosity (['~]AS) of the propylene
homopolymer (A5) and the intrinsic viscosity ( ['t'1]A6) of the
propylene polymer (A6) has a relation of ['BIAS < [~1]AS~ it
is desired that [t~]AS is in the range of 0.2 to 1.5 dl/g,
preferably 0.3 to 1.0 dl/g; [t~]A6 is in the range of 1 to
10 dl/g, preferably 2 to 5 dl/g; and ( ['~ ] A6/ ['1'] ] As) is in the
range of 3 to 30, preferably 4 to 20.
The sixth propylene polymer composition is desired to
have MFR, as measured at 230 °C under a load of 2.16 kg, of
2 0 0.01 to 1,000 g/10 min, preferably 0.5 to 200 g/10 min. In
this composition, Mw/Mn of all the propylene components for
constituting the composition is desirably in the range of 4
to 15.
The density of the sixth propylene polymer composition
2 5 is desired to be in the range of 0.89 to 0.92 g/cm3,
preferably 0.90 to 0.92 g/cm3.
CA 02295395 2000-O1-13
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The flexural modulus (FM) thereof is desired to be in
the range of 12,000 to 21,000 kg/cm2, preferably 14,000 to
20,000 kg/cm2.
The Izod impact strength (IZ) thereof at 23 °C is
desired to be in the range of 2 to 10 kg~cm/cm, preferably
2 to 5 kg~cm/cm.
The tensile elongation at break (EL) thereof is
desired to be in the range of 100 to 500 ~, preferably 200
to 400 $.
1~ The heat distortion temperature (HDT) thereof is
desired to be not lower than 95 °C, preferably in the range
of 100 to 140 °C .
The sixth propylene polymer composition may contain,
if necessary, additives which may be added to the first
propylene polymer composition, with the proviso that the
object of the invention is not marred.
The sixth propylene polymer composition can be
prepared by known processes. For example, the composition
can be prepared in accordance with the processes (1) to (5)
2 0 described for the first propylene polymer composition,
using the propylene homopolymer (A5) and the propylene
polymer (A6) .
Such sixth propylene polymer composition is excellent
in not only heat resistance, rigidity and tensile
elongation at break but also moldability.
The sixth propylene polymer composition can be
favorably used for various structural materials such as
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those of automobiles and electrical appliances, daily
necessaries, various films and sheets.
Next, the catalyst used for the preparation of the
propylene polymer (AS) and the process for preparing the
propylene homopolymer are described.
The olefin polymerization catalyst used for preparing
the propylene homopolymer (A5) is an olefin polymerization
catalyst [olefin polymerization catalyst (4)] comprising:
(i) (h) a transition metal compound represented by
the aforesaid formula (I), and
(ii) at least one compound selected from the group
consisting of
(b) the organoaluminum oxy-compound, and
(i) a compound which reacts with the transition
metal compound (h) to form an ion pair.
Fig. 4 illustrates steps of a process for preparing
the olefin polymerization catalyst which is used for the
preparation of the propylene homopolymer (AS).
The compound (i) which reacts with the transition
2 0 metal compound (h) to form an ion pair is identical with
the compound (c) Which reacts with the transition metal
compound (a) to form an ion pair.
The compound (i) which reacts with the transition
metal compound (h) to form an ion pair can be used in
2 $ combination of two or more kinds.
The olefin polymerization catalyst used for the
preparation of the propylene homopolymer (A5) may contain
CA 02295395 2000-O1-13
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the aforesaid organoaluminum compound (j) in addition to
the transition metal compound (h) and at least one compound
selected from the group consisting of the organoaluminum
oxy-compound (b) and the compound (i).
The olefin polymerization catalyst (4) can be prepared
by mixing the transition metal compound (h) [component (h)]
and the organoaluminum oxy-compound (b) [component (b)] (or
the compound (i) which reacts with the transition metal
compound (h) to form an ion pair, [component (i)]), and if
desired, the organoaluminum compound (j) [component (j)] in
an inert hydrocarbon solvent or an olefin solvent.
As the inert hydrocarbon solvent used for preparing
the catalyst, the same inert hydrocarbon solvent as used
for preparing the olefin polymerization catalyst (1) can be
employed.
In the preparation of the olefin polymerization
catalyst (4), each components may be mixed in an optional
order, but preferably they are mixed in the following
manner:
2 ~ the component (b) [or the component (i)] is mixed with
the component (h);
the component (b) is mixed with the component (j), and
the resulting mixture is then mixed with the component (h);
the component (h) is mixed with the component (b) [or
2 S the component (i)], and the resulting mixture is then mixed
with the component (j); or
CA 02295395 2000-O1-13
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the component (h) is mixed with the component (j), and
the resulting mixture is then mixed with the component (b)
[or the component (i)].
In the mixing of each components, an atomic ratio
(A1/transition metal) of the aluminum in the component (b)
to the transition metal in the component (h) is in the
range of usually 10 to 10,000, preferably 20 to 5,000; and
a concentration of the component (h) is in the range of
about 10'8 to 10'1 mol/1-solvent, preferably 10'~ to 5 x 10'2
mol/1-solvent.
When the component (i) is used, a molar ratio
[component (h)/component (i)] of the component (h) to the
component (i) is in the range of usually 0.01 to 10,
preferably 0.1 to 5; and a concentration of the component
(h) is in the range of about 10'8 to 10'1 mol/1-solvent,
preferably 10'' to 5 x 10'2 mol/1-solvent.
when the component (j) is used, an atomic ratio
(Alj/Alb) of the aluminum atom (A1~) in the component (j) to
the aluminum atom (Alb) in the component (b) is in the
2 0 range of usually 0.02 to 20, preferably 0.2 to 10.
The above-mentioned components may be mixed in a
polymerizer. Otherwise, a mixture of the components
beforehand prepared may be fed to a polymerizer.
If the components are beforehand mixed, the mixing
temperature is in the range of usually -SO to 150 °C,
preferably -20 to 120 °C; and the contact time is in the
range of 1 to 1,000 minutes, preferably 5 to 600 minutes.
CA 02295395 2000-O1-13
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The mixing temperature may be varied while the components
are mixed and contacted with each other.
The olefin polymerization catalyst (4) may be an
olefin polymerization catalyst in which at least one of the
component (h), the component (b) [or the component (i)] and
the component (j) is supported on an inorganic or organic
carrier of granular or particulate solid.
The inorganic carrier is preferably a porous oxide,
for example, Si02 or A1Z03.
Examples of the granular or particulate solid organic
compounds include polymers or copolymers produced mainly
from a-olefins such as ethylene, propylene and 1-butene or
styrene.
The olefin polymerization catalyst (4) may be an
olefin polymerization catalyst formed from the particulate
carrier, the component (h), the component (b) [or the
component (i)] and an olefin polymer prepared by
prepolymerization, and if desired, the component (j).
The olefin used for the prepolymerization includes
2 0 olefins such as propylene, ethylene and 1-butene, but a
mixture of these olefins and other olefin may also be
employed.
In addition to the above components, the olefin
polymerization catalyst (4) may contain other components
2 5 which are useful for the olefin polymerization, for
example, water as a catalyst component.
CA 02295395 2000-O1-13
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The propylene homopolymer (A5) can be prepared by
polymerizing propylene in the presence of the olefin
polymerization catalyst (4). The polymerization may be
carried out by either a liquid phase polymerization process
S such as a suspension polymerization process and a solution
polymerization process, or a gas phase polymerization
process.
In the liquid phase polymerization process, the same
inert hydrocarbon solvent as used in the preparation of the
catalyst described before can be used, or propylene can be
also used as a solvent.
In the suspension polymerization process, the
temperature for polymerizing propylene is in the range of
usually -50 to 100 °C, preferably 0 to 90 °C. In the
solution polymerization process, the polymerization
temperature is in the range of usually 0 to 250 °C,
preferably 20 to 200 °C. In the gas phase polymerization
process, the polymerization temperature is in the range of
usually 0 to 120 °C, preferably 20 to 100 °c. The
2 0 polymerization pressure is in the range of usually
atmospheric pressure to 100 kg/cm2, preferably atmospheric
pressure to 50 kg/cm2. The polymerization reaction may be
carried out either batchwise, semi-continuously or
continuously. Further, it is also possible to conduct the
2 5 polymerization in two or more steps having different
reaction conditions.
The seventh propylene polymer composition
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The seventh propylene polymer composition of the
invention comprises:
(A5) a propylene homopolymer which is obtained by
polymerizing propylene in the presence of an olefin
S polymerization catalyst comprising:
(i) (h) a transition metal compound represented
by the aforesaid formula (I), and
(ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(i) a compound which reacts with the
transition metal compound (h) to form an ion pair; and
(D) an olefin elastomer which is characterized in
that:
(1) the elastomer is obtained by polymerizing or
copolymerizing at least one monomer selected from olefins
of 2 to 20 carbon atoms and polyenes of 5 to 20 carbon
atoms,
(2) the elastomer contains constituent units derived
2 0 from ethylene, propylene, butene or 4-methyl-1-pentene in
an amount of less than 90 ~ by mol, and
(3) the elastomer has a glass transition temperature
(Tg) of not higher than 10 °C.
Propylene homopol,ymer (A5)
The propylene homopolymer (A5) for constituting the
seventh propylene polymer composition is identical with the
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propylene homopolymer (AS) for constituting the sixth
propylene polymer composition.
Olefin elastomer (D)
The olefin elastomer (D) is a polymer of one monomer
selected from the group consisting of olefins of 2 to 20
carbon atoms and polyenes of 5 to 20 carbon atoms, or a
random or block copolymer of two or more monomers selected
from olefins of 2 to 20 carbon atoms and polyenes of 5 to
20 carbon atoms. This olefin elastomer (D) contains
constituent units derived from ethylene, propylene, butene
or 4-methyl-1-pentene in an amount of less than 90 ~,
preferably not more than 85 ~, and has a glass transition
temperature (Tg) of not higher than 10 °C, preferably -100
to 0 °C, more preferably -100 to -10 °C.
Examples of the olefins of 2 to 20 carbon atoms
include ethylene, propylene, 1-butene, 1-pentene, 2-methyl-
1-butene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene,
4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene,
methyl-1-hexene, dimethyl-1-pentene, trimethyl-1-butene,
2 0 ethyl-1-pentene, 1-octene, methyl-1-pentene, dimethyl-1-
hexene, trimethyl-1-pentene, ethyl-1-hexene, methylethyl-1-
pentene, diethyl--1-butene, propyl-1-pentene, 1-decene,
methyl-1-nonene, dimethyl-1-octene, trimethyl-1-heptene,
ethyl-1-octene, methylethyl-1-heptene, diethyl-1-hexene, 1-
2 $ dodecene, hexadodecene and styrene.
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Examples of the polyenes of 5 to 20 carbon atoms
include polyenes exemplified for the ethylene/olefin random
polymer (C).
Such olefin elastomer (D) is desired to have a density
of 0.85 to 0.92 g/cm3, preferably 0.85 to 0.90 g/cm3, and
an intrinsic viscosity (~], as measured in decalin at 135
°C, of 0.1 to 20 dl/g, preferably 0.5 to 10 dl/g, more
preferably 1 to 5 dl/g.
Further, the olefin elastomer (D) is desired to have a
crystallinity, as measured by X-ray diffractometry, of less
than 30 ~ or to be amorphous.
As the olefin elastomer (D), there can be mentioned,
for example, a copolymer of two or more monomers selected
from olefins of 2 to 20 carbon atoms, a copolymer of one
monomer selected from olefins of 2 to 20 carbon atoms and
one monomer selected from polyenes of 5 to 20 carbon atoms,
and a copolymer of two or more monomers selected from
olefins of 2 to 20 carbon atoms and one monomer selected
from polyenes of 5 to 20 carbon atoms.
2 0 More specifically, there can be mentioned:
an elastomer containing constituent units derived from
ethylene in an amount of 50 to 90 o by mol and constituent
units derived from a monomer selected from olefins of 3 to
carbon atoms and polyenes of 5 to 20 carbon atoms in an
2 5 amount of 10 to 50 ~ by mol;
an elastomer containing constituent units derived from
ethylene in an amount of 60 to 90 o by mol and constituent
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units derived from a monomer selected from olefins of 3 to
6 carbon atoms and polyenes of 5 and 6 carbon atoms in an
amount of 10 to 40 ~ by mol;
an elastomer containing constituent units derived from
ethylene in an amount of 65 to 90 o by mol and constituent
units derived from a monomer selected from propylene and
butene in an amount of 10 to 35 ~ by mol;
an elastomer containing constituent units derived from
propylene in an amount of 50 to 90 ~ by mol and constituent
units derived from a monomer selected from ethylene,
olefins of 4 to 20 carbon atoms and polyenes of 5 to 20
carbon atoms in an amount of 10 to 50 ~ by mol;
an elastomer containing constituent units derived from
propylene in an amount of 50 to 85 ~ by mol and constituent
units derived from a monomer selected from ethylene,
olefins of 4 to 6 carbon atoms and polyenes of 5 and 6
carbon atoms in an amount of 15 to 50 $ by mol;
an elastomer containing constituent units derived from
propylene in an amount of 50 to 80 ~ by mol and constituent
2 0 units derived from a monomer selected from ethylene and
butene in an amount of 20 to 50 $ by mol; and
and others, such as a styrene/butadiene rubber (SBR)
and a styrene block copolymer (SEBS) having poly(ethylene-
butene) in the rubber intermediate block.
2 S The olefin elastomer (D) can be obtained by
polymerizing or copolymerizing at least one monomer
selected from the group consisting of olefins of 2 to 20
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carbon atoms and polyenes of 5 to 20 carbon atoms by
conventionally known processes. The polymerization
reaction can be carried out in a gas phase (gas phase
process) or in a liquid phase (liquid phase process).
The olefin elastomer (D) can be used in combination of
two or more kinds.
Propylene polymer composition
The seventh propylene polymer composition comprises
the propylene homopolymer (A5) and the olefin elastomer
(D). In this composition, it is desired that the propylene
homopolymer (A5) is contained in an amount of 5 to 95 ~ by
weight, preferably 30 to 90 ~ by weight, more preferably 50
to 80 $ by weight; and the olefin elastomer (D) is
contained in an amount of 5 to 95 $ by weight, preferably
10 to 70 ~ by weight, more preferably 20 to 50 $ by weight.
The seventh propylene polymer composition is desired
to have MFR, as measured at 230 °C under a load of 2.16 kg,
of 0.01 to 1,000 g/10 min, preferably 0.5 to 200 g/10 min.
In this composition, Mw/Mn of all the propylene components
2 0 for constituting the composition is desirably in the range
of 1.5 to 3.5.
The density of the seventh propylene polymer
composition is desired to be in the range of 0.88 to 0.92
g/cm3, preferably 0.90 to 0.92 g/cm3.
2 5 The flexural modulus (FM) thereof is desired to be in
the range of 8,000 to 21,000 kg/cm2, preferably 12,000 to
20,000 kg/cm2.
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The Izod impact strength (IZ) thereof at 23 °C is
desired to be in the range of 10 to 60 kg~cm/cm, preferably
to 40 kg~cm/cm.
The tensile elongation at break (EL) thereof is
5 desired to be in the range of 200 to 1,000 ~, preferably
300 to 500
The heat distortion temperature (HDT) thereof is
desired to be not lower than 85 °C, preferably in the range
of 95 to 140 °C.
10 The seventh propylene polymer composition may contain,
if necessary, additives which may be added to the first
propylene polymer composition, with the proviso that the
object of the invention is not marred.
The seventh propylene polymer composition can be
1$ prepared by known processes. For example, the composition
can be prepared in accordance with the processes (1) to (5)
described for the first propylene polymer composition,
using the propylene homopolymer (A5) and the olefin
elastomer (D).
2 0 Such propylene polymer composition is excellent in not
only heat resistance, rigidity and tensile elongation at
break but also impact resistance.
The seventh propylene polymer composition can be
favorably used for various structural materials such as
25 those of automobiles and electrical appliances, daily
necessaries and various sheets.
The eighth pro~vlene p~mer composition
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The eighth propylene polymer composition of the
invention comprises:
(AS) a propylene homopolymer which is obtained by
polymerizing propylene in the presence of an olefin
polymerization catalyst comprising:
(i) (h) a transition metal compound represented
by the aforesaid formula (I), and
(ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(i) a compound which reacts with the
transition metal compound (h) to form an ion pair; and
(E) an olefin polymer which contains constituent
units derived from one monomer selected from the group
consisting of ethylene, butene and 4-methyl-1-pentene in an
amount of not less than 90 ~ by mol.
Propylene homopolymer (AS)
The propylene homopolymer (AS) for constituting the
eighth propylene polymer composition is identical with the
2 0 propylene homopolymer (A5) for constituting the sixth
propylene polymer composition.
Olefin polymer (E)
The olefin polymer (E) is either an ethylene
(co)polymer containing constituent units derived from
2 $ ethylene in an amount of not less than 90 % by mol,
preferably not less than 95 $ by mol, a butene (co)polymer
containing constituent units derived from butene in an
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amount of not less than 90 ~ by mol, preferably not less
than 95 ~ by mol, or a 4-methyl-1-pentene (co)polymer
containing constituent units derived from 4-methyl-1-
pentene in an amount of not less than 90 ~ by mol,
preferably not less than 95 ~ by mol.
The ethylene copolymer may contain constituent units
derived from a monomer selected from the group consisting
of olefins of 3 to 20 carbon atoms and polyenes of 5 to 20
carbons atoms in an amount of less than 10 $ by mol.
The butene copolymer may contain constituent units
derived from a monomer selected from the group consisting
of other olefins of 2 to 20 carbon atoms than butene and
polyenes of 5 to 20 carbons atoms in an amount of less than
10 ~ by mol.
The 4-methyl-1-pentene copolymer may contain
constituent units derived from a monomer selected from the
group consisting of other olefins of 2 to 20 carbon atoms
than 4-methyl-1-pentene and polyenes of 5 to 20 carbons
atoms in an amount of less than 10 ~ by mol.
2 0 Examples of the olefins of 2 to 20 carbon atoms
include olefins exemplified for the olefin elastomer (D).
Examples of the polyenes of 5 to 20 carbon atoms
include polyenes exemplified for the olefin elastomer (D).
Such olefin polymer (E) is desired to have a density
2 S of 0.80 to 0.98 g/cm3, preferably 0.85 to 0.96 g/cm3, and
an intrinsic viscosity (1~], as measured in decalin at 135
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°C, of 0.1 to 20 dl/g, preferably 0.5 to 10 dl/g, more
preferably 1 to 5 dl/g.
The olefin polymer (E) is preferably an ethylene
homopolymer or an ethylene copolymer, and more preferably
an ethylene homopolymer.
The olefin polymer (E) can be obtained by polymerizing
one monomer selected from the group consisting of ethylene,
butene and 4-methyl-1-pentene or copolymerizing one monomer
selected from the group consisting of ethylene, butene and
4-methyl-1-pentene with at least one monomer selected from
other olefins of 2 to 20 carbon atoms than the above
monomers and polyenes of 5 to 20 carbon atoms, in
accordance with conventionally known processes. The
polymerization reaction can be carried out in a gas phase
(gas phase process) or in a liquid phase (liquid phase
process).
The olefin polymer (E) can be used in combination of
two or more kinds.
Propylene polymer composition
2 0 The eighth propylene polymer composition comprises the
propylene homopolymer (A5) and the olefin polymer (E). In
this composition, it is desired that the propylene
homopolymer (A5) is contained in an amount of 5 to 95 ~ by
weight, preferably 30 to 90 ~ by weight, more preferably 50
to 80 a by weight; and the olefin polymer (E) is contained
in an amount of 5 to 95 o by weight, preferably 10 to 70 0
by weight, more preferably 20 to 50 o by weight.
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The eighth propylene polymer composition is desired to
have MFR, as measured at 230 °C under a load of 2.16 kg, of
0.1 to 200 g/10 min, preferably 1 to 100 g/10 min. In this
composition, Mw/Mn of all the propylene components for
constituting the composition is desirably in the range of
1.5 to 3.5.
The density of the eighth propylene polymer
composition is desired to be in the range of 0.80 to 0.98
g/cm3, preferably 0.85 to 0.94 g/cm3.
The flexural modulus (FM) thereof is desired to be in
the range of 12,000 to 21,000 kg/cm2,.preferably 14,000 to
20, 000 kg/cm2 .
The Izod impact strength (IZ) thereof at 23 °C is
desired to be in the range of 2 to 20 kg~cm/cm, preferably
2 to 10 kg~cm/cm.
The tensile elongation at break (EL) thereof is
desired to be in the range of 100 to 500 $, preferably 200
to 400 $.
The heat distortion temperature (HDT) thereof is
2 0 desired to be not lower than 85 °C, preferably in the range
of 100 to 140 °C.
The eighth propylene polymer composition may contain,
if necessary, additives which may be added to the first
propylene polymer composition, with the proviso that the
2 S object of the invention is not marred.
This propylene polymer composition can be prepared by
known processes. For example, the composition can be
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prepared in accordance with the processes (1) to (5)
described for the first propylene polymer composition,
using the propylene homopolymer (AS) and the olefin polymer
(E) .
Such propylene polymer composition is excellent in
heat resistance, rigidity and tensile elongation at break.
The ninth propylene polymer com,_position
The ninth propylene polymer composition of the
invention comprises:
(AS) a propylene homopolymer which is obtained by
polymerizing propylene in the presence of an olefin
polymerization catalyst comprising:
(i) (h) a transition metal compound represented
by the aforesaid formula (I), and
~ (ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(i) a compound which reacts with the
transition metal compound (h) to form an ion pair;
2 0 (A6) a propylene polymer which contains constituent
units derived from propylene in an amount of not less than
90 ~ by mol and is different from the propylene homopolymer
(A5); and
(D) an olefin elastomer which is characterized in
2 S that
(1) the elastomer is obtained by polymerizing or
copolymerizing at least one monomer selected from olefins
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of 2 to 20 carbon atoms and polyenes of 5 to 20 carbon
atoms,
(2) the elastomer contains constituent units derived
from ethylene, propylene, butene or 4-methyl-1-pentene in
S an amount of less than 90 ~ by mol, and
(3) the elastomer has a glass transition temperature
(Tg) of not higher than 10 °C.
The propylene homopolymer (AS) for constituting the
ninth propylene polymer composition is identical with the
propylene homopolymer (AS) for constituting the sixth
propylene polymer composition.
Propylene polymer (A6)
The propylene polymer (A6) for constituting the ninth
propylene polymer composition is identical with the
propylene polymer (A6) for constituting the sixth propylene
polymer composition.
Olefin elastomer (D)
The olefin elastomer (D) for constituting the ninth
2 0 propylene polymer composition is identical with the olefin
elastomer (D) for constituting the seventh propylene
polymer composition.
The olefin elastomer can be used in combination of two
or more kinds.
2 5 Propylene polymer composition
The ninth propylene polymer composition contains, as
its essential components, the propylene homopolymer (AS),
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the propylene polymer (A6) which is different from the
propylene homopolymer (A5), and the olefin elastomer (D).
This composition contains the propylene homopolymer (A5) in
an amount of 5 to 95 ~ by weight, the propylene polymer
(A6) in an amount of not more than 95 ~ by weight and the
olefin elastomer (D) in an amount of not more than 95 ~ by
weight.
In the ninth propylene polymer composition, it is
desired that the propylene homopolymer (A5) is contained in
an amount of 5 to 95 ~ by weight, preferably 30 to 85 ~ by
weight, more preferably 30 to 60 $ by weight; the propylene
polymer (A6) is contained in an amount of 3 to 93 $ by
weight, preferably 5 to 60 ~ by weight, more preferably 30
to 60 ~ by weight; and the olefin elastomer (D) is
contained in an amount of 2 to 92 $ by weight, preferably
10 to 65 ~ by weight, more preferably 10 to 40 ~ by weight.
In the ninth propylene polymer composition, when the
intrinsic viscosity (['~]AS) of the propylene homopolymer
(A5) and the intrinsic viscosity ( [r]]A6) of the propylene
polymer (A6) has a relation of ['~]AS >_ ['~]AS~ it is desired
that ['~]AS is in the range of 1 to 10 dl/g, preferably 2 to
5 dl/g; ['~]A6 is in the range of 0.2 to 1.5 dl/g,
preferably 0.3 to 1.0 dl/g; and ( [r1]AS/ [r1]A6) is in the
range of 3 to 30, preferably 4 to 20.
2 5 When the intrinsic viscosity (['~]AS) of the propylene
homopolymer (A5) and the intrinsic viscosity ( ['r~]A6) of the
propylene polymer (A6) has a relation of ['~ ) As < [~1 ] a,s~ it
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is desired that ['~]A5 is in the range of 0.2 to 1.5 dl/g,
preferably 0.3 to 1.0 dl/g; [~]A6 is in the range of 1 to
dl/g, preferably 2 to 5 dl/g; and ( ['n ] As/ [~l ] As) is in the
range of 3 to 30, preferably 4 to 20.
5 The ninth propylene polymer composition is desired to
have MFR, as measured at 230 °C under a load of 2.16 kg, of
0.01 to 1,000 g/10 min, preferably 0.5 to 200 g/10 min. In
this composition, Mw/Mn of all the propylene components for
constituting the composition is desirably in the range of 4
1 0 to 15 .
The density of the ninth propylene polymer composition
is desired to be in the range of 0.88 to 0.92 g/cm3,
preferably 0.90 to 0.92 g/cm3.
The flexural modulus (FM) thereof is desired to be in
the range of 8,000 to 21,000 kg/cm2, preferably 12,000 to
20, 000 kg/cm2 .
The Izod impact strength (I2) thereof at 23 °C is
desired to be in the range of 10 to 60 kg~cm/cm, preferably
15 to 60 kg~cm/cm.
2 0 The tensile elongation at break (EL) thereof is
desired to be in the range of 200 to 1,000 ~, preferably
300 to 1,000 $.
The heat distortion temperature (HDT) thereof is
desired to be not lower than 85 °C, preferably in the range
2 S of 95 to 140 °C .
The ninth propylene polymer composition may contain,
if necessary, additives which may be added to the first
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propylene polymer composition, with the proviso that the
object of the invention is not marred.
The ninth propylene polymer composition can be
prepared by known processes. For example, the composition
can be prepared in accordance with the processes (1) to (5)
described for the first propylene polymer composition,
using the propylene homopolymer (AS), the propylene polymer
(A6) and the olefin elastomer (D).
Such ninth propylene polymer composition is excellent
in not only heat resistance, rigidity and tensile
elongation at break but also moldability and impact
resistance.
The ninth propylene polymer composition can be
favorably used for various structural materials such as
1S those of automobiles and electrical appliances, daily
necessaries, various films and sheets.
The tenth propylene polymer composition
The tenth propylene polymer composition of the
invention comprises:
2 0 (A5) a propylene homopolymer which is obtained by
polymerizing propylene in the presence of an olefin
polymerization catalyst comprising:
(i) (h) a transition metal compound represented
by the aforesaid formula (I), and
2 S (ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
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(i) a compound which reacts with the
transition metal compound (h) to form an ion pair;
(A6) a propylene polymer which contains constituent
units derived from propylene in an amount of not less than
90 ~ by mol and is different from the propylene homopolymer
(AS ) : and
(E) an olefin polymer which contains constituent
units derived from one monomer selected from the group
consisting of ethylene, butene and 4-methyl-1-pentene in an
amount of not less than 90 ~ by mol.
The propylene homopolymer (AS) for constituting the
tenth propylene polymer composition is identical with the
propylene homopolymer (AS) for constituting the sixth
propylene polymer composition.
Progvlene polymer (A6)
The propylene polymer (A6) for constituting the tenth
propylene polymer composition is identical with the
propylene polymer (A6) for constituting the sixth propylene
2 0 polymer composition.
The olefin polymer (E) for constituting the tenth
propylene polymer composition is identical with the olefin
polymer (E) for constituting the eighth propylene polymer
composition.
The olefin polymer (E) can be used in combination of
two or more kinds.
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Pronvlene ~ymer composition
The tenth propylene polymer composition contains, as
its essential components, the propylene homopolymer (A5),
the propylene polymer (A6) which is different from the
propylene homopolymer (A5), and the olefin polymer (E).
This composition contains the propylene homopolymer (A5) in
an amount of 5 to 95 ~ by weight, the propylene polymer
(A6) in an amount of not more than 95 ~ by weight and the
olefin polymer (E) in an amount of not more than 95 o by
1 0 weight .
In the tenth propylene polymer composition, it is
desired that the propylene homopolymer (A5) is contained in
an amount of 5 to 95 ~ by weight, preferably 30 to 85 $ by
weight, more preferably 30 to 60 o by weight; the propylene
polymer (A6) is contained in an amount of 3 to 93 ~ by
weight, preferably 5 to 60 $ by weight, more preferably 30
to 60 $ by weight; and the olefin polymer (E) is contained
in an amount of 2 to 92 $ by weight, preferably 10 to 65 ~
by weight, more preferably 10 to 40 ~ by weight.
2 0 In the tenth propylene polymer composition, when the
intrinsic viscosity (['~]AS) of the propylene homopolymer
(A5) and the intrinsic viscosity ( [1'1]A6) of the propylene
polymer (A6) has a relation of ['~]AS >_ ['r]]A6, it is desired
that ['1'~]AS is in the range of 1 to 10 dl/g, preferably 2 to
5 dl/g; [ri]A6 is in the range of 0.2 to 1.5 dl/g,
preferably 0.3 to 1.0 dl/g; and ( ['rl]AS/ [11]A6) is in the
range of 3 to 30, preferably 4 to 20.
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When the intrinsic viscosity ([11]AS) of the propylene
homopolymer (A5) and the intrinsic viscosity ([t]]A6) of the
propylene polymer (A6) has a relation of ['~] As < [~1l As~ it
is desired that ['~]AS is in the range of 0.2 to 1.5 dl/g,
preferably 0.3 to 1.0 dl/g; [Tl]A6 is in the range of 1 to
dl/g, preferably 2 to 5 dl/g; and ( ['~ ] A6/ ['i~ ] As ) is in the
range of 3 to 30, preferably 4 to 20.
The tenth propylene polymer composition is desired to
have MFR, as measured at 230 °C under a load of 2.16 kg, of
10 0.01 to 1,000 g/10 min, preferably 0.5 to 200 g/10 min. In
this composition, Mw/Mn of all the propylene components for
constituting the composition is desirably in the range of 4
to 15.
The density of the tenth propylene polymer composition
is desired to be in the range of 0.80 to 0.98 g/cm3,
preferably 0.85 to 0.94 g/cm3.
The flexural modulus (FM) thereof is desired to be in
the range of 12,000 to 21,000 kg/cmz, preferably 14,000 to
20, 000 kg/cmz .
The Izod impact strength (IZ) thereof at 23 °C is
desired to be in the range of 2 to 20 kg~cm/cm, preferably
2 to 10 kg~cm/cm.
The tensile elongation at break (EL) thereof is
desired to be in the range of 100 to 500 ~, preferably 200
to 400
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The heat distortion temperature (HDT) thereof is
desired to be not lower than 85 °C, preferably in the range
of 100 to 140 °C .
The tenth propylene polymer composition may contain,
S if necessary, additives which may be added to the first
propylene polymer composition, with the proviso that the
object of the invention is not marred.
The tenth propylene polymer composition can be
prepared by known processes. For example, the composition
can be prepared in accordance with the processes (1) to (5)
described for the first propylene polymer composition,
using the propylene homopolymer (A5), the propylene polymer
(A6) and the olefin polymer (E).
Such tenth propylene polymer composition is excellent
1$ in not only heat resistance, rigidity and tensile
elongation at break but also moldability.
The eleventh propylene polymer compos;r;~r,
The eleventh propylene polymer composition of the
invention comprises:
2 0 (A5) a propylene homopolymer which is obtained by
polymerizing propylene in the presence of an olefin
polymerization catalyst comprising:
(i) (h) a transition metal compound represented
by the aforesaid formula (I), and
2 5 (ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
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(i) a compound which reacts with the
transition metal compound (h) to form an ion pair;
(D) an olefin elastomer which is characterized in
that:
(1) the elastomer is obtained by polymerizing or
copolymerizing at least one monomer selected from olefins
of 2 to 20 carbon atoms and polyenes of 5 to 20 carbon
atoms,
(2) the elastomer contains constituent units derived
from ethylene, propylene, butene or 4-methyl-1-pentene in
an amount of less than 90 ~ by mol, and
(3) the elastomer has a glass transition temperature
(Tg) of not higher than 10 °C; and
(E) an olefin polymer which contains constituent
units derived from one monomer selected from the group
consisting of ethylene, butene and 4-methyl-1-pentene in an
amount of not less than 90 ~ by mol.
Propylene homopolymer (A5)
The propylene homopolymer (A5) for constituting the
2 0 eleventh propylene polymer composition is identical with
the propylene homopolymer (A5) for constituting the sixth
propylene polymer composition.
Qlefin elastomer (D)
The olefin elastomer (D) for constituting the eleventh
2 5 propylene polymer composition is identical with the olefin
elastomer (D) for constituting the seventh propylene
polymer composition.
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The olefin polymer (D) can be used in combination of
two or more kinds.
The olefin polymer (E) for constituting the eleventh
S propylene polymer composition is identical with the olefin
polymer (E) for constituting the eighth propylene polymer
composition.
The olefin polymer (E) can be used in combination of
two or more kinds.
Propylene polymer composition
The eleventh propylene polymer composition contains,
as its essential components, the propylene homopolymer
(A5), the olefin elastomer (D) and the olefin polymer (E).
This composition contains the propylene homopolymer (A5) in
an amount of 5 to 95 $ by weight, the olefin elastomer (D)
in an amount of not more than 95 $ by weight and the olefin
polymer (E) in an amount of not more than 95 ~ by weight.
In the eleventh propylene polymer composition, it is
desired that the propylene homopolymer (AS) is contained in
2 0 an amount of 5 to 95 ~ by weight, preferably 30 to 85 ~ by
weight, more preferably 50 to 70 o by weight; the olefin
elastomer (D) is contained in an amount of 3 to 93 ~ by
weight, preferably 10 to 65 ~ by weight, more preferably 20
to 40 g by weight; and the olefin polymer (E) is contained
2 5 in an amount of 2 to 92 o by weight, preferably 5 to 60 $
by weight, more preferably 10 to 30 o by weight.
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The eleventh propylene polymer composition is desired
to have MFR, as measured at 230 °C under a load of 2.16 kg,
of 0.01 to 1,000 g/10 min, preferably 0.5 to 200 g/10 min.
In this composition, Mw/Mn of all the propylene components
for constituting the composition is desirably in the range
of 1.5 to 3.5.
The density of the eleventh propylene polymer
composition is desired to be in the range of 0.88 to 0.93
g/cm3, preferably 0.90 to 0.93 g/cm3.
The flexural modulus (FM) thereof is desired to be in
the range of 8,000 to 21,000 kg/cm2, preferably 12,000 to
20, 000 kg/cmz .
The Izod impact strength (IZ) thereof at 23 °C is
desired to be in the range of 10 to 60 kg~cm/cm, preferably
20 to 60 kg~cm/cm.
The tensile elongation at break (EL) thereof is
desired to be in the range of 200 to 1,000 ~, preferably
300 to 1,000 ~.
The heat distortion temperature (HDT) thereof is
2 0 desired to be not lower than 85 °C, preferably in the range
of 95 to 140 °C .
The eleventh propylene polymer composition may
contain, if necessary, additives which may be added to the
first propylene polymer composition, with the proviso that
2 5 the object of the invention is not marred.
The eleventh propylene polymer composition can be
prepared by known processes. For example, the composition
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can be prepared in accordance with the processes (1) to (5)
described for the first propylene polymer composition,
using the propylene homopolymer (AS), the olefin elastomer
(D) and the olefin polymer (E).
Such eleventh propylene polymer composition is
excellent in not only heat resistance, rigidity and tensile
elongation at break but also impact resistance.
The eleventh propylene polymer composition can be
favorably used for various structural materials such as
those of automobiles and electrical appliances, daily
necessaries, various films and sheets.
The twelfth progvlene ~olvmer composition
The twelfth propylene polymer composition of the
invention comprises:
(AS) a propylene homopolymer which is obtained by
polymerizing propylene in the presence of an olefin
polymerization catalyst comprising:
(i) (h) a transition metal compound represented
by the aforesaid formula (I), and
2 0 (ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(i) a compound which reacts with the
transition metal compound (h) to form an ion pair;
2 S (A6) a propylene polymer which contains constituent
units derived from propylene in an amount of not less than
CA 02295395 2000-O1-13
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90 ~ by mol and is different from the propylene homopolymer
(AS) ;
(D) an olefin elastomer which is characterized in
that:
S (1) the elastomer is obtained by polymerizing or
copolymerizing at least one monomer selected from olefins
of 2 to 20 carbon atoms and polyenes of 5 to 20 carbon
atoms,
(2) the elastomer contains constituent units derived
from ethylene, propylene, butene or 4-methyl-1-pentene in
an amount of less than 90 ~ by mol, and
(3) the elastomer has a glass transition temperature
(Tg) of not higher than 10 °C; and
(E) an olefin polymer which contains constituent
units derived from one monomer selected from the group
consisting of ethylene, butene and 4-methyl-1-pentene in an
amount of not less than 90 ~ by mol.
Propylene hom2polymer (A5)
The propylene homopolymer (A5) for constituting the
2 0 twelfth propylene polymer composition is identical with the
propylene homopolymer (A5) for constituting the sixth
propylene polymer composition.
Propylene polymer (A6)
The propylene polymer (A6) for constituting the
2 5 twelfth propylene polymer composition is identical with the
propylene polymer (A6) for constituting the sixth propylene
polymer composition.
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Olefin elastomer (D)
The olefin elastomer (D) for constituting the twelfth
propylene polymer composition is identical with the olefin
elastomer (D) for constituting the seventh propylene
polymer composition.
The olefin elastomer (D) can be used in combination of
two or more kinds.
The olefin polymer (E) for constituting the twelfth
1 0 propylene polymer composition is identical with the olefin
polymer (E) for constituting the eighth propylene polymer
composition.
The olefin polymer (E) can be used in combination of
two or more kinds.
1$ Eropylene polymer composition
The twelfth propylene polymer composition contains, as
its essential components, the propylene homopolymer (A5),
the propylene polymer (A6) which is different from the
propylene homopolymer (A5), the olefin elastomer (D) and
2 0 the olefin polymer (E). This composition contains the
propylene homopolymer (A5) in an amount of 5 to 95 ~ by
weight, the propylene polymer (A6) in an amount of not more
than 95 g by weight, the olefin elastomer (D) in an amount
of not more than 95 ~ by weight and the olefin polymer (E)
2 5 in an amount of not more than 95 ~ by weight.
In the twelfth propylene polymer composition, it is
desired that the propylene homopolymer (A5) is contained in
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an amount of 5 to 95 ~ by weight, preferably 30 to 85 ~ by
weight, more preferably 30 to 50 $ by weight; the propylene
polymer (A6) is contained in an amount of 2 to 92 ~ by
weight, preferably 5 to 60 ~ by weight, more preferably 30
S to 50 ~ by weight; the olefin elastomer (D) is contained in
an amount of 2 to 92 $ by weight, preferably 5 to 60 ~ by
weight, more preferably 10 to 30 ~ by weight; and the
olefin polymer (E) is contained in an amount of 1 to 91 ~
by weight, preferably 5 to 60 ~ by weight, more preferably
10 to 30 ~ by weight.
In the twelfth propylene polymer composition, when the
intrinsic viscosity (['~]AS) of the propylene homopolymer
(A5) and the intrinsic viscosity ( [t']]A6) of the propylene
polymer (A6) has a relation of (t']]AS > [rl]AS, it is desired
that ['~]AS is in the range of 1 to 10 dl/g, preferably 2 to
5 dl/g; ['~]A6 is in the range of 0.2 to 1.5 dl/g,
preferably 0.3 to 1.0 dl/g; and ( ('~]AS/ ('n]AS) is in the
range of 3 to 30, preferably 4 to 20.
When the intrinsic viscosity ([r)]AS) of the propylene
homopolymer (A5) and the intrinsic viscosity ( ['t~]A6) of the
propylene polymer (A6) has a relation of ['~]AS < ['~lAS~ it
is desired that ('~]AS is in the range of 0.2 to 1.5 dl/g,
preferably 0.3 to 1.0 dl/g; [r)]A6 is in the range of 1 to
10 dl/g, preferably 2 to 5 dl/g; and ( ['~]AS/ (~1]AS) is in the
2 S range of 3 to 30, preferably 4 to 20.
The twelfth propylene polymer composition is desired
to have MFR, as measured at 230 °C under a load of 2.16 kg,
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of 0.01 to 1,000 g/10 min, preferably 0.5 to 200 g/10 min.
In this composition, Mw/Mn of all the propylene components
for constituting the composition is desirably in the range
of 4 to 15.
S The density of the twelfth propylene polymer
composition is desired to be in the range of 0.88 to 0.93
g/cm3, preferably 0.90 to 0.93 g/cm3.
The flexural modulus (FM) thereof is desired to be in
the range of 8,000 to 21,000 kg/cm2, preferably 12,000 to
1 0 20, 000 kg/cmz .
The Izod impact strength (IZ) thereof at 23 °C is
desired to be in the range of 10 to 60 kg~cm/cm, preferably
20 to 60 kg~cm/cm.
The tensile elongation at break (EL) thereof is
15 desired to be in the range of 200 to 1,000 ~, preferably
300 to 1,000 0.
The heat distortion temperature (HDT) thereof is
desired to be not lower than 85 °C, preferably in the range
of 95 to 140 °C.
2 0 The twelfth propylene polymer composition may contain,
if necessary, additives which may be added to the first
propylene polymer composition, with the proviso that the
object of the invention is not marred.
The twelfth propylene polymer composition can be
2 5 prepared by known processes. For example, the composition
can be prepared in accordance with the processes (1) to (5)
described for the first propylene polymer composition,
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using the propylene homopolymer (AS), the propylene polymer
(A6), the olefin elastomer (D) and the olefin polymer (E).
Such propylene polymer composition is excellent in not
only heat resistance, rigidity and tensile elongation at
break but also moldability and impact resistance.
The twelfth propylene polymer composition can be
favorably used for various structural materials such as
those of automobiles and electrical appliances, daily
necessaries, various films and sheets.
1~ The thirteenth ~~ronvlene polymer composition
The thirteenth propylene polymer composition
comprises:
(A7) a propylene copolymer which is characterized in
that:
the propylene copolymer is obtained by copolymerizing
propylene and at least one a-olefin selected from ethylene
and a-olefins of 4 to 20 carbon atoms in the presence of an
olefin polymerization catalyst comprising:
(i) (h) a transition metal compound represented
2 0 by the aforesaid formula (I), and
(ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(i) a compound which reacts with the
2 5 transition metal compound (h) to form an ion pair, and
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the propylene copolymer contains constituent units
derived from propylene in an amount of not less than 90 ~
by mol; and
(A6) a propylene polymer which contains constituent
units derived from propylene in an amount of not less than
90 ~ by mol and is different from the propylene copolymer
(A7) .
Propylene co~ymer (A71
The propylene copolymer (A7) is a random copolymer of
propylene and at least one oc-olefin selected from the group
consisting of ethylene and oc-olefins of 4 to 20 carbon
atoms, which is prepared by the use of the olefin
polymerization catalyst (4) used for preparation of the
propylene homopolymer (A5).
In the propylene copolymer (A7), the propylene units
are contained in an amount of not less than 90 ~ by mol,
preferably 90 to 98 ~ by mol, more preferably 90 to 96 ~;
and the comonomer units derived from an oc-olefin selected
from ethylene and oc-olefins of 4 to 20 carbon atoms in an
2 0 amount of not more than 10 ~ by mol, preferably 2 to 10 ~
by mol, more preferably 4 to 10 ~ by mol.
Examples of the Ct-olefins of 4 to 20 carbon atoms
include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene,
1-heptene, 1-octene, 2-ethyl-1-hexene, 1-decene, 1-
2 5 dodecene, 1-tetradecene and 1-eicosene.
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Preferably used as the comonomers for the
copolymerization are ethylene, 1-butene, 1-pentene, 1-
hexene, 1-octene and 1-decene.
The propylene copolymer (A7) is desired to have MFR,
as measured at 230 °C under a load of 2.16 kg, of 0.01 to
1,000 g/10 min, preferably 0.5 to 200 g/10 min, and Mw/Mn,
as measured by GPC, of 1.5 to 3.5, preferably 2.0 to 3.0,
more preferably 2.0 to 2.5.
Further, the propylene. copolymer (A7) is desired to
have an intrinsic viscosity [~] of 0.1 to 20 dl/g,
preferably 0.5 to 10 dl/g, more preferably 1 to 5 dl/g, and
a weight-average molecular weight of 1 x 103 to 500 x 104,
preferably 1 x 104 to 100 x 10q.
The crystallinity of the propylene copolymer (A7), as
measured by X-ray diffractometry, is desired to be not less
than 20 ~, preferably not less than 30 $.
The triad tacticity (mm fraction) of the propylene
copolymer (A7) is desired to be not less than 98.0 ~,
preferably not less than 98.2 ~, more preferably not less
2 0 than 98.5
The proportion of the irregularly positioned units
based on the 2,1-insertion of the propylene monomer is
desired to be not more than 0.5 $, preferably not more than
0.18 ~, more preferably not more than 0.15 ~.
2 5 The proportion of the irregularly positioned units
based on the 1,3-insertion of the propylene monomer is
CA 02295395 2000-O1-13
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desired to be less than the detected lower limit by the
13C_NMR measurement (less than 0.03 ~).
Propylene ~ymer (A6)
The propylene polymer (A6) for constituting the
S thirteenth propylene polymer composition is identical with
the propylene polymer (A6) for constituting the sixth
propylene polymer composition.
Propylene polymer comDOSition
The thirteenth propylene polymer composition comprises
the propylene copolymer (A7) and the propylene polymer (A6)
which is different from the propylene copolymer (A7), In
the composition, it is desired that the propylene copolymer
(A7) is contained in an amount of 5 to 95 ~ by weight,
preferably 15 to 85 o by weight, more preferably 30 to 70
by weight; and the propylene polymer (A6) is contained in
an amount of 5 to 95 $ by weight, preferably 15 to 85 ~ by
weight, more preferably 30 to 70 ~ by weight.
In the thirteenth propylene polymer composition, when
the intrinsic viscosity ([~]A~) of the propylene copolymer
2 0 (A7) and the intrinsic viscosity ([t~]A6) of the propylene
polymer (A6) has a relation of ['r']]A> >_ [~]A6, it is desired
that ['~]A~ is in the range of 1 to 10 dl/g, preferably 2 to
5 dl/g; [r~]A6 is in the range of 0.2 to 1.5 dl/g,
preferably 0.3 to 1.0 dl/g; and ( [t~]A~/['~)AS) is in the
2 5 range of 3 to 30, preferably 4 to 20.
When the intrinsic viscosity ( ['1'i] A~) of the propylene
homopolymer (A7) and the intrinsic viscosity ([T))A6) of the
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propylene polymer (A6) has a relation of [~]A~ < [>1]A6, it
is desired that ['~]A~ is in the range of 0.2 to 1.5 dl/g,
preferably 0.3 to 1.0 dl/g; [1~]A6 is in the range of 1 to
dl/g, preferably 2 to S dl/g; and ( [r1 l As/ [~1 ] A~ ) is in the
S range of 3 to 30, preferably 4 to 20.
The thirteenth propylene polymer composition is
desired to have MFR, as measured at 230 °C under a load of
2.16 kg, of 0.01 to 1,000 g/10 min, preferably 0.5 to 200
g/10 min. In this composition, Mw/Mn of all the propylene
10 components for constituting the composition is desirably in
the range of 4 to 15.
The density of the thirteenth propylene polymer
composition is desired to be in the range of 0.88 to 0.92
g/cm3, preferably 0.89 to 0.92 g/cm3.
The flexural modulus (FM) thereof is desired to be in
the range of 2,000 to 20,000 kg/cmz, preferably 4,000 to
15, 000 kg/cm2 .
The Izod impact strength (IZ) thereof at 23 °C is
desired to be in the range of 2 to 20 kg~cm/cm, preferably
2 0 5 to 20 kg~cm/cm.
The tensile elongation at break (EL) thereof is
desired to be in the range of 100 to 2,000 g, preferably
200 to 1,000 $.
The heat distortion temperature (HDT) thereof is
2 5 desired to be not lower than 80 °C, preferably in the range
of 90 to 140 °C.
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The thirteenth propylene polymer composition may
contain, if necessary, additives which may be added to the
first propylene polymer composition, with the proviso that
the object of the invention is not marred.
S The thirteenth propylene polymer composition can be
prepared by known processes. For example, the composition
can be prepared in accordance with the processes (1) to (5)
described for the first propylene polymer composition,
using the propylene copolymer (A7) and the propylene
I 0 polymer (A6) .
Such propylene polymer composition is excellent in not
only heat resistance, rigidity and tensile elongation at
break but also moldability.
15 The fourteenth propylene polymer composition
comprises:
(A7) a propylene copolymer which is characterized in
that:
the propylene copolymer is obtained by copolymerizing
2 0 propylene and at least one oc-olefin selected from ethylene
and Cc-olefins of 4 to 20 carbon atoms in the presence of an
olefin polymerization catalyst comprising:
(i) (h) a transition metal compound represented
by the aforesaid formula (I), and
2 5 (ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
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(i) a compound which reacts with the
transition metal compound (h) to form an ion pair, and
the propylene copolymer contains constituent units
derived from propylene in an amount of not less than 90 ~
by mol; and
(D) an olefin elastomer which is characterized in
that:
(1) the elastomer is obtained by polymerizing or
copolymerizing at least one monomer selected from olefins
of 2 to 20 carbon atoms and polyenes of S to 20 carbon
atoms,
(2) the elastomer contains constituent units derived
from ethylene, propylene, butene or 4-methyl-1-pentene in
an amount of less than 90 ~ by mol, and
(3) the elastomer has a glass transition temperature
(Tg) of not higher than 10 °C.
Proovlene copol5rmer (A7)
The propylene copolymer (A7) for constituting the
fourteenth propylene polymer composition is identical with
2 0 the propylene copolymer (A7) for constituting the
thirteenth propylene polymer composition.
Olefin elastomer (D)
The olefin elastomer (D) for constituting the
fourteenth propylene polymer composition is identical with
the olefin elastomer (D) for constituting the seventh
propylene polymer composition.
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The olefin elastomer (D) can be used in combination of
two or more kinds.
Frog ene polymer composition
The fourteenth propylene polymer composition comprises
the propylene copolymer (A7) and the olefin elastomer (D).
In this composition, it is desired that the propylene
copolymer (A7) is contained in an amount of 5 to 95 a by
weight, preferably 30 to 90 ~ by weight, more preferably 50
to 80 ~ by weight; and the olefin elastomer (D) is
contained in an amount of 5 to 95 $ by weight, preferably
10 to 70 ~ by weight, more preferably 20 to 50 ~ by weight.
The fourteenth propylene polymer composition is
desired to have MFR, as measured at 230 °C under a load of
2.16 kg, of 0.01 to 1,000 g/10 min, preferably 0.5 to 200
g/10 min. In this composition, Mw/Mn of all the propylene
components for constituting the composition is desirably in
the range of 1.5 to 3.5.
The density of the fourteenth propylene polymer
composition is desired to be in the range of 0.87 to 0.92
2 0 g/cm3, preferably 0.88 to 0.92 g/cm3.
The flexural modulus (FM) thereof is desired to be in
the range of 2,000 to 20,000 kg/cmz, preferably 4,000 to
15,000 kg/cmz.
The Izod impact strength (IZ) thereof at 23 °C is
2 5 desired to be in the range of 10 to 60 kg~cm/cm, preferably
to 60 kg~cm/cm.
CA 02295395 2000-O1-13
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The tensile elongation at break (EL) thereof is
desired to be in the range of 200 to 2,000 $, preferably
200 to 1,000 $.
The heat distortion temperature (HDT) thereof is
desired to be not lower than 80 °C, preferably in the range
of 90 to 140 °C .
The fourteenth propylene polymer composition may
contain, if necessary, additives which may be added to the
first propylene polymer composition, with the proviso that
the object of the invention is not marred.
This propylene polymer composition can be prepared by
known processes. For example, the composition can be
prepared in accordance with the processes (1) to (5)
described for the first propylene polymer composition,
using the propylene copolymer (A7) and the olefin elastomer
(D) .
Such propylene polymer composition is excellent in not
only heat resistance, rigidity and tensile elongation at
break but also impact resistance.
2 0 The fourteenth propylene polymer composition can be
favorably used for various structural materials such as
those of automobiles and electrical appliances, daily
necessaries and various sheets.
The fifteenth propylene polymer composition
2 5 The fifteenth propylene polymer composition of the
invention comprises:
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(A7) a propylene copolymer which is characterized in
that:
the propylene copolymer is obtained by copolymerizing
propylene and at least one a-olefin selected from ethylene
$ and a-olefins of 9 to 20 carbon atoms in the presence of an
olefin polymerization catalyst comprising:
(i) (h) a transition metal compound represented
by the aforesaid formula (I), and
(ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(i) a compound which reacts with the
transition metal compound (h) to form an ion pair, and
the propylene copolymer contains constituent units
derived from propylene in an amount of not less than 90 ~
by mol; and
(E) an olefin polymer which contains constituent
units derived from one monomer selected from the group
consisting of ethylene, butene and 4-methyl-1-pentene in an
2 0 amount of not less than 90 ~ by mol.
propylene copolymer (A7)
The propylene copolymer (A7) for constituting the
fifteenth propylene polymer composition is identical with
the propylene copolymer (A7) for constituting the
2 S thirteenth propylene polymer composition.
Qlefin polymer !E)
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The olefin polymer (E) for constituting the fifteenth
propylene polymer composition is identical with the olefin
polymer (E) for constituting the eighth propylene polymer
composition.
The olefin polymer (E) can be used in combination of
two or more kinds.
Propylene polymer composition
The fifteenth propylene polymer composition comprises
the propylene copolymer (A7) and the olefin polymer (E).
1~ In this composition, it is desired that the propylene
copolymer (A7) is contained in an amount of 5 to 95 ~ by
weight, preferably 30 to 90 ~ by weight, more preferably 50
to 80 ~ by weight; and the olefin polymer (E) is contained
in an amount of 5 to 95 $ by weight, preferably 10 to 70 ~
by weight, more preferably 20 to 50 $ by weight.
The fifteenth propylene polymer composition is desired
to have MFR, as measured at 230 °C under a load of 2.16 kg,
of 0.1 to 1,000 g/10 min, preferably 0.5 to 200 g/10 min.
In this composition, Mw/Mn of all the propylene components
2 0 for constituting the composition is desirably in the range
of 1.5 to 3.5.
The density of the fifteenth propylene polymer
composition is desired to be in the range of 0.80 to 0.98
g/cm3, preferably 0.85 to 0.94 g/cm3.
2 5 The flexural modulus (FM) thereof is desired to be in
the range of 2,000 to 20,000 kg/cm2, preferably 4,000 to
15, 000 kg/cm2 .
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The Izod impact strength (IZ) thereof at 23 °C is
desired to be in the range of 2 to 20 kg~cm/cm, preferably
to 20 kg~cm/cm.
The tensile elongation at break (EL) thereof is
5 desired to be in the range of 100 to 2,000 ~, preferably
200 to 1,000 ~.
The heat distortion temperature (HDT) thereof is
desired to be not lower than 80 °C, preferably in the range
of 90 to 140 °C.
The fifteenth propylene polymer composition may
contain, if necessary, additives which may be added to the
first propylene polymer composition, with the proviso that
the object of the invention is not marred.
This propylene polymer composition can be prepared by
known processes. For example, the composition can be
prepared in accordance with the processes (1) to (5)
described for the first propylene polymer composition,
using the propylene copolymer (A7) and the olefin polymer
(E) .
2 0 Such propylene polymer composition is excellent in
heat resistance, rigidity and tensile elongation at break.
The sixteenth propylene polymer composition
The sixteenth propylene polymer composition of the
invention comprises:
2 5 (A7) a propylene copolymer which is characterized in
that:
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the propylene copolymer is obtained by copolymerizing
propylene and at least one oc-olefin selected from ethylene
and a-olefins of 4 to 20 carbon atoms in the presence of an
olefin polymerization catalyst comprising:
(i) (h) a transition metal compound represented
by the aforesaid formula (I), and
(ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(i) a compound which reacts with the
transition metal compound (h) to form an ion pair, and
the propylene copolymer contains constituent units
derived from propylene in an amount of not less than 90 ~
by mol;
1$ (A6) a propylene polymer which contains constituent
units derived from propylene in an amount of not less than
90 o by mol and is different from the propylene copolymer
(A7); and
(D) an olefin elastomer which is characterized in
2 0 that
(1) the elastomer is obtained by polymerizing or
copolymerizing at least one monomer selected from olefins
of 2 to 20 carbon atoms and polyenes of 5 to 20 carbon
atoms,
2 5 (2) the elastomer contains constituent units derived
from ethylene, propylene, butene or 4-methyl-1-pentene in
an amount of less than 90 ~ by mol, and
CA 02295395 2000-O1-13
185
(3) the elastomer has a glass transition temperature
(Tg) of not higher than 10 °C.
Propylene copolymer (A7)
The propylene copolymer (A7) for constituting the
sixteenth propylene polymer composition is identical with
the propylene copolymer (A7) for constituting the
thirteenth propylene polymer composition.
The propylene polymer.(A6) for constituting the
sixteenth propylene polymer composition is identical with
the propylene polymer (A6) for constituting the sixth
propylene polymer composition.
Olefin elastomer (D)
The olefin elastomer (D) for constituting the
sixteenth propylene polymer composition is identical with
the olefin elastomer (D) for constituting the seventh
propylene polymer composition.
The olefin elastomer (D) can be used in combination of
two or more kinds.
2 0 ProR,ylene polymer composition
The sixteenth propylene polymer composition contains,
as its essential components, the propylene copolymer (A7),
the propylene polymer (A6) which is different from the
propylene copolymer (A7), and the olefin elastomer (D).
2 5 This composition contains the propylene copolymer (A7) in
an amount of 5 to 95 ~ by weight, the propylene polymer
(A6) in an amount of not more than 95 o by weight and the
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olefin elastomer (D) in an amount of not more than 95 ~ by
weight.
In the sixteenth propylene polymer composition, it is
desired that the propylene copolymer (A7) is contained in
S an amount of 5 to 95 ~ by weight, preferably 30 to 85 ~ by
weight, more preferably 30 to 60 $ by weight; the propylene
polymer (A6) is contained in an amount of 3 to 93 ~ by
weight, preferably 5 to 60 ~ by weight, more preferably 30
to 60 ~ by weight; and the olefin elastomer (D) is
contained in an amount of 2 to 92 $ by weight, preferably
10 to 65 $ by weight, more preferably 10 to 40 ~ by weight.
In the sixteenth propylene polymer composition, when
the intrinsic viscosity ([rJ]A~) of the propylene copolymer
(A7) and the intrinsic viscosity (['~]A6) of the propylene
1 S polymer (A6) has a relation of ['~]A> >_ [~]A6, it is desired
that [T]]A~ is in the range of 1 to 10 dl/g, preferably 2 to
5 dl/g; ['t1]A6 is in the range of 0.2 to 1.5 dl/g,
preferably 0 . 3 to 1 . 0 dl/g; and ( ['~ l A~/ [~1] a,s) is in the
range of 3 to 30, preferably 4 to 20.
2 0 When the intrinsic viscosity ([t~]A~) of the propylene
copolymer (A7) and the intrinsic viscosity ( [7~)A6) of the
propylene polymer (A6) has a relation of ['r~]A~ < f111AS, it
is desired that [r]]A~ is in the range of 0.2 to 1.5 dl/g,
preferably 0.3 to 1.0 dl/g; (r~]A6 is in the range of 1 to
2 S 10 dl/g, preferably 2 to 5 dl/g; and ( [t~ ] A6/ [t~ ] A~ ) is in the
range of 3 to 30, preferably 4 to 20.
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The sixteenth propylene polymer composition is desired
to have MFR, as measured at 230 °C under a load of 2.16 kg,
of 0.01 to 1,000 g/10 min, preferably 0.5 to 200 g/10 min.
In this composition, Mw/Mn of all the propylene components
for constituting the composition is desirably in the range
of 4 to 15.
The density of the sixteenth propylene polymer
composition is desired to be in the range of 0.87 to 0.92
g/cm3, preferably 0.88 to 0.92 g/cm3.
1 0 The flexural modulus (FM) thereof is desired to be in
the range of 2,000 to 20,000 kg/cmz, preferably 4,000 to
15,000 kg/cm2.
The Izod impact strength (IZ) thereof at 23 °C is
desired to be in the range of 10 to 60 kg~cm/cm, preferably
20 to 60 kg~cm/cm.
The tensile elongation at break (EL) thereof is
desired to be in the range of 200 to 2,000 $, preferably
200 to 1,000 $.
The heat distortion temperature (HDT) thereof is
2 0 desired to be not lower than 80 °C, preferably in the range
of 90 to 140 °C.
The sixteenth propylene polymer composition may
contain, if necessary, additives which may be added to the
first propylene polymer composition, with the proviso that
2 5 the object of the invention is not marred.
The sixteenth propylene polymer composition can be
prepared by known processes. For example, the composition
CA 02295395 2000-O1-13
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can be prepared in accordance with the processes (1) to (5)
described for the first propylene polymer composition,
using the propylene copolymer (A7), the propylene polymer
(A6) and the olefin elastomer (D).
Such sixteenth propylene polymer composition is
excellent in not only heat resistance, rigidity and tensile
elongation at break but also moldability and impact
resistance.
The sixteenth propylene polymer composition can be
favorably used for various structural materials such as
those of automobiles and electrical appliances, daily
necessaries, various films and sheets.
The seventeenth,_p~pylPnP polymer composition
The seventeenth propylene polymer composition of the
invention comprises:
(A7) a propylene copolymer which is characterized in
that:
the propylene copolymer is obtained by copolymerizing
propylene and at least one a-olefin selected from ethylene
2 0 and a-olefins of 4 to 20 carbon atoms in the presence of an
olefin polymerization catalyst comprising:
(i) (h) a transition metal compound represented
by the aforesaid formula (I), and
(ii) at least one compound selected from the
2 S group consisting of
(b) an organoaluminum oxy-compound, and
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(i) a compound which reacts with the
transition metal compound (h) to form an ion pair, and
the propylene copolymer contains constituent units
derived from propylene in an amount of not less than 90 ~
by mol;
(A6) a propylene polymer which contains constituent
units derived from propylene in an amount of not less than
90 ~ by mol and is different from the propylene copolymer
(A7 ) ; and
(E) an olefin polymer which contains constituent
units derived from one monomer selected from the group
consisting of ethylene, butene and 4-methyl-1-pentene in an
amount of not less than 90 ~ by mol.
Propylene copolymer (A7)
The propylene copolymer (A7) for constituting the
seventeenth propylene polymer composition is identical with
the propylene copolymer (A7) for constituting the
thirteenth propylene polymer composition.
propylene polymer (A6)
2 0 The propylene polymer (A6) for constituting the
seventeenth propylene polymer composition is identical with
the propylene polymer (A6) for constituting the sixth
propylene polymer composition.
Olefin polymer (E)
The olefin polymer (E) for constituting the
seventeenth propylene polymer composition is identical with
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the olefin polymer (E) for constituting the eighth
propylene polymer composition.
The olefin polymer (E) can be used in combination of
two or more kinds.
$ Propylene polymer composition
The seventeenth propylene polymer composition
contains, as its essential components, the propylene
copolymer (A7), the propylene polymer (A6) which is
different from the propylene copolymer (A7), and the olefin
polymer (E). This composition contains the propylene
copolymer (A7) in an amount of 5 to 95 ~ by weight, the
propylene polymer (A6) in an amount of not more than 95 $
by weight and the olefin polymer (E) in an amount of not
more than 95 ~ by weight.
In the seventeenth propylene polymer composition, it
is desired that the propylene copolymer (A7) is contained
in an amount of 5 to 95 ~ by weight, preferably 30 to 85 $
by weight, more preferably 30 to 60 ~ by weight; the
propylene polymer (A6) is contained in an amount of 3 to 93
2 0 ~ by weight, preferably 5 to 60 ~ by weight, more
preferably 30 to 60 ~ by weight; and the olefin polymer (E)
is contained in an amount of 2 to 92 ~ by weight,
preferably 10 to 65 ~ by weight, more preferably 10 to 40
by weight.
2 5 In the seventeenth propylene polymer composition, when
the intrinsic viscosity (['r~]A~) of the propylene copolymer
(A7) and the intrinsic viscosity ( [t~]A6) of the propylene
CA 02295395 2000-O1-13
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polymer (A6) has a relation of [1~]A7 >_ ['t']]A6, it is desired
that ['~]A~ is in the range of 1 to 10 dl/g, preferably 2 to
dl/g; [~]A6 is in the range of 0.2 to 1.5 dl/g,
preferably 0.3 to 1.0 dl/g; and ( ['~]A7/ [1~]A6) is in the
5 range of 3 to 30, preferably 4 to 20.
When the intrinsic viscosity ([1~]A~) of the propylene
copolymer (A7) and the intrinsic viscosity ([1~]A6) of the
propylene polymer (A6) has a relation of ['rl) A~ < [~1l As, it
is desired that [r)]A~ is in. the range of 0.2 to 1.5 dl/g,
1 0 preferably 0.3 to 1.0 dl/g; [~)A6 is in the range of 1 to
dl/g, preferably 2 to 5 dl/g; and ( ['r~]p6/ [1'~]A~) is in the
range of 3 to 30, preferably 4 to 20.
The seventeenth propylene polymer composition is
desired to have MFR, as measured at 230 °C under a load of
2.16 kg, of 0.01 to 1,000 g/10 min, preferably 0.5 to 200
g/10 min. In this composition, Mw/Mn of all the propylene
components for constituting the composition is desirably in
the range of 4 to 15.
The density of the seventeenth propylene polymer
2 0 composition is desired to be in the range of 0.80 to 0.98
g/cm3, preferably 0.85 to 0.94 g/cm3.
The flexural modulus (FM) thereof is desired to be in
the range of 2,000 to 20,000 kg/cmz, preferably 4,000 to
15,000 kg/cm2.
2 5 The Izod impact strength (IZ) thereof at 23 °C is
desired to be in the range of 2 to 20 kg~cm/cm, preferably
5 to 20 kg~cm/cm.
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The tensile elongation at break (EL) thereof is
desired to be in the range of 100 to 2,000 ~, preferably
200 to 1, 000 ~ .
The heat distortion temperature (HDT) thereof is
desired to be not lower than 80 °C, preferably in the range
of 90 to 140 °C.
The seventeenth propylene polymer composition may
contain, if necessary, additives which may be added to the
first propylene polymer composition, with the proviso that
the object of the invention is not marred.
The seventeenth propylene polymer composition can be
prepared by known processes. For example, the composition
can be prepared in accordance with the processes (1) to (S)
described for the first propylene polymer composition,
using the propylene copolymer (A7), the propylene polymer
(A6) and the olefin polymer (E).
Such seventeenth propylene polymer composition is
excellent in not only heat resistance, rigidity and tensile
elongation at break but also moldability.
2 0 The eiqhteenth ~gylene polymer composition
The eighteenth propylene polymer composition of the
invention comprises:
(A7) a propylene copolymer which is characterized in
that:
2 5 the propylene copolymer is obtained by copolymerizing
propylene and at least one a-olefin selected from ethylene
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and a-olefins of 4 to 20 carbon atoms in the presence of an
olefin polymerization catalyst comprising:
(i) (h) a transition metal compound represented
by the aforesaid formula (I), and
(ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(i) a compound which reacts with the
transition metal compound (h) to form an ion pair, and
the propylene copolymer contains constituent units
derived from propylene in an amount of not less than 90 $
by mol;
(D) an olefin elastomer which is characterized in
that:
(1) the elastomer is obtained by polymerizing or
copolymerizing at least one monomer selected from olefins
of 2 to 20 carbon atoms and polyenes of 5 to 20 carbon
atoms,
(2) the elastomer contains constituent units derived
2 0 from ethylene, propylene, butene or 4-methyl-1-pentene in
an amount of less than 90 ~ by mol, and
(3) the elastomer has a glass transition temperature
(Tg) of not higher than 10 °C; and
(E) an olefin polymer which contains constituent
2 S units derived from one monomer selected from the group
consisting of ethylene, butene and 4-methyl-1-pentene in an
amount of not less than 90 o by mol.
CA 02295395 2000-O1-13
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~ro~,vlene copolymer (A7)
The propylene copolymer (A7) for constituting the
eighteenth propylene polymer composition is identical with
the propylene copolymer (A7) for constituting the
S thirteenth propylene polymer composition.
The olefin elastomer (D) for constituting the
eighteenth propylene polymer composition is identical with
the olefin elastomer (D) for constituting the seventh
propylene polymer composition.
The olefin elastomer (D) can be used in combination of
two or more kinds.
The olefin polymer (E) for constituting the eighteenth
propylene polymer composition is identical with the olefin
polymer (E) for constituting the eighth propylene polymer
composition.
The olefin polymer (E) can be used in combination of
two or more kinds.
2 0 Propylene polymer composition
The eighteenth propylene polymer composition contains,
as its essential components, the propylene copolymer (A7),
the olefin elastomer (D) and the olefin polymer (E). This
composition contains the propylene copolymer (A7) in an
2 5 amount of 5 to 95 $ by weight, the olefin elastomer (D) in
an amount of not more than 95 $ by weight and the olefin
polymer (E) in an amount of not more than 95 g by weight.
CA 02295395 2000-O1-13
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In the eighteenth propylene polymer composition, it is
desired that the propylene copolymer (A7) is contained in
an amount of 5 to 95 $ by weight, preferably 30 to 85 ~ by
weight, more preferably 50 to 70 ~ by weight: the olefin
elastomer (D) is contained in an amount of 3 to 93 ~ by
weight, preferably 10 to 65 g by weight, more preferably 20
to 40 ~ by weight; and the olefin polymer (E) is contained
in an amount of 2 to 92 $ by weight, preferably 5 to 60 ~
by weight, more preferably 10 to 30 o by weight.
The eighteenth propylene polymer composition is
desired to have MFR, as measured at 230 °C under a load of
2.16 kg, of 0.01 to 1,000 g/10 min, preferably 0.5 to 200
g/10 min. In this composition, Mw/Mn of all the propylene
components for constituting the composition is desirably in
the range of 1.5 to 3.5.
The density of the eighteenth propylene polymer
composition is desired to be in the range of 0.87 to 0.92
g/cm3, preferably 0.88 to 0.92 g/cm3.
The flexural modulus (FM) thereof is desired to be in
2 0 the range of 2,000 to 20,000 kg/cm2, preferably 4,000 to
15, 000 kg/cmz .
The Izod impact strength (IZ) thereof at 23 °C is
desired to be in the range of 10 to 60 kg~cm/cm, preferably
to 60 kg~cm/cm.
2 5 The tensile elongation at break (EL) thereof is
desired to be in the range of 200 to 2,000 0, preferably
200 to 1,000 $.
CA 02295395 2000-O1-13
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The heat distortion temperature (HDT) thereof is
desired to be not lower than 80 °C, preferably in the range
of 90 to 140 °C .
The eighteenth propylene polymer composition may
contain, if necessary, additives which may be added to the
first propylene polymer composition, with the proviso that
the object of the invention is not marred.
The eighteenth propylene polymer composition can be
prepared by known processes. For example, the composition
can be prepared in accordance with the processes (1) to (5)
described for the first propylene polymer composition,
using the propylene copolymer (A7), the olefin elastomer
(D) and the olefin polymer (E).
Such eighteenth propylene polymer composition is
excellent in not only heat resistance, rigidity and tensile
elongation at break but also impact resistance.
The eighteenth propylene polymer composition can be
favorably used for various structural materials such as
those of automobiles and electrical appliances, daily
2 0 necessaries, various films and sheets.
The nineteenth propylene polymer composition
The nineteenth propylene polymer composition of the
invention comprises:
(A7) a propylene copolymer which is characterized in
2 5 that
the propylene copolymer is obtained by copolymerizing
propylene and at least one Cc-olefin selected from ethylene
CA 02295395 2000-O1-13
197
and oc-olefins of 4 to 20 carbon atoms in the presence of an
olefin polymerization catalyst comprising:
(i) (h) a transition metal compound represented
by the aforesaid formula (I), and
(ii) at least one compound selected from the
group consisting of
(b) an organoaluminum oxy-compound, and
(i) a compound which reacts with the
transition metal compound (h) to form an ion pair, and
the propylene copolymer contains constituent units
derived from propylene in an amount of not less than 90 ~
by mol;
(A6) a propylene polymer which contains constituent
units derived from propylene in an amount of not less than
90 ~ by mol and is different from the propylene copolymer
(A7 )
(D) an olefin elastomer which is characterized in
that:
(1) the elastomer is obtained by polymerizing or
2 0 copolymerizing at least one monomer selected from olefins
of 2 to 20 carbon atoms and polyenes of 5 to 20 carbon
atoms,
(2) the elastomer contains constituent units derived
from ethylene, propylene, butene or 4-methyl-1-pentene in
an amount of less than 90 g by mol, and
(3) the elastomer has a glass transition temperature
(Tg) of not higher than 10 °C; and
v
CA 02295395 2000-O1-13
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(E) an olefin polymer which contains constituent
units derived from one monomer selected from the group
consisting of ethylene, butene and 4-methyl-1-pentene in an
amount of not less than 90 ~ by mol.
Propylene copolymer (A7)
The propylene copolymer (A7) for constituting the
nineteenth propylene polymer composition is identical with
the propylene copolymer (A7) for constituting the
thirteenth propylene polymer composition.
Propylene polymer lA6)
The propylene polymer (A6) for constituting the
nineteenth propylene polymer composition is identical with
the propylene polymer (A6) for constituting the sixth
propylene polymer composition.
~$ Olefin elastomer (D)
The olefin elastomer (D) for constituting the
nineteenth propylene polymer composition is identical with
the olefin elastomer (D) for constituting the seventh
propylene polymer composition.
2 0 The olefin elastomer (D) can be used in combination of
two or more kinds.
The olefin polymer (E) for constituting the nineteenth
propylene polymer composition is identical with the olefin
2 $ polymer (E) for constituting the eighth propylene polymer
composition.
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The olefin polymer (E) can be used in combination of
two or more kinds.
propylene polymer composition
The nineteenth propylene polymer composition contains,
as its essential components, the propylene copolymer (A7),
the propylene polymer (A6) which is different from the
propylene copolymer (A7), the olefin elastomer (D) and the
olefin polymer (E). This composition contains the
propylene copolymer (A7) in an amount of 5 to 95 ~ by
weight, the propylene polymer (A6) in an amount of not more
than 95 ~ by weight, the olefin elastomer (D) in an amount
of not more than 95 $ by weight and the olefin polymer (E)
in an amount of not more than 95 ~ by weight.
In the nineteenth propylene polymer composition, it is
desired that the propylene copolymer (A7) is contained in
an amount of 5 to 95 $ by weight, preferably 30 to 85 ~ by
weight, more preferably 30 to 50 ~ by weight; the propylene
polymer (A6) is contained in an amount of 2 to 92 ~ by
weight, preferably 5 to 60 $ by weight, more preferably 30
2 0 to 50 $ by weight; the olefin elastomer (D) is contained in
an amount of 2 to 92 o by weight, preferably 5 to 60 ~ by
weight, more preferably 10 to 30 ~ by weight; and the
olefin polymer (E) is contained in an amount of 1 to 91 $
by weight, preferably 5 to 60 ~ by weight, more preferably
2 5 10 to 30 ~ by weight.
In the nineteenth propylene polymer composition, when
the intrinsic viscosity ([~]R~) of the propylene copolymer
CA 02295395 2000-O1-13
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(A7) and the intrinsic viscosity (['~]A6) of the propylene
polymer (A6) has a relation of ['t']]A~ >_ ['rl]AS, it is desired
that ['~]A~ is in the range of 1 to 10 dl/g, preferably 2 to
dl/g; ['~]A6 is in the range of 0.2 to 1.5 dl/g,
5 preferably 0.3 to 1.0 dl/g; and ( ['~]A~/ ['~]AS) is in the
range of 3 to 30, preferably 4 to 20.
when the intrinsic viscosity (['~]A~) of the propylene
copolymer (A7) and the intrinsic viscosity ([1~]A6) of the
propylene polymer (A6) has a relation of [t~]A~ < [t~]A6, it
1 0 is desired that ['~]A, is in the range of 0.2 to 1.5 dl/g,
preferably 0.3 to 1.0 dl/g; ['t~]A6 is in the range of 1 to
dl/g, preferably 2 to 5 dl/g; and ( [~1 ] As/ [71 ] A~ ) is in the
range of 3 to 30, preferably 4 to 20.
The nineteenth propylene polymer composition is
desired to have MFR, as measured at 230 °C under a load of
2.16 kg, of 0.01 to 1,000 g/10 min, preferably 0.5 to 200
g/10 min. In this composition, Mw/Mn of all the propylene
components for constituting the composition is desirably in
the range of 4 to 15.
2 0 The density of the nineteenth propylene polymer
composition is desired to be in the range of 0.87 to 0.92
g/cm3, preferably 0.88 to 0.92 g/cm3.
The flexural modulus (FM) thereof is desired to be in
the range of 2,000 to 20,000 kg/cmz, preferably 4,000 to
2 5 15, 000 kg/cm2 .
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The Izod impact strength (IZ) thereof at 23 °C is
desired to be in the range of 10 to 60 kg~cm/cm, preferably
20 to 60 kg-cm/cm.
The tensile elongation at break (EL) thereof is
desired to be in the range of 200 to 2,000 ~, preferably
200 to 1,000 $.
The heat distortion temperature (HDT) thereof is
desired to be not lower than 80 °C, preferably in the range
of 90 to 140 °C .
The nineteenth propylene polymer composition may
contain, if necessary, additives which may be added to the
first propylene polymer composition, with the proviso that
the object of the invention is not marred.
The nineteenth propylene polymer composition can be
prepared by known processes. For example, the composition
can be prepared in accordance with the processes (1) to (S)
described for the first propylene polymer composition,
using the propylene copolymer (A7), the propylene polymer
(A6), the olefin elastomer (D) and the olefin polymer (E).
2 0 Such propylene polymer composition is excellent in not
only heat resistance, rigidity and tensile elongation at
break but also moldability and impact resistance.
The nineteenth propylene polymer composition can be
favorably used for various structural materials such as
those of automobiles and electrical appliances, daily
necessaries, various films and sheets.
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EFFECT OF THE INVENTION
The propylene polymer compositions of the invention
are excellent in heat resistance, rigidity and tensile
elongation at break.
The present invention is described in more detail with
reference to the following examples, but it should be
construed that the invention is in no way limited to those
examples.
In the present invention, physical properties were
measured by the following methods.
Intrinsic viscosity fnl
The intrinsic viscosity ['~] was measured in decalin at
1 5 135 °C .
Melt flow rate IMFRI
The melt flow rate (MFR) was measured in accordance
with ASTM D1238 under the following conditions.
Conditions: 230 °C, 2.16 kg
2 0 flexural modulus (FM3
The flexural modulus (FM) was measured in accordance
with ASTM D790 under the following conditions.
Size of specimen:
12.7 (width) x 6.4 (thickness) x 127 (length)
2 5 Span: 100 mm
Flexure rate: 2 mm/min
~zod impact strength lIZ)
CA 02295395 2000-O1-13
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The Izod impact strength (IZ) was measured in
accordance with ASTM D256 under the following conditions.
Temperature : 23 °C, -30 °C
Size of specimen:
12.7 (width) x 6.4 (thickness) x 64 (length)
The specimen was mechanically notched.
The tensile elongation at break (EL) was measured in
accordance with ASTM D638 under the following conditions.
Temperature: 23 °C
HPat distortion temperature IHDT)
The heat distortion temperature was measured in
accordance with ASTM D648 under the following conditions.
Size of specimen:
12.7 (width) x 6.4 (thickness) x 127 (length)
[Preparation of a propylene polymer (1)]
A catalyst component was prepared by mixing 0.0030
mmol (in terms of Zr atom) of rac-dimethylsilylbis(2-
2 0 methylindenyl)zirconium dichloride and 1.50 mmol of
methylaluminoxane.
Into a 4-liter stainless steel autoclave thoroughly
purged with nitrogen was introduced 1 liter of purified
toluene, followed by stirring for 20 minutes in a propylene
atmosphere. Then, the temperature of the reaction system
was raised. When the temperature became 30 °C, 1.5 mmol of
methylaluminoxane and the catalyst component prepared above
CA 02295395 2000-O1-13
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were added to the system, thereby to perform polymerization
for 1 hour at 40 °C under a propylene pressure of 3 kg/cm2-
G. After the polymerization, the solvent was removed by
filtration, and the resulting product was washed with
methanol and dried in vacuo at 80 °C for 10 hours.
Thus, a polymer [propylene polymer (1)] was obtained
in an amount of 146 g, and the polymerization activity was
48,700 g-PP/mmol-Zr. This polymer had [~] of 2.58 dl/g,
MFR of 1.9 g/10 min, Mw of 339,000 and Mw/Mn of 2.03.
[Preparation of a propylene polymer (2)]
Preparation of a solid catalyst component
A 500-ml reactor thoroughly purged with nitrogen was
charged with 25 g of silica (i.e., F-948 of Fuji Davison
Co. having been dried at 200 °C for 6 hours in a stream of
nitrogen) and 310 ml of toluene, and the temperature of the
system was made 0 °C with stirring. To the system was
dropwise added 90 ml of an organoaluminum oxy-compound
(i.e., methylaluminoxane of Schering Co. having been
diluted with toluene, 2.1 mol/1) over a period of 60
2 0 minutes in a nitrogen atmosphere. Then, the reaction was
carried out at the same temperature for 30 minutes,
successively at 90 °C for 4 hours. Thereafter, the
reaction system was cooled by allowing it to stand. When
the temperature became 60 °C, the supernatant liquid was
2 5 removed by decantation, and the resulting reaction liquid
was washed three times with 150 ml of toluene.
CA 02295395 2000-O1-13
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Thus, a solid catalyst component (C-1) containing 6.8
mmol of A1 based on 1 g of silica was obtained.
Preparation of a ~re_polymerized catalyst comDOnent (C-2)
A 500-ml reactor thoroughly purged with nitrogen was
S charged with 320 ml of n-hexane. Then, to the reactor were
added 40 mmol (in terms of A1 atom) of the solid catalyst
component (C-1) obtained above and 0.04 mmol (in terms of
Zr atom) of rac-dimethylsilylbis(2-methylindenyl)zirconium
dichloride, and the contents in the reactor were stirred
for 10 minutes. Further, 1.2 mmol of triisobutylaluminum
was added, followed by stirring for another 10 minutes.
Then, a propylene gas (13.4 1/hr) was passed through the
reactor for 1 hour at 20 °C to perform prepolymerization of
propylene. The supernatant liquid was removed by
decantation, and the resulting product was washed three
times with 150 ml of decane.
Thus, a prepolymerized catalyst component (C-2) in
which Zr and Al were supported in amounts of 0.0042 mmol
and 4.35 mmol, respectively, based on 1 g of the solid
2 0 catalyst was obtained.
Po ,ymerization
Into a 4-liter stainless steel autoclave thoroughly
purged with nitrogen was introduced 1.5 liters of n-hexane,
followed by stirring for 20 minutes in a propylene
2 5 atmosphere. Then, the temperature of the reaction system
was raised. When the temperature became 50 °C, 2.90 mmol
of triisobutylaluminum, 0.0030 mmol (in terms of Zr atom)
CA 02295395 2000-O1-13
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of the prepolymerized catalyst component (C-2) prepared
above and 150 ml of hydrogen were added to the system,
thereby to perform polymerization for 2 hours at 60 °C
under a propylene pressure of 7 kg/cm2-G. After the
S polymerization, the solvent was removed by filtration, and
the resulting product was washed with methanol and dried in
vacuo at 80 °C for 10 hours.
Thus, a polymer (propylene polymer (2)] was obtained
in an amount of 304 g, and the polymerization activity was
101,000 g-PP/mmol-Zr. This polymer had (~] of 1.01 dl/g,
MFR of 145 g/10 min and Mw/Mn of 3.78.
[Preparation of a propylene polymer (3)]
Preparation of a prepolymerized catal,,yst component (C-3)
A 500-ml reactor thoroughly purged with nitrogen was
charged With 350 ml of n-hexane. To the reactor were added
16 mmol (in terms of A1 atom) of the solid catalyst
component (C-1) prepared above and 0.04 mmol (in terms of
Zr atom) of rac-dimethylsilylbis(2-methylindenyl)zirconium
dichloride, and the contents in the reactor were stirred
2 0 for 10 minutes. Further, 1.2 mmol of triisobutylaluminum
was added, followed by stirring for another 10 minutes.
Then, a propylene gas (13.4 1/hr) was passed through the
reactor for 1 hour at 20 °C to perform prepolymerization of
propylene. The supernatant liquid was removed by
2 5 decantation, and the resulting product was washed three
times with 150 ml of decane.
CA 02295395 2000-O1-13
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Thus, a prepolymerized catalyst component (C-3) in
which Zr and A1 were supported in amounts of 0.0011 mmol
and 4.50 mmol, respectively, based on 1 g of the solid
catalyst was obtained.
S Polymerization
Into a 2-liter stainless steel autoclave thoroughly
purged with nitrogen was introduced 750 ml of n-hexane,
followed by stirring for 20 minutes in a propylene
atmosphere. Then, the temperature of the reaction system
was raised. When the temperature became 50 °C, 2.7 mmol of
triisobutylaluminum and 0.045 mmol (in terms of Zr atom) of
the prepolymerized catalyst component (C-3) prepared above
were added to the system, thereby to perform polymerization
for 1.5 hours at 60 °C under a propylene pressure of 7
kg/cm2-G. After the polymerization, the solvent was
removed by filtration, and the resulting product was washed
with methanol and dried in vacuo at 80 °C for 10 hours.
Thus, a polymer [propylene polymer (3)) was obtained
in an amount of 403 g, and the polymerization activity was
89, 600 g-PP/mmol-Zr. This polymer had ['1'~~ of 1 .33 dl/g,
MFR of 34 g/10 min and Mw/Mn of 2.93.
[Preparation of a propylene polymer (4)~
Preparation of a solid titanium catalyst component
95.2 g of anhydrous magnesium chloride, 442 ml of
decane and 390.6 g of 2-ethylhexyl alcohol were mixed and
then heated at 130 °C for 2 hours to give a homogeneous
solution. To the solution was added 21.3 g of phthalic
CA 02295395 2000-O1-13
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anhydride, and they were further stirred at 130 °C for 1
hour to dissolve the phthalic anhydride in the homogeneous
solution. After the resulting solution was cooled to room
temperature, 75 ml of the solution was dropwise added to
S 200 ml of titanium tetrachloride kept at -20 °C over a
period of 1 hour. After the addition was completed, the
temperature of the mixed solution was raised to 110 °C over
a period of 4 hours. When the temperature of the solution
reached 110 °C, 5.22 g of diisobutyl phthalate (DIBP) was
added to the solution, followed by stirring at the same
temperature for 2 hours. After the 2-hour reaction was
completed, the solid portion was collected by hot
filtration, and resuspended in 275 ml of titanium
tetrachloride. The resulting suspension was again heated
at 110 °C for 2 hours to perform reaction.
After the reaction was completed, the solid portion
was collected again by hot filtration, and sufficiently
washed with decane and hexane at 110 °C until any titanium
compound liberated in the washing liquid was not detected.
2 0 Through the above process, the solid titanium catalyst
component was obtained in the form of a decane slurry, and
a part of this decane slurry was dried for the purpose of
examining the catalyst composition.
As a result, the solid titanium catalyst component had
2 S a composition comprising 2.4 $ by weight of titanium, 60 ~
by weight of chlorine, 20 o by weight of magnesium and 13.0
$ by weight of DIBP.
CA 02295395 2000-O1-13
209
pr~paratinn of a grepolymerized catalyst component (C-41
A 400-ml four-necked glass reactor equipped with a
stirrer was charged with 150 ml of purified hexane, 15 mmol
of triethylaluminum, 3 mmol of dicyclopentyldimethoxysilane
(DCPMS) and 1.5 mmol (in terms of Ti atom) of the solid
titanium catalyst component prepared above in a nitrogen
atmosphere. Then, to the reactor was fed propylene at 20
°C for 1 hour at a feed rate of 3.2 1/hr. After feeding of
propylene was completed, the reactor was purged with
nitrogen, and washing operation consisting of removal of a
supernatant liquid and addition of purified hexane was
carried out twice. Then, the resulting product was
resuspended in purified hexane, and all the resulting
suspension was transferred into a catalyst bottle to obtain
a prepolymerized catalyst component (C-4).
Polymerization
Into a 17-liter autoclave was introduced 4 kg of
propylene at room temperature in a propylene atmosphere.
To the autoclave was added 11 liters of hydrogen, and the
2 0 temperature of the reaction system was raised to 60 °C. To
system were further added 5 mmol of triethylaluminum, 5
mmol of DCPMS and 0.05 mmol (in terms of Ti atom) of the
prepolymerized catalyst component (C-4) prepared above, and
the temperature of the system was further raised to 70 °C
2 5 to perform polymerization reaction at the same temperature
for 40 minutes. Immediately after the reaction was
completed, a small amount of ethanol was added to the
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system to decompose the catalyst, thereafter the unreacted
propylene and hydrogen were purged. Thus, a white powdery
polymer was obtained. The white powdery polymer thus
obtained was dried in vacuo at 80 °C for 10 hours.
S The amount of the white powdery polymer [propylene
polymer (4)] obtained after drying was 1,630 g, and
therefore the polymerization activity was 32,600 g-PP/mmol-
Ti. This polymer had a boiling heptane extraction residue
proportion (I.I.) of 99.1 ~, [~] of 3.0 dl/g, MFR of 1.2
g/10 min and Mw/Mn of 5.1.
[Preparation of a propylene polymer (5)]
The procedures of the polymerization and the post
treatment for preparing the propylene polymer (4) were
repeated except that the addition amount of hydrogen was
varied to 150 liters.
The amount of the polymer [propylene polymer (5)] thus
obtained was 2,030 g, and the polymerization activity
corresponded to 40,600 g-PP/mmol-Ti. This polymer had [~]
of 1.10 dl/g, MFR of 155 g/10 min, Mw/Mn of 4.9 and a
2 0 boiling heptane extraction residue proportion (I.I.) of
97.0 ~.
[Preparation of a propylene polymer (6)]
The procedures of the polymerization and the post
treatment for preparing the propylene polymer (4) were
2 5 repeated except the addition amount of hydrogen was varied
to 60 liters.
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The amount of the polymer [propylene polymer (6)] thus
obtained was 1,905 g, and the polymerization activity
corresponded to 38,100 g-PP/mmol-Ti. This polymer had
of 1.55 dl/g, MFR of 25 g/10 min, Mw/Mn of 5.0 and a
boiling heptane extraction residue proportion (I.I.) of
98.8 ~.
[Preparation of a propylene polymer (7)]
Synthesis of 3-l2-biphenylyl)-2-ethylpropionic acid
To a 2-liter four-necked round flask (equipped with a
stirrer, a Zimroth condenser, a dropping funnel and a
thermometer) were fed 40.4 g (360 mmol) of potassium t-
butoxide, 300 ml of toluene and 60 ml of N-
methylpyrrolidone. Then, a solution obtained by dissolving
62.1 g (330 mmol) of diethyl ethylmalonate in 150 ml of
toluene was dropwise added to the system while heating at
60 °C in a nitrogen atmosphere. After the addition was
completed, the resulting mixture was reacted for 1 hour at
the same temperature. Then, to the mixture was dropwise
added at the same temperature a solution obtained by
2 0 dissolving 60.8 g (300 mmol) of 2-phenylbenzyl bromide in
90 ml of toluene. After the addition was completed, the
temperature of the system was elevated, and the reaction
mixture was refluxed for 2 hours. The reaction mixture was
poured in 600 ml of water, and adjusted to pH 1 by adding
2N-HC1. The organic phase was separated, and the aqueous
phase was extracted three times with 200 ml of toluene.
The whole organic phase was washed with a saturated salt
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solution until the organic phase became neutral, and dried
with anhydrous Na2S04. The solvent was concentrated under
reduced pressure to obtain 110 g of an yellow-orange
concentrated solution.
To a 2-liter four-necked round flask (equipped with a
stirrer, a Zimroth condenser, a dropping funnel and a
thermometer) were fed 202 g (3.06 mol) of potassium
hydroxide and 480 ml of an aqueous solution of methanol
(methanol/water = 4/1 (v/v)). Then, a solution obtained by
dissolving the above-obtained concentrate in 150 ml of an
aqueous solution of methanol (methanol/water = 4/1 (v/v))
was dropwise added at room temperature. After the
addition, the temperature of the system was elevated, and
the resulting mixture was refluxed for 4 hours. Then, the
mixture was cooled to room temperature, and the
precipitated solid was filtered. The product obtained by
filtration was dissolved in water. The resulting solution
was adjusted to pH 1 (acidic) by adding a sulfuric acid and
extracted five times with 200 ml of methylene chloride.
2 0 The whole organic phase was dried with anhydrous NazSOq.
The solvent was concentrated under reduced pressure to
obtain 72.6 g of a white solid product.
To a 1-liter three-necked round flask (equipped with a
stirrer, a Zimroth condenser and a thermometer) were fed
2 5 72.6 g of the above-obtained white solid, 168 ml of an
acetic acid, 111 ml of water and 39.3 ml of a concentrated
sulfuric acid, and the contents in the flask were refluxed
CA 02295395 2000-O1-13
213
for 6 hours in a nitrogen atmosphere. After the reaction
was completed, the acetic acid was distilled off under
reduced pressure, then to the resulting solution was added
150 ml of water, and the solution was extracted three times
$ with 150 ml of methylene chloride. The whole organic phase
was washed with 150 ml of a saturated salt solution, and
dried with anhydrous Na2S0q. The solvent was distilled off
under reduced pressure, and the residue was separated and
purified by silica gel chromatography (developed with
hexane/ethyl acetate (2/1 -~ 1/1, by parts by volume)), to
obtain 41.1 g of a white solid (yield: 54
The physical properties of the product obtained are as
follows.
FD-MS : 254 (M+)
m.p.. 91.2 - 94.0 °C
NMR (CDC13, 90 MHz )
8 = 0 .71 (t, J = 7 .2 Hz, 3H, CH3) ;
1.16 - 1.58 (m, 2H);
2.32 (bquin, J = 7.0 Hz, 1H, -CH-;
2.61 - 2.99 (m, 2H);
6.89 - 7.47 (m, 9H)
IR (KBr disk) : 1, 696 cm'1 (v~ao)
2 5 Synthesis of 3-(2-biphenylyl)-2-ethyl~ropionyl chloride
To a 300-ml three-necked round flask (equipped with a
stirrer tip, a Zimroth condenser, a thermometer and a NaOH
trap) were fed 39.9 g (157.2 mmol) of 3-(2-biphenylyl)-2-
ethylpropionic acid and 77.7 ml (1,065 mmol) of thionyl
CA 02295395 2000-O1-13
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chloride, and the contents in the flask were refluxed for
2.5 hours in a nitrogen atmosphere. After the reaction was
completed, the unreacted thionyl chloride was distilled off
under reduced pressure to obtain 45.6 g of a coarse product
S of an yellow-orange liquid. This acid chloride was used
for the next reaction without any further purification.
The physical properties of the product obtained are as
follows.
IR (Neat) : 1, 786 cm-1 (v~=o)
Synthesis of 4-ethyl-2-phenyl-1-indanone
To a 500-ml three-necked round flask (equipped with a
stirrer, a Zimroth condenser, a dropping funnel, a
thermometer and a NaOH trap) were fed 24.1 g (181 mmol) of
anhydrous aluminum chloride and 150 ml of carbon disulfide.
i5 Then, a solution obtained by dissolving 45.6 g (52.4 mmol)
of 3-(2-biphenylyl)-2=ethylpropionyl chloride in 63 ml of
carbon disulfide was dropwise added to the system while
cooling with ice in a nitrogen atmosphere. After the
addition was completed, the temperature in the flask was
2 0 raised to room temperature to perform reaction for 1 hour.
The reaction solution was poured in 600 ml of ice water to
decompose the solution, and extracted twice with 300 ml of
ether. The whole organic phase was successively washed
with 300 ml of a saturated NaHC03 solution and 300 ml of a
2 5 saturated salt solution, and dried with anhydrous Na2S04.
The solvent was distilled off under reduced pressure, and
the residue was separated and purified by silica gel
CA 02295395 2000-O1-13
215
chromatography (developed with hexane/ethyl acetate (10/1,
by parts by volume)), to obtain 32.4 g of the aimed product
as an yellow solid (yield: 88 ~).
The physical properties of the product obtained are as
follows.
NMR (CDC13, 90 MHz)
8 = 0. 98 (t, J = 7.2 Hz, 3H, CH3) ;
1.60 - 2.20 (m, 2H);
I
2.42 - 2.82 (m, 1H, -CH-);
2.80 (dd, J = 3.8 Hz, 16.5 Hz, 1H);
3.36 (dd, J = 7.6 Hz, 16.5 Hz, 1H);
7.09 - 7.91 (m, 8H)
1 5 IR (Neat) : 1, 705 cm-1 (v~_o)
synthesis of 2-ethyl-1-hydroxy-2-phenylindane
To a 500-ml three-necked round flask (equipped with a
stirrer tip, a Zimroth condenser, a dropping funnel and a
thermometer) were fed 2.55 g (67.8 mmol) of sodium boron
2 0 hydride and 84 ml of ethanol. Then, a solution obtained by
dissolving 31.8 g (135.3 mmol) of 2-ethyl-4-phenyl-1-
indanone in 60 ml of ethanol was dropwise added to the
system at room temperature in a nitrogen atmosphere. After
the addition was completed, the temperature of the system
2 5 was raised to 50 °C to perform reaction for another 3.5
hours. After the reaction, the reaction solution was
cooled, and acetone was dropwise added thereto to decompose
the unreacted sodium boron hydride. Then, the reaction
mixture was concentrated under reduced pressure, and
CA 02295395 2000-O1-13
216
extracted by the addition of 150 ml of water and 150 ml of
ether. After the organic phase was separated, the aqueous
phase was extracted twice with 100 ml of ether. The whole
organic phase was washed with 300 ml of a saturated salt
solution, and dried with anhydrous Na2S0q. The solvent was
distilled off under reduced pressure, to obtain 32 g of the
aimed product (mixture of two kinds of isomers) as a
viscous light yellow liquid (yield: 99 $).
The physical properties of the product obtained are as
follows.
NMR (CDC13, 90 MHz) : .
8 = 1 .02 (t, J = 7 .1 Hz, 3H, CH3) ;
1.31 - 3.28 (m, 5H);
4.86, 5.03 (each d, J = 6.4 Hz, 5.1 Hz,
respectively, total 1H, -CH-O-);
7.10 - 7.66 (m, 8H)
2 ~ IR (Neat) : 3, 340 cm'1 (v~_o)
Synthesis of 2-ethyl-4-phenylindene
To a 1-liter four-necked round flask (equipped with a
stirrer, a dropping funnel and a thermometer) were fed 29.3
g (123.9 mmol) of 2-ethyl-1-hydroxy-4-phenylindane, 51.6 g
(371.4 mmol) of triethylamine, 0.75 g (6.3 mmol) of 4-
dimethylaminopyridine and 294 ml of methylene chloride.
Then, a solution obtained by dissolving 19.2 ml (247.5
mmol) of methanesulfonyl chloride in 19.5 ml of methylene
chloride was dropwise added slowly to the system while
cooling with ice in a nitrogen atmosphere. After the
CA 02295395 2000-O1-13
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addition was completed, the resulting mixture was reacted
for another 3.5 hours at the same temperature. The
reaction mixture was poured in 500 ml of ice water, then
the organic phase was separated, and the aqueous phase was
S further extracted twice with 150 ml of methylene chloride.
The whole organic phase was successively washed with a
saturated NaHC03 solution and a saturated salt solution,
and dried with anhydrous NaZSOq. The solvent was distilled
off under reduced pressure, and the residue was separated
by silica gel chromatography (developed with hexane), to
obtain 19.7 g of the aimed product (mixture of two kinds of
isomers) as a light yellow liquid (yield: 73 $).
The physical properties of the product obtained are as
follows.
1 S 1~TMR 1CDC13, 90 MHz )
8 = 1 .20 (t, J = 7. 6 Hz, 3H, CH3) ;
2.49 (q, J = 7.6 Hz, 2H);
3.41 (s, 2H);
6.61, 6.72 (each bs, total 1H);
7.09 - 8.01 (m, 8H)
To a 500-ml three-necked round flask (equipped with a
stirrer tip, a Zimroth condenser, a dropping funnel and a
thermometer) were fed 15 g (68.4 mmol) of 2-ethyl-4-
phenylindene, 240 mg (1.89 mmol) of copper thiocyanate and
150 ml of anhydrous ether. Then, 47.1 ml (75.3 mmol) of a
hexane solution of n-butyllithium having a concentration of
CA 02295395 2000-O1-13
218
1.6 M was dropwise added slowly to the system while cooling
with ice in a nitrogen atmosphere. After the addition was
completed, the temperature of the system was raised to room
temperature to perform reaction for another 1 hour. Then,
to the reaction mixture was dropwise added slowly a
solution obtained by 4.56 ml (37.8 mmol) of
dimethyldichlorosilane in 13.5 ml of anhydrous ether.
After the addition was completed, the mixture was further
reacted for 12 hours at room temperature. The reaction
mixture was filtered with Celite, and the filtrate was
poured in 150 ml of saturated ammonium chloride water.
After the organic phase was separated, the aqueous phase
was extracted with 150 ml of ether. The whole organic
phase was washed with a saturated salt solution, and dried
with anhydrous Na2S04. The solvent was distilled off under
reduced pressure, and the residue was separated by silica
gel chromatography (developed with hexane
hexane/methylene chloride (20/1, by parts by volume)), to
obtain 13.5 g of the aimed product (mixture of two kinds of
2 0 isomers) as a light yellow solid (yield: 80 ~).
The physical properties of the product obtained are as
follows.
NMR (CDC13, 90 MHz)
8 = -0.23, -0.17 (each s, total 6H, Si-CH3);
2 S 1.12, 1.19 (each t, each J = 7.4 Hz,
total 6H, CH3) ;
2.44 (bq, J = 7.4 Hz, 4H);
CA 02295395 2000-O1-13
219
i
3.81 (s, 2H, -CH-Si);
6 . 75 (bs, 2H, 3-H-Ind) ;
6.88 - 7.74 (m, 16H)
Synthesis of rac-dimethylsilyl-bis(2-ethyl-4-
ghenylindenyl)zirconium dichloride
To a 200-ml three-necked round flask (equipped with a
stirrer tip, a ball condenser, a dropping funnel and a
thermometer) were fed 2.52 g (5.07 mmol) of dimethylsilyl-
bis(2-ethyl-4-phenylindene). and 51 ml of anhydrous ether in
an argon atmosphere. Then, 6.75 ml (10.68 mmol) of a
hexane solution of n-butyllithium having a concentration of
1.58 M was dropwise added slowly to the system at room
temperature. After the addition, the resulting mixture was
further reacted for 13.5 hours. The reaction solution was
cooled in a dry ice-acetone bath to -70 °C, and thereto was
slowly added 1.185 g (5.07 mmol) of a ZrCl4 powder. After
the addition was completed, the mixture was left overnight
with stirring. Then, the solvent was distilled off at room
2 0 temperature under reduced pressure. After addition of 90
ml of methylene chloride, the insolubles were filtered and
the filtrate was concentrated at room temperature to give a
solid. The solid was filtered, then washed twice with 5 ml
of anhydrous ether, and dried under reduced pressure to
2 5 obtain 0.68 g of the aimed product as an orange-yellow
solid (yield: 20 ~).
The physical properties of the product obtained are as
follows.
CA 02295395 2000-O1-13
220
NMR (CDC13, 90 MHz )
8 = 1.09 (t, J = 7.3 Hz, 6H, CH3);
1 .34 (s, 6H, Si-CH3) ;
2.46 (quin, J = 7.3 Hz, 2H);
2.73 (quin, J = 7.3 Hz, 2H);
6.96 (s, 2H, 3-H-Ind);
6.99 - 7.88 (m, 16H)
Pol,yme.rization
To a 100-liter stainless steel polymerizer was fed 50
liters of toluene in a nitrogen atmosphere, and the system
was cooled to 0 °C. Then, propylene and hydrogen were fed
to the system for 2 hours at feed rates of 4 Nm3/hr and 400
N1/hr, respectively, to saturate the system sufficiently.
After the feed rate of propylene was reduced to 2 Nm3/hr,
~5 to the system were added 15.0 mmol of triisobutylaluminum,
30.0 mmol (in terms of A1 atom) of methylaluminoxane and
0.10 mmol (in terms of Zr atom) of rac-dimethylsilyl-bis(2-
ethyl-4-phenylindenyl)zirconium dichloride to perform
polymerization for 1 hour while keeping the system at 0 °C.
2 0 The polymerization was terminated by adding 0.5 liter of
methanol to the system. The resulting polymer suspension
was allowed to stand for 6 hours while purging the system
with nitrogen. Then, about a half amount of toluene was
taken out by decantation, and the remaining polymer
2 5 suspension was transferred into a 200-liter reactor
containing therein 0.1 liter of a hydrochloric acid and 60
liters of methanol, followed by stirring for 30 minutes.
CA 02295395 2000-O1-13
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After the polymer suspension was allowed to stand and
subjected to decantation, the suspension was again
subjected to washing with 50 liters of methanol and
decantation. Then, the polymer suspension was taken out
from the bottom of the reactor, and the solvent was
separated by filtration. The resulting polymer was dried
at 100 °C under high vacuum for one day.
The amount of the propylene homopolymer [propylene
polymer (7)] obtained was 1,950 g, and the polymerization
activity corresponded to 19,500 g-PP/mmol-Zr. This polymer
had ['rl] of 0.68 dl/g, MFR of 900 g/l0~min and Mw/Mn of
2.02. In this polymer, the triad tacticity was 99.5 ~, the
proportion of the irregularly positioned units based on the
2,1-insertion of the propylene monomer was 0.11 $, and the
proportion of the irregularly positioned units based on the
1,3-insertion of the propylene monomer was below the
detected lower limit (less than 0.03
[Preparation of a propylene polymer (8)]
The procedures of the polymerization and the post
2 0 treatment for preparing the propylene polymer (7) described
above were repeated except that the feed rate of hydrogen
was varied to 90 N1/hr.
The amount of the propylene homopolymer [propylene
polymer (8)] thus obtained corresponded to 2,720 g, and the
2 5 polymerization activity corresponded to 27,200 g-PP/mmol-
Zr. This polymer had [t~] of 3.25 dl/g, MFR of 0.75 g/10
min and Mw/Mn of 2.20. In this polymer, the triad
CA 02295395 2000-O1-13
222
tacticity was 99.6 0, the proportion of the irregularly
positioned units based on the 2,1-insertion of the
propylene monomer was 0.16 $, and the proportion of the
irregularly positioned units based on the 1,3-insertion of
S the propylene monomer was below the detected lower limit
(less than 0.03 ~).
[Preparation of a propylene polymer (9)]
The procedures of the polymerization and the post
treatment for preparing the propylene polymer (7) described
1 0 above were repeated except that the feed rate of hydrogen
was varied to 120 N1/hr.
The amount of the propylene homopolymer [propylene
polymer (9)] thus obtained was 3,350 g, and the
polymerization activity corresponded to 33,500 g-PP/mmol-
15 Zr. This polymer had (~] of 1.64 dl/g, MFR of 13.5 g/10
min and Mw/Mn of 2.03. In this polymer, the triad
tacticity was 99.5 ~, the proportion of the irregularly
positioned units based on the 2,1-insertion of the
propylene monomer was 0.13 0, and the proportion of the
2 0 irregularly positioned units based on the 1,3-insertion of
the propylene monomer was below the detected lower limit
(less than 0.03 ~).
[Preparation of a propylene polymer (10)]
The procedures of the polymerization and the post
2 5 treatment for preparing the propylene polymer (4) described
above were repeated except that the addition amount of
hydrogen was varied to 45 liters.
CA 02295395 2000-O1-13
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The amount of the propylene homopolymer (propylene
polymer (10)] thus obtained was 1,930 g, and the
polymerization activity corresponded to 38,600 g-PP/mmol-
Ti. This polymer had (~] of 1.75 dl/g, MFR of 15 g/10 min,
Mw/Mn of 5.0 and a boiling heptane extraction residue
proportion (I.I.) of 98.8 ~.
[Preparation of a propylene polymer (11)]
The procedures of the polymerization and the post
treatment for preparing the propylene polymer (7) described
above were repeated except that the feed rate of hydrogen
was varied to 350 N1/hr.
The amount of the propylene homopolymer (propylene
polymer (11)] thus obtained was 2,060 g, and the
polymerization activity corresponded to 20,600 g-PP/mmol-
~5 Zr. This polymer had [~] of 0.72 dl/g, MFR of 670 g/10 min
and Mw/Mn of 1.95. In this polymer, the triad tacticity
was 99.5 ~, the proportion of the irregularly positioned
units based on the 2,1-insertion of the propylene monomer
was 0.14 ~, and the proportion of the irregularly
2 0 positioned units based on the 1,3-insertion of the
propylene monomer was below the detected lower limit (less
than 0.03
[Preparation of a propylene polymer (12)]
To a 100-liter stainless steel polymerizer was fed 50
2 S liters of toluene, and the system was cooled to 0 °C.
Then, propylene, ethylene and hydrogen were fed to the
system for 2 hours at feed rates of 4 Nm3/hr, 2 Nm3/hr and
CA 02295395 2000-O1-13
224
N1/hr, respectively, to saturate the system
sufficiently. The feed rates of propylene and ethylene
were reduced to 1 Nm3/hr and 300 N1/hr, respectively, and
the system was allowed to stand for 1 hour. Then, to the
5 system were added 8.0 mmol of triisobutylaluminum, 12.0
mmol (in terms of A1 atom) of methylaluminoxane and 0.040
mmol (in terms of Zr atom) of rac-dimethylsilyl-bis(2-
ethyl-4-phenylindenyl)zirconium dichloride, to perform
polymerization for 1 hour while keeping the system at 0 °C.
10 The termination of the polymerization and the post
treatment were carried out in the same manner as described
for the propylene polymer (7).
The amount of the propylene copolymer [propylene
polymer (12)] thus obtained was 1,550 g, and the
~5 polymerization activity corresponded to 38,700 g-
polymer/mmol-Zr. This polymer had [~] of 0.68 dl/g, MFR of
950 g/10 min and Mw/Mn of 2.33, and contained constituent
units derived from ethylene in an amount of 5.1 ~ by mol.
In this polymer, the triad tacticity was 99.2 ~, the
2 ~ proportion of the irregularly positioned units based on the
2,1-insertion of the propylene monomer was 0.08 ~, and the
proportion of the irregularly positioned units based on the
1,3-insertion of the propylene monomer was below the
detected lower limit (less than 0.03
2 5 [Preparation of a propylene polymer (13)]
To a 100-liter stainless steel polymerizer was fed 35
liters of toluene, and the system was cooled to 0 °C.
CA 02295395 2000-O1-13
225
Then, propylene and ethylene were fed to the system for 2
hours at feed rates of 4 Nm3/hr and 2 Nm3/hr, respectively,
while adjusting the pressure in the system at 2.5 kg/cmz-G,
so as to saturate the system sufficiently. The feed rates
of propylene and ethylene were reduced to 1 Nm3/hr and 300
N1/hr, respectively, and the system was allowed to stand
for 1 hour. Then, to the system were added 5.0 mmol of
triisobutylaluminum, 10.0 mmol (in terms of A1 atom) of
methylaluminoxane and 0.014 mmol (in terms of Zr atom) of
rac-dimethylsilyl-bis(2-ethyl-4-phenylindenyl)zirconium
dichloride, to perform polymerization~for 1 hour at 0 °C
while adjusting the pressure in the polymerizer at 2.5
kg/cm2-G. After the polymerization was terminated by
methanol, the pressure in the system was released, and the
system was purged with nitrogen. The post treatment was
carried out in the same manner as described for the
propylene polymer (7).
The amount of the propylene copolymer [propylene
polymer (13)] thus obtained was 1,310 g, and the
2 0 polymerization activity corresponded to 13,100 g-
polymer/mmol-Zr. This polymer had (~] of 3.10 dl/g, MFR of
0.72 g/10 min and Mw/Mn of 2.3, and contained constituent
units derived from ethylene in an amount of 5.6 ~ by mol.
In this polymer, the triad tacticity was 99.3 $, the
2 5 proportion of the irregularly positioned units based on the
2,1-insertion of the propylene monomer was 0.13 ~, and the
proportion of the irregularly positioned units based on the
CA 02295395 2000-O1-13
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1,3-insertion of the propylene monomer was below the
detected lower limit (less than 0.03
(Preparation of a propylene polymer (14)]
The procedures of the polymerization and the post
S treatment for preparing the propylene polymer (12)
described above were repeated except that hydrogen was not
used.
The amount of the propylene copolymer (propylene
polymer (14)] thus obtained was 1,750 g, and the
polymerization activity corresponded to 17,500 g-
polymer/mmol-Zr. This polymer had [~] of 1.67 dl/g, MFR of
9.5 g/10 min and Mw/Mn of 2.10, and contained constituent
units derived from ethylene in an amount of 5.6 ~ by mol.
In this polymer, the triad tacticity was 99.2 ~, the
i5 proportion of the irregularly positioned units based on the
2,1-insertion of the propylene monomer was 0.11 $, and the
proportion of the irregularly positioned units based on the
1,3-insertion of the propylene monomer was below the
detected lower limit (less than 0.03
2 0 [Preparation of a soft polymer (ethylene/propylene random
copolymer)]
23.8 g of anhydrous magnesium chloride, 122 ml of
decane and 116.1 g of 2-ethylhexyl alcohol were together
2 5 heated at 130 °C for 2 hours to give a homogeneous
solution. To the solution was added 5.72 ml of ethyl
benzoate. The resulting homogeneous solution was dropwise
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added to 1 liter of titanium tetrachloride kept at -20 °C
over a period of 20 minutes with stirring, and the
resulting solution was further stirred for 1 hour at -20
°C. Then, the temperature of the solution was slowly
raised. When the temperature of the solution reached 80
°C, 12.2 ml of ethyl benzoate was further added to the
solution, and the mixture was stirred for 2 hours at 80 °C.
After the reaction was completed, the solid material
was collected by filtration. The solid material was
resuspended in 1 liter of titanium tetrachloride, and the
suspension was stirred for 2 hours at 90 °C. The solid
material was again collected by filtration and washed
sufficiently with purified hexane until any titanium
compound liberated in the washing liquid was not detected.
The solid titanium catalyst component thus obtained
contained titanium, chlorine, magnesium and ethyl benzoate
in amounts of 3.7 ~ by weight, 59 $ by weight, 17 ~ by
weight and 15 $ by weight, respectively.
polymerszatson
2 0 In a 15-liter stainless steel polymerizer equipped
with a stirrer, copolymerization of ethylene and propylene
was carried out.
To the polymerizer were continuously fed, through the
top thereof, hexane as a polymerization solvent at a feed
2 5 rate of 3 1/hr, a hexane slurry of the solid titanium
catalyst component obtained above (0.15 mmol/1 in terms of
titanium atom) at a feed rate of 1 1/hr, a hexane solution
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of triethylaluminum (15 mmol/1) at a feed rate of 0.5 1/hr
and a hexane solution of ethyl benzoate (5 mmol/1) at a
feed rate of 0.5 1/hr. Further, to the polymerizer were
continuously fed, through the top thereof, ethylene at a
feed rate of 90 1/hr and propylene at a feed rate of 270
1/hr, and was also continuously fed hydrogen so that the
hydrogen concentration in the gas phase of the polymerizer
was 2.3 ~.
On the other hand, the polymer solution was
continuously drawn out from the bottom of the polymerizer
so that the amount of the polymer solution in the
polymerizer was 5 liters.
The copolymerization was carried out at 80 °C by
circulating warm water within a jacket equipped on the
outside of the polymerizer. The pressure in the
polymerizer was 6.5 kg/cm2-G.
To the polymer solution drawn out from the polymerizer
was added a small amount of methanol to terminate the
polymerization reaction. The polymer solution was
2 0 subjected to steam stripping to separate the polymer from
the solvent, and the polymer was dried at 80 °C under
reduced pressure for one day.
Through the above operation, an ethylene/propylene
random copolymer (EPR-1) was obtained in an amount of 235
2 5 g/hr .
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The ethylene/propylene random copolymer (EPR-1)
contained constituent units derived from ethylene in an
amount of 42 ~ by mol, and had ['t'~] of 2.7 dl/g.
[Preparation of an ethylene/propylene random copolymer
(EPR-2 ) ]
In a 15-liter autoclave equipped with a stirrer,
copolymerization of ethylene and propylene was carried out.
To the polymerizer were fed, through the top thereof,
2.4 liters of dehydrated and purified hexane, 3.3 kg of
1 0 propylene, 0.72 ml of a toluene solution of
methylaluminoxane (1.3 mg~atom/ml in terms of aluminum
atom) and 7.7 ml of a hexane solution of
triisobutylaluminum (1 mmol/ml).
After the temperature of the system was raised to 37
~S °C, ethylene was fed to the system so that the total
pressure was 14 kg/cmZ, and 2.4 ml of a toluene solution of
bis(1,3-dimethylcyclopentadienyl)zirconium dichloride
(0.004 mmol/ml) was fed to the system using a pressure
equalizing tube. The polymerization was performed for 1
2 0 hour with keeping the temperature at 37 °C and the total
pressure at 14 kg/cm2. After release of pressure, the
polymer solution was taken out and dried. An yield of the
resulting polymer was 320 g.
The ethylene/propylene random copolymer (EPR-2) thus
2 $ obtained contained constituent units derived from ethylene
in an amount of 43 ~ by mol, and had ['~] of 2.8 dl/g.
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[Synthesis of an ethylene/propylene random copolymer (EPR-
3) ]
In a 2-liter autoclave equipped with a stirrer,
copolymerization of ethylene and propylene was carried out.
In detail, to the autoclave were fed, through the top
thereof, 0.9 liter of dehydrated and purified hexane, 1 ml
of a hexane solution of triisobutylaluminum (1 mmol/ml) and
0.27 ml of a toluene solution of methylaluminoxane (0.9
mmol/ml in terms of A1 atom). After the temperature of the
system was raised to 50 °C, propylene was fed to the system
so that the total pressure was 3.8 kg/cm2-G, and ethylene
was further fed to the system so that the total pressure
was 8 kg/cmz-G. Then, to the system was added 0.0008 mmol
(in terms of zirconium) of rac-dimethylsilyl-bis(2-ethyl-4-
~5 phenylindenyl)zirconium dichloride to perform
polymerization for 30 minutes with keeping the temperature
at 50 °C and the total pressure at 8 kg/cmz. After release
of pressure, the polymer solution was added to a large
amount of methanol. The resulting polymer was taken out
2 0 and dried at 130 °C for 12 hours under reduced pressure.
An yield of the ethylene/propylene random copolymer
(EPR-3) thus obtained was 49.6 g. This copolymer contained
constituent units derived from ethylene in an amount of 39
by mol, and had ['~] of 3.1 dl/g and MFR of 0.4 g/10 min.
2 S [Synthesis of an ethylene/propylene random copolymer (EPR-
4)]
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An ethylene/propylene random copolymer (EPR-4) was
synthesized by a conventional ethylene/propylene
copolymerization process using a VO (OC2Hs) C12- (C2Hs) i.sAlCll,s
catalyst.
The ethylene/propylene random copolymer (EPR-4) thus
obtained had ['~) of 2.4 dl/g and MFR of 0.6 g/10 min, and
contained constituent units derived from ethylene in an
amount of 81 $ by mol.
[Synthesis of an ethylene/propylene random copolymer (EPR-
1 0 5) 1
In a 2-liter autoclave equipped with a stirrer,
copolymerization of ethylene and propylene was carried out.
In detail, to the polymerizer were fed, through the
top thereof, 1 liter of dehydrated and purified hexane, 11
N1 of propylene in the form of a gas, 0.85 ml of a hexane
solution of triisobutylaluminum (1 mmol/ml) and 0.13 ml of
a toluene solution of methylaluminoxane (1.2 mmol/ml in
terms of A1 atom). After the temperature of the system was
raised to 80 °C, ethylene was fed to the system so that the
2 0 total pressure was 8 kg/cm2-G. Then, to the system was
added 0.0005 mmol (in terms of Zr atom) of rac-
dimethylsilyl-bis(2-ethyl-4-phenylindenyl)zirconium
dichloride to perform polymerization for 30 minutes with
keeping the temperature at 80 °C and the total pressure at
2 5 8 kg/cm2-G. After release of pressure, the polymer
solution was added to a large amount of methanol. The
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resulting polymer was taken out and dried at 130 °C for 12
hours under reduced pressure.
An yield of the ethylene/propylene random copolymer
(EPR-5) thus obtained was 58.4 g. This copolymer contained
constituent units derived from ethylene in an amount of 79
by mol, and had ['~] of 2.2 dl/g and MFR of 0.7 g/10 min.
[Synthesis of an ethylene/1-butene random copolymer (EBR-
1) ]
In a 2-liter autoclave equipped with a stirrer,
copolymerization of ethylene and 1-butene was carried out.
In detail, to the polymerizer were fed, through the
top thereof, 1 liter of dehydrated and purified hexane, 55
ml of 1-butene, 0.85 ml of a hexane solution of
triisobutylaluminum (1 mmol/ml) and 0.13 ml of a toluene
solution of methylaluminoxane (1.2 mmol/ml in terms of A1
atom). After the temperature of the system was raised to
90 °C, ethylene was fed to the system so that the total
pressure was 8 kg/cm2-G. Then, to the system was added
0.0005 mmol (in terms of Zr atom) of rac-dimethylsilyl-
2 0 bis(2-ethyl-4-phenylindenyl)zirconium dichloride to perform
polymerization for 20 minutes with keeping the temperature
at 90 °C and the total pressure at 8 kg/cmz-G. After
release of pressure, the polymer solution was added to a
large amount of methanol. The resulting polymer was taken
out and dried at 130 °C for 12 hours under reduced
pressure.
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An yield of the ethylene/1-butene random copolymer
(EBR-5) thus obtained was 52.8 g. This copolymer contained
constituent units derived from ethylene in an amount of 82
by mol, and had [~] of 2.3 dl/g and MFR of 0.6 g/10 min.
[Synthesis of ethylene polymers (PE-1) and (PE-2)]
Ethylene polymers (PE-1) and (PE-2) were synthesized
by a conventional ethylene copolymerization process using a
combined catalyst of MgCl2-supported Ti catalyst-
triethylaluminum.
1 0 The ethylene polymer (PE-1) had [~) of 1.20 dl/g, MFR
of 29 g/10 min and Mw/Mn of 4.1.
The ethylene polymer (PE-2) had (~] of 2.11 dl/g, MFR
of 1.3 g/10 min and Mw/Mn of 4.8.
A propylene polymer composition consisting of 40 ~ by
weight of the propylene polymer (1) and 60 $ by weight of
the propylene polymer (2) prepared by the above
polymerization was molded into ASTM specimens by means of
an injection molding machine under the conditions of a
2 0 resin temperature of 200 °C and a mold temperature of 40
°C, to measure the physical properties.
The results are set forth in Table 1.
Comparatsve Example 1
The propylene polymer (3) prepared by the above
2 S polymerization was molded into ASTM specimens in the same
manner as described in Example 1, to measure the physical
properties.
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The results are set forth in Table 1.
Comparative Exam,pl_e 2
A propylene polymer composition consisting of 40 ~ by
weight of the propylene polymer (4) and 60 ~ by weight of
S the propylene polymer (5) prepared by the above
polymerization was molded into ASTM specimens in the same
manner as described in Example 1, to measure the physical
properties.
The results are set forth in Table 1.
Table 1
Ex. 1 Com .Ex. Com .Ex.
1 2
Propylene polymer (1) 40 - -
Propylene polymer (2) 60 - -
Propylene polymer (3) - 100 -
Propylene polymer (4) - - 40
Pro lene of mer (5) - - 60
MFR (g/10 min) 20 31 18
FM (kg/cm2) 15, 000 11, 100 19, 500
IZ (23C) (kg~cm/cm) 2 2 2
EL (~) 420 340 30
HDT (load: 4.6 k ) (C) 110 94 117
A propylene polymer composition consisting of 40 parts
by weight of the propylene polymer (1), 60 parts by weight
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of the propylene polymer (2) and 20 parts by weight of the
soft polymer (EPR-1) prepared by the above polymerization
was molded into ASTM specimens in the same manner as
described in Example 1, to measure the physical properties.
The results are set forth in Table 2.
jomoarative Exampple 33
A propylene polymer composition consisting of 100
parts by weight of the propylene polymer (3) and 20 parts
by weight of the soft polymer (EPR-1) prepared by the above
polymerization was molded into ASTM specimens in the same
manner as described in Example 1, to measure the physical
properties.
The results are set forth in Table 2.
omparative Example 4
A propylene polymer composition consisting of 40 parts
by weight of the propylene polymer (4), 60 parts by weight
of the propylene polymer (S) and 20 parts by weight of the
soft polymer (EPR-1) prepared by the above polymerization
was molded into ASTM specimens in the same manner as
2 0 described in Example 1, to measure the physical properties.
The results are set forth in Table 2.
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Table 2
Ex. 2 Com .Ex. Com .Ex.
3 4
Propylene polymer (1) 40 - -
Propylene polymer (2) 60 - -
Propylene polymer (3) - 100 -
Propylene polymer (4) - - 40
Propylene polymer (5) - - 60
Soft of mer '20 20 20
MFR (g/10 min) 15 25 12
FM (kg/cmz) 11, 000 9, 100 13, 000
IZ (23C) (kg-cm/cm) 35 37 12
EL (~) 720 740 180
HDT (load: 4.6 k ) (C) 95 88 110
A propylene polymer composition consisting of 50 ~ by
weight of the propylene polymer (4) and 50 ~ by weight of
the propylene polymer (5) prepared by the above
polymerization was molded into ASTM specimens in the same
manner as described in Example 1, to measure the physical
properties.
The results are set forth in Table 3.
Comparative Examn~P 5
A propylene polymer composition consisting of 50 ~ by
weight of the propylene polymer (4) and 50 o by weight of
the propylene polymer (5) prepared by the above
CA 02295395 2000-O1-13
237
polymerization was molded into ASTM specimens in the same
manner as described in Example 1, to measure the physical
properties.
The results are set forth in Table 3.
Table 3
Ex. 3 Com Ex. 5
Propylene polymer (4) 50 50
Propylene polymer (2) 50 -
Pro lene of mer (5) - 50
MFR (g/10 min) 15 15
FM (kg/cmz) 18, 000 19, 000
IZ (23C) (kg ~ cm/cm) 2 2
EL (~) 180 28
HDT ( load 115 115
: 4 . 6 k
) ( C )
1~ A propylene polymer composition consisting of 50 parts
by weight of the propylene polymer (4), 50 parts by weight
of the propylene polymer (2) and 20 parts by weight of the
soft polymer (EPR-1) prepared by the above polymerization
was molded into ASTM specimens in the same manner as
described in Example 1, to measure the physical properties.
The results are set forth in Table 4.
Comparative Example 6
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A propylene polymer composition consisting of 50 parts
by weight of the propylene polymer (4), 50 parts by weight
of the propylene polymer (5) and 20 parts by weight of the
soft polymer (EPR-1) prepared by the above polymerization
Was molded into ASTM specimens in the same manner as
described in Example 1, and to measure the physical
properties.
The results are set forth in Table 4.
Table 4
Ex. 4 Com Ex. 6
Propylene polymer (4) 50 50
Propylene polymer (2) 50 -
Propylene polymer (5) - 50
Soft of mer 20 20
MFR (g/10 min) 12 15
FM (kg/cmz) 12, 500 13, 000
IZ (23C) (kg~cm/cm) 30 12
EL (~) 400 180
HDT (load: 95 105
4.6 k ) (C)
A propylene polymer composition consisting of 100
parts by weight of the propylene polymer (6) and 20 parts
by weight of the ethylene/propylene random copolymer (EPR-
2) prepared by the above polymerization was molded into
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ASTM specimens in the same manner as described in Example
l, to measure the physical properties.
The results are set forth in Table 5.
Comparative Example 7
S A propylene polymer composition consisting of 100
parts by weight of the propylene polymer (6) and 20 parts
by weight of the ethylene/propylene random copolymer (EPR-
1) prepared by the above polymerization was molded into
ASTM specimens in the same manner as described in Example
1, to measure the physical properties.
The results are set forth in Table 5.
Table 5
Ex. 5 Com Ex. 7
Propylene polymer (6) 100 100
EPR-2 20 -
EPR-1 - 20
MFR (g/10 min) 17 17
FM (kg/cm2) 13, 100 13, 300
IZ (23C) (kg~cm/cm) 18 12
IZ (-30C) (kg~cm/cm) 8 3
EL (~) 350 250
HDT (load: 4.6 k ) (C) 95 95
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A propylene polymer composition consisting of 50 parts
by weight of the propylene polymer (7) and 50 parts by
weight of the propylene polymer (8) prepared by the above
polymerization was molded into ASTM specimens in the same
S manner as described in Example 1, to measure the physical
properties.
The results are set forth in Table 6.
Comparative Example 8
The propylene polymer (9) prepared by the above
polymerization was molded into ASTM specimens in the same
manner as described in Example 1, to measure the physical
properties.
The results are set forth in Table 6.
Table 6
Ex. 6 Comp. Ex. 8
Propylene polymer (7) 50 -
Propylene polymer (8) 50 -
Pro lene of mer ( 9) - 100
MFR (g/10 min) 12.3 13.5
FM (kg/cm2) 18, 200 17, 000
IZ (23C) (kg~cm/cm) 2.1 3.4
EL ($) 380 340
HDT (load: 128 125
4.6 k ) (C)
Example 7
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A propylene polymer composition consisting of 50 parts
by weight of the propylene polymer (12) and 50 parts by
weight of the propylene polymer (13) prepared by the above
polymerization was molded into ASTM specimens in the same
S manner as described in Example 1, to measure the physical
properties. Further, a film was produced from the above
composition under the following conditions, to measure the
haze.
The film (width: 30 cm, thickness: 50 Vim) was produced
by means of a single-screw extruder having a diameter of 30
mm equipped with a T-die under the conditions of a cooling
roll temperature of 25 °C and a take-up rate of 3 m/min.
The results are set forth in Table 7.
Comparat,'_ve Example 9
1$ The propylene polymer (14) prepared by the above
polymerization was molded into ASTM specimens, to measure
the physical properties.
The results are set forth in Table 7.
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242
Table 7
Ex. 7 Com Ex. 9
Propylene polymer (12) 50 -
Propylene polymer (13) 50 -
Pro lene of mer (14) - 100
MFR (g/10 min) 13.0 9.5
FM (kg/cm2) 8,200 7,700
IZ (23C) (kg~cm/cm) 4.0 4.6
EL (~) 440 480
Film haze (~) 0.7 2.0
A propylene polymer composition consisting of 50 parts
by weight of the propylene polymer (4) and 50 parts by
weight of the propylene polymer (11) prepared by the above
polymerization was molded into ASTM specimens in the same
manner as described in Example 1, to measure the physical
properties.
The results are set forth in Table 8.
omparative Example 10
A propylene polymer composition consisting of 50 parts
by weight of the propylene polymer (4) and 50 parts by
weight of the propylene polymer (5) prepared by the above
polymerization was molded into ASTM specimens in the same
manner as described in Example 1, to measure the physical
properties.
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243
The results are set forth in Table 8.
Table 8
Ex. 8 Com Ex. 10
Propylene polymer (4) 50 50
Propylene polymer (11) 50 -
Pro lene of mer (5) - 50
MFR (g/10 min) 16 15
FM ( kg/cm~ ) 19, 000 19, 000
IZ (23C) (kg~cm/cm) 2 2
EL (~) 280 28
HDT ( load 118 115
: 4 . 6 k
) ( C )
A propylene polymer composition consisting of 50 parts
by weight of the propylene polymer (7), 50 parts by weight
of the propylene polymer (8) and 20 parts by weight of the
ethylene/propylene random copolymer (EPR-1) prepared by the
above polymerization was molded into ASTM specimens in the
same manner as described in Example 1, to measure the
physical properties.
The results are set forth in Table 9.
1$ Example 10
A propylene polymer composition consisting of 50 parts
by weight of the propylene polymer (7), 50 parts by weight
of the propylene polymer (8), 10 parts by weight of the
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244
ethylene/propylene random copolymer (EPR-3) and 10 parts by
weight of the ethylene/propylene random copolymer (EPR-5)
prepared by the above polymerization was molded into ASTM
specimens in the same manner as described in Example 1, to
S measure the physical properties.
The results are set forth in Table 9.
Table 9
Ex. 9 Ex. 10
Propylene polymer (7) 50 50
Propylene polymer (8) 50 50
EPR-1 2p -
EPR-3 - 10
EPR-5 - 10
MFR (g/10 min) 9,1 g.l
FM (kg/cmz) 12, 800 13, 600
IZ (23C) (kg ~ cm/cm) 38 34
EL (~) 720 560
HDT (load: 4.6 k ) (C) 98 104
A propylene polymer composition consisting of 50 parts
by weight of the propylene polymer (12), 50 parts by weight
of the propylene polymer (13) and 20 parts by weight of the
ethylene/propylene random copolymer (EPR-1) prepared by the
above polymerization was molded into ASTM specimens in the
same manner as described in Example 1, to measure the
CA 02295395 2000-O1-13
245
physical properties. Further, a film was produced from the
above composition in the same manner as described in
Example 7, to measure the haze.
The results are set forth in Table 10.
Comparative Example 11
A propylene polymer composition consisting of 100
parts by weight of the propylene polymer (14) and 20 parts
by weight of the ethylene/propylene random copolymer (EPR-
1) prepared by the above polymerization was molded into
ASTM specimens in the same manner as described in Example
1, to measure the physical properties. Further, a film was
produced from the above composition in the same manner as
described in Example 7, to measure the haze.
The results are set forth in Table 10.
Table 10
Ex. 11 Com Ex. 11
Propylene polymer (12) 50 -
Propylene polymer (13) 50 -
Propylene polymer (14) - 100
EPR-1 20 20
MFR (g/10 min) 13.0 7.2
FM (kg/cm2) 6, 200 5, 600
IZ (23C) (kg~cm/cm) 38 46
EL ($) 520 540
Film haze (~) 0.7 2.0
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246
A propylene polymer composition consisting of 50 parts
by weight of the propylene polymer (4), 50 parts by weight
of the propylene polymer (11) and 20 parts by weight of the
ethylene/propylene random copolymer (EPR-1) prepared by the
above polymerization was molded into ASTM specimens in the
same manner as described in Example 1, to measure the
physical properties.
The results are set forth in Table 11.
Table 11
Ex. 12 Com Ex. 6
Propylene polymer (4) 50 50
Propylene polymer (11) 50 -
Propylene polymer (5) - 50
EPR-1 20 20
MFR (g/10 min) 12 15
FM (kg/cmz) 13, 000 13, 000
IZ (23C) (kg~cm/cm) 28 12
EL ( a ) 430 180
HDT (load: 4.6 k ) (C) 97 105
A propylene polymer composition consisting of 50 parts
by weight of the propylene polymer (7), 50 parts by weight
of the propylene polymer (8), 10 parts by weight of the
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247
ethylene/propylene random copolymer (EPR-1) and 10 parts by
weight of the ethylene polymer (PE-1) prepared by the above
polymerization Was molded into ASTM specimens in the same
manner as described in Example 1, to measure the physical
properties.
The results are set forth in Table 12.
A propylene polymer composition consisting of 50 parts
by weight of the propylene polymer (7), 50 parts by weight
of the propylene polymer (8), 10 parts by weight of the
ethylene/propylene random copolymer (EPR-3) and 10 parts by
weight of the ethylene polymer (PE-2) prepared by the above
polymerization was molded into ASTM specimens in the same
manner as described in Example 1, to measure the physical
properties.
The results are set forth in Table 12.
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248
Table 12
Ex. 13 Ex. 14
Propylene polymer (7) 50 50
Propylene polymer (8) 50 50
EPR-1 15 -
EPR-3 - 15
PE-1 10 -
PE-2 ~ - 10
MFR (g/10 min) 9.7 g.5
FM (kg/cmz) 13, 900 13, 800
IZ (23C) (kg ~ cm/cm) 35 37
EL ($) 440 480
HDT (load: 4.6 k ) (C) 105 10
S A propylene polymer composition consisting of 100
parts by weight of the propylene polymer (9) and 25 parts
by weight of the ethylene/propylene random copolymer (EPR-
1) prepared by the above polymerization was molded into
ASTM specimens in the same manner as described in Example
1, to measure the physical properties.
The results are set forth in Table 13.
A propylene polymer composition consisting of 100
parts by weight of the propylene polymer (9), 20 parts by
weight of the ethylene/propylene random copolymer (EPR-1),
CA 02295395 2000-O1-13
249
both prepared by the above polymerization, and 15 parts by
weight of a filler (talc) was molded into ASTM specimens in
the same manner as described in Example 1, to measure the
physical properties.
The results are set forth in Table 13.
ExamQle 17
A propylene polymer composition consisting of 100
parts by weight of the propylene polymer (9), 10 parts by
weight of the ethylene/propylene random copolymer (EPR-3),
10 parts by weight of the ethylene/1-butene random
copolymer (EBR-1), all prepared by the above
polymerization, and 15 parts by weight of a filler (talc)
was molded into ASTM specimens in the same manner as
described in Example 1, to measure the physical properties.
The results are set forth in Table 13.
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250
Table 13
Ex. 15 Ex. 16 Ex. 17
Propylene polymer (9) 100 100 100
EPR-1 25 20 10
EBR-1 - - 10
Filler (talc) - 15 15
MFR (g/10 min) 9.0 9.8 10.3
FM (kg/cm2) 11, 800 15, 800 18, 800
IZ (23C) (kg~cm/cm) 55 44 40
EL (a) 750 310 310
HDT (load: 4.6 k ) (C) 96 125 125
A propylene polymer composition consisting of 100
parts by weight of the propylene polymer (9), 10 parts by
weight of the ethylene/propylene random copolymer (EPR-3)
and 10 parts by weight of the ethylene/propylene random
copolymer (EPR-4) prepared by the above polymerization was
molded into ASTM specimens in the same manner as described
in Example 1, to measure the physical properties.
The results are set forth in Table 14.
A propylene polymer composition consisting of 100
parts by weight of the propylene polymer (9), 10 parts by
weight of the ethylene/propylene random copolymer (EPR-3)
and 10 parts by weight of the ethylene/propylene random
CA 02295395 2000-O1-13
251
copolymer (EPR-5) prepared by the above polymerization was
molded into ASTM specimens in the same manner as described
in Example 1, to measure the physical properties.
The results are set forth in Table 14.
S omQarative Example
A propylene polymer composition consisting of 100
parts by weight of the propylene polymer (10) and 20 parts
by weight of the ethylene/propylene random copolymer (EPR-
1) prepared by the above polymerization was molded into
ASTM specimens in the same manner as described in Example
1, to measure the physical properties.
The results are set forth in Table 14.
Table 14
Ex. 18 Ex. 19 Com .Ex.l2
Propylene polymer (9) 100 100 -
Propylene polymer (10) - - 100
EPR-1 - - 20
EPR-3 10 10 -
EPR-4 10 _ _
EPR-5 - 10 -
MFR (g/10 min) 10.2 10.1 10.4
FM (kg/cm2) 13, 000 12, 700 12, 000
IZ (23C) (kg ~ cm/cm) 38 35 20
EL (~y 540 560 250
HDT ( load : 4 . 6 k 102 100 95
) ( C )
1$
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Example 20
A propylene polymer composition consisting of 100
parts by weight of the propylene polymer (14) and 20 parts
by weight of the ethylene/propylene random copolymer (EPR-
1) prepared by the above polymerization was molded into
ASTM specimens in the same manner as described in Example
1, to measure the physical properties.
The results are set forth in Table 15.
ompa_rative Example
The propylene polymer (14) prepared by the above
polymerization was molded into ASTM specimens in the same
manner as described in Example 1, to measure the physical
properties.
The results are set forth in Table 15.
1 S Table 15
--,- Ex . 2 0 Com Ex . 13
Propylene polymer (14) 100 100
EPR-1 20 -
MFR (g/10 min) 7.2 9.5
FM (kg/cm2) 5, 600 7, 700
IZ (23C) (kg~cm/cm) 46 4.6
EL (g) 540 480
Example 21
A propylene polymer composition consisting of 100
2 0 parts by weight of the propylene polymer (9), 15 parts by
weight of the ethylene/propylene random copolymer (EPR-1)
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253
and 10 parts by weight of the ethylene polymer (PE-1)
prepared by the above polymerization was molded into ASTM
specimens in the same manner as described in Example 1, to
measure the physical properties.
The results are set forth in Table 16.
ExamxLe 22
A propylene polymer composition consisting of 100
parts by weight of the propylene polymer (9), 15 parts by
weight of the ethylene/propylene random copolymer (EPR-3)
and 10 parts by weight of the ethylene polymer (PE-2)
prepared by the above polymerization was molded into ASTM
specimens in the same manner as described in Example 1, to
measure the physical properties.
The results are set forth in Table 16.
Table 16
Ex. 21 Ex. 22
Propylene polymer (9) 100 100
EPR-1 15 -
EPR-3 - 15
PE-1 10 -
PE-2 - 10
MFR (g/10 min) 10.5 10.1
FM (kg/cm2) 13,500 13,200
IZ (23C) (kg~cm/cm) 38 40
EL (~) 480 500
HDT (load: 4.6 k ) (C) 101 9g
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254
A propylene polymer composition consisting of 100
parts by weight of the propylene polymer (6) and 20 parts
by weight of the ethylene/propylene random copolymer (EPR-
S 3) prepared by the above polymerization was molded into
ASTM specimens in the same manner as described in Example
1, to measure the physical properties.
The results are set forth in Table 17.
Table 17
Ex. 23
Propylene polymer (6) ~ 100
EPR-3 20
MFR (g/10 min) 17
FM (kg/cm2) 13, 600
IZ (23C) (kg~cm/cm) lg
EL (~) 340
HDT (load: 4.6 k ) (C) 95
