Note: Descriptions are shown in the official language in which they were submitted.
21 00999
TITLE
PROPYLENE POLYMER, PROPYLENE BLOCK COPOLYMER, PROCESS FOR
PREPARING SAID POLYMER AND SAID BLOCK COPOLYMER, AND
; PROPYLENE POLYMER COMPOSITION
FIELD OF THE INVF.NTION
The present invention relates to a propylene polymer,
a propylene block copolymer and process for preparing
thereof, and a propylene polymer composition comprising the
propylene polymer or the propylene block copolymer and an
stabilizer. More particularly, the invention relates to a
propylene polymer having a high cristallinity, a high
stereoregularity and an extremely long mesochain
(continuous propylene units wherein directions of a-methy
carbons are the same as each other), a propylene block
copolymer containing a crystalline propylene portion having
a high crystallinity, a high stereoregularity and an
extremely long mesochain, and a propylene polymer
composition comprising the above propylene polymer or
propylene block copolymer and a specific stabilizer.
BACKGROUND OF THE INVENTION
It has been well known that polyolefins such as
crystalline polypropylene are obtained by polymerizing
olefins in the presence of so-called Ziegler-Natta catalyst
which comprises a compound of a transition metal of Group
IV to Group VI in the periodic table and an organometallic
-- 21 00999
compound of a metal of Group I to Group III of the periodic
table. Recently, there have been made studies on a process
in which crystalline polyolefins of high stereoregularity
can be obtained with high polymerization activity using
S such catalysts as mentioned above.
For example, Japanese Patent Laid-Open Publications
No. 209207/1986, No. 104810/1987, No. 104811/1987, No.
104812/1987, No. 104813/1987, No. 311106/1989, No.
318011/1989 and No. 166104/1990 disclose that polyolefins
of high stereoregularity can be obtained with high
polymerization activity by polymerizing olefins in the
presence of a catalyst formed from a titanium-containing
sold catalyst component which contains titanium, magnesium,
halogen and an electron donor, an organoaluminum compound
and an electron donor.
The present applicant has also made a number of
proposals with respect to a catalyst for olefin
polymerization and an olefin polymerization process by
which crystalline polyolefin of high stereoregularity can
be obtained with high polymerization activity, as described
in, for example, Japanese Patent Laid-Open Publications No.
108385/1975, No. 126590/1975, No. 20297/1976, No.
28189/1976, No. 64586/1976, No. 92885/1976, No.
133625/1976, No. 87489/1977, No. 100596/1977, No.
147688/1977, No. 104593/1977, No. 2580/1978, No.
40093/1978, No. 40094/1978, No. 43094/1978, No.
135102/1980, No. 135103/1980, No. 152710/1980, No.
3 21 OO99~t
811/1981, No. 11908/1981, No. 18606/1981, No. 83006/1983,
No. 138705/1983, No. 138706/1983, No. 138707/1983, No.
138708/1983, No. 138709/1983, No. 138710/1983, No.
138715/1983, No. 138720/1983, No. 138721/1983, No.
215408/1983, No. 47210/1984, No. 117508/1984, No.
117509/1984, No. 207904/1984, No. 206410/1984, No.
206408/1984, No. 206407/1984, No. 69815/1986, No.
69821/1986, No. 69822/1986, No. 69823/1986, No. 22806/1988,
No. 95208/1988, No. 199702/1988, No. 199703/1988, No.
0 202603/1988, No. 202604/1988, No. 223008/1988, No.
223009/1988, No. 264609/1988, No. 87610/1989, No.
156305/1989, No. 77407/1990, No. 84404/1990, No.
229807/1990, No. 229806/1990 and No. 229805/1990.
By the way, crystalline polypropylene is rigid and
lS usually has a high heat distortion temperature, a high
melting point and a high crystallization temperature, and
hence it shows excellent properties such as high heat
resistance, high crystallization speed and high
transparency. Accordingly, crystalline polypropylene has
been applied to various uses such as containers and films.
Since rigldity and heat resistance of polypropylene are
enhanced with increase of crystallinity, polypropylene
having high crystallinity can be applied to such uses as
require higher rigidity and higher heat resistance.
Further, in the conventional uses, a product formed from
the polypropylene can be made thin or an amount of a filler
4 21 0099~
to be added can be reduced, that is, weight-saving can be
attained.
A propylene block copolymer usually comprises a
crystalline polypropylene portion and a non-crystalline
5 polymer portion, and has excellent properties such as
lightweight and good balance between rigidity, a heat
distortion temperature and impact resistance. Accordingly,
the propylene block copolymer has been applied to various
uses such as structural materials for containers and
electrical appliances and automotive interior trims. Since
rigidity and heat resistance of a propylene block copolymer
are enhanced with increase of crystallinity of the
crystalline polypropylene portion, a propylene block
copolymer containing a polypropylene portion of high
- 15 crystallinity can be applied to such uses as require higher
rigidity and higher heat resistance. Further, in the
conventional uses, a product formed from the the propylene
block copolymer can be made thin or an amount of a filler
to be added can be reduced, that is, weight-saving can be
attained.
The crystallinity of crystalline polypropylene has
been conventionally heightened by a method of adding a
nucleating agent or other method, but the conventional
crystalline polypropylene has an isotactic pentad value
(pentad isotacticity) by the NMR measurement of about 90 to
95 %, and the improvement of the rigidity and the heat
resistance is limited to a certain extent. Accordingly,
21 00999
s
there have been keenly desired the advent of a crystalline
polypropylene having a prominently high isotactic pentad
value, namely a crystalline polypropylene having a high
stereoregularity, and the advent of a propylene block
copolymer containing a crystalline polypropylene portion
having a prominently high isotactic pentad value, namely a
propylene block copolymer containing a crystalline
polypropylene portion having a high stereoregularity.
Films made of the conventional crystalline
polypropylene are not always sufficient in moisture
resistance, and hence the advent of a crystalline
polypropylene excellent in the moisture resistance as well
as in the rigidity and the heat resistance has been also
desired.
In the case of molding the above-mentioned crystalline
polypropylene, moldability of a resin is improved when a
melt viscosity of the resin is low, and hence a resin
temperature is generally elevated to lower the melt
viscosity of the resin. However, if the resin is molded at
a high temperature, the resin tends to be thermally
decomposed or deteriorated to sometimes cause various
problems such as coloring of the resulting molded product,
occurrence of cracks, lowering of long-term heat stability
and weathering resistance, and reduction of rigidity and
heat resistance.
Further, sheets or films made of the conventional
crystalline polypropylene are not always sufficient in the
6 2 1 03999
moisture resistance in some uses, and accordingly the
advent of a crystalline polypropylene excellent in the
moisture resistance as well as in the rigidity and the heat
resistance has been desired.
The present inventors have earnestly studied to solve
the above-mentioned problems, and as a result, they have
found that a propylene polymer composition comprising a
propylene polymer (or a propylene block copolymer~ which
has a much higher stereoregularity than a conventional one
and an extremely long mesochain and a specific stabilizer
shows high rigidity, high heat resistance and high moisture
resistance, and moreover is excellent in heat stability
during the molding stage, long-term heat stability of the
molded product and weathering resistance thereof as
compared with a conventional crystalline polypropylene.
Thus, the present invention has been accomplished.
OBJECT OF THE INVENTION
It is an object of the present invention to provide a
propylene polymer which is excellent in rigidity, heat
resistance and moisture resistance and a process for
preparing said propylene polymer.
It is another object of the present invention to
provide a propylene block copolymer which is well balanced
between rigidity, heat resistance and impact resistance and
a process for preparing said propylene block copolymer.
~_ 7 2 l 0 a q 9 9
It is a further object of the present invention to
provide a propylene polymer composition comprising the
above-mentioned propylene polymer or propylene block
copolymer and a stabilizer, which has excellent properties
S of the propylene polymer or the propylene block copolymer
and is capable of forming a molded product excellent in
heat stability during the molding stage, long-term heat
stability and weathering resistance.
1 0 SUMMARY OF THE INVENTION
The propylene polymer of the present invention is a
propylene polymer having such properties that:
a melt flow rate (MFR) of said polymer at 230 C under
a load of 2.16 kg is in the range of 0.1 to 500 g/10 min,
a pentad isotacticity [Ms] obtained from the following
formula (1) using absorption intensity [Pmmmm] and [Pw] in
a 13C-NMR spectrum of a boiled heptane-insoluble component
contained in said polymer is in the range of 0.970 to
0.995,
a pentad tacticity [M3 ] obtained from the following
formula (2) using absorption intensity [Pmmrm], [Pmrmr],
[Pmrrr], [Prmrr], [Prmmr], [Prrrr] and [Pw] in a 13C-NMR
spectrum of a boiled heptane-insoluble component contained
in said polymer is in the range of 0.0020 to 0.0050, and
a crystallinity of a boiled heptane-insoluble
component contained in said polymer is not less than 60 %;
8 21 00999
[Pmmmm]
[Ms]=
[Pw] ... (1)
wherein
[Pmmmm] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
5 units which are bonded to each other with meso form, and
[Pw] is absorption intensity of all methyl groups in a
propylene unit;
[Pmmrm]+[Pmrmr]+[Pmrrr]+[Prmrr]+[Prmmr]+[Prrrr]
[M3]=
[Pw] ... (2)
0 wherein
[Pmmrm] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by 1 1 in which ~ and 1 are each a
propylene unit,
[Pmrmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by ~ 1 in which ~ and 1 are each a
propylene unit,
[Pmrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by ~ ~ in which ~ and l-are each
a propylene unit,
[Prmrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
9 21 OOq99
units represented by ~ ~ in which ~ and 1 are each a
propylene unit,
[Prmmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
5 units represented by ~ ~ in which I and 1 are each a
propylene unit,
[Prrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by ~ ~ in which J and 1 are each a
0 propylene unit, and
[Pw] is absorption intensity of all methyl groups in a
propylene unit.
The propylene polymer of the invention desirably
contains 10 - 10,000 ppm of polymer comprising constituent
units derived from a compound represented by the following
formula (i) or (ii): .
H2C=CH-X ( i )
H2C=CH-CH2-X ( ii )
wherein X is a cycloalkyl group, an aryl group or
IRl 2
- M - R
R3 ~ M is carbon or silicon, R1 and R2 are each a
hydrocarbon group, and R3 is hydrogen or a hydrocarbon
group.
The propylene block copolymer of the present invention
is a propylene block copolymer having such properties that:
21 00999
a melt flow rate (MFR) of said copolymer at 230 C
under a load of 2.16 kg is in the range of 0.1 to 500 g/10
min,
a pentad isotacticity [M5] obtained from the following
S formula (lA) using absorption intensity [Pmmmm], [Pw],
[sa~]~ [sa~+] and [T~+~+] in a l3C-NMR spectrum of a boiled
heptane-insoluble component contained in said copolymer is
in the range of 0.970 to 0.995,
a pentad tacticity [M3] obtained from the following
formula (2A) using absorption intensity [Pmmrm], [Pmrmr],
[Pmrrr], [Prmrr], [Prmmr], [Prrrr], [Pw], [sa~]~ [Sa~+] and
[T~+~+] in a l3C-NMR spectrum of a boiled heptane-insoluble
component contained in said copolymer is in the range of
0.0020 to 0.0050, and
a crystallinity of a boiled heptane-insoluble
component contained in said copolymer is not less than 60
%;
[Pmmmm]
[Ms]=
[pw] -2 ( [sa~f] + [sa~+] )+3[T~+~+] ... (lA)-
wherein
[Pmmmm] and [Pw] have the same meanings as defined in
the aforementioned formula (1),
[sa~] is absorption intensity of such secondary
carbons that are present in a main chain and out of two
kinds of tertiary carbons positioned nearest to said
secondary carbons one is situated at the a position and the
other is situated at the ~ position,
1 1 21 00999
[sa~+] is absorption intensity of such secondary
carbons that are present in a main chain and out of two
kinds of tertiary carbons positioned nearest to said
secondary carbons one is situated at the a position and the
other is situated at the ~ position or farther than the
position, and
[T~+~+] is absorption intensity of such tertiary
carbons that are present in a main chain and out of two
kinds of tertiary carbons positioned nearest to said
tertiary carbons one is situated at the ~ position or
farther than the ~ position and the other is also situated
at the ~ position or farther than the ~ position;
[Pmmrm]+[Pmrmr]+[Pmrrr]+[Prmrr]+[Prmmr]+[Prrrr]
[M3]=
[Pw]-2([Sa~]+[Sa~+])+3[T~+~+] ... (2A)
wherein
[Pmmrm], [Pmrmr], [Pmrrr], [Prmrr], [Prmmr], [Prrrr]
and [Pw] have the same meanings as defined in the
aforementioned formula (2), and
[sar]~ [sa~+] and [T~+~+] have the same meanings as
20 defined in the above-mentioned formula (lA).
The propylene block copolymer of the invention
desirably contains 10 - 10,000 ppm of polymer comprising
constituent units derived from a compound represented by
the aforementioned formula (i) or (ii).
The first process for preparing a propylene polymer
according to the present invention is a process for
12 21 00999
preparing a propylene polymer having a crystallinity of not
less than 60 %, which comprises polymerizing propylene in
the presence of a catalyst for olefin polymerization
comprising:
S [I] a prepolymerized catalyst obtained by
prepolymerizing at least one reactive monomer represented
by the following formula (i) or (ii) using (a) a solid
titanium catalyst component containing magnesium, titanium,
halogen and an electron donor as essential components and
(b) an organometallic catalyst component, said reactive
monomer being prepolymerized in an amount of 0.1 to 1,000 g
per 1 g of the solid titanium catalyst component (a);
H2C=CH-X ( i )
H2 C=CH-CH2 -X ( i i )
wherein X is a cycloalkyl group, an aryl group or
- M - R2
R3 ~ M is carbon or silicon, R1 and R2 are each a
hydrocarbon group, and R3 is hydrogen or a hydrocarbon
group;
[II] the organometallic catalyst component (b); and
[III] a silicon compound represented by the following
formula (iii) or a compound having at least two ether
linkages existing via plurality of atoms:
Ran-Si- (ORb) 4-n (iii)
wherein, n is 1, 2 or 3; when n is 1, Ra is a secondary or
a tertiary hydrocarbon group; when n is 2 or 3, at least
13 21 00999
one of Ra is a secondary or a tertiary hydrocarbon group,
Ra may be the same or different, and Rb is a hydrocarbon
group of 1 to 4 carbon atoms; and when 4-n is 2 or 3, Rb
may be the same or different;
S in said process, propylene being polymerized in an
amount of 3,000 to 1,000,000 g per 1 g of the solid
titanium catalyst component (a) contained in the
prepolymerized catalyst.
The second process for preparing a propylene polymer
0 according to the present invention is a process which
comprises preparing a propylene polymer having an intrinsic
viscosity [~] of 3 to 40 dl/g in an amount of 0.1 to 55 %
by weight based on the amount of the resulting polymer
using one or more polymerizers out of two or more
polymerizers and then further preparing a propylene polymer
using the residual polymerizers, in the presence of a
catalyst for olefin polymerization comprising:
[I] a prepolymerized catalyst obtained by
prepolymerizing at least one reactive monomer represented
by the following formula (i) or (ii) using (a) a solid
titanium catalyst component containing magnesium, titanium,
halogen and an electron donor as essential components and
(b) an organometallic catalyst component, said reactive
monomer being prepolymerized in an amount of 0.1 to 1,000 g
per 1 g of the solid titanium catalyst component (a);
H2c=cH-x ( i )
H2C=CH-CH2 -X ( i i )
14 21 ooqq9
wherein X is a cycloalkyl group, an aryl group or
- M - R2
R3 r M is carbon or silicon, Rl and R2 are each a
hydrocarbon group, and R3 is hydrogen or a hydrocarbon
group;
[II] the organometallic catalyst component (b); and
[III] a silicon compound represented by the following
formula (iii) or a compound having at least two ether
linkages existing via plurality of atoms:
Ran-S i- (ORb ) 4-n ( i i i )
0 wherein, n is 1, 2 or 3; when n is 1, Ra is a secondary or
a tertiary hydrocarbon group; when n is 2 or 3, at least
one of Ra is a secondary or a tertiary hydrocarbon group,
Ra may be the same or different, and Rb is a hydrocarbon
group of 1 to 4 carbon atoms; and when 4-n is 2 or 3, Rb
may be the same or different;
the propylene polymer obtained by said process
satisfying the following requisites:
(a) a crystallinity of said polymer is not less than
60 %,
(b) a melt flow rate of said polymer at 230 C is in
the range of 0.1 to 500 g/10 min, and
(c) said polymer is a propylene polymer obtained by
polymerizing propylene in an amount of 3,000 to 100,000 g
per 1 g of the solid titanium catalyst component (a).
1 S 2 1 009q9
The process for preparing a propylene block copolymer
according to the present invention is a process which
comprises a first polymerization stage for homopolymerizing
propylene or copolymerizing propylene with ethylene and/or
5 a-olefin of 4 to 10 carbon atoms to prepare a crystalline
polymer and a second polymerization stage for
copolymerizing two or more monomers selected from ~-olefin
of 2 to 20 carbon atoms to prepare a low-crystalline or
non-crystalline copolymer, in the presence of a catalyst
for olefin polymerization comprising:
[I] a prepolymerized catalyst obtained by
prepolymerizing at least one reactive monomer represented
by the following formula (i) or (ii) using (a) a solid
titanium catalyst component containing magnesium, titanium,
lS halogen and an electron donor as essential components and
(b) an organometallic catalyst component, said reactive
monomer being prepolymerized in an amount of 0.1 to 1,000 g
per 1 g of the solid titanium catalyst component (a);
H2c=cH-x ( i )
H2C=CH-CH2-X (ii)
wherein X is a cycloalkyl group, an aryl group or
IRl 2
- M - R
R3 ~ M is carbon or silicon, R1 and R2 are each a
hydrocarbon group, and R3 is hydrogen or a hydrocarbon
group;
[II] the organometallic catalyst component (b); and
16 21 03999
[III] a silicon compound represented by the following
formula (iii) or a compound having at least two ether
linkages existing via plurality of atoms:
Ran-Si- (ORb) 4-n (iii)
wherein, n is l, 2 or 3; when n is l, Ra is a secondary or
a tertiary hydrocarbon group; when n is 2 or 3, at least
one of Ra is a secondary or a tertiary hydrocarbon group,
Ra may be the same or different, and Rb is a hydrocarbon
group of 1 to 4 carbon atoms; and when 4-n is 2 or 3, Rb
0 may be the same or different.
The first propylene polymer composition of the present
invention comprises:
[A1] a propylene polymer having such properties that
a melt flow rate (MFR) of said polymer at 230 C under
a load of 2.16 kg is in the range of 0.1 to 500 g/10 min,
a pentad isotacticity [Ms] obtained from the aforesaid
formula (1) using absorption intensity [Pmmmm] and [Pw] in
a l3C-NMR spectrum of a boiled heptane-insoluble component
contained in said polymer is in the range of 0.970 to
0.995,
a pentad tacticity [M3] obtained from the aforesaid
formula (2) using absorption intensity [Pmmrm], [Pmrmr],
[Pmrrr], [Prmrr], [Prmmr], [Prrrr] and [Pw] in a 13C-NMR
spectrum of a boiled heptane-insoluble component contained
in said polymer is in the range of 0.0020 to 0.0050, and
21 00999
17
a crystallinity of a boiled heptane-insoluble
component contained in said polymer is not less than 60 %;
and
[B] a phenol type stabilizer in an amount of 0.001 to
10 parts by weight based on 100 parts by weight of the
propylene polymer.
The second propylene polymer composition of the
present invention comprises:
[A1] the above mentioned propylene polymer,
0 [B] a phenol type stabilizer in an amount of 0.001 to
10 parts by weight based on 100 parts by weight of the
propylene polymer; and
at least one compound selected from the group
consisting of [C] an organophosphite type stabilizer, [D] a
thioether type stabilizer, [E] a hindered amine type
stabilizer and [F] a metallic salt of a higher aliphatic
acid in an amount of 0.001 to 10 parts by weight based on
100 parts by weight of the propylene polymer.
The third propylene polymer composition of the present
invention comprises:
[A1] the above-mentioned propylene polymer, and
[C] an organophosphite type stabilizer in an amount
of 0.001 to 10 parts by weight based on 100 parts by weight
of the propylene polymer.
The fourth propylene polymer composition of the
present invention comprises:
[A1] the above-mentioned propylene polymer,
18 2 1 00999
[C] an organophosphite type stabilizer in an amount
of 0.001 to 10 parts by weight based on 100 parts by weight
of the propylene polymer, and
at least one compound selected from the group
5 consisting of [D] a thioether type stabilizer, [E] a
hindered amine type stabilizer and [F] a metallic salt of a
higher aliphatic acid in an amount of 0.001 to 10 parts by
weight based on 100 parts by weight of the propylene
polymer.
0 The fifth propylene polymer composition of the present
invention comprises:
[A1] the above-mentioned propylene polymer, and
[D] a thioether type stabilizer in an amount of 0.001
to 10 parts by weight based on 100 parts by weight of the
propylene polymer.
The sixth propylene polymer composition of the present
invention comprises:
[A1] the above-mentioned propylene polymer,
[D] a thioether type stabilizer in an amount of 0.001
to 10 parts by weight based on 100 parts by weight of the
propylene polymer, and
at least one compound selected from the group
consisting of [E] a hindered amine type stabilizer and [F]
a metallic salt of a higher aliphatic acid in an amount of
0.001 to 10 parts by weight based on 100 parts by weight of
the propylene polymer.
1 9 2 1 0099y
The seventh propylene polymer composition of the
present invention comprises: -
[A1] the above-mentioned propylene polymer, and
[E] a hindered amine type stabilizer in an amount of
0.001 to 10 parts by weight based on 100 parts by weight of
the propylene polymer.
The eighth propylene polymer composition of the
present invention comprises:
[A1] the above-mentioned propylene polymer,
[E] a hindered amine type stabilizer in an amount of
0.001 to 10 parts by weight based on 100 parts by weight of
the propylene polymer, and
[F] a metallic salt of a higher aliphatic acid in an
amount of 0.001 to 10 parts by weight based on 100 parts by
weight of the propylene polymer.
The ninth propylene polymer composition of the present
invention comprises:
[A1] the above-mentioned propylene polymer, and
[F] a metallic salt of a higher aliphatic acid in an
amount of 0.001 to 10 parts by weight based on 100 parts by
weight of the propylene polymer.
The propylene polymer used in each of the first to
ninth propylene polymer compositions of the invention
preferably contains 10 - 10,000 ppm of polymer comprising
constituent units derived from a compound represented by
the aforesaid formula (i) or (ii).
20 21 00999
Such propylene polymer compositions as described above
have properties of the propylene polymer and is excellent
in heat stability during the molding stage, long-term heat
stability and weathering resistance.
The tenth propylene polymer composition of the present
invention comprises:
[A2] a propylene block copolymer having such
properties that
a melt flow rate (MFR) of said copolymer at 230 C
under a load of 2.16 kg is in the range of 0.1 to 500 g/10
min,
a pentad isotacticity [M5] obtained from the aforesaid
formula (lA) using absorption intensity [Pmmmm], [Pw],
[sa~]~ [S~+] and [T~+~+] in a l3C-NMR spectrum of a boiled
heptane-insoluble component contained in said copolymer is
in the range of 0.970 to 0.995,
a pentad tacticity [M3] obtained from the aforesaid
formula (2A) using absorption intensity [Pmmrm], [Pmrmr],
[Pmrrr], [Prmrr], [Prmmr], [Prrrr], [Pw], [S~], [S~+] and
[T~+~+] in a l3C-NMR spectrum of a boiled heptane-insoluble
component contained in said copolymer is in the range of
0.0020 to 0.0050, and
a crystallinity of a boiled heptane-insoluble
component contained in said copolymer is not less than 60
%; and
21 2100999
[B] a phenol type stabilizer in an amount of 0.001 to
10 parts by weight based on 100 parts by weight of the
propylene block copolymer.
The eleventh propylene polymer composition of the
present invention comprises:
[A2] the above-mentioned propylene block copolymer,
- [B] a phenol type stabilizer in an amount of 0.001 to
10 parts by weight based on 100 parts by weight of the
propylene block copolymer; and
0 at least one compound selected from the group
consisting of [C] an organophosphite type stabilizer, [D] a
thioether type stabilizer, [E] a hindered amine type
stabilizer and [F] a metallic salt of a higher aliphatic
acid in an amount of 0.001 to 10 parts by weight based on
100 parts by weight of the propylene block copolymer.
The twelfth propylene polymer composition of the
present invention comprises:
[A2] the above-mentioned propylene block copolymer,
and
[C] an organophosphite type stabilizer in an amount
of 0.001 to 10 parts by weight based on 100 parts by weight
of the propylene block copolymer.
The thirteenth propylene polymer composition of the
present invention comprises:
[A2] the above-mentioned propylene block copolymer,
22 2 1 00999
[C] an organophosphite type stabilizer in an amount
of 0.001 to 10 parts by weight based on 100 parts by weight
of the propylene block copolymer, and
at least one compound selected from the group
5 consisting of [D] a thioether type stabilizer, [E] a
hindered amine type stabilizer and [F] a metallic salt of a
higher aliphatic acid in an amount of 0.001 to 10 parts by
weight based on 100 parts by weight of the propylene block
copolymer.
The fourteenth propylene polymer composition of the
present invention comprises:
[A2] the above-mentioned propylene block copolymer,
and
[D] a thioether type stabilizer in an amount of 0.001
to 10 parts by weight based on 100 parts by weight of the
propylene block copolymer.
The fifteenth propylene polymer composition of the
present invention comprises:
[A2] the above-mentioned propylene block copolymer,
[D] a thioether type stabilizer in an amount of 0.001
to 10 parts by weight based on 100 parts by weight of the
propylene block copolymer, and
at least one compound selected from the group
consisting of [E] a hindered amine type stabilizer and [F]
a metallic salt of a higher aliphatic acid in an amount of
0.001 to 10 parts by weight based on 100 parts by weight of
the propylene block copolymer.
23 21 00999
The sixteenth propylene polymer composition of the
present invention comprises:
[A2] the above-mentioned propylene block copolymer,
and
[E] a hindered amine type stabilizer in an amount of
0.001 to 10 parts by weight based on 100 parts by weight of
the propylene block copolymer.
The seventeenth propylene polymer composition of the
present invention comprises:
[A2] the above-mentioned propylene block copolymer,
[E] a hindered amine type stabilizer in an amount of
0.001 to 10 parts by weight based on 100 parts by weight of
the propylene block copolymer, and
[F] a metallic salt of a higher aliphatic acid in an
amount of 0.001 to 10 parts by weight based on 100 parts by
weight of the propylene block copolymer.
The eighteenth propylene polymer composition of the
present invention comprises:
[A2] the above-mentioned propylene block-copolymer,
and
[F] a metallic salt of a higher aliphatic acid in an
amount of 0.001 to 10 parts by weight based on 100 parts by
weight of the propylene block copolymer.
The propylene block copolymer used in each of the
tenth to eighteenth propylene polymer compositions of the
invention preferably contains 10 - 10,000 ppm of polymer
24 2 1 00999
comprising constituent units derived from a compound
represented by the aforesaid formula (i) or (ii).
Such propylene polymer compositions as described above
have properties of the propylene polymer and is excellent
in heat stability during the molding stage, long-term heat
stability and weathering resistance.
BRIEF DESCRIPTION OF TRF. DRAWING
Fig. 1 illustrate steps of a process for preparing a
catalyst for olefin polymerization which is used for the
preparation of a propylene polymer or a propylene block
copolymer according to the present invention.
Fig. 2 also illustrate steps of a process for
preparing a catalyst for olefin polymerization which is
used for the preparation of a propylene polymer or a
propylene block copolymer according to the present
invention.
DETAILED DESCRIPTION OF THE INVENTION
The propylene polymer, the propylene block copolymer,
the process for preparing said polymer or said copolymer
and the propylene polymer composition according to the
present invention are described in detail hereinafter.
The term "polymerization" used in this specification
means not only homopolymerization but also
copolymerization, and the term "polymer" used in this
2s 21 00999
specification means not only homopolymer but also
copolymer.
The propylene polymer according to the invention is a
homopolymer of propylene.
The propylene polymer has a melt flow rate (MFR), as
measured at 230 C under a load of 2.16 kg, of 0.1 to 500
g/10 min, preferably 0.2 to 300 g/10 min. Measurement of
the melt flow rate (MFR) is carried out in accordance with
ASTM D1238-65T under the conditions of a temperature of 230
0 C and a load of 2.16 kg.
In the propylene polymer of the invention, a pentad
isotacticity ~M5] obtained from the following formula (1)
using absorption intensity [Pmmmm] and [Pw] in a 13C-NMR
spectrum of a boiled heptane-insoluble component contained
in said polymer is in the range of 0.970 to 0.995,
preferably 0.980 to 0.995, more preferably 0.982 to 0.995.
[Pmmmm]
[Ms]=
[Pw] ...(1)
wherein
[Pmmmm] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units which are bonded to each other with meso form, and
[Pw] is absorption intensity of all methyl groups in a
propylene unit.
The propylene block copolymer according to the
invention is a block copolymer comprises:
2,, 21 00999
a crystalline polypropylene portion wh~ch comprises
constituent units derived from ethylene and~or olefin of 4
to 10 carbon atoms in an amount of 0 to 20 % by mol and
constituent units derived from propylene, and
a low-crystalline or non-crystalline copolymer portion
which contains two or more kinds of constituent units
derived from olefin of 2 to 20 carbon atoms.
In this propylene block copolymer, ~t is desired that
the constituent un~.t9 derived from pro~ylene are contained
in an amount of 50 to 98 ~ by mol, preferably 60 to 97 ~ by
mol, and the constituent units derived from ethylene and/or
olefin of q to 10 carbon atoms are contained in an amount
of 50 to 2 ~ by mol, preferably 40 to 3 ~ by mol.
Concrete examples of the olefins of q to 20 carbon
atoms include 1-butene, l-pentene, l-hexene, 9-methyl-1-
pentene, 3-methyl-1-pentene, 1-octene, 3-methyl-1-butene,
1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-
octadecene, 1-eicosene, cyclopentene, cycloheptene,
norbornene, 5-ethyl-2-norbornene, tetracyclododecene and 2-
ethyl-1,4,5,8-dimethano-1,2,3,4,qa,5,8,8a-
octahydronaphthalene. The constituent units derived from
the above-exemplified olefins of q to 20 carbon atoms or
derived from ethylene may be contained in comb~nation of
two or more kinds.
The propylene block copolymer has a melt flow rate
(MF~), as measured at 230 C under a load of 2.16 kg, of
0.1 to 500 g/10 min, preferably 0.2 to 300 g/10 min.
72932-160
27 21 00999
Measurement of the melt flow rate (MFR) is carried out in
accordance with ASTM D1238-65T under the conditions of a
temperature of 230 C and a load of 2.16 kg.
In the propylene block copolymer of the invention, a
pentad isotacticity [Ms] obtained from the following
formula (lA) using absorption intensity [Pmmmm], [Pw],
[sa~], [sa~+] and [T~+~+] in a l3C-NMR spectrum of a boiled
heptane-insoluble component is in the range of 0.970 to
0.995, preferably 0.980 to 0.995, more preferably 0.982 to
0 0.995.
[Pmmmm]
[Ms]=
[Pw]-2([Sa~]+[Sa~+])+3[T~+~+] ... (lA)
wherein
[Pmmmm] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units which are bonded to each other with meso form,
[Pw] is absorption intensity of all methyl groups in a
propylene unit,
[sa~] is absorption intensity of such secondary
carbons that are present in a main chain and out of two
kinds of tertiary carbons positioned nearest to said
secondary carbons one is situated at the a position and the
other is situated at the ~ position,
[sa~+] is absorption intensity of such secondary
carbons that are present in a main chain and out of two
kinds of tertiary carbons positioned nearest to said
secondary carbons one is situated at the a position and the
.,. . - - :~
28 21 00999
other is situated at the ~ position or farther than the
position, and
[T~+~+] is absorption intensity of such tertiary
carbons that are present in a main chain and out of two
kinds of tertiary carbons positioned nearest to said
tertiary carbons one is situated at the ~ position or
farther than the ~ position and the other is also situated
at the ~ position or farther than the ~ position.
Next, the pentad isotacticity [Ms] used for evaluating
0 the stereoregularity of the boiled heptane-insoluble
component contained in the propylene polymer and the
propylene block copolymer of the invention is concretely
described below.
When the boiled heptane-insoluble component is a
homopolymer of propylene, this insoluble component can be
expressed by the following formula (A):
Mel Me 2 Me3 Me4 Mes Me 6
-(C-C)-(C-C)-(C-C)-(C-C)-(C-C)-(C-C)-(C-C)---- (A)
Me7
Me -(C-C)-
If a propylene unit -(C-C)- or Me is symbolized by
~ or 1, ~ ~ is expressed by "m" (meso form), and ~ 1 is
expressed by "r" (racemo form), continuous five propylene
' ~ I J I J
isotactic units are expressed by m m m m . When
absorption intensity, in a l3C-NMR spectrum, of methyl
groups (e.g., Me3, Me4) in the third unit among the
. _
-
29 21 00999
continuous five propylene units which are bonded to each
other with meso form is expressed by [Pmmmm], and
absorption intensity of the whole methyl groups (e.g., Mel,
Me2, Me3 ) in the propylene units is expressed by [Pw],
S the stereoregularity of the boiled heptane-insoluble
component represented by the above formula (A) can be
evaluated by a ratio of [Pmmmm] to [Pw], namely a value of
[M5] obtained from the following formula (1).
Accordingly, the stereoregularity of the boiled
heptane-insoluble component in the propylene polymer of the
invention can be evaluated by a value of the pentad
isotacticity [Ms] obtained from the following formula (1)
using the absorption intensity [Pmmmm] and [Pw] in a 13C-
NMR spectrum of the boiled heptane-insoluble component.
[Pmmmm]
[Ms]=
[Pw] ...(1)
Further, when the boiled heptane-insoluble component
contains constituent units derived from other olefins than
propylene, for example, ethylene units, in a small amount,
said insoluble component can be expressed by the following
formula (B-l) or (B-2). The formula (B-1) shows that one
ethylene unit is contained in a propylene unit chain, and
the formula (B-2) shows that an ethylene unit chain
composed of two or more ethylene units is contained in a
propylene unit chain.
21 Oû999
Mel Me2 Me3 Me4 Me5 Me6 Me7 Me3
(c-c)-(c-c)-(c-c)-(c-c)-(c-ca)-(cr-c2)-(c~-cb)-(c-c)-(c-c)-
S Sccy sa~
-- (B-l)
Me1 Me2 Me3 Me4 Mes
0 -(C-C)-(C-C)-(C-C)-(C-C)-(C-Cd)-(C4-C)-(C-C) n~ (C-C5)-
1`
S~+
Me6 Me7 Me3
(C6--Ce)--(C--C)--(C-C)--
S~+
(B-2 )
(n is 0 or a positive integer)
In the above cases, for measurement of the pentad
isotacticity, the absorption intensity of other methyl
groups (Me4, Me5, Me6 and Me7 in the formulas (B-1) and (B-
2)) than the methyl group in the third unit among the
continuous five isotactic propylene units should be
theoretically excluded. However, absorption of these
methyl groups are observed to be overlapped on absorption
of other methyl groups, and hence it is difficult to
quantitatively determine the absorption intensity of those
methyl groups.
On that account, when the boiled heptane-insoluble
component is represented by the formula (B-1), absorption
intensity (so~)~ in the l3C-NMR spectrum, of a secondary
carbon (Cl) which is in the ethylene unit and bonded to a
tertiary carbon (Ca) in the propylene unit and absorption
intensity (so~) of a secondary carbon (C3) which is in the
il
3 1 2 ~ 00999
propylene unit and bonded to the secondary carbon (C2) in
the ethylene unit are excluded.
In other words, the absorption intensity of other
methyl groups (Me9, Me5, Me6 and Me7) than the methyl groups
in the third unit among the continuous five isotactic
propylene units are excluded by subtracting, from Pw, two
times value of the absorption intensity (Sa~) of such a
secondary carbon (C1 or C3) that said secondary carbon is
present in a main chain and out of two tertiary carbons
0 positioned nearest to said secondary carbon one (ca or Cb)
is situated at the a position and the other (Cb or Ca) is
situated at the ~ position.
When the boiled heptane-insoluble component is
represented by the formula (B-2), absorption intensity
15 (sa~+), in the l3C-NMR spectrum, of a secondary carbon (C4)
which is in the ethylene unit chain composed of two or more
ethylene units and bonded to a tertiary carbon (Cd) in the
propylene unit and absorption intensity (sa~+) of a
secondary carbon (C6) which is in the propylene unit and
bonded to a secondary carbon (C5) in the ethylene unit
chain composed of two or more ethylene units are excluded.
In other words, the absorption intensity of other
methyl groups (Me4, Me5, Me6 and Me7) than the methyl groups
in the third unit among the continuous five isotactic
propylene units are excluded by subtracting, from Pw, two
times value of the absorption intensity [sa~+] of such a
secondary carbon (C4 or C6) that said secondary carbon is
21 00999
32
present in a main chain and out of two tertiary carbons
positioned nearest to said secondary carbon one (Cd or Ce)
is situated at the a position and the other (Ce or Cd) is
situated at the ~ position or farther than the ~ position.
Accordingly, the stereoregularity of the boiled
heptane-insoluble component represented by the above
formula (B-1) or (B-2) can be evaluated by a value obtained
from the following formula (lB).
[Pmmmm]
[Pw]-2 t [So~] + [Sa~+] ) . . . (lB)
When the boiled heptane-insoluble component contains a
small amount of ethylene units and the ethylene unit chain
contains one propylene unit, this insoluble component can
be represented by the following formula (C).
Me' Me2 Me3 Me~ Me6 \ Me~ Me7 Me~ Me9
. 1 1 '~1 ., I I I
---(C-C)-(C-C)-(C-C)-(C-C)-(C-C')-(C-C)-(C-C7)-(C-G)-(C-C~)-(C-C)-(C-C)- --
Sar Sa7
-- (C)
If the aforementioned formula (lB) is applied to the
above case, a further correction should be carried out.
The reason is that there are four methyl groups
corresponding to sa~ or Sa~+ in spite that the number of
the methyl groups to be excluded is five (Me4, Me5, Me6,
. Me7 and Me8), and hence if the formula (lB) is applied, the
number of the excluded methyl groups is larger by three
- - . ~ - - . -
21 009~9
33
than the number of other methyl groups than the methyl
group in the third unit among the continuous five propylene
units.
Accordingly, a further correction is made by using
S absorption intensity, in the l3C-NMR spectrum, of a
tertiary carbon in the propylene unit contained in the
ethylene unit chain. In other words, the correction is
made by adding, to Pw, a value of three times of absorption
intensity [T~+~+] of such a tertiary carbon (C7) that said
0 tertiary carbon is present in a main chain and out of two
tertiary carbons (cf, Cg) positioned nearest to said
tertiary carbon one (Cf ) iS situated at the ~ position or
farther than the ~ position and the other (Cg) is also
situated at the ~ position or farther than the ~ position.
lS Thus, the stereoregularity of the boiled heptane-
insoluble component represented by the above formula (C)
can be evaluated by a value of the pentad isotacticity [M5]
obtained from the following formula (lA).
Accordingly, the stereoregularity of the boiled
heptane-insoluble component in the propylene block
copolymer of the invention can be evaluated by a value of
the pentad isotacticity [Ms] obtained from the following
formula (lA).
[Pmmmm]
[Ms]=
[Pw] -2 ( [sa~] + [sa~+] ) +3[T~+~+] ... (lA)
. ,,, - -
21 00999
34
The formula (1) and the formula (lB) are not different
from the formula (lA), and they can be said to be special
cases of the formula (lA). Further, the above-mentioned
correction may become unnecessary depending on the kind of
5 constitution unit other than propylene which is contained
in the boiled heptane-insoluble components.
In the propylene polymer of the invention, the pentad
isotacticity [M5] of the boiled heptane-insoluble component
obtained from the above formula (1) is in the range of
0.970 to 0.995, and a pentad tacticity [M3] obtained from
the following formula (2) using absorption intensity
[Pmmrm], [Pmrmr], [Pmrrr], [Prmrr], [Prmmr], [Prrrr] and
[Pw] in a l3C-NMR spectrum of the boiled heptane-insoluble
component is in the range of 0.0020 to 0.0050, preferably
0.0023 to 0.0045, more preferably 0.0025 to 0.0040.
[Pmmrm]+[Pmrmr]+[Pmrrr]+[Prmrr]+[Prmmr]+[Prrrr]
[M3]=
[Pw] ... (2)
wherein
[Pmmrm] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by 1 1 in which J and 1 are each a
propylene unit,
[Pmrmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by ~ 1 in which J and 1 are each a
propylene unit,
2l oo9q9
[Pmrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by ~ ~ in which J and 1 are each
a propylene unit,
[Prmrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by ~ ~ in which J and 1 are each a
propylene unit,
[Prmmr] is absorption intensity of methyl groups
0 present in the third unit among continuous five propylene
units represented by ~ ~ in which ~ and 1 are each a
propylene unit,
[Prrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by ~ ~ in which ~ and 1 are each a
propylene unit, and
[Pw] has the same meaning as defined in the above
formula (1).
In the propylene block copolymer of the invention, the
pentad isotacticity [Ms] of the boiled heptane-insoluble
component obtained from the aforesaid formula (lA) is in
the range of 0.970 to 0.995, and a pentad tacticity [M3]
obtained from the following formula (2A) using absorption
intensity [Pmmrm], [Pmrmr], [Pmrrr], [Prmrr], [Prmmr],
[Prrrr], [Pw], [sa~], [sa~+] and [T~+~+] in a l3C-NMR
spectrum of the boiled heptane-insoluble component is in
21 00999
36
the range of 0.0020 to 0.0050, preferably 0.0023 to 0.0045,
more preferably 0.0025 to 0.0040.
[Pmmrm]+[Pmrmr]+[Pmrrr]+[Prmrr]+[Prmmr]+[Prrrr]
[M3]=
[Pw]-2([Sa~]+[Sa~+])+3[T~+~+] ...(2A)
wherein [Pmmrm], [Pmrmr], [Pmrrr], [Prmrr], [Prmmr] and
[Prrrr] have the same meanings as defined in the formula
(2), and [Pw], [sa~]~ [Sa~+] and [T~+~+] have the same
meanings as defined in the formula (lA).
In the formula (2) and the formula (2A), each of
0 [Pmmrm], [Pmrmr], [Pmrrr] ! [Prmrr], [Prmmr] and [Prrrr]
shows absorption intensity of a methyl group in the third
unit among continuous five propylene units having such a
structure that three out of five methyl groups in the
continuous five propylene units are the same in the
direction and the residual two are different in the
direction (sometimes referred to as "M3 structure"
hereinafter). That is, the value of the pentad tacticity
[M3] obtained from the above formula (2) exhibits a
proportion of the M3 structure in the propylene unit chain,
2 0 while the value of the pentad tacticity [M3] obtained from
the above formula (2A) exhibits a proportion of the M3
structure in the propylene unit chain containing a small
amount of other monomer units than the propylene units.
The propylene polymer of the invention has an
extremely long mesochain (i.e., propylene unit chain in
which directions of a-methyl carbons are the same as each
:, ,.
~' 37 21 00999
other), because the value of the pentad isotacticity [M5]
of the boiled heptane-insoluble component obtained from the
formula (1) is in the range of 0.970 to 0.995, and the
value of the pentad tacticity [M3] of the boiled heptane-
5 insoluble component obtained from the formula (2) is in therange of 0.0020 to 0.0050.
The crystalline propylene portion of the propylene
block copolymer of the invention has an extremely long
mesochain, because the value of the pentad isotacticity
1 0 [Ms] of the boiled heptane-insoluble component obtained
from the formula (lA) is in the range of 0.970 to 0.995,
and the value of the pentad tacticity [M3] of the boiled
heptane-insoluble component obtained from the formula (2A)
is in the range of 0.0020 to 0.0050.
In general, polypropylene has a longer mesochain as
the value of the pentad tacticity [M3] becomes smaller.
However, when the value of the pentad isotacticity [Ms] is
extremely large and the value of the pentad tacticity [M3]
is extremely small, polypropylene having a larger value of
the pentad tacticity [M3] sometimes has a longer mesochain
with the proviso that the pentad isotacticity [Ms] is
almost the same.
For example, when polypropylene having the following
structure (a) is compared with polypropylene having the
following structure (b), the polypropylene represented by
the structure (a) having the M3 structure has a longer
mesochain than the polypropylene represented by the
~ 21 00999
38
structure (b) not having the M3 structure. (Each of the
following structures (a) and (b) is composed of 1,003
propylene units.)
Structure (a)
m.... m r m r r r r m r m............ m
J
mesochain [M3]structure [M3]structure mesochain
Structure (b)
m.... m m.......... m m.... m m............ m
~ , . ~ , ~ .
mesochain mesochain mesochain mesochain
0 The pentad isotacticity [M5] of polypropylene
represented by the structure (a) is 0.986, and the pentad
isotacticity [M5] of polypropylene represented by the
structure (b) is 0.985, so that those values are almost the
same. However, in the polypropylene represented by the
structure (a) having the M3 structure, the number of
propylene units contained in the mesochain is 497 on an
average, while in the polypropylene represented by the
structure (b) not having the M3 structure, the number of
propylene units contained in the mesochain is 250 on an
average. That is, in the polypropylene having an extremely
large value of the pentad isotacticity [M5], a proportion
of the structure represented by "r" (racemo) contained in
the propylene unit chain becomes extremely small. Hence,
the polypropylene wherein structures represented by "r"
(racemo) are concentrated (i.e., polypropylene having the
39 21 00999
M3 structure) has a longer mesochain as compared with the
polypropylene wherein structures represented by "r"
(racemo) are scattered (i.e., polypropylene not having the
M3 structure).
The propylene polymer of the invention is a highly
crystalline polypropylene having the M3 structure
represented by the above structure (a), and in this
polymer, the pentad isotacticity [M5] of the boiled
heptane-insoluble component is in the range of 0.970 to
0 0.995, and the pentad tacticity [M3] of the boiled heptane-
insoluble component is in the range of 0.0020 to 0.0050.
Such propylene polymer of the invention has higher
rigidity, heat resistance and moisture resistance than
those of the conventional highly crystalline polypropylene,
though the reason has not been clarified. If the pentad
tacticity [M3] of the boiled heptane-insoluble component is
out of the range of 0.0020 to 0.0050, the above-mentioned
properties are sometimes deteriorated.
The propylene block copolymer of the invention
contains a highly crystalline polypropylene portion having
the M3 structure represented by the above structure (a),
and in this copolymer, the pentad isotacticity [M5] of the
boiled heptane-insoluble component is in the range of 0.970
to 0.995, and the pentad tacticity [M3] of the boiled
heptane-insoluble component is in the range of 0.0020 to
0.0050. Such propylene block copolymer of the invention
has a better balance between rigidity, heat resistance and
. . .
-- 21 00999
impact resistance than the conventional highly crystalline
polypropylene, though the reason has not been clarified.
If the pentad tacticity [M3] of the boiled heptane-
insoluble component is out of the range of 0.0020 to
0.0050, the above-mentioned properties are sometimes
deteriorated.
In the invention, the boiled heptane-insoluble
component is prepared as follows. In a 1-liter flask
equipped with a stirring device is charged 3 g of a polymer
0 sample, 20 mg of 2,6-di-tert-butyl-4-methylphenol and 500
ml of n-decane, and the flask is heated in an oil bath of
145 C to dissolve the polymer sample. After the polymer
sample is dissolved, the flask is cooled to room
temperature over about 8 hours and then kept for 8 hours in
an water bath of 23 C. The n-decane suspension containing
the precipitated polymer (23 C-decane-insoluble component)
is filtered on a glass filter of G-4 tor G-2) and dried
under a reduced pressure. Then, 1.5 g of the polymer is
subjected to Soxhlet extraction for not shorter than 6
hours using heptane. Thus, a boiled heptane-insoluble
component as a test sample is obtained.
The amount of the boiled heptane-insoluble component
in the propylene polymer of the invention is usually not
less than 80 % by weight, preferably not less than 90 % by
weight, more preferably not less than 94 % by weight, much
more preferably not less than 95 % by weight, particularly
preferably not less than 96 % by weight.
21 00999
41
The amount of the boiled heptane-insoluble component
in the propylene block copolymer of the invention largely
depends upon the amount of the 23 C-decane-soluble
component and cannot be determined unconditionally, but the
5 boiled heptane-insoluble component in the 23 C-decane-
insoluble portion is usually not less than 80 % by weight,
preferably not less than 85 % by weight, more preferably
not less than 90 % by weight, much more preferably not less
than 93 % by weight, particularly preferably not less than
94 % by weight.
The amount of the boiled heptane-insoluble component
is determined on the assumption that the 23 C-decane-
soluble component is also soluble in the boiled heptane.
In the invention, the NMR measurement of the boiled
lS heptane-insoluble component is carried out, for example, in
the following manner. That is, 0.35 g of the boiled
heptane-insoluble component is dissolved in 2.0 ml of
hexachlorobutadiene under heating. The resulting solution
is filtered over a glass filter (G2), to the filtrate is
added 0.5 ml of deuterated benzene, and the mixture is
charged in a NMR tube having an inner diameter of 10 mm.
Then, l3C-NMR measurement is conducted at 120 C using a
NMR measuring apparatus (GX-500 type produced by Japan
Electron Co., Ltd). The number of integration times is not
less than 10,000. The values of the pentad isotacticity
[Ms] and the pentad tacticity [M3] can be sought from peak
42 21 00999
intensity based on each structures obtained by the above-
mentioned measurement or the sum of the peak intensity.
The boiled heptane-insoluble component ln the
propylene polymer of the invention has a crystallinity of
S usually not less than 60 %, preferably not less than 65 ~,
more preferably not less than 70 ~.
Tile boiled heptane-insoluble component in the
propylene block copolymer of the invention has a
crystallinity of usually not less than 60 %, preferably not
tO less than 65 ~, more preferably not less than 68 %.
The crystallinity can be determined as follows. A
sample is molded into an angular plate having a thickness
of 1 mm by means of a pressure molding machine of 180 C,
and immediately the plate is water cooled to obtain a
pressed sheet. Using this pressed sheet, the crystallinity
is measured by a measuring device (Rotor Flex RU300
produced by Rigaku Denki K.K., output: 50kV, 250 mA). In
this measurement, a transmlssion method is utillzed, and
the measurement is conducted while rotating the sample.
The propylene polymer or the propylene block copolymer
of the invention desirably contains polymer comprising
constituent units derived from a compound represented by
the following formula (i) or (ii) in an amount of 10 to
10,000 ~m, preferably 100 to 5,000 p~m.
~l2C=CH-X ~i)
~2C=CI~ -C~2 -x ( i i )
wherein X is a cycloalkyl group, an aryl group or
*Trade-mark
72932-160
43 21 00999
Rl
- M - R2
R3 ~ M is carbon or silicon, Rl and R2 are each a
hydrocarbon group, and R3 is hydrogen or a hydrocarbon
group.
Examples of the cycloalkyl group indicated by X in the
above formula (i) or (ii) include a cyclopentyl group,
cyclohexyl group, a cycloheptyl group, and examples of the
aryl group indicated by X is a phenyl group, a tolyl group,
a xylyl group-and a naphthyl group.
Examples of the hydrocarbon group indicated by Rl, R2
0 or R3 in the above formula (i) or (ii) include an alkyl
group such as a methyl group, an ethyl group, a propyl
group and a butyl group; an aryl group such as a phenyl
group and a naphthyl group; and a norbornyl group.
Further, the hydrocarbon group indicated by Rl, R2 or R3 may
contain silicon and halogen.
Concrete examples of the compound represented by the
formula (i) or (ii) include 3-methyl-1-butene, 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-l-hexene, 3-ethyl-1-hexene, allylnaphthalene,
allylnorbornane, styrene, dimethylstyrenes,
vinylnaphthalenes, allyltoluenes, allylbenzene,
vinylcyclohexane, vinylcyclopentane, vinylcycloheptane and
allyltrialkylsilanes. Of these, preferred are 3-methyl-1-
butene, 3-methyl-1-pentene, 3-ethyl-1-hexene,
21 00999
-
44
vinylcyclohexane, allyltrimethylsilane and dimethylstyrene.
More preferred are 3-methyl-1-butene, vinylcyclohexane and
allyltrimethylsilane. Particularly preferred is 3-methyl-
1-butene.
S Further, the propylene polymer of the invention may
contain constituent units derived from olefins having 20 or
less carbon atoms other than propylene in a small amount or
may contain constituent units derived from diene compounds
having 4 to 20 carbon atoms in a small amount.
The propylene block copolymer of the invention may
contain constituent units derived from diene compounds
having 4 to 20 carbon atoms such as 1,3-butadiene, 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-nonadienej 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, isoprene,
butadiene, ethylidenenorbornene, vinylnorbornene and
dicylopentadiene, in an amount of not more than 5 % by mol.
The propylene polymer of the invention desirably has a
density of 0.900 to 0.936 g/cm3, preferably 0.910 to 0.936
g/cm3. The propylene block copolymer of the invention
desirably has a density of 0.900 to 0.936 g/cm3, preferably
0.910 to 0.936 g/cm3.
21 00999
`_
In the propylene polymer of the invention, it is
desired that the amount of the 23 C-decane-soluble
component is not more than 3.0 %, preferably not more than
2.5 %, more preferably not more than 2.0 %, particularly
preferably not more than 1.5 %. In the propylene block
copolymer of the invention, it is desired that the amount
of the 23 C-decane-soluble component is not more than 50
%, preferably not more than 30 %, more preferably not more
than 20 %, particularly preferably not more than 15 %.
0 The amount of the 23 C-decane-soluble component in
the propylene polymer or the propylene block copolymer of
the invention is measured as follows. In a 1-liter flask
equipped with a stirring device is charged 3 g of a polymer
sample, 20 mg of 2,6-di-tert-butyl-4-methylphenol and 500
ml of n-decane, and the flask is heated in an oil bath of
145 C to dissolve the polymer sample. After the polymer
sample is dissolved, the flask is cooled to room
temperature over about 8 hours and then kept for 8 hours in
an water bath of 23 C. The n-decane suspension containing
the precipitated polymer and the dissolved polymer is
separated by filteration on a glass filter of G-4 (or G-2).
The resulting solution is dried at 150 C and 10 mmHg until
its weight becomes unvaried, and the weight is measured.
The weight thus measured is the amount of the polymer
component soluble in the above-mentioned mixture solvent,
and the amount is calculated as percentage to the weight of
the sample polymer.
~ 21 00999
46
The boiled heptane-insoluble component in the
propylene polymer of the invention desirably has a semi-
crystallization period at 135 C of not longer than 500
seconds, preferably not longer than 100 seconds, more
preferably not longer than 80 seconds, particularly
preferably not longer than 70 seconds. The 23 C-decane-
insoluble component in the propylene block copolymer of the
invention desirably has a semi-crystallization period at
135 C of not longer than 500 seconds, preferably not
0 longer than 100 seconds, more preferably not longer than 80
seconds, particularly preferably not longer than 70
seconds.
The semi-crystallization period at 135 C of the
boiled heptane-insoluble componènt in the propylene polymer
or the propylene block copolymer is measured as follows.
That is, a relation between the exotherm caused by the
crystallization at 135 C of the boiled heptane-insoluble
component of the polymer and the period required for the
crystallization is measured by the use of a differential
calorimeter (produced by Perkin Elmer Co.), and the period
of time necessary for the exotherm to reach 50 % of the
whole exotherm is determined as the semi-crystallization
period.
In the propylene polymer of the invention, it is
desired that a difference between the melting point of the
boiled heptane-insoluble component and the crystallization
temperature thereof is not more than 45 C, preferably not
21 00999
47
more than 43 C, particularly preferably not more than 40
C. In the propylene block copolymer of the invention, it
is desired that a difference between the melting point of
the boiled heptane-insoluble component and the
S crystallization temperature thereof is not more than 45 C,
preferably not more than 43 C, particularly preferably not
more than 40 C.
The propylene polymer of the invention desirably has
an intrinsic viscosity [~], as measured in decalin at 135
0 C, of usually 30 to 0.001 dl/g, preferably 10 to 0.01
dl/g, particularly preferably 5 to 0.05 dl/g. The
propylene block copolymer of the invention desirably has an
intrinsic viscosity [~], as measured in decalin at 135 C,
of usually 30 to 0.001 dl/g, preferably 10 to 0.01 dl/g,
lS particularly preferably 8 to O.OS dl/g.
The propylene polymer of the invention mentioned as
above can be prepared, for example, by a process comprising
polymerizing propylene in the presence of a catalyst for
olefin polymerization (i.e., olefin polymerization
catalyst) formed from:
[Ia] a solid titanium catalyst component (a)
containing magnesium, titanium, halogen and an electron
donor as essential components;
[II] an organometallic catalyst component (b); and
[III] a silicon compound represented by the following
formula (iii) or a compound having at least two ether
linkages existing via plurality of atoms:
21 ooq9~
48
Ran-Si-(ORb)4-n (iii)
wherein, n is 1, 2 or 3; when n is 1, Ra is a secondary or
a tertiary hydrocarbon group; when n is 2 or 3, at least
one of Ra is a secondary or a tertiary hydrocarbon group,
Ra may be the same or different, and Rb is a hydrocarbon
group of 1 to 4 carbon atoms; and when 4-n is 2 or 3, Rb
may be the same or different.
The olefin polymerization catalyst used in the above
process is preferably formed from:
0 [Ib] a prepolymerized catalyst obtained by
prepolymerizing at least one olefin selected from olefins
represented by the following formula (i) or (ii) in the
presence of (a) a solid titanium catalyst component
containing magnesium, titanium, halogen and an electron
donor as essential components and (b) an organometallic
catalyst component;
H2C=CH-X ( i )
H2C=CH-CH2 -X ( i i )
wherein X is a cycloalkyl group, an aryl group or
- M - R2
R3 ~ M is carbon or silicon, R1 and R2 are each a
hydrocarbon group, and R3 is hydrogen or a hydrocarbon
group;
[II] the organometallic catalyst component (b); and
21 00999
49
[III] the silicon compound represented by the above-
mentioned formula (iii) or the compound having at least two
ether linkages existing via plurality of atoms.
The propylene block copolymer of the invention can be
prepared, for example, by a process comprising a first
polymerization stage for homopolymerizing propylene or
copolymerizing propylene with ethylene and/or olefin of 4
to 10 carbon atoms to prepare a crystalline polymer
(crystalline polypropylene portion) and a second
0 polymerization stage for copolymerizing ethylene with two
or more monomers selected from olefins of 3 to 20 carbon
atoms to prepare a low-crystalline copolymer (low-
crystalline copolymer portion) or a non-crystalline
copolymer (non-crystalline copolymer portion), in the
presence of a catalyst for olefin polymerization (i.e.,
olefin polymerization catalyst) formed from:
[Ia] the solid titanium catalyst component (a)
containing magnesium, titanium, halogen and an electron
donor as essential componentsi
[II] the organometallic catalyst component (b); and
[III] the silicon compound represented by the above-
mentioned formula (iii) or the compound having at least two
ether linkages existing via plurality of atoms.
The olefin polymerization catalyst used in the above
process is preferably formed from:
[Ib] the prepolymerized catalyst obtained by
prepolymerizing at least one olefin selected from olefins
: . . ~
2 1 00999
represented by the above-mentioned formula (i) or (ii) in
the presence of ~a) the solid titanium catalyst component
containing magnesium, titanium, halogen and an electron
donor as essential components and (b) the organometallic
catalyst component;
[II] the organometallic catalyst component (b); and
[III] the silicon compound catalyst component
represented by the above-mentioned formula (iii) or the
compound having at least two ether linkages existing via
plurality of atoms.
Each of Fig. 1 and Fig. 2 illustrates steps of a
process for preparing the olefin polymerization catalyst
which is used for preparing the propylene polymer or the
propylene block copolymer of the present invention.
Each components for forming the olefin polymerization
catalyst used for preparing the propylene polymer or the
propylene block copolymer of the invention are described in
detail hereinafter.
The solid titanium catalyst component (a) can be
prepared by bringing a magnesium compound, a titanium
compound and an electron donor described below into contact
with each other.
The titanium compound used for preparing the solid
titanium catalyst component (a) is, for example, a
tetravalent titanium compound represented by the following
formula:
Ti(OR)9x4-s
21 00999
51
wherein R is a hydrocarbon group, X is a halogen atom, and
g is a number satisfying the condition of O < g < 4.
Concrete examples of the titanium compounds include:
titanium tetrahalide such as TiCl4, TiBr4 and TiI4;
alkoxytitanium trihalide such as Ti~OCH3)Cl3,
Ti(OC2Hs)Cl3, Ti(On-C4Hg)Cl3, Ti(OC2H5)Br3 and Ti(O-iso-
C4Hg)Br3;
dialkoxytitanium dihalide such as Ti(OCH3)2Cl2,
Ti(OC2Hs)2Cl2, Ti(On-C4Hg)2Cl2 and Ti(OC2H5)2Br2;
trialkoxytitanium monohalide such as Ti(OCH3)3Cl,
ti(OC2H5)3Cl, Ti(On-C4Hg)3Cl and Ti(OC2H5)3Br; and
tetraalkoxytitanium such as Ti(OCH3)4, Ti(OC2H5)4,
Ti(On-C4Hg)4, Ti(O-iso-C4Hg) 4 and Ti(0-2-ethylhexyl).
Of the above-exemplified compounds, preferred are
halogen-containing compounds, more 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 magnesium compound used for preparing the solid
titanium catalyst component (a) includes a magnesium
compound having reduction properties and a magnesium
compound having no reduction properties.
The magnesium compound having reduction properties is,
for example, a magnesium compound having a magnesium-to-
carbon bond or a magnesium-to-hydrogen bond. Concrete
examples of the magnesium compound having reduction
21 00999
52
properties include dimethylmagnesium, diethylmagnesium,
dipropylmagnesium, dibutylmagnesium, diamylmagnesium,
dihexylmagnesium, didecylmagnesium, ethylmagnesium
chloride, propylmagnesium chloride, butylmagnesium
chloride, hexylmagnesium chloride, amylmagnesium chloride,
butylethoxylmagnesium, ethylbutylmagnesium and
butylmagnsium hydride. These magnesium compounds may be
used singly or may be used in combination with
organometallic compounds described later to form complex
compounds. Further, these magnesium compounds may be
liquid or solid, and may be derived by causing metallic
magnesium to react with a compound corresponding to the
metallic magnesium. Furthermore, they may be derived from
metallic magnesium by the above method during the
preparation of the catalyst.
Concrete examples of the magnesium compound having no
reduction properties include magnesium halide such as
magnesium chloride, magnesium bromide, magnesium iodide and
magnesium fluoride; alkoxymagnesium halide such as
methoxylmagnesium chloride, ethoxymagnesium chloride,
isopropoxymagnesium chloride, butoxymagnesium chloride and
octoxymagnesium chloridei allyloxymagnesium halide such as
phenoxymagnesium chloride and methylphenoxymagnesium
chloride; alkoxymagnesium such as ethoxymagnesium,
isopropoxymagnesium butoxymagnesium, n-octoxymagnesium and
2-ethylhexoxymagnesium; allyloxymagnesium such as
phenoxymagnesium and dimethylphenoxymagnesium; and manesium
-- 21 oo999
carboxylate such as magnesium laurate and magnesium
stearate.
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.
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 halogen,
a polysiloxane compound, a halogen-containing silane
compound, a halogen-containing aluminum compound, a
compound having an active carbon-to-oxygen bond such as
alcohol, ester, ketone and aldehyde.
As the magnesium compound, there can be used complex
compounds or composite compounds of the above-mentioned
magnesium compounds having or not having reduction
properties with other metals, or mixtures of the above-
mentioned magnesium compounds having or not having
reduction properties with other metallic compounds.
Further, these compounds may be used in combination of two
or more kinds.
Other various magnesium compounds than the above-
mentioned ones can be used for preparing the solid titanium
catalyst component (a), but it is preferred that the
magnesium compound takes a form of a halogen-containing
magnesium compound in the solid titanium catalyst component
2 1 OO9q9
54
(a) finally obtained. Accordingly, if a magnesium compound
containing no halogen is used, the compound is preferably
brought into contact with a halogen-containing compound in
the course of the catalyst preparation.
Of the above-mentioned magnesium compounds, preferred
are magnesium compounds having no reduction properties.
More preferred are halogen-containing magnesium compounds.
Particularly preferred are magnesium chloride,
alkoxymagnesium chloride and allyloxymagnesium chloride.
The solid titanium catalyst component (a) used in the
invention is formed by bringing such a magnesium compound
as mentioned above into contact with the aforesaid titanium
compound and an electron donor.
Concrete examples of the electron donor employable for
preparing the solid titanium catalyst component (a)
include:
amines such as methylamine, ethylamine, dimethylamine,
diethylamine, ethylenediamine, tetramethylenediamine,
hexamethylenediamine, tributylamine and tribenzylamine;
pyrroles such as pyrrole, methylpyrrole and
dimethylpyrrole;
pyrroline;
pyrrolidine;
indole;
pyridines such as pyridine, methylpyridine,
ethylpyridine, propylpyridine, dimethylpyridine,
2 1 ~0999
ethylmethylpyridine, trimethylpyridine, phenylpyridine,
benzylpyridine and pyridine chloride;
nitrogen-containing cyclic compounds such as
piperidines, quinolines and isoquinolines;
oxygen-containing cyclic compounds such as
tetrahydrofuran, l,4-cineol, 1,8-cineol, pinolfuran,
methylfuran, dimethylfuran, diphenylfuran, benzofuran,
coumaran, phthalan, tetrahydropyran, pyran and
dihydropyran;
alcohols of 1 to 18 carbon atoms such as methanol,
ethanol, propanol, pentanol, hexanol, octanol, 2-
ethylhexanol, dodecanol, octadecyl alcohol, oleyl alcohol,
benzyl alcohol, phenylethyl alcohol, cumyl alcohol,
isopropyl alcohol and isopropylbenzyl alcohol;
phenols of 6 to 20 carbon atoms which may have lower
alkyl group such as phenol, cresol, xylenol, ethylphenol,
propylphenol, nonylphenol, cumylphenol and naphthol;
ketones of 3 to 15 carbon atoms such as acetone,
methyl ethyl ketone, methyl isobutyl ketone, acetophenone,
0 benzophenone, acetylacetone and benzoquinonei
aldehydes of 2 to 15 carbon atoms such as
acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde,
tolualdehyde and naphthaldehyde;
organic esters of 2 to 30 carbon atoms such as methyl
formate, methyl acetate, ethyl acetate, vinyl acetate,
propyl acetate, octyl acetate, cyclohexyl acetate, ethyl
propionate, methyl butyrate, ethyl valerate, methyl
21 00999
56
chloroacetate, ethyl dichloroacetate, methyl methacrylate,
ethyl crotonate, ethyl cyclohexanecarboxylate, methyl
benzoate, ethyl benzoate, propyl benzoate, butyl benzoate,
octyl benzoate, cyclohexyl benzoate, phenyl benzoate,
benzyl benzoate, methyl toluate, ethyl toluate, amyl
toluate, ethyl ethylbenzoate, methyl anisate, n-butyl
maleate, diisobutyl methylmalonate, di-n-hexyl
cyclohexenecarboxylate, diethyl nadiate, diisopropyl
tetrahydrophthalate, diethyl phthalate, diisobutyl
phthalate, di-n-butyl phthalate, di-2-ethylhexyl phthalate,
~-butyrolactone, ~-valerolactone, coumarin, phthalide and
ethyl carbonate;
acid halides of 2 to 15 carbon atoms such as
acetylchloride, benzoylchloride, toluic acid chloride and
5 anisic acid chloride;
ethers of 2 to 20 carbon atoms such as methyl ether,
ethyl ether, isopropyl ether, butyl ether, amyl ether,
anisole and diphenyl ether epoxy-p-menthane;
diethers such as 2-isopentyl-2-isopropyl-1,3-
dimethoxypropane, 2,2-isobutyl-1,3-dimethoxypropane, 2,2-
isoproyl-1,3-dimethoxypropane, 2-cyclohexylmethyl-2-
isopropyl-1,3-dimethoxypropane, 2,2-isopentyl-1,3-
dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-
dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-
dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-
dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane,
1,2-bis-methoxymethyl-bicyclo-[2,2,1]-heptane,
57 21 00999
diphenyldimethoxysilane, isopropyl-t-butyldimethoxysilane,
2,2-diisobutyl-1,3-dimethoxyhexane and 2-isopentyl-2-
isopropyl-1,3-dimethoxycylohexane;
acid amides such as acetic acid amide, benzoic acid
S amide and toluic acid amide;
nitriles such as acetonitrile, benzonitrile and
tolunitrile; and
acid anhydrides such as acetic anhydride, phthalic
anhydride and benzoic anhydride.
Also employable as the electron donor is a silicon
compound represented by the formula (iii) described later.
When the titanium compound, the magnesium compound and
the electron donor are brought into contact with each
other, a carrier compound may be used to prepare a solid
titanium catalyst component (a) supported on a carrier.
Examples of the carrier compounds include Al203, SiO2,
B203, MgO, CaO, TiO2, ZnO, ZnO2, SnO2, BaO, ThO and resins
such as a styrene/divinylbenzene copolymer. Of these
carrier compounds, preferred are Sio2, Al203, MgO, ZnO and
ZnO2.
The above-mentioned components may be brought into
contact with each other in the presence of a reaction agent
such as silicon, phosphorus and aluminum.
The solid titanium catalyst component (a) is prepared
by bringing the aforementioned titanium compound, magnesium
compound and the electron donor into contact with each
other by known methods.
58 21 00999
Examples of the processes for preparing the solid
titanium catalyst component (a) are briefly described
below.
(1) A process comprising bringing a solution
S consisting of a magnesium compound, an electron donor and a
hydrocarbon solvent into contact with an organometallic
compound, after or simultaneously with 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 into contact
with an organometallic compound, and then bringing 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
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 and/or an organometallic compound.
(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 (and further a hydrogen solvent in some cases), and
then bringing the obtained carrier into contact with a
titanium compound.
- 2100999
ss
(S) A process comprising bringing a solution
containing a magnesium compound, a titanium compound and an
electron donor (and further a hydrogen solvent in 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
titanium compound. In this case, an electron donor is used
at least one time.
(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. In this case, an
electron donor is used at least one time
(8) A process comprising bringing an alkoxy group-
containing magnesium compound into contact with a halogen-
containing titanium compound. In this case, an electron
donor is used at least one time
(9) A process comprising bringing a complex composed
of an alkoxy group-containing magnesium compound and an
electron donor 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 into contact with an organometallic
compound, and then bringing the product thus obtained into
contact with a titanium compound.
21 00999
(11) A process comprising bringing a magnesium
compound, an electron donor 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 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
an electron donor, 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.
(14) A process comprising further bringing the
reaction product obtained in the above process (11) or (12)
into contact with an electron donor and a titanium
compound.
(15) A process comprising pulverizing a magnesium
compound and a titanium compound (and if necessary an
electron donor) 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
61 2100999
compound and an electron donor, 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
5 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
compound into contact with a titanium compound. In this
case, an electron donor or a reaction assistant may be used
in the pulverization stage and/or the contacting reaction
stage.
117) A process comprising treating the compound
obtained in any of the above processes tll) to (16) with
halogen, a halogen compound or aromatic hydrocarbon.
(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
necessary an electron donor.
(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.
21 oo99ol
62
(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. 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
magnesium/metal (aluminum) complex compound, and then
bringing the resulting compound into contact with an
electron donor and a titanium compound.
The amount of each component used in the preparation
of the solid titanium catalyst component (a) differs from
each preparation method, and can not be defined in general.
However, for example, the electron donor is used in an
amount 0.01 to 10 mol, preferably 0.1 to 5 mol, and the
titanium compound is used in an amount of 0.01 to 1000 mol,
preferably 0.1 to 200 mol, both based on 1 mol of the
magnesium compound.
The solid titanium catalyst component (a) thus
obtained contains titanium, magnesium, halogen and an
electron donor as its essential ingredients.
In the solid titanium catalyst component (a), a ratio
of halogen/titanium (atomic ratio) is about 2 to 200,
preferably about 4 to 100, the a ratio of electron
donor/titanium (molar ratio) is about 0.01 to 100,
63 21 00999
preferably about 0.02 to 10 and, a ratio of
magnesium/titanium (atomic ratio) is 1 to 100, preferably 2
to 50.
The solid titanium catalyst component (a) (catalyst
component [Ia]) is desirably used as a prepolymerized
catalyst component [Ib] obtained by prepolymerization of
olefin in the presence of said solid titanium catalyst
component (a) and the following organometallic catalyst
component (b).
The organometallic catalyst component (b) used in the
preparation of the prepolymerized catalyst component [Ib]
includes a organometallic compound of the metals belonging
to the Group I to III of the periodic table,in concrete,
such compounds as mentioned below;
organoaluminum compounds represented by the foIlowing
formula (b-1)
R1mAl(OR2)nHpXq (b-1)
wherein R1 and R2 may be the same or different and
represent independently a hydrocarbon group having normally
1 to 15 carbon atoms, preferably 1 to 4 carbon atoms; X is
halogen; and m, n, p and q are numbers satisfying 0 < m _
3, 0 < n < 3, 0 < p < 3, 0 _ q < 3 and m + n + p + q = 3;
complex alkyl compounds of aluminum with Group I
metals of the periodic table, represented by the following
formula (b-2)
M1AlR14 (b-2)
64 2 1 00999
wherein Ml is Li, Na or K and Rl is as defined above; and
dialkyl compounds of Group II or III metals
represented by the following formula
RlR2M2 (b-3)
wherein R1 and R2 are as defined above, and M2 is Mg, Zn or
Cd.
Examples of the organoaluminum compounds having the
formula (b-l) include:
compounds having the general formula of RlmAl (oR2) 3-m
wherein Rl and R2 are as defined above, and m is a number
preferably satisfying 1.5 < m < 3;
compounds having the general formula of RlmAlX3_m
wherein Rl and X are as defined above, and m is a number
preferably satisfying 0 < m < 3;
compounds having the general formula of RlmAlH3_m
wherein Rl is as defined above, and m is a number
preferably satisfying 2 < m < 3; and
compounds having the general formula of RlmAl (oR2) n Xq
wherein R1, R2 and X are as defined above, and m, n and q
are numbers satisfying 0 < m < 3, 0 < n < 3, 0 < q < 3 and
m + n + q = 3.
Concrete examples of the organoaluminum compounds
having the formula (b-1) include
trialkylaluminum compounds such as triethylaluminum
and tributylaluminum;
2 1 00999
trialkenylaluminum compounds such as
triisoprenylaluminum;
dialkylaluminum alkoxides such as diethylaluminum
ethoxide and dibutylaluminum butoxide;
S alkylaluminum sesquialkoxides such as ethylaluminum
sesquiethoxide and butylaluminum sesquibutoxide;
partially alkoxylated alkylaluminum compounds such as
those having an average composition represented by, for
example, the formula of R12.sAl(OR2)o 5;
dialkylaluminum halides such as diethylaluminum
chloride, dibutylaluminum chloride and diethylaluminum
bromide;
alkylaluminum sesquihalides such as ethylaluminum
sesquichloride, butylaluminum sesquichloride and
5 ethylaluminum sesquibromide;
partially halogenated alkylaluminum compounds such as
alkylaluminum dihalides such as ethylaluminum dichloride,
propylaluminum dichloride and butylaluminum dibromide;
dialkylaluminum hydrides such as diethylaluminum
0 hydride and dibutylaluminum hydride;
partially hydrogenated alkylaluminum compounds such as
alkylaluminum dihydride, for example, ethylaluminum
dihydride and propylaluminum dihydride; and
partially alkoxylated and halogenated alkylaluminum
compounds such as ethylaluminum ethoxychloride,
butylaluminum butoxychloride and ethylaluminum
ethoxybromide.
66 21 00999
Furthermore, the organoaluminum compounds similar to
the above-mentioned compounds represented by formula (b-1)
include organoaluminum compounds in which two or more
aluminum atoms are bonded together via, for example, an
5 oxygen atom or a nitrogen atom. Concrete examples of such
compounds are as follows:
(C2Hs)2AlOAl~C2H5)2~
(C4Hg)2AlOAl(C4H9)2,
and
(C2Hs)2AlNAl(C2Hs)2, and methylaluminoxane.
C2H5
Examples of the organoaluminum compounds having the
- formula (b-2) include
LiAl(c2Hs)4
and
LiAl(C7H15)4
Among the above-exemplified compounds, preferred are
organoaluminum compounds.
The olefin used in the preparation of the
prepolymerization catalyst component [Ib] includes the
compound represented by the above-mentioned formula (i) or
(ii), concretely, olefins having a branched structure such
as 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-
25 pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-
dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-
21 00999
67
hexene, 3-ethyl-1-hexene, allylnaphthalene,
allylnorbornene, stylene, dimethylstylenes,
vinylnaphthalene, allyltoluenes, allylbenzene,
vinylcyclohexane, vinylcyclopentane, vinylcycloheptane and
allyltrialkylsilanes. Of these, preferred are 3-methyl-1-
butene, 3-methyl-1-pentene, 3-ethyl-1-hexene,
vinylcyclohexane, allyltrimethylsilane and dimethylstylene,
more preferred are 3-methyl-1-butene, vinylcyclohexane and
allyltrimethylsilane, and particularly preferred is 3-
methyl-1-butene.
Furthermore, linear chain olefins such as ethylene,
propylene, 1-butene, 1-octene, 1-hexadecene and 1-eicocene
may be used in combination with the above-mentioned
branched olefins.
The prepolymerization can be carried out in the
presence of considerably higher-concentration of catalyst
compared to the catalyst concentration in the system of
propylene polymerization.
In the pre-polymerization, the solid titanium catalyst
component (a) is desirably used in aconcentration of
normally about 0.01 to 200 mmol, preferably about 0.05 to
100 mmol, in terms of titanium atom, based on 1 liter of
the later-described inert hydrocarbon solvent.
The organometallic catalyst component (b) is used in
an amount so as to produce a polymer of 0.1 to 1000 g,
2 1 00999
68
preferably 0.3 to 500 g per 1 gram of the solid titanium
catalyst component (a), and is used in a concentration of
normally about 0.1 to 100 mmol, preferably about 0.5 to 50
mmol based on 1 mol of titanium atom in the solid titanium
catalyst component (a).
In the prepolymerization, an electron donor may be
optionally used with the solid titanium catalyst component
(a) and organometallic catalyst component (b). The
electron donor employable in the prepolymerization include,
concretely, the aforementioned electron donor used in the
preparation of the solid titanium catalyst component (a),
the later-described silicon compound represented by the
formula (iii), a compound having at least two ether
linkages exsisting via plurality of atoms, and an
organosilicon compound represented by the following formula
( c--i ) ;
RnSi (OR ) s-n (c-i)
wherein each of R and R ' is a hydrocarbon group, and n is a
number satisfying the condition of O < n < 4.
T~e later-described silicon compounds represented by
the formula (iii) are not included in the organosilicon
compounds represented by this formula (c-i).
Concrete examples of the organosilicon compounds
represented by the above formula (c-i) include:
trimethylmethoxysilane, trimethylethoxysilane,
dimethyldimethoxysilane, dimethyldiethoxysilane,
diisopropyldimethoxysilane, diphenyldimethoxysilane,
21 00999
69
phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-
tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-
tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bis-
ethylphenyldimethoxysilane, ethyltrimethoxysilane,
ethyltriethoxysilane, vinyltrimethoxysilane,
methyltrimethoxysilane, n-propyltriethoxysilane,
decyltrimethoxysilane, decyltriethoxysilane,
phenyltrimethoxysilane, ~-chloropropyltrimethoxysilane,
methyltriethoxysilane, ethyltriethoxysilane,
vinyltriethoxysilane, n-butyltriethoxysilane,
phenyltriethoxysilane, ~-aminopropyltriethoxysilane,
chlorotriethoxysilane, ethyltriisopropoxysilane,
vinyltributoxysilane, ethyl silicate, butyl silicate,
trimethylphenoxysilane, methyltriallyoxysilane,
vinyltris(~-methoxyethoxysilane), vinyltriacetoxysilane and
dimethyltetraethoxysiloxane.
The above-mentioned electron donors (c) may be used in
combination of two or more kinds.
In the case of using an electron donor in the
prepolymerization, the amount of the electron donor is in
the range of 0.1 to 50 mol, preferably 0.5 to 30 mol, more
preferably 1 to 10 mol, per 1 mol to titanium atom
contained in the solid titanium catalyst component (a).
The prepolymerization is preferably carried out under
a mild condition by adding the olefin represented by the
above formula (i) or (ii) and the above mentioned catalyst
components into an inert hydrocarbon solvent.
21 00999
Concrete examples of the above-mentioned inert
solvents include:
aliphatic hydrocarbons such as propane, butane,
pentane, hexane, heptane, octane, decane, dodecane and
5 kerosine;
alicyclic hydrocarbons such as cyclopentane,
cyclohexane and methylcyclopentane;
aromatic hydrocarbons such as benzene, toluene and
xylene;
halogenated hydrocarbons such as ethylene chloride and
chlorobenzene; and
mixtures of these hydrocarbons.
Of these inert hydrocarbon media, preferably used are
aliphatic hydrocarbons.
The reaction temperature in the prepolymerization is a
temperature at which the resulting prepolymer is not
substantially dissolved in the inert hydrocarbon solvent,
and is desired to be in the range of usually about -20 to
+100 C, preferably about -20 to +80 C, more preferably -
10 to +40 C. A molecular weight regulator such as
hydrogen can be used in the prepolymerization.
The prepolymerization is desirably carried out so as
to obtain about 0.1 to 1000 g, preferably about 0.3 to 500
g of polymer, per 1 g of the above mentioned solid titanium
catalyst component (a). When the amount of the polymer
produced in the prepolymerization is too much, the
productive efficiency of the (co)polymer produced in the
~ 1 009q9
71
main polymerization is lowered, and the films formed from
the resulting (co)polymer have a tendency to Greate a fish-
eye.
The prepolymerization can be carried out by any
process of a batch process and a continuous process.
The olefin polymerization catalyst used for the
preparation of the propylene polymer or propylene block
copolymer according to the present invention is formed from
the above mentioned solid titanium catalyst component [Ia]
or the prepolymerized catalyst component [Ib], an
organometallic catalyst component [II], and [III] a silicon
compound or a compound having at least two ether linkages
exsisting via plurality of atoms.
As the organometallic catalyst component [II], the
aforementioned organometallic catalyst component (b) used
in the preparation of the prepolymerized catalyst component
[Ib] can be employed.
The silicon compound [III] is the compound represented
by the following formula (iii);
2 0 Ran-Si- (ORb) 4-n (iii)
wherein, n is 1, 2 or 3; when n is 1, Ra is a secondary or
a tertiary hydrocarbon group; when n is 2 or 3, at least
one of Ra is a secondary or a tertiary hydrocarbon group,
Ra may be the same or different, and Rb is a hydrocarbon
group of 1 to 4 carbon atoms; and when 4-n is 2 or 3, Rb
may be the same or different.
- 2 1 00999
72
In the silicon compound represented by the formula
(iii), the secondary or the tertiary hydrocarbon group
includes cyclopentyl, cyclopentenyl and cyclopentadienyl,
and substituted thereof, and the hydrocarbon group in which
S the carbon adjacent to Si is a secondary or tertiary.
More concretely, the substituted cyclopentyl group
includes cyclopentyl group having alkyl group such as 2-
methylcyclopentyl, 3-methylcyclopentyl, 2-ethylcyclopentyl,
2-n-butylcyclopentyl, 2,3-dimethylcyclopentyl, 2,4-
dimethylcyclopentyl, 2,5-dimethylcyclopentyl, 2,3-
diethylcyclopentyl, 2,3,4-trimethylcyclopentyl, 2,3,5-
trimethylcyclopentyl, 2,3,4-triethylcyclopentyl,
tetramethylcyclopentyl and tetraethylcyclopentyl;
the substituted cyclopentenyl group includes
lS cyclopentenyl group having alkyl group such as 2-
methylcyclopentenyl, 3-methylcyclopentenyl, 2-
ethylcyclopentenyl, 2-n-butylcyclopentenyl, 2,3-
dimethylcyclopentenyl, 2,4-dimethylcyclopentenyl, 2,5-
dimethylcyclopentenyl, 2,3,4-trimethylcyclopentenyl, 2,3,5-
trimethylcyclopentenyl, 2,3,4-triethylcyclopentenyl,
tetramethylcyclopentenyl and tetraethylcyclopentenyl;
the substituted cyclopentadienyl group includes
cyclopentadienyl group having alkyl group such as 2-
methylcyclopentadienyl, 3-methylcyclopentadienyl, 2-
ethylcyclopentadienyl, 2-n-butylcyclopentadienyl, 2,3-
dimethylcyclopentadienyl, 2,4-dimethylcyclopentadienyl,
2,5-dimethylcyclopentadienyl, 2,3-diethylcyclopentadienyl,
21 0099q
73
2,3,4-trimethylcyclopentadienyl, 2,3,5-
trimethylcyclopentadienyl, 2,3,4-triethylcyclopentadienyl,
2,3,4,5-tetramethylcyclopentadienyl, 2,3,4,5-
tetraethylcyclopentadienyl, 1,2,3,4,5-
5 pentamethylcyclopentadienyl and 1,2,3,4,5-
pentaethylcyclopentadienyl.
The hydrocarbon group in which the carbon adjacent to
Si is a secondary includes i-propyl, s-butyl, s-amyl and a-
benzyl; and
the hydrocarbon group in which the carbon adjacent to
Si is a tertiary includes t-butyl, t-amyl, ~,a'-
diemethylbenzyl and admantyl.
When n is 1, the silicon compound represented by the
formula (iii) includes trialkoxysilanes such as
lS cyclopentyltrimethoxysilane,
2-methylcyclopentyltrimethoxysilane,
2,3-dimethylcyclopentyltrimethoxysilane,
cyclopentyltriethoxysilane,
iso-butyltriethoxysilane,
t-butyltriethoxysilane,
cyclohexyltrimethoxysilane,
cyclohexyltriethoxysilane,
2-norbornanetrimethoxysilane, and
2-norbornanetriethoxysilane;
when n is 2, the silicon compound represented by the
formula (iii) includes dialkoxysilanes such as
dicyclopentyldiethoxysilane,
21 009q9
74
t-butylmethyldimethoxysilane,
t-butylmethyldiethoxysilane,
t-amylmethyldiethoxysilane,
dicyclohexyldimethoxysilane,
cyclohexylmethyldimethoxysilane,
cyclohexylmethyldiethoxysilane, and
2-norbornanemethyldimethoxysilane.
When n is 2, the silicon compound represented by the
formula (iii) is preferably dimethoxy compound represented
0 by the following formula (iv);
Ra OCH3
si ( iv)
RC / OCH3
wherein, Ra and Rc are each independently a cyclope15 group, a substituted cyclopentyl group, a cyclopentenyl
group, a substituted cyclopentenyl group, cyclopentadienyl
group, a substituted cyclopentadienyl group or a
hydrocarbon group whose carbon adjacent to Si is a
secondary carbon or a tertiary carbon.
The silicon compound represented by the formula (iv)
includes, for example, dicyclopentyldimethoxysilane,
dicyclopentenyldimethoxyxilane,
dicyclopentadienyldimethoxyxilane,
di-t-butyldimethoxysilane,
di-(2-methylcyclopentyl)dimethoxysilane,
di-(3-methylcyclopentyl)dimethoxysilane,
di-(2-ethylcyclopentyl)dimethoxysilane,
- 21 00999
di-(2,3-dimethylcyclopentyl)dimethoxysilane,
di-(2,4-dimethylcyclopentyl)dimethoxysilane,
di-(2,5-dimethylcyclopentyl)dimethoxysilane,
di-(2,3-diethylcyclopentyl)dimethoxysilane,
5 di-(2,3,4-trimethylcyclopentyl)dimethoxysilane,
di-(2,3,S-trimethylcyclopentyl)dimethoxysilane,
di-(2,3,4-triethylcyclopentyl)dimethoxysilane,
di-(tetramethylcyclopentyl)dimethoxysilane,
di-(tétraethylcyclopentyl)dimethoxysilane,
di-(2-methylcyclopentenyl)dimethoxysilane,
di-(3-methylcyclopentenyl)dimethoxysilane,
di-(2-ethylcyclopentenyl)dimethoxysilane,
di-(2-n-butylcyclopentenyl)dimethoxysilane,
di-(2,3-dimethylcyclopentenyl)dimethoxysilane,
di-(2,4-dimethylcyclopentenyl)dimethoxysilane,
di-(2,5-dimethylcyclopentenyl)dimethoxysilane,
di-(2,3,4-trimethylcyclopentenyl)dimethoxysilane,
di-(2,3,5-trimethylcyclopentenyl)dimethoxysilane,
di-(2,3,4-triethylcyclopentenyl)dimethoxysilane,
di-(tetramethylcyclopentenyl)dimethoxysilane,
di-(tetraethylcyclopentenyl)dimethoxysilane,
di-(2-methylcyclopentadienyl)dimethoxysilane,
di-(3-methylcyclopentadienyl)dimethoxysilane,
di-(2-ethylcyclopentadienyl)dimethoxysilane,
di-(2-n-butylcyclopentadienyl)dimethoxysilane,
di-(2,3-dimethylcyclopentadienyl)dimethoxysilane,
di-(2,4-dimethylcyclopentadienyl)dimethoxysilane,
2 1 00999
76
di-(2,5-dimethylcyclopentadienyl)dimethoxysilane,
di-(2,3-diethylcyclopentadienyl)dimethoxysilane,
di-(2,3,4-trimethylcyclopentadienyl)dimethoxysilane,
di-(2,3,5-trimethylcyclopentadienyl)dimethoxysilane,
S di-(2,3,4-triethylcyclopentadienyl)dimethoxysilane,
di-(2,3,4,5-tetramethylcyclopentadienyl)dimethoxysilane,
di-(2,3,4,5-tetraethylcyclopentadienyl)dimethoxysilane,
di-(1,2,3,4,5-pentamethylcyclopentadienyl)dimethoxysilane,
di-(1,2,3,4,5-pentaethylcyclopentadienyl)dimethoxysilane,
0 di-t-amyl-dimethoxysilane,
di-( a, a ~ -dimethylbenzyl)dimethoxysilane,
di-(admantyl)dimethoxysilane,
admantyl-t-butyldimethoxysilane,
cyclopentyl-t-butyldimethoxysilane,
di-isopropyldimethoxysilane,
di-s-butyldimethoxysilane,
di-s-amyldimethoxysilane, and
isopropyl-s-butyldimethoxysilane.
When n is 3, the silicon compound represented by the
formula (iii) includes monoalkoxysilanes such as
tricyclopentylmethoxysilane, tricyclopentylethoxysilane,
dicyclopentylmethylmethoxysilane,
dicyclopentylethylmethoxysilane,
dicyclopentylmethylethoxysilane,
dicyclopentyldimethylmethoxysilane,
cyclopentyldiethylmethoxysilane, and
cyclopentyldimethylethoxysilane.
2l oo999
77
Of these, preferred are dimethoxysilanes, particularly
preferred are dimethoxysilanes represented by the formula
(iv), to be concretely, preferably used is
dicyclopentyldimethoxysilane, di-t-butyldimethoxysilane,
di-(2-methylcyclopentyl)dimethoxysilane, di-(3-
methylcyclopentyl)dimethoxysilane or do-t-
amyldimethoxysilane.
In the compound (hereinafter sometimes referred as
"polyether compound") having at least two ether linkages
existing via plurality of atoms used in the present
invention, the atoms existing between these ether linkages
are at least one kind of atom selected from the group
consisting of carbon, silicon, oxygen, sulfur, phosphorus
and boron, and the number of the atoms are not less than
two. Of these compounds mentioned above, preferred are
those in which a relatively bulky substituent attaches to
the atom intermediately existing between the ether
linkages. The relatively bulky substituent concretely
means the substituent having 2 or more of carbon atoms,
preferably the substituent having a structure of linear,
branched or cyclic contaning 3 or more of carbon atoms,
particularly the substituent having branched or cyclic
structure. Further, preferred is a compound containing
plurality of, preferably 3 to 20, more preferably 3 to 10,
particularly prefereably 3 to 7 carbon atoms in the atoms
intermediately existing between at least two ether
linkages.
21 00999
78
Such polyether compound as mentioned above includes,
for example, those represented by the following formula
R22 R ... R R24
R2l C t C_ . . f ~ o-- ~-- R26
R23 R ... R R25
S wherein n is an integer of 2<n<10, R1-R26 are each a
substituent having at least one element selected from among
carbon, hydrogen, oxygen, halogen, nitrogen, sulfur,
phosphorus, boron and silicon, any of Rl-R26, preferably
R1-R2n may form, together a ring other than a benzene ring,
0 and the main chain of the compound may contain atoms other
than carbon.
The polyether compound as illustrated above includes
2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-
dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-s-butyl-
1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-
phenyl-1,3-dimethoxypropane, 2-cumyl-1,3-dimethoxypropane,
2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-
cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-
1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-
dimethoxypropane, 2-(1-naphthyl)-1,3-dimethoxypropane, 2-
(2-fluorophenyl)-1,3-dimethoxypropane, 2-(1- -
decahydronaphthyl)-1,3-dimethoxypropane, 2-(p-t-
butylphenyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-
dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane,
2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-
79 21 00999
dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane,
2,2-dibutyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-
dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane,
2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-iso-
propyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-
dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-
dimethoxypropane, 2,2-bis(p-chlorophenyl)-1,3-
dimethoxypropane, 2,2-bis(2-cyclohexylethyl)-1,3-
dimethoxypropane, 2-methyl-2-iso-butyl-1,3-
0 dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-
dimethoxypropane, 2,2-di-iso-butyl-1,3-dimethoxypropane,
2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-
dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-
dimethoxypropane, 2,2-di-iso-butyl-1,3-diethoxypropane,
2,2-di-iso-butyl-1,3-dibutoxypropane, 2-iso-butyl-2-iso-
propyl-1,3-dimethoxypropane, 2-(1-methylbutyl)-2-isopropyl-
1,3-dimethoxypropane, 2-(1-methylbutyl)-2-s-butyl-1,3-
dimethoxypropane, 2,2-di-s-butyl-1,3-dimethoxypropane, 2,2-
di-t-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-
dimethoxypropane, 2-iso-propyl-2-iso-pentyl-1,3-
dimethoxypropane, 2-phenyl-2-isopropyl-1,3-
dimethoxypropane, 2-phenyl-2-s-butyl-1,3-dimethoxypropane,
2-benzyl-2-isopropyl-1,3-dimethoxypropane, 2-benzyl-2-s-
butyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-
dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-
dimethoxypropane, 2-cyclopentyl-2-s-butyl-1,3-
dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-
21 00999
dimethoxypropane, 2-cyclohexyl-2-s-butyl-1,3-
dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-
dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-
dimethoxypropane, 2,3-diphenyl-1,4-diethoxybutane, 2,3-
dicyclohexyl-1,4-diethoxybutane, 2,2-dibenzyl-1,4-
diethoxybutane, 2,3-dicyclohexyl-1,4-diethoxybutane, 2,3-
di-iso-propyl-1,4-diethoxybutane, 2,2-bis(p-methylphenyl)-
1,4-dimethoxybutane, 2,3-bis(p-chlorophenyl)-1,4-
dimethoxybutane, 2,3-bis(p-fluorophenyl)-1,4-
0 dimethoxybutane, 2,4-diphenyl-1,5-dimethoxypentane, 2,5-
diphenyl-1,5-dimethoxyhexane, 2,4-di-iso-propyl-1,5-
dimethoxypentane, 2,4-di-iso-butyl-1,5-dimethoxypentane,
2,4-di-iso-amyl-1,5-dimethoxypentane, 3-
methoxymethyltetrahydrofuran, 3-methoxymethyldioxane, 1,3-
di-iso-butoxypropane, 1,2-di-iso-butoxypropane, 1,2-di-iso-
butoxyethane, 1,3-di-iso-amyloxypropane, 1,3-di-iso-
neopentyloxyethane, 1,3-dineopentyloxypropane, 2,2-
tetramethylene-1,3-dimethoxypropane, 2,2-pentamethylene-
1,3-dimethoxypropane, 2,2-hexamethylene-1,3-
dimethoxypropane, 1,2-bis(methoxymethyl)cyclohexane, 2,8-
dioxaspiro[5,5]undecane, 3,7-dioxabicyclo[3,3,1]nonane,
3,7-dioxabicyclo[3,3,0]octane, 3,3-di-iso-butyl-1,5-
oxononane, 6,6-di-iso-butyldioxyheptane, 1,1-
dimethoxymethylcyclopentane, 1,1-
bis(dimethoxymethyl)cyclohexane, 1,1-
bis(methoxymethyl)bicyclo[2,2,1]heptane, 1,1-
dimethoxymethylcyclopentane, 2-methyl-2-methoxymethyl-1,3-
-
81 2 1 00999
dimethoxypropane, 2-cyclohexyl-2-ethoxymethyl-1,3-
diethoxypropane, 2-cyclohexyl-2-methoxymethyl-1,3-
dimethoxypropane, 2,2-di-iso-butyl-1,3-
dimethoxycyclohexane, 2-iso-propyl-2-iso-amyl-1,3-
5 dimethoxycyclohexane, 2-cyclohexyl-2-methoxymethyl-1,3-
dimethoxycyclohexane, 2-iso-propyl-2-methoxymethyl-1,3-
dimethoxycyclohexane, 2-iso-butyl-2-methoxymethyl-1,3-
dimethoxycyclohexane, 2-cyclohexyl-2-ethoxymethy-1,3-
diethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-
0 dimethoxycyclohexane, 2-iso-propyl-2-ethoxymethyl-1,3-
diethoxycyclohexane, 2-iso-propyl-2-ethoxymethyl-1,3-
dimethoxycyclohexane, 2,-iso-butyl-2-ethoxymethyl-1,3-
diethoxycyclohexane, 2-iso-butyl-2-ethoxymethyl-1,3-
dimethoxycyclohexane, tris(p-methoxyphenyl)phospine,
methlphenylbis(methoxymethyl)silane,
diphenylbis(methoxymethyl)silane,
methylcyclohexylbis(methoxymethyl)silane, di-t-
butylbis(methoxymethyl)silane, cyclohexyl-t-
butylbis(methoxymethyl)silane and iso-propyl-t-
butylbis(methoxymethyl)silane.
Of these compounds, preferred are 1,3-diethers,
espesially, 2,2-di-iso-butyl-1,3-dimethoxypropane, 2-iso-
propyl-2-iso-pentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-
1,3 dimethoxypropane and 2,2-bis(cyclohexylmethyl)1,3-
dimethoxypropane. These compounds may be used eithersingly or in combination.
2 1 00999
82
Next, processes for.preparing the propylene polymer
and the propylene block copolymer of the invention are
described.
The propylene polymer of the invention can be obtained
5 by polymerizing propylene in the presence of the olefin
polymerization catalyst formed from the solid titanium
catalyst component [Ia], the organometallic catalyst
component [II] and the silicon compound represented by the
formula (iii) or the polyether compound [III], preferably
in the presence of the olefin polymerization catalyst
formed from the prepolymerized catalyst component [Ib], the
organometallic catalyst component [II] and the silicon
compound catalyst component represented by the formula
(iii) or the polyether compound [III].
In the polymerization of propylene, a small amount of
other olefin than propylene or a small amount of a diene
compound may be present in the polymerization system in
addition to propylene.
Examples of the olefin other than propylene include
ethylene and olefins of 3 to 8 carbon atoms such as 1-
butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-
1-pentene, 1-octene and 3-methyl-1-butene.
Examples of the diene compound include diene compounds
of 4 to 20 carbon atoms such as 1,3-butadiene, 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,
21 00~99
83
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-
S undecadiene, 1,7-octadiene, 1,9-decadiene, isoprene,
butadiene, ethylidenenorbornene, vinylnorbornene and
dicyclopentadiene.
The polymerization of propylene is generally conducted
in a gas phase or a liquid phase.
When the polymerization is a slurry polymerization or
a solution polymerization, the same inert hydrocarbon as
used for preparing the aforesaid prepolymerized catalyst
component [Ib] can be employed as a reaction solvent.
In the polymerization system, the solid titanium
catalyst component [Ia] or the prepolymerized catalyst
component [Ib] is used in an amount of usually about 0.0001
to 50 mmol, preferably about 0.001 to 10 mmol, in terms of
titanium atom contained in the solid titanium catalyst
component [Ia] or contained in the prepolymerized catalyst
component [Ib], per 1 liter of the polymerization volume.
The organometallic catalyst component [II] is used in such
an amount that the amount of the metal atom contained in
the organometallic catalyst component [II] might be in the
range of usually about 1 to 2,000 mol, preferably about 2
to 500 mol, per 1 mol of the titanium atom in the
polymerization system. The silicon compound or the
polyether compound [III] is used in an amount of usually
21 0~999
84
about 0.001 to 50 mol, preferably about 0.01 to 20 mol, per
1 mol of the metal atom in the organometallic catalyst
component [II].
If hydrogen is used in the polymerization stage, a
propylene polymer having a high melt flow rate can be
obtained. Further, the molecular weight of the propylene
polymer can be controlled by adjusting the amount of
hydrogen. Even in the case of using hydrogen, the obtained
propylene polymer of the invention is never lowered in the
crystallinity and the pentad isotacticity, and moreover the
catalytic activity is not reduced.
In the invention, the polymerization of propylene is
carried out at a temperature of usually about -50 to 200
C, preferably about 20 to 100 C, under a pressure of
usually an ordinary pressure to 100 kg/cm2, preferably
about 2 to 50 kg/cm2. The polymerization may be carried
out either batchwise, semi-continuously or continuously.
In this process of the invention, propylene is
desirably polymerized in an amount of 3,000 to 1,000,000 g
per 1 g of the solid titanium catalyst component (a) in the
aforesaid prepolymerized catalyst component [Ib].
When a propylene polymer is prepared as above, an
yield of the propylene polymer per unit amount of the solid
catalyst component can be increased, and hence the amount
of the catalyst residue (particularly halogen content) in
the propylene polymer can be relatively reduced.
Accordingly, an operation for removing the catalyst residue
85 2~ 00999
contained in the propylene polymer can be omitted, and
moreover in the case of molding the obtained propylene
polymer, a mold can be easily prevented from occurrence of
rust.
In the propylene polymer obtained as above, an amount
of an amorphous component (amorphous portion) is extremely
small, and thereby an amount of the hydrocarbon-soluble
component is also small. Accordingly, when a film is
formed from the propylene polymer, the film is low in the
0 surface tackiness.
The propylene polymer of the invention may be prepared
in two or more polymerization stages having different
reaction conditions. In this case, the polymerization is
carried out in a gas phase or a liquid phase using 2 to 10
polymerizers.
When the polymerization is a slurry polymerization or
a solution polymerization, the same inert hydrocarbon as
used for preparing the aforesaid prepolymerized catalyst
component [Ib] can be employed as a reaction solvent.
In this polymerization process, polymerization of
propylene is conducted in at least one polymerizer among
the two or more polymerizers, to prepare a polymer having
an intrinsic viscosity [~] of 3 to 40 dl/g, preferably 5 to
30 dl/g, particularly preferably 7 to 25 dl/g. This
polymerization is sometimes referred to as "A
polymerization" hereinafter.
86 21 00999
It is desired that the isotactic pentad value (pentad
isotacticity) [M5] determined by the NMR measurement of the
boiled heptane-insoluble component in the polymer obtained
in this A polymerization is in the range of 0.960 to 0.995,
S preferably 0.970 to 0.995, more preferably 0.980 to 0.995,
most preferably 0.982 to 0.995.
It is also desired that the amount of the boiled
heptane-insoluble component in the polymer is not less than
80 %, preferably not less than 90 %, more preferably not
less than 94 %, much more preferably not less than 95 %,
particularly preferably not less than 96 %.
In the A polymerization, the polymer is desirably
prepared in such a manner that the amount of the polymer
obtained in the A polymerization might be in the range of
lS 0.1 to 55 %, preferably 2 to 35 %, particularly preferably
5 to 30 %, based on the amount of the polymer finally
obtained.
In the case of preparing the propylene polymer using
two or more polymerizers, polymerization of propylene is
also conducted in the residual polymerizers out of the two
or more polymerizers to prepare a propylene polymer having
a melt flow rate of 0.1 to 500 g/10 min as a final polymer.
This polymerization is sometimes referred to as "B
polymerization" hereinafter.
In the A polymerization and the B polymerization, the
solid titanium catalyst component [Ia] or the
prepolymerized catalyst component [Ib] is used in an amount
21 00999
87
of usually about 0.0001 to 50 mmol, preferably about 0.001
to 10 mmol, in terms of titanium atom contained in the
solid titanium catalyst component [Ia] or contained in the
prepolymerized catalyst component [Ib], per 1 liter of the
5 polymerization volume. The organometallic catalyst
component [II] is used in such an amount that the amount of
the metal atom contained in the organometallic catalyst
component [II] might be in the range of usually about 1 to
2,000 mol, preferably about 2 to 500 mol, per 1 mol of the
0 titanium atom in the polymerization system. The silicon
compound or the polyether compound [III] is used in an
amount of usually about 0.001 to 50 mol, preferably about
0.01 to 20 mol, per 1 mol of the metal atom in the
organometallic catalyst component [II].
If necessary, the solid titanium catalyst component
[Ia] or the prepolymerized catalyst component [Ib], the
organometallic catalyst component [II] and the silicon
compound or the polyether compound [III] may be added to
any of the plural polymerizers. Further, the electron
donor used in the preparation of the solid titanium
catalyst component (a) and/or the organosilicon compound
represented by the above formula tc-i) may be added to any
of the plural polymerizers.
Further, in any of the A polymerization and the B
polymerization, hydrogen may be fed or removed, whereby the
molecular weight of the propylene polymer can be easily
regulated. Even in this case, the obtained propylene
88 21 00999
polymer of the invention is never lowered in the
crystallinity and the pentad isotacticity, and moreover the
catalytic activity is not reduced. The feed amount of
hydrogen varies according to the reaction conditions, but
S generally, the feed amount of hydrogen is such an amount
that the melt flow rate of the polymer finally obtained
might be in the range of 0.1 to 500 g/10 min.
The value [Ms] of the boiled heptane-insoluble
component is usually in the range of 0.975 to 0.995,
preferably 0.980 to 0.995, more preferably 0.982 to 0.995;
and the value [M3] of the boiled heptane-insoluble
component is usually in the range of 0.0020 to 0.0050,
preferably 0.0023 to 0.0045, more preferably 0.0025 to
0.0040.
In the A polymerization and the B polymerization, the
polymerization of propylene is carried out at a temperature
of usually about -50 to 200 C, preferably about 20 to 100
C, under a pressure of usually an ordinary pressure to 100
kg/cm2, preferably about 2 to 50 kg/cm2. The
polymerization may be carried out either batchwise, semi-
continuously or continuously.
In this process of the invention, propylene is
desirably polymerized in an amount of 3,000 to 100,000 g
per 1 g of the solid titanium catalyst component (a) in the
aforesaid prepolymerized catalyst component [Ib].
The propylene block copolymer of the invention can be
prepared by a process comprising a first polymerization
89 21 00999
stage for homopolymerizing propylene or copolymerizing
propylene with ethylene and/or olefin of 4 to 10 carbon
atoms to prepare a crystalline polymer (crystalline
polypropylene portion) and a second polymerization stage
for copolymerizing two or more monomers selected from
olefins of 2 to 20 carbon atoms to prepare a low-
crystalline copolymer (low-crystalline copolymer portion)
or a non-crystalline copolymer ~non-crystalline copolymer
portion), in the presence of a catalyst for olefin
polymerization (i.e., olefin polymerization catalyst)
formed from the solid titanium catalyst component [Ia], the
organometallic catalyst component [II] and the silicon
compound represented by the aforesaid formula (iii) or the
polyether compound (III), preferably in the presence of the
olefin polymerization catalyst formed from the
prepolymerized catalyst component [Ib], the organometallic
catalyst component [II] and the silicon compound
represented by the aforesaid formula (iii) or the polyether
compound [III].
In this process for preparing a propylene block
copolymer, at first, homopolymerization of propylene or
copolymerization of propylene with ethylene and/or olefin
of 4 to 10 carbon atoms is carried out in the first
polymerization stage.
Concrete examples of the olefin of 4 to 10 carbon
atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-
pentene, 3-methyl-1-pentene, 1-octene, 3-methyl-1-butene,
21 OO9q9
1-decene, 1-dodecene, 1-tetradecene, l-hexadecene, 1-
octadecene, 1-eicosene, cyclopentené, cycloheptene,
norbornene, 5-methyl-2-norbornene, tetracyclododecene and
2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-
octahydronaphthalene.
In the first polymerization stage, the polymerizationis carried out generally in a gas phase or a liquid phase.
When the polymerization is a slurry polymerization or
a solution polymerization, the same inert hydrocarbon as
0 used for preparing the aforesaid prepolymerized catalyst
component [Ib] can be employed as a reaction solvent.
In the first polymerization stage, the solid titanium
catalyst component [Ia] or the prepolymerized catalyst
component [Ib] is used in an amount of usually about 0.0001
to 50 mmol, preferably about 0.001 to 10 mmol, in terms of
titanium atom contained in the solid titanium catalyst
component [Ia] or contained in the prepolymerized catalyst
component [Ib], per 1 liter of the polymerization volume.
The organometallic catalyst component [II] is used in such
an amount that the amount of the metal atom contained in
the organometallic catalyst component [II] might be in the
range of usually about 1 to 2,000 mol, preferably about 2
to 500 mol, per 1 mol of the titanium atom in the
polymerization system. The silicon compound or the
polyether compound [III] is used in an amount of usually
about 0.001 to 50 mol, preferably about 0.01 to 20 mol, per
- 21 00999
91
1 mol of the metal atom in the organometallic catalyst
component [II].
Hydrogen may be used in the first polymerization
stage, whereby the molecular weight of the polymer obtained
can be regulated.
In the first polymerization stage, the polymerization
of propylene is carried out at a temperature of usually
about -50 to 200 C, preferably about 20 to 100 C, under a
pressure of usually an ordinary pressure to 100 kg/cm2,
preferably about 2 to 50 kg/cm2. The polymerization may be
carried out either batchwise, semi-continuously or
continuously.
It is desired that a content of the constituent units
derived from ethylene and/or olefin of 4 to 10 carbon atoms
in the polymer obtained in the first polymerization stage
is in the range of 0 to 20 % by mol, preferably 0 to 15 %
by mol, particularly preferably 0 to 10 % by mol.
It is also desired that the polymer obtained in the
first polymerization stage has an intrinsic viscosity [~],
as measured in decalin at 135 C, of 40 to 0.001 dl/g,
preferably 30 to 0.01 dl/g, particularly preferably 20 to
0.05 dl/g.
- In the first polymerization stage, in addition to
propylene and ethylene and/or olefin of 4 to 10 carbon
atoms, a small amount of a diene compound may be added to
the polymerization system so as to introduce constituent
-- 21 00999
92
units derived from the diene compound into the polymer
obtained in the first polymerization stage.
Examples of the diene compounds employable herein
include diene compounds of 4 to 20 carbon atoms such as
1,3-butadiene, 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, isoprene, butadiene, ethylidenenorbornene,
vinylnorbornene and dicyclopentadiene. Of these, preferred
are diene compounds of 5 to 12 carbon atoms such as 1,4-
hexadiene, 1,5-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-
1,4-hexadiene, 7-methyl-1,6-octadiene, ethylidenenorbornene
and vinylnorbornene.
In the preparation of the propylene block copolymer
according to the invention, there is a method, for example,
after the first polymerization stage, copolymerization of
two or more monomers selected from olefins of 2 to 20
carbon atoms is carried out in the presence of the polymer
obtained in the first polymerization stage.
Examples of the olefins of 2 to 20 carbon atoms used
herein include ethylene, propylene, 1-butene, 1-pentene, 1-
hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene,
93 21 00999
3-methyl-1-butene, 1-decene, 1-dodecene, 1-tetradecene, 1-
hexadecene, 1-octadecene, 1-eicosene, cyclopentene,
cycloheptene, norbornene, 5-ethyl-2-norbornene,
tetracyclododecene and 2-ethyl-1,4,5,8-dimethano-
1,2,3,4,4a,5,8,8a-octahydronaphthalene. Preferably used
are olefins of 3 to 12 carbon atoms.
In the second polymerization stage, the polymerization
is carried out generally in a gas phase or a liquid phase.
When the polymerization is a slurry polymerization or
a solution polymerization, the same inert hydrocarbon as
used for preparing the aforesaid prepolymerized catalyst
component [Ib] can be employed as a reaction solvent.
In the second polymerization stage, if necessary, the
solid titanium catalyst component [Ia] or the
lS prepolymerized catalyst component [Ib], organometallic
catalyst component [II], and the silicon compound or the
polyether compound [III] may be added. The solid titanium
catalyst component [Ia] or the prepolymerized catalyst
component [Ib] may be added in an amount of usually about
0.0001 to 50 mmol, preferably about 0.001 to 10 mmol, in
terms of titanium atom contained in the solid titanium
catalyst component [Ia] or contained in the prepolymerized
catalyst component [Ib], per 1 liter of the polymerization
volume. The organometallic catalyst component [II]-may be
added in such an amount that the amount of the metal atom
contained in the organometallic catalyst component [II]
might be in the range of usually about 1 to 2,000 mol,
- 21 00999
94
preferably about 2 to 500 mol, per 1 mol of the titanium
atom added in the polymerization system. The silicon
compound or the polyether compound [III] may be used in an
amount of usually about 0.001 to S0 mol, preferably about
0.01 to 20 mol, per 1 mol of the metal atom in the
organometallic catalyst component [II].
If hydrogen is used in the second polymerization
system, the molecular weight of resulting low-crystalline
or non-crystalline olefin copolymer can be regulated by
adjusting the amount of hydrogen.
In the second polymerization stage, the polymerization
of propylene is carried out at a temperature of usually
about -50 to 200 C, preferably about 20 to 100 C, under a
pressure of usually an ordinary pressure to 100 kg/cm2,
preferably about 2 to 50 kg/cm2. The polymerization may be
carried out either batchwise, semi-continuously or
continuously.
In the second polymerization stage, small amount of
diene compound may be introduced into the reaction system
as similar to the above-mentioned first polymerization
stage. Further, the electron donor used in the preparation
of the solid titanium catalyst component (a) and/or the
organosilicon compound represented by the above formula (c-
i) may be added to any of the first and second
polymerization stage.
When a propylene block copolymer is prepared as above,
an yield of the propylene block copolymer per unit amount
21 00999
of the solid catalyst component can be increased, and hence
the amount of the catalyst residue (particularly halogen
content) in the propylene block copolymer can be relatively
reduced. Accordingly, an operation for removing the
catalyst residue contained in the propylene block copolymer
can be omitted, and moreover in the case of molding the
obtained propylene block copolymer, a mold can be easily
prevented from occurrence of rust.
In the propylene block copolymer obtained by the above
process, a content of the propylene units is in the range
of 50 to 98 % by mol, preferably 60 to 97 % by mol.
The amount of the decane-soluble component in the
propylene block copolymer is not more than 50 %, and this
decane-soluble component mainly contains a copolymer
lS obtained in the second polymerization stage. The
composition of the copolymer varies depending on the kind
of olefin used, and hence it cannot be determined
generally. However, in the copolymerization of ethylene
with propylene, it is desired that a content of the
propylene units in the copolymer is in the range of 20 to
80 % by mol, preferably 25 to 75 % by mol, particularly
preferably 30 to 70 % by mol. The decane-soluble component
desirably has an intrinsic viscosity [~], as measured in
decalin at 135 C, of 0.5 to 20 dl/g, preferably 1 to 15
dl/g, more preferably 2 to 12 dl/g, particularly preferably
2.5 to 10 dl/g.
-- 2100999
96
Further, the MFR of the prepylene bloack copolymer is
in the range of 0.1 to 500 g/10 min, preferably 0.2 to 300
g/10 min, and is easily controlled by varying the
conditions of first or second polymerization stage, such as
5 an amount of feeding hydrogen and polymerization
temperature.
The propylene polymer and the propylene block
copolymer according to the invention may contain such a
nucleating agent as described later. By adding the
0 nucleating agent to the propylene polymer or the propylene
block copolymer, the crystal particles can be made more
fine and the crystallization speed can be heightened,
whereby high-speed molding is attained.
There is no specific limitation on the nucleating
agent employable herein, and various nucleating agents
conventionally known can be used. Of various nucleating
agents, preferred are those represented by the following
formulas. _ _
R
R ~ O\ O
Rl P - O M
R3~ 0
R - n
wherein R1 is oxygen, sulfur or a hydrocarbon group of 1 to
10 carbon atoms; each of R2 and R3 iS hydrogen or a
hydrocarbon group of 1 to 10 carbon atoms; R2 and R3 may be
the same as or different from each other; two of R2, two of
97 21 00999
R3, or R2 and R3 may be bonded together to form a ring, M is
a monovalent to trivalent metal atom; and n is an integer
of 1 to 3.
Concrete examples of the nucleating agents represented
by the above formula include sodium-2,2'-methylene-bis(4,6-
di-t-butylphenyl)phosphate, sodium-2,21-ethylidene-bis(4,6-
di-t-butylphenyl)phosphate, lithium-2,2'-methylene-bis(4,6-
di-t-butylphenyl)phosphate, lithium-2,2'-ethylidene-
bis(4,6-di-t-butylphenyl)phosphate, sodium-2,2'-ethylidene-
bis(4-i-propyl-6-t-butylphenyl)phosphate, lithium-2,2'-
methylene-bis(4-methyl-6-t-butylphenyl)phosphate, lithium-
2,2'-methylene-bis(4-ethyl-6-t-butylphenyl)phosphate,
calcium-bis[2,2'-thiobis(4-methyl-6-t-
butylphenyl)phosphate], calcium-bis[2,2'-thiobis(4-ethyl-6-
t-butylphenyl)phosphate], calcium-bis[2,2'-thiobis-(4,6-di-
t-butylphenyl)phosphate], magnesium-bis[2,2'-thiobis-(4,6-
di-t-butylphenyl)phosphate], magnesium-bis[2,2'-thiobis-(4-
t-octylphenyl)phosphate], sodium-2,2'-butylidene-bis(4,6-
dimethylphenyl)phosphate, sodium-2,2'-butylidene-bis(4,6-
di-t-butylphenyl)phosphate, sodium-2,2'-t-octylmethylene-
bis(4,6-dimethylphenyl)phosphate, sodium-2,2'-t-
octylmethylene-bis(4,6-di-t-butylphenyl)phosphate, calcium-
bis[2,2'-methylene-bis(4,6-di-t-butylphenyl)phosphate],
magnesium-bis[2,2'-methylene-bis(4,6-di-t-
butylphenyl)phosphate], barium-bis[2,2'-methylene-bis(4,6-
di-t-butylphenyl)phosphate], sodium-2,2'-methylene-bis(4-
methyl-6-t-butylphenyl)phosphate, sodium-2,2'-methylene-
21 00999
98
bis(4-ethyl-6-t-butylphenyl)phosphate, sodium(4,4'-
dimethyl-5,6'-di-t-butyl-2,2'-biphenyl)phosphate, calcium-
bis[(4,4'-dimethyl-6,6'-di-t-butyl-2,2'-
biphenyl)phosphate], sodium-2,2'-ethylidene-bis(4-m-butyl-
5 6-t-butylphenyl)phosphate, sodium-2,2'-methylene-bis(4,6-
dimethylphenyl)phosphate, sodium-2,2'-methylene-bis(4,6-
diethylphenyl)phosphate, potassium-2,2'-ethylidene-bis(4,6-
di-t-butylphenyl)phosphate, calcium-bis[2,2'-ethylidene-
bis(4,6-di-t-butylphenyl)phosphate], magnesium-bis[2,2'-
ethylidene-bis(4,6-di-t-butylphenyl)phosphate], barium-
bis[2,2'-ethylidene-bis(4,6-di-t-butylphenyl)phosphate],
aluminum-tris[2,2'-methylene-bis(4,6-di-t-
butylphenyl)phosphate] and aluminum-tris[2,2'-ethylidene-
bis(4,6-di-t-butylphenyl)phosphate]. Mixtures of two or
more of these nucleating agents are also employable. Of
these, sodium-2,2'-methylene-bis(4,6-di-t-
butylphenyl)phosphate is particularly preferred.
( R ~ ) 2 P - O M
- n
wherein R4 is hydrogen or a hydrocarbon group of 1 to 10
carbon atoms; M is a monovalent to trivalent metal atom;
and n is an integer of 1 to 3.
Concrete examples of the nucleating agents represented
by the above formula include sodium-bis(4-t-butylphenyl)
phosphate, sodium-bis(4-methylphenyl)phosphate, sodium-
bis(4-ethylphenyl)phosphate, sodium-bis(4-i-propylphenyl)
-- 99 2 1 00999
phosphate, sodium-bis(4-t-octylphenyl)phosphate, potassium-
bis(4-t-butylphenyl)phosphate, calcium-bis(4-t-butylpheyl)
phosphate, magnesium-bis(4-t-butylpheyl)phosphate, lithium-
bis(4-t-butylpheyl)phosphate and aluminum-bis(4-t-
S butylpheyl)phosphate. Mixtures of two or more of thesenucleating agents are also employable. Of these, sodium-
bis(4-t-butylphenyl)phosphate is particularly preferred.
Rs ~ ~ ~ R5
OH
OH
wherein R5 is hydrogen or a hydrocarbon group of 1 to 10
carbon atoms.
Concrete examples of the nucleating agents represented
by the above formula include 1,3,2,4-dibenzylidenesorbitol,
1,3-benzylidene-2,4-p-methylbenzylidenesorbitol,
1,3-benzylidene-2,4-p-ethylbenzylidenesorbitol,
1,3-p-methylbenzylidene-2,4-benzylidenesorbitol,
1,3-p-ethylbenzylidene-2,4-benzylidenesorbitol,
1,3-p-methylbenzylidene-2,4-p-ethylbenzylidenesorbitol,
1,3-p-ethylbenzylidene-2,4-p-methylbenzylidenesorbitol,
1,3,2,4-di(p-methylbenzylidene)sorbitol,
1,3,2,4-di(p-ethylbenzylidene)sorbitol,
1,3,2,4-di(p-n-propylbenzylidene)sorbitol,
1,3,2,4-di(p-i-propylbenzylidene)sorbitol,
1,3,2,4-di(p-n-butylbenzylidene)sorbitol,
1,3,2,4-di(p-s-butylbenzylidene)sorbitol,
2 1 00999
100
1,3,2,4-di(p-t-butylbenzylidene)sorbitol,
1,3,2,4-di(2',4'-dimethylbenzylidene)sorbitol,
1,3,2,4-di(p-methoxybenzylidene)sorbitol,
1,3,2,4-di(p-ethoxybenzylidene)sorbitol,
1,3-benzylidene-2,4-p-chlorobenzylidenesorbitol,
1,3-p-chlorobenzylidene-2,4-benzylidenesorbitol,
1,3-p-chlorobenzylidene-2,4-p-methylbenzylidenesorbitol,
1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidenesorbitol,
1,3-p-methylbenzylidene-2,4-p-chlorobenzylidenesorbitol,
1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidenesorbitol and
1,3,2,4-di(p-chlorobenzylidene)sorbitol. Mixtures of two
or more of these nucleating agents are also employable. Of
these, 1,3,2,4-dibenzylidenesorbitol, 1,3,2,4-di(p-
methylbenzylidene)sorbitol, 1,3,2,4-di(p-ethylbenzylidene)
sorbitol, 1,3-p-chlorobenzylidene-2,4-p-
methylbenzylidenesorbitol, 1,3,2,4-di(p-chlorobenzylidene)
sorbitol and mixtures of two or more of these nucleating
agents are particularly preferred.
Also employable are other nucleating agents such as
metallic salts of aromatic carboxylic acids and metallic
salts of aliphatic carboxylic acids. Concrete examples
thereof include aluminum benzoate, aluminum p-t-
butylbenzoate, sodium adipate, sodium thiophenecarboxylate
and sodium pyrrolecarboxylate.
Inorganic compounds such as talc described later may
be also used.
-- lol 2 1 00999
In the propylene polymer of the invention, the
nucleating agent is used in an amount of 0.001 to 10 parts
by weight, preferably 0.01 to 5 parts by weight, more
preferably 0.1 to 3 parts by weight, based on 100 parts by
weight of the propylene polymer.
By the use of the nucleating agent in the above-
mentioned amount, there can be obtained a propylene polymer
having extremely fine crystalline particles and enhanced in
crystallinity without deterioration of excellent properties
0 inherently belonging to the propylene polymer.
In the propylene block copolymer of the invention, the
nucleating agent is used in an amount of 0.001 to 10 parts
by weight, preferably 0.01 to 5 parts by weight, more
preferably 0.1 to 3 parts by weight, based on 100 parts by
weight of the propylene block copolymer.
By the use of the nucleating agent in the above-
mentioned amount, there can be obtained a propylene block
copolymer having extremely fine crystalline particles and
enhanced in crystallinity without deterioration of
excellent properties inherently belonging to the propylene
block copolymer.
To the propylene polymer and the propylene block
copolymer of the invention may be added various additives
such as rubber component to enhance impact strength, heat
stabilizer, weathering stabilizer, antioxidant, slip agent,
antiblocking agent, antifogging agent, lubricant, dye,
21 00999
~ 102
pigment, natural oil, synthetic oil and wax. They can be
added in appropriate amounts.
Further, to the propylene polymer and the propylene
block copolymer of the invention may be added fillers such
as silica, diatomaceous earth, alumina, titanium oxide,
magnesium oxide, pumice powder, pumice balloon, aluminum
oxide, magnesium oxide, basic magnesium carbonate,
dolomite, calcium sulfate, potassium titanate, barium
sulfate, calcium sulfite, talc, clay, mica, asbestos, glass
fiber, glass flake, glass bead, calcium silicate,
montmorillonite, bentonite, graphite, aluminum powder,
molybdenum sulfide, borone fiber, silicon carbide fiber,
polyethylene fiber, polypropylene fiber, polyester fiber
and polyamide fiber, with the proviso that the objects of
the invention are not marred.
The propylene polymer of the invention can be used
without specific limitation in a field where polypropylene
has been conventionally used, and particularly it can be
favorably used for extruded sheet, unstretched film,
stretched film, filament, injection molded product and blow
molded product.
There is no specific limitation on the shape and the
kind of the extrusion molded product made of the propylene
polymer of the invention. Concretely, there can be
mentioned sheet, film (unstretched film), pipe, hose,
electric wire cover and filament. The extrusion molded
product made of the propylene polymer is particularly
. : -
21 00999
_ 103
preferably used as sheet, film (unstretched film) and
filament.
In order to extrusion mold the propylene polymer of
the invention into a sheet, a film (unstretched film) or
the like, conventionally known extrusion apparatuses such
as a single screw extruder, a kneading extruder, a ram
extruder and a gear extruder can be used. Using such
extruder, a molten propylene polymer is extruded from a T-
die or the like to prepare an extrusion molded product.
0 The extrusion molding can be carried out under the molding
conditions conventionally known.
The extruded sheet and film (unstretched film)
prepared as above are excellent in rigidity, heat
resistance and moisture resistance.
A stretched film can be prepared from the above-
mentioned sheet or film made of the propylene polymer by
conventional stretching methods using known stretching
machines, such as tentering (lengthwise-crosswise
stretching, crosswise-lengthwise stretching), simultaneous
biaxial stretching (biaxial orientation) and monoaxial
stretching. The stretch ratio of the biaxially stretched
(oriented) film is preferably in the range of 20 to 70
times, while the stretch ratio of the monoaxially stretched
film is preferably in the range of 2 to lO times. The
thickness of the stretched film is desirably in the range
of 5 to 200 ~m.
104 21 00999
Such stretched film is excellent in rigidity, heat
resistance and moisture resistance.
From the propylene polymer of the invention, an
inflation film can be also prepared.
Since the sheet, the unstretched film and the
stretched film composed of the propylene polymer of the
invention are excellent in heat resistance, transparency,
see-through properties, glossiness, rigidity, moisture
resistance, gas barrier properties, etc., they can be
0 widely applied to packaging films or other uses. In
particular, they are very suitable for press through pack
used for packaging of pharmaceutical tablets or capsules.
The filament composed of the propylene polymer of the
invention can be prepared, for example, by extruding a
molten propylene polymer through a spinning nozzle. The
filament thus obtained may be further subjected to
stretching. This stretching is carried out in such a
manner that the molecular orientation at least in the
monoaxial direction is effectively given to the propylene
polymer, and the stretch ratio is desirably in the range of
5 to 10 times.
Such filament is excellent in rigidity and heat
resistance.
The injection molded product composed of the propylene
polymer of the invention can be prepared using a
conventionally known injection molding apparatus. The
injection molding can be carried out under the molding
-- loS 21 00999
conventionally known. Since the injection molded product
is excellent in rigidity, heat resistance, impact
resistance, surface glossiness, chemical resistance,
abrasion resistance, etc., it can be widely used for
S automotive interior trims, automotive exterior trims,
housings for electrical appliances, containers, etc.
The blow molded product composed of the propylene
polymer of the invention can be prepared using a
conventionally known blow molding apparatus. The blow
molding can be carried out under the molding conditions
conventionally known. For example, in the extrusion blow
molding, a molten propylene polymer is extruded from a die
to form a tubular parison at a resin temperature of 100 to
300 C, then the parison is kept within a mold having an
aimed shape, and air is blown into the mold at a resin
temperature of 130 to 300 C to obtain a hollow molded
product. In this case, the stretch ratio is desirably
within the range of 1.5 to 5 times in the crosswise
direction.
In the injection blow molding, a molten propylene
polymer is injected into a mold to form a parison at a
resin temperature of 100 to 300 C, then the parison is
kept within a mold having an aimed shape, and air is blown
into the mold at a resin temperature of 120 to 300 C to
obtain a hollow molded product. In this case, the stretch
ratio is desirably within the range of 1.1 to 1.8 times in
il
106 2 1 0 g g g
the lengthwise direction and within the range of 1.3 to 2.5
times in the crosswise direction.
Such blow molded product is excellent in rigidity,
heat resistance and moisture resistance.
The propylene polymer of the invention can be used as
a substrate in a method wherein a skin material and a
substrate are subjected to press molding at the same time
to prepare an integrally molded product (i.e., mold
stamping method). The molded product obtained by the mold
stamping can be favorably used as automotive interior trims
such as door trim, rear package trim, sheet back garnish
and instrument panel.
The molded product obtained by the mold stamping is
excellent in rigidity and heat resistance.
The propylene block copolymer of the invention can be
used without specific limitation in a field where
polypropylene has been conventionally used, and
particularly it can be favorably used for extruded sheet,
filament, injection molded product and blow molded product.
There is no specific limitation on the shape and the
kind of the extrusion molded product composed of the
propylene block copolymer of the invention. Concretely,
there can be mentioned sheet, pipe, hose, electric wire
cover and filament. The extrusion molded product made of
the propylene block copolymer is particularly preferably
used as sheet and filament.
.
~ 107 21 00999
In order to extrusion mold the propylene block
copolymer of the invention into a sheet, or the like,
conventionally known extrusion apparatuses such as a single
screw extruder, a kneading extruder, a ram extruder and a
gear extruder can be used. Using such extruder, a molten
propylene block copolymer is extruded from a T-die or the
like to prepare an extrusion molded product. The extrusion
molding can be carried out under the molding conditions
conventionally known.
The extruded sheet prepared as above is excellent in a
balance between rigidity, heat resistance and impact
resistance.
The filament composed of the propylene block copolymer
of the invention can be prepared, for example, by extruding
a molten propylene block copolymer through a spinning
nozzle. The filament thus obtained may be further
subjected to stretching. This stretching is carried out in
such a manner that the molecular orientation at least in
the monoaxial direction is effectively given to the
propylene block copolymer, and the stretch ratio is
desirably in the range of 5 to lO times.
Such filament is excellent in rigidity and heat
resistance.
The injection molded product composed of the propylene
block copolymer of the invention can be prepared using a
conventionally known injection molding apparatus. The
injection molding can be carried out under the molding
., , . ~
21 00999
108
conditions conventionally known. Since the injection
molded product is excellent in rigidity, heat resistance,
impact resistance, surface glossiness, chemical resistance,
abrasion resistance, etc., it can be widely used for
automotive interior trims, automotive exterior trims,
housings for electrical appliances, containers, etc.
The blow molded product composed of the propylene
block copolymer of the invention can be prepared using a
conventionally known blow molding apparatus. The blow
molding can be carried out under the molding conditions
conventionally known. For example, in the extrusion blow
molding, a molten propylene block copolymer is extruded
from a die to form a tubular parison at a resin temperature
of 180 to 300 C, then the parison is kept within a mold
having an aimed shape, and air is blown into the mold at a
resin temperature of 130 to 300 C to obtain a hollow
molded product. In this case, the stretch ratio is
desirably within the range of l.5 to 5 times in the
crosswise direction.
In the injection blow molding, a molten propylene
block copolymer is injected into a mold to form a parison
at a resin temperature of llO to 300 C, then the parison
is kept within a mold having an aimed shape, and air is
blown into the mold at a resin temperature of 120 to 300 C
to obtain a hollow molded product. In this case, the
stretch ratio is desirably within the range of l.l to l.8
.~.
21 00999
_ 109
times in the lengthwise direction and within the range of
1.3 to 2.5 times in the crosswise direction.
Such blow molded product is excellent in rigidity,
heàt resistance and moisture resistance.
The propylene block copolymer of the invention can be
used as a substrate in a method wherein a skin material and
a substrate are subjected to press molding at the same time
to prepare an integrally molded product (i.e., mold
stamping method). The molded product obtained by the mold
stamping can be favorably used as automotive interior trims
such as door trim, rear package trim, sheet back garnish
and instrument panel.
The molded product obtained by the mold stamping is
excellent in a balance between rigidity, heat resistance
and impact resistance.
Next, the propylene polymer compositions of the
invention are described.
The first propylene polymer composition of the
invention is formed from:
[A1] the aforesaid propylene polymer, and
[B] a phenol type stabilizer in an amount of 0.001 to
10 parts by weight, preferably 0.003 to 5 parts by weight,
more preferably 0.005 to 3 parts by weight, based on 100
parts by weight of the above propylene polymer.
The second propylene polymer composition of the
invention is formed from:
[A1] the aforesaid propylene polymer,
1 lo 2 1 00999
[B] a phenol type stabilizer in an amount of 0.001 to
10 parts by weight, preferably 0.003 to 5 parts by weight,
more preferably 0.005 to 3 parts by weight, based on 100
parts by weight of the above propylene polymer, and
at least one compound selected from the group
consisting of [C] an organophosphite type stabilizer, [D] a
thioether type stabilizer, [E] a hindered amine type
stabilizer and [F] a metallic salt of a higher aliphatic
acid in an amount of 0.001 to 10 parts by weight,
0 preferably 0.003 to 5 parts by weight, more preferably
0.005 to 3 parts by weight, based on 100 parts by weight of
the above propylene polymer.
When the content of the phenol type stabilizer [B] is
within the above range based on 100 parts by weight of the
propylene polymer, heat resistance can be highly improved,
the stabilizer is available at a low cost, and properties
of the propylene polymer such as tensile strength are not
deteriorated.
When the content of at least one compound selected
from the group consisting of the organophosphite type
stabilizer [C], the thioether type stabilizer [D], the
hindered amine type stabilizer [E] and the metallic salt of
a higher aliphatic acid [F] is within the above range based
on 100 parts by weight of the propylene polymer, heat
resistance can be highly improved, the stabilizer is
available at a low cost, and properties of the propylene
polymer such as tensile strength are not deteriorated.
- -
1 1 1 2 1 00999
When the content of the metallic salt of a higher
aliphatic acid [F] is within the above range, a residual
chlorine of the catalyst remained in the propylene polymer
can be sufficiently absorbed, whereby properties of the
5 propylene polymer are never deteriorated.
It is particularly preferred that the second propylene
polymer composition of the invention contains the phenol
type stabilizer [B] in an amount of 0.005 to 2 parts by
weight, the organophosphite type stabilizer [C] in an
0 amount of 0.005 to 2 parts by weight, the thioether type
stabilizer [D] in an amount of 0.005 to 2 parts by weight,
the hindered amine type stabilizer [E] in an amount of
0.005 to 2 parts by weight and the metallic salt of higher
aliphatic acid [F] in an amount of 0.005 to 2 parts by
weight, each based on 100 parts by weight of the propylene
polymer.
The third propylene polymer composition of the
invention is formed from:
[A1] the aforesaid propylene polymer, and
[C] an organophosphite type stabilizer in an amount
of 0.001 to 10 parts by weight, preferably 0.003 to 5 parts
by weight, more preferably 0.005 to 3 parts by weight,
based on 100 parts by weight of the above propylene
polymer.
The fourth propylene polymer composition of the
invention is formed from:
[A1] the aforesaid propylene polymer,
. .
- . - -: ,
112 2 1 00999
[C] an organophosphite type stabilizer in an amount
of 0.001 to 10 parts by weight, preferably 0.003 to 5 parts
by weight, more preferably 0.005 to 3 parts by weight,
based on 100 parts by weight of the above propylene
polymer, and
at least one compound selected from the group
consisting of [D] a thioether type stabilizer, [E] a
hindered amine type stabilizer and [F] a metallic salt of a
higher aliphatic acid in an amount of 0.001 to 10 parts by
weight, preferably 0.003 to 5 parts by weight, more
preferably 0.005 to 3 parts by weight, based on 100 parts
by weight of the above propylene polymer.
When the content of the organophosphite type
stabilizer [C] is within the above range based on 100 parts
by weight of the propylene polymer, heat resistance can be
highly improved, the stabilizer is available at a low cost,
and properties of the propylene polymer such as tensile
strength are not deteriorated.
When the content of at least one compound selected
from the group consisting of the thioether type stabilizer
[D], the hindered amine type stabilizer [E] and the
metallic salt of a higher aliphatic acid [F] is within the
above range based on 100 parts by weight of the propylene
polymer, heat resistance can be highly improved, the
stabilizer is available at a low cost, and properties of
the propylene polymer such as tensile strength are not
deteriorated.
- -
~ 113 21 00999
When the content of the metallic salt of a higher
aliphatic acid [F] is within the above range, a residual
chlorine of the catalyst remained in the propylene polymer
can be sufficiently absorbed, whereby properties of the
S propylene polymer are never deteriorated.
It is particularly preferred that the fourth propylene
polymer composition of the invention contains the
organophosphite type stabilizer [C] in an amount of 0.005
to 2 parts by weight, the thioether type stabilizer [D] in
0 an amount of 0.005 to 2 parts by weight, the hindered amine
type stabilizer [E] in an amount of 0.005 to 2 parts by
weight and the metallic salt of higher aliphatic acid [F]
in an amount of 0.005 to 2 parts by weight, each based on
100 parts by weight of the propylene polymer [A1].
lS The fifth propylene polymer composition of the
invention is formed from:
[A1] the aforesaid propylene polymer, and
[D] a thioether type stabilizer in an amount of 0.001
to 10 parts by weight, preferably 0.003 to 5 parts by
weight, more preferably 0.005 to 3 parts by weight, based
on 100 parts by weight of the above propylene polymer.
The sixth propylene polymer composition of the
invention is formed from:
[A1] the aforesaid propylene polymer,
[D] a thioether type stabilizer in an amount of 0.001
to 10 parts by weight, preferably 0.003 to 5 parts by
1~
.. . , ' . ' -: ~
114 21 00999
weight, more preferably 0.005 to 3 parts by weight, based
on 100 parts by weight of the above propylene polymer, and
at least one compound selected from the group
consisting of [E] a hindered amine type stabilizer and [F]
S a metallic salt of a higher aliphatic acid in an amount of
0.001 to 10 parts by weight, preferably 0.003 to 5 parts by
weight, more preferably 0.005 to 3 parts by weight, based
on 100 parts by weight of the above propylene polymer.
When the content of the thioether type stabilizer [D]
0 is within the above range based on 100 parts by weight of
the propylene polymer, heat resistance can be highly
improved, the stabilizer is available at a low cost, and
properties of the propylene polymer such as tensile
strength are not deteriorated.
When the content of at least one compound selected
from the group consisting of the hindered amine type
stabilizer [E] and the metallic salt of a higher aliphatic
acid [F] is within the above range based on 100 parts by
weight of the propylene polymer, heat resistance can be
highly improved, the stabilizer is available at a low cost,
and properties of the propylene polymer such as tensile
strength are not deteriorated.
When the content of the metallic salt of a higher
aliphatic acid [F] is within the above range, a residual
chlorine of the catalyst remained in the propylene polymer
can be sufficiently absorbed, whereby properties of the
propylene polymer are never deteriorated.
- ~
.
115 2 1 00999
It is particularly preferred that the sixth propylene
polymer composition of the invention contains the thioether
type stabilizer [D] in an amount of 0.005 to 2 parts by
weight, the hindered amine type stabilizer [E] in an amount
5 of 0.005 to 2 parts by weight and the metallic salt of
higher aliphatic acid [F] in an amount of 0.005 to 2 parts
by weight, each based on lOO parts by weight of the
propylene polymer [Al].
The seventh propylene polymer composition of the
0 invention is formed from:
[Al] the aforesaid propylene polymer, and
[E] a hindered amine type stabilizer in an amount of
O.OOl to lO parts by weight, preferably 0.003 to 5 parts by
weight, more preferably 0.005 to 3 parts by weight, based
on lOO parts by weight of the above propylene polymer.
The eighth propylene polymer composition of the
invention is formed from:
[Al] the aforesaid propylene polymer,
[E] a hindered amine type stabilizer in an amount of
O.OOl to lO parts by weight, preferably 0.003 to 5 parts by
weight, more preferably 0.005 to 3 parts by weight, based
on lOO parts by weight of the above propylene polymer, and
[F] a metallic salt of a higher aliphatic acid in an
amount of O.OOl to lO parts by weight, preferably 0.003 to
5 parts by weight, more preferably 0.005 to 3 parts by
weight, based on lOO parts by weight of the above propylene
polymer.
. .
- ,. ,;".
~ 116 21 00999
When the content of the hindered amine type stabilizer
[E] is within the above range based on 100 parts by weight
of the propylene polymer, heat resistance can be highly
improved, the stabilizer is available at a low cost, and
5 properties of the propylene polymer such as tensile
strength are not deteriorated.
When the content of the metallic salt of a higher
aliphatic acid [F] is within the above range based on 100
parts by weight of the propylene polymer, a residual
chlorine of the catalyst remained in the propylene polymer
can be sufficiently absorbed, the stabilizer is available
at a low cost, and properties of the propylene polymer are
never deteriorated.
The ninth propylene polymer composition of the
invention is formed from:
[A1] the aforesaid propylene polymer, and
[F] a metallic salt of a higher aliphatic acid in an
amount of 0.001 to 10 parts by weight, preferably 0.003 to
5 parts by weight, more preferably 0.005 to 3 parts by
weight, based on 100 parts by weight of the above propylene
polymer.
When the content of the metallic salt of a higher
aliphatic acid [F] is within the above range based on 100
parts by weight of the propylene polymer, a residual
chlorine of the catalyst remained in the propylene polymer
can be sufficiently absorbed, the stabilizer is available
- : ~
- 117 2 1 00999
at a low cost, and properties of the propylene polymer such
as tensile strength are not deteriorated.
The tenth propylene polymer composition of the
invention is formed from:
[A2] the aforesaid propylene block copolymer,
[B] a phenol type stabilizer in an amount of 0.001 to
10 parts by weight, preferably 0.003 to 5 parts by weight,
more preferably 0.005 to 3 parts by weight, based on 100
parts by weight of the above propylene block copolymer.
0 The eleventh propylene polymer composition of the
invention is formed from:
[A2] the aforesaid propylene block copolymer,
[B] a phenol type stabilizer in an amount of 0.001 to
10 parts by weight, preferably 0.003 to 5 parts by weight,
more preferably 0.005 to 3 parts by weight, based on 100
parts by weight of the above propylene block copolymer, and
at least one compound selected from the group
consisting of [C] an organophosphite type stabilizer, [D] a
thioether type stabilizer, [E] a hindered amine type
stabilizer and [F] a metallic salt of a higher aliphatic
acid in an amount of 0.001 to 10 parts by weight,
preferably 0.003 to 5 parts by weight, more preferably
0.005 to 3 parts by weight, based on 100 parts by weight of
the above propylene block copolymer.
When the content of the phenol type stabilizer [B] is
within the above range based on 100 parts by weight of the
propylene block copolymer, heat resistance can be highly
;~
2 1 00999
118
improved, the stabilizer is available at a low cost, and
properties of the propylene block copolymer such as tensile
strength are not deteriorated.
When the content of at least one compound selected
from the group consisting of the organophosphite type
stabilizer [C], the thioether type stabilizer [D], the
hindered amine type stabilizer [E] and the metallic salt of
a higher aliphatic acid [F] is within the above range based
on 100 parts by weight of the propylene block copolymer,
0 heat resistance can be highly improved, the stabilizer is
available at a low cost, and properties of the propylene
block copolymer such as tensile strength are not
deteriorated.
When the content of the metallic salt of a higher
aliphatic acid [F] is within the above range, a residual
chlorine of the catalyst remained in the propylene block
copolymer can be sufficiently absorbed, whereby properties
of the propylene block copolymer are never deteriorated.
It is particularly preferred that the eleventh
propylene polymer composition of the invention contains the
phenol type stabilizer [B] in an amount of 0.005 to 2 parts
by weight, the organophosphite type stabilizer [C] in an
amount of 0.005 to 2 parts by weight, the thioether type
stabilizer [D] in an amount of 0.005 to 2 parts by weight,
the hindered amine type stabilizer [E] in an amount of
0.005 to 2 parts by weight and the metallic salt of higher
aliphatic acid [F] in an amount of 0.005 to 2 parts by
1 19 2 1 009~9
weight, each based on 100 parts by weight of the propylene
block copolymer.
The twelfth propylene polymer composition of the
invention is formed from:
[A2] the aforesaid propylene block copolymer, and
[C] an organophosphite type stabilizer in an amount
of 0.001 to 10 parts by weight, preferably 0.003 to 5 parts
by weight, more preferably 0.005 to 3 parts by weight,
based on 100 parts by weight of the above propylene block
copolymer.
The thirteenth propylene polymer composition of the
invention is formed from:
[A2] the aforesaid propylene block copolymer,
[C] an organophosphite type stabilizer in an amount
of 0.001 to 10 parts by weight, preferably 0.003 to 5 parts
by weight, more preferably 0.005 to 3 parts by weight,
based on 100 parts by weight of the above propylene block
copolymer, and
at least one compound selected from the group
consisting of [D] a thioether type stabilizer, [E] a
hindered amine type stabilizer and [F] a metallic salt of a
higher aliphatic acid in an amount of 0.001 to 10 parts by
weight, preferably 0.003 to 5 parts by weight, more
preferably 0.005 to 3 parts by weight, based on 100 parts
by weight of the above propylene block copolymer.
When the content of the organophosphite type
stabilizer [C] is within the above range based on 100 parts
~ 120 21 00999
by weight of the propylene block copolymer, heat resistance
can be highly improved, the stabilizer is available at a
low cost, and properties of the propylene block copolymer
such as tensile strength are not deteriorated.
S When the content of at least one compound selected
from the group consisting of the thioether type stabilizer
[D], the hindered amine type stabilizer [E] and the
metallic salt of a higher aliphatic acid [F] is within the
above range based on 100 parts by weight of the propylene
0 block copolymer, heat resistance can be highly improved,
the stabilizer is available at a low cost, and properties
of the propylene block copolymer such as tensile strength
are not deteriorated.
When the content of the metallic salt of a higher
aliphatic acid [F] is within the above range, a residual
chlorine of the catalyst remained in the propylene block
copolymer can be sufficiently absorbed, whereby properties
of the propylene block copolymer are never deteriorated.
It is particularly preferred that the thirteenth
propylene polymer composition of the invention contains the
organophosphite type stabilizer [C] in an amount of 0.005
to 2 parts by weight, the thioether type stabilizer [D] in
an amount of O.OOS to 2 parts by weight, the hindered amine
type stabilizer [E] in an amount of 0.005 to 2 parts by
weight and the metallic salt of higher aliphatic acid [F]
in an amount of 0.005 to 2 parts by weight, each based on
100 parts by weight of the propylene block copolymer [A2].
L
Il
.
121 2 1 00999
The fourteenth propylene polymer composition of the
invention is formed from:
[A2] the aforesaid propylene block copolymer, and
[D] a thioether type stabilizer in an amount of 0.001
S to 10 parts by weight, preferably 0.003 to 5 parts by
weight, more preferably 0.005 to 3 parts by weight, based
on 100 parts by weight of the above propylene block
copolymer.
The fifteenth propylene polymer composition of the
0 invention is formed from:
[A2] the aforesaid propylene block copolymer,
[D] a thioether type stabilizer in an amount of 0.001
to 10 parts by weight, preferably 0.003 to 5 parts by
weight, more preferably 0.005 to 3 parts by weight, based
lS on 100 parts by weight of the above propylene block
copolymer, and
at least one compound selected from the group
consisting of [E] a hindered amine type stabilizer and [F]
a metallic salt of a higher aliphatic acid in an amount of
0.001 to 10 parts by weight, preferably 0.003 to 5 parts by
weight, more preferably 0.005 to 3 parts by weight, based
on 100 parts by weight of the above propylene block
copolymer.
When the content of the thioether type stabilizer [D]
is within the above range based on 100 parts by weight of
the propylene block copolymer, heat resistance can be
highly improved, the stabilizer is available at a low cost,
i~
~ 122 21 00999
and properties of the propylene block copolymer such as
tensile strength are not deteriorated.
When the content of at least one compound selected
from the group consisting of the hindered amine type
stabilizer [E] and the metallic salt of a higher aliphatic
acid [F] is within the above range based on lOO parts by
weight of the propylene block copolymer, heat resistance
can be highly improved, the stabilizer is available at a
low cost, and properties of the propylene block copolymer
0 such as tensile strength are not deteriorated.
When the content of the metallic salt of a higher
aliphatic acid [F] is within the above range, a residual
chlorine of the catalyst remained in the propylene block
copolymer can be sufficiently absorbed, whereby properties
lS of the propylene block copolymer are never deteriorated.
It is particularly preferred that the fifteenth
propylene polymer composition of the invention contains the
thioether type stabilizer [D] in an amount of 0.005 to 2
parts by weight, the hindered amine type stabilizer [E] in
an amount of 0.005 to 2 parts by weight and the metallic
salt of higher aliphatic acid [F] in an amount of 0.005 to
2 parts by weight, each based on lOO parts by weight of the
propylene block copolymer [A2].
The sixteenth propylene polymer composition of the
invention is formed from:
[A2] the aforesaid propylene block copolymer, and
L
-
21 OO~q9
123
[E] a hindered amine type stabilizer in an amount of
0.001 to 10 parts by weight, preferably 0.003 to 5 parts by
weight, more preferably 0.005 to 3 parts by weight, based
on 100 parts by weight of the above propylene block
copolymer.
The seventeenth propylene polymer composition of the
invention is formed from:
[A2] the aforesaid propylene block copolymer,
[E] a hindered amine type stabilizer in an amount of
0 0.001 to 10 parts by weight, preferably 0.003 to 5 parts by
weight, more preferably 0.005 to 3 parts by weight, based
on 100 parts by weight of the above propylene block
copolymer, and
[F] a metallic salt of a higher aliphatic acid in an
lS amount of 0.001 to 10 parts by weight, preferably 0.003 to
5 parts by weight, more preferably 0.005 to 3 parts by
weight, based on 100 parts by weight of the above propylene
block copolymer.
When the content of the hindered amine type stabilizer
[E] is within the above range based on 100 parts by weight
of the propylene block copolymer, heat resistance can be
highly improved, the stabilizer is available at a low cost,
and properties of the propylene block copolymer such as
tensile strength are not deteriorated.
When the content of the metallic salt of a higher
aliphatic acid [F] is within the above range based on 100
parts by weight of the propylene block copolymer, a
- ,
21 00999
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124
residual chlorine of the catalyst remained in the propylene
block copolymer can be sufficiently absorbed, the
stabilizer is available at a low cost, and properties of
the propylene block copolymer are never deteriorated.
The eighteenth propylene polymer composition of the
invention is formed from:
[A2] the aforesaid propylene block copolymer, and
[F] a metallic salt of a higher aliphatic acid in an
amount of 0.001 to 10 parts by weight, preferably 0.003 to
10 5 parts by weight, more preferably 0.005 to 3 parts by
weight, based on 100 parts by weight of the above propylene
block copolymer.
When the content of the metallic salt of a higher
aliphatic acid [F] is within the above range based on 100
parts by weight of the propylene block copolymer, a
residual chlorine of the catalyst remained in the propylene
block copolymer can be sufficiently absorbed, the
stabilizer is available at a iow cost, and properties of
the propylene block copolymer such as tensile strength are
not deteriorated.
Next, the stabilizers used in the present invention
are explained below in the order of [B] Phenol type
stabilizer, [C] Organophosphite type stabilizer, [D]
Thioether type stabilizer,[E] Hindered amine type
stabilizer, and [F] Metallic salt of higher aliphatic acid.
Phenol Type Stabilizers ~Bl
125 2 1 00999
Though conventionally known phenolic compounds are
used as phenol type stabilizers without specific
restriction, concrete examples of the phenol type
stabilizers include
2,6-di-tert-butyl-4-methylphenol,
2,6-di-tert-butyl-4-ethylphenol,
2,6-dicyclohexyl-4-methylphenol,
2,6-diisopropyl-4-ethylphenol,
2,6-di-tert-amyl-4-methylphenol,
0 2,6-di-tert-octyl-4-n-propylphenol,
2,6-dicyclohexyl-4-n-octylphenol,
2-isopropyl-4-methyl-6-tert-butylphenol,
2-tert-butyl-2-ethyl-6-tert-octylphenol,
2-isobutyl-4-ethyl-6-tert-hexylphenol,
2-cyclohexyl-4-n-butyl-6-isopropylphenol,
dl-~-tocopherol,
tert-butylhydroquinone,
2,2'-methylenebis(4-methyl-6-tert-butylphenol),
4,4'-butylidenebis(3-methyl-6-tert-butylphenol),
4,4'-thiobis(3-methyl-6-tert-butylphenol),
2,2-thiobis(4-methyl-6-tert-butylphenol),
4,4'-methylenebis(2,6-di-tert-butylphenol),
2,2'-methylenebis[6-(1-methylcyclohexyl)-p-cresol],
2,2'-ethylidenebis(2,4-di-tert-butylphenol),
2,2'-butylidenebis(2-tert-butyl-4-methylphenol),
1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)-
butane,
126 2 1 00999
triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-
hydroxyphenyl)propionate],
1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxy-
phenyl)propionate],
2,2'-thiodiethylenebis[3-(3,5-di-tert-butyl-4-
hydroxyphenyl)propionate],
N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-
hydrocinnamamide),
3,5-di-tert-butyl-4-hydroxybenzyl phosphonate diethyl
0 ester,
1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)
isocyanurate,
1,3,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)-
propionyloxyethyl] isocyanurate,
tris(4-tert-butyl-2,6-dimethyl-3-hydroxybenzyl)
isocyanurate,
2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butyl-
anilino)-1,3,5-triazine,
tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxy-
phenyl)propionate]methane,
bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid
ethyl ester) calcium,
bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid
ethyl ester) nickel,
bis[3,3-bis(3-tert-butyl-4-hydroxyphenyl)butyric acid]
glycol ester,
21 00999
127
N,N'-bis[(3,5-di-tert-butyl-4-hydroxyphenyl)-
propionyl]hydrazine,
2,2'-oxamidobis[ethyl-3-(3,5-di-tert-butyl-4-
hydroxyphenyl)propionate],
2,2'-methylenebis(4-methyl-6-tert-butylphenol)
terephthalate,
1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-
hydroxybenzyl)benzene,
3,9-bis[l,l-dimethyl-2-{~-(3-tert-butyl-4-hydroxy-5-
0 methylphenyl)propionyloxy}ethyl]-2,4,8,10-
tetraoxaspiro[5,5]-undecane,
2,2-bis[4-(2-(3,5-di-tert-butyl-4-hydroxyhydro-
cinnamoyloxy))ethoxyphenyl]propane, and
alkyl esters of ~-(3,5-di-tert-butyl-4-hydroxyphenyl)-
propionic acid.
Of these compounds, preferred are
triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-
hydroxyphenyl)propionate],
1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxy-
phenyl)propionate],
2,2-thiodiethylenebis[3-(3,5-di-tert-butyl-4-
hydroxyphenyl)propionate],
N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-
hydrocinnamamide),
3,5-di-tert-butyl-4-hydroxybenzyl phosphonate-diethyl
ester,
128 21 0099'~
1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)
isocyanurate,
1,3,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)-
propionyloxyethyl] isocyanurate,
tris(4-tert-butyl-2,6-dimethyl-3-hydroxybenzyl)
isocyanurate,
2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butyl-
anilino)-1,3,5-triazine,
tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxy-
phenyl)propionate]methane,
bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid
ethyl ester) calcium,
bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid
ethyl ester) nickel,
bis[3,3-bis(3-tert-4-hydroxyphenyl)butyric acid]
glycol ester,
N,N'-bis[(3,5-di-tert-butyl-4-hydroxyphenyl)-
propionyl]hydrazine,
2,2'-oxamidobis[ethyl-3-(3,5-di-tert-butyl-4-
hydroxyphenyl)propionate],
2,2'-methylenebis(4-methyl-6-tert-butylphenol)
terephthalate,
1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-
hydroxybenzyl)benzene,
3,9-bis[l,l-dimethyl-2-{~-(3-tert-butyl-4-hydroxy-5-
methylphenyl)propionyloxy}ethyl]-2,4,8,10-
tetraoxaspiro[5,5]-undecane,
~1 00999
129
2,2-bis[4-(2-(3,5-di-tert-butyl-4-hydroxyhydro-
cinnamoyloxy))ethoxyphenyl]propane, and
alkyl esters of ~-(3,5-di-tert-butyl-4-hydroxyphenyl)-
propionic acid.
Of the alkyl esters of ~-(3,5-di-tert-butyl-4-
hydroxyphenyl)propionic acid mentioned above, particularly
preferred are alkyl esters having alkyl group of not
greater than 18 carbon atoms.
Furthermore, the following compounds are particularly
preferably used in the present invention:
tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxy-
phenyl)propionate]methane,
bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid
ethyl ester) calcium,
lS bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid
ethyl ester) nickel,
bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid]
glycol ester,
N,N'-bis[(3,5-di-tert-butyl-4-hydroxyphenyl)-
propionyl]hydrazine,
2,2'-oxamidobis[ethyl-3-(3,5-di-tert-butyl-4-
hydroxyphenyl)propionate],
2,2'-methylenebis(4-methyl-6-tert-butylphenol)
terephthalate,
1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-
hydroxybenzyl)benzene,
130 21 00999
3,9-bis[1,1-dimethyl-2-{~-(3-tert-butyl-4-hydroxy-5-
methylphenyl)propionyloxy}ethyl]-2,4,8,10-
tetraoxaspiro[5,5]-undecane,
1,3,5-tris[(3,5-di-tert-butyl-4-
hydroxyphenyl)propionyloxyethyl]isocyanurate, and
2,2-bis[4-(2-(3,5-di-tert-butyl-4-hydroxyhydro-
cinnamoyloxy))ethoxyphenyl]propane.
These phenol type stabilizers are used singly or in
combination.
Org~nophosphite Type Stabilizers rcl
Though conventionally known organophosphite type
stabilizers are used without specific restriction in the
present invention, concrete examples of the organophosphite
type stabilizers include
trioctyl phosphite, trilauryl phosphite, tridecyl
phosphite, octyl diphenyl phosphite, tris(2,4-di-tert-
butylphenyl) phosphite, triphenyl phosphite,
tris(butoxyethyl) phosphite, tris~nonylphenyl) phosphite,
distearylpentaerithrytol diphosphite, tetra(tridecyl)-
1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane
diphosphite, tetra(C12-C1s mixed alkyl)-4,4'-
isopropylidenediphenyl diphosphite, tetra(tridecyl)-4,4'-
butylidenebis(3-methyl-6-tert-butylphenol) diphosphite,
tris(3,5-di-tert-butyl-4-hydroxyphenyl) phosphite,
tris(mixed monononylphenyl, dinonylphenyl) phosphite,
hydrogenated-4,4'-isopropylidenediphenol polyphosphite,
bis(octylphenyl)-bis[4,4'-butylidenebis(3-methyl-6-tert-
-- 21 00999
131
butylphenol)]-1,6-hexanediol diphosphite, phenyl-4,4'-
isopropylidenediphenol-pentaerythritol diphosphite,
tris[4,4'-isopropylidenebis(2-tert-butylphenol)] phosphite,
phenyl-diisodecyl phosphite, di(nonylphenyl)
pentaerythritol diphosphite, tris(1,3-di-
stearoyloxyisopropyl) phosphite, 4,4'-isopropylidenebis(2-
tert-butylphenol)-di(nonylphenyl) phosphite, and 9,10-
dihydro-9-oxa-9-oxa-10-phosphaphenanthrene-10-oxide.
In addition, bis(dialkylphenyl) pentaerythritiol
0 diphosphite esters having the formula (iv) of spiro type or
the formula (v) of cage type illustrated below are also
used:
Usually, a mixture of both isomers is most often used
due to utilization of an economically advantageous process
for manufacturing such phosphite ester.
R1 R3
3~5/ P C \ p _ O _ ~ R
R2 OCH2 CH2O R3 R
.. (iv)
R23~) \ / CH20 ~
P - OCH2 - C - CH20 - P
R ~ _ O / \ CH2O
... (v)
wherein R1~ R2 and R3 are each a hydrogen or an alkyl group
having 1 to 9 carbon atoms, preferably a branched alkyl
group, particularly preferably a tert-butyl group, the most
21 00999
132
preferable substitution positions of R1~ R2 and R3 on the
phenyl groups being 2-, 4- and 6-positions. Preferable
phosphite esters include bis(2,4-di-tert-
butylphenyl)pentaerythritol diphosphite and bis(2,6-di-
tert-butyl-4-methylphenyl)pentaerythritol diphosphite, and
there may also be mentioned phosphonites having a structure
wherein a carbon atom is directly bonded to a phosphorus
atom, such as tetrakis(2,4-di-tert-butylphenyl)-4,4'-
biphenylene diphosphonite.
0 These organophosphite type stabilizers are used singly
or in combination.
Thioether Type Stabilizers rDl
Though conventionally known thioether type stabilizers
are used without specific restriction in the present
invention, concrete examples of the thioether type
stabilizers include
dialkyl esters such as dilauryl, dimyristyl and
distearyl ester of thiodipropionic acid, esters of
alkylthiopropionic acid such as butyl-, octyl-, lauryl- and
stearylthiopropionic acid with a polyhydric alcohol (for
example, glycerine, trimethylolethane, trimethylolpropane,
pentaerythritol and trishydroxyethyliscyanurate), such as
pentaerythritoltetralaurylthiopropionate. More concretely,
the thioether stabilizers include dilauryl
thiodipropionate, dimyristyl thiodipropionate, lauryl
stearyl thiodipropionate and distearyl thiodibutyrate.
- ~ .
2 1 00999
133
These thioether type stabilizers are used singly or in
combination.
Hin~ered Amine Type Stabilizers rEl
There are used without specific restriction as the
hindered amine type stabilizers conventionally known
compounds having a structure wherein methyl groups are
substituted for all the hydrogen atoms bonded to the carbon
atoms at the 2- and 6-positions of piperidine. Concrete
examples of the hindered amine type stabilizers include
(1) bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate,
(2) dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-
2,2,6,6-tetramethylpiperidine polycondensate,
(3) poly[[6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-
triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-
piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-
piperidyl)imino]],
(4) tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-
butanetetracarboxylate,
(5) 2,2,6,6-tetramethyl-4-piperidyl benzoate
(6) bis~1,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-tert-
butyl-4-hydroxybenzyl)-2-n-butyl malonate,
(7) bis-(N-methyl-2,2,6,6-tetramethyl-4-piperidyl)
sebacate,
(8) 1,1'-(1,2-ethanediyl)bis(3,3,5,5-tetramethyl-
piperazinone),
(9) (mixed 2,2,6,6-tetramethyl-4-piperidyl/tridecyl)
1,2,3,4-butanetetracarboxylate,
21 00999
134
(10) (mixed 1,2,2,6,6-pentamethyl-4-piperidyl/tridecyl)
1,2,3,4-butanetetracarboxylate,
(11) mixed {2,2,6,6-tetramethyl-4-piperidyl/~
tetramethyl-3,9-[2,4,8,10-tetraoxasprio(5,5)-
undecane]diethyl} 1,2,3,4-butanetetracarboxylate,
(12) mixed {1,2,2,6,6-pentamethyl-4-piperidyl/~
tetramethyl-3,9-[2,4,8,10-tetraoxaspiro(5,5)-
undecane]diethyl} 1,2,3,4-butanetetracarboxylate,
(13) N,N'-bis(3-aminopropyl)ethylenediamine-2,4-bis[N-
butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-6-chloro-
1,3,5-triazine condensate,
(14) poly[[6-N-morpholinyl-1,3,5-triazine-2,4-diyl]-
[(2,2,6,6-tetramethyl-4-
piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-
piperidyl)imino]],
(15) condensate of N,N'-bis(2,2,6,6-tetramethyl-4-
piperidyl)hexamethylenediamine with 1,2-dibromoethane, and
(16) [N-(2,2,6,6-tetramethyl-4-piperidyl)-2-methyl-2-
(2,2,6,6-tetramethyl-4-piperidyl)imino]propionamide.
Of the hindered amine type stabilizers, those
especially preferably employed are the compounds denoted by
(1), (2), (3), (4), (8), (10), (11), (14) and (15).
These hindered amine type stabilizers are used singly
or in combination.
Metallic Salts of Higher Aliphatic Acid rFl
Examples of metallic salts of the higher aliphatic
acid which may be used in the invention include alkaline
21 00999
135
earth metal salts such as magnesium salts, calcium salts
and barium salts, alkali metal salts such as sodium salts,
potassium salts and lithium salts, cadmium salts, zinc
salts and lead salts of higher aliphatic acids such as
stearic acid, oleic acid, lauric acid, capric acid,
ariachidic acid, palmitic acid, behenic acid, 12-
hydroxystearic acid, ricinolic acid, and montanic acid.
Concrete examples of the metallic salt of higher aliphatic
acid include
magnesium stearate, magnesium laurate, magnesium
palmitate, calcium stearate, calcium oleate, calcium
laurate, barium stearate, barium oleate, barium laurate,
barium arachidate, barium behenate, zinc stearate, zinc
oleate, zinc laurate, lithium stearate, sodium stearate,
sodium palmitate, sodium laurate, potassium stearate,
potassium laurate, calcium 12-hydroxystearate and calcium
montanate.
These metallic salts of higher aliphatic acid are used
singly or in combination.
Metallic salts of higer aliphatic acid as described
above act as a lubricant and a rust-preventive agent.
Propylene polymer compositions containing such metallic
salts of higher aliphatic acid therefore are excellent in
moldability and effective in rust prevention of molding
machines, etc.
The propylene polymer compositions of the invention
can be used without specific limitation in a field where
21 00999
136
polypropylene has been conventionally used, and
particularly they can be favorably used for extruded sheet,
unstretched film, stretched film, filament, injection
molded product and blow molded product.
There is no specific limitation on the shape and the
kind of the extrusion molded product made of the propylene
polymer composition of the invention. Concretely, there
can be mentioned sheet, film (unstretched film), pipe,
hose, electric wire cover and filament. The extrusion
molded product of the propylene polymer composition is
particularly preferably used as sheet, film (unstretched
film) and filament.
In order to extrusion mold the propylene polymer
composition of the invention into a sheet, a film
(unstretched film) or the like, conventionally known
extrusion apparatuses such as a single screw extruder, a
kneading extruder, a ram extruder and a gear extruder can
be used. Using such extruder, a molten propylene polymer
composition is extruded from a T-die or the like to prepare
an extrusion molded product. The extrusion molding can be
carried out under the molding conditions conventionally
known.
The extruded sheet and film (unstretched film)
prepared as above are excellent in rigidity, heat
resistance and moisture resistance.
A stretched film can be prepared from the above-
mentioned sheet or film made of the propylene polymer
,
21 00999
-
137
composition by conventional stretching methods using known
stretching machines, such as tentering (lengthwise-
crosswise stretching, crosswise-lengthwise stretching),
simultaneous biaxial stretching (biaxial orientation) and
monoaxial stretching. The stretch ratio of the biaxially
stretched (oriented) film is preferably in the range of 20
to 70 times, while the stretch ratio of the monoaxially
stretched film is preferably in the range of 2 to 10 times.
The thickness of the stretched film is desirably in the
range of 5 to 200 ~m.
Such stretched film is excellent in rigidity, heat
resistance and moisture resistance.
From the propylene polymer composition of the
invention, an inflation film can be also prepared.
Since the sheet, the unstretched film and the
stretched film composed of the propylene polymer
composition of the invention are excellent in heat
resistance, transparency, see-through properties,
glossiness, rigidity, moisture resistance, gas barrier
properties, etc., they can be widely applied to packaging
films or other uses. In particular, they are very suitable
for press through pack used for packaging of pharmaceutical
tablets or capsules.
The filament composed of the propylene polymer
composition of the invention can be prepared, for example,
by extruding a molten propylene polymer composition through
a spinning nozzle. The filament thus obtained may be
.
2 1 00999
138
further subjected to stretching. This stretching is
carried out in such a manner that the molecular orientation
at least in the monoaxial direction is effectively given to
the propylene polymer, and the stretch ratio is desirably
in the range of 5 to 10 times.
Such filament is excellent in rigidity and heat
resistance.
The injection molded product composed of the propylene
polymer composition of the invention can be prepared using
a conventionally known injection molding apparatus. The
injection molding can be carried out under the molding
conditions conventionally known.
Since the injection molded product is excellent in
rigidity, heat resistance, impact resistance, surface
glossiness, chemical resistance, abrasion resistance, etc.,
it can be widely used for automotive interior trims,
automotive exterior trims, housings for electrical
appliances, containers, etc.
The blow molded product composed of the propylene
polymer composition of the invention can be prepared using
a conventionally known blow molding apparatus. The blow
molding can be carried out under the molding conditions
conventionally known. For example, in the extrusion blow
molding, a molten propylene polymer composition is extruded
from a die to form a tubular parison at a resin temperature
of 100 to 300 C, then the parison is kept within a mold
having an aimed shape, and air is blown into the mold at a
21 00999
-
139
resin temperature of 130 to 300 C to obtain a hollow
molded product. In this case, the stretch ratio is
desirably within the range of 1.5 to 5 times in the
crosswise direction.
In the injection blow molding, a molten propylene
polymer composition is injected into a mold to form a
parison at a resin temperature of 100 to 300 C, then the
parison is kept within the mold having an aimed shape, and
air is blown into the mold at a resin temperature of 120 to
300 C to obtain a hollow molded product. In this case,
the stretch ratio is desirably within the range of 1.1 to
1.8 times in the lengthwise direction and within the range
of 1.3 to 2.5 times in the crosswise direction.
Such blow molded product is excellent in rigidity,
heat resistance and moisture resistance.
The propylene polymer compositions of the invention
can be used as a substrate in a method wherein a skin
material and a substrate are subjected to press molding at
the same time to prepare an integrally molded product
(i.e., mold stamping method). The molded product obtained
by the mold stamping can be favorably used as automotive
interior trims such as door trim, rear package trim, sheet
back garnish and instrument panel.
The molded product obtained by the mold stamping is
excellent in rigidity and heat resistance.
21 00999
140
EFFECT OF THE INVENTION
The propylene polymer of the invention has a high
crystallinity of a boiled heptane-insoluble component
contained therein and a high stereoregularity, and moreover
S it has an extremely long mesochain. Hence, the propylene
polymer is excellent in rigidity, heat resistance and
moisture resistance.
The propylene block copolymer of the invention has a
high crystallinity of a boiled heptane-insoluble component
contained therein and a high stereoregularity, and moreover
it has an extremely long mesochain. Hence, the propylene
block copolymer is well-balanced between rigidity, heat
resistance and impact resistance.
The propylene polymer composition of the invention is
formed from the propylene polymer or the propylene block
copolymer which has a high crystallinity of a boiled
heptane-insoluble component contained therein, a high
stereoregularity and an extremely long mesochain, and a
specific stabilizer. Hence, the propylene polymer
composition is excellent in heat stability during the
molding stage, long-term heat stability, weathering
resistance, etc., and moreover a molded product obtained
from this propylene polymer composition is excellent in
rigidity, heat resistance and moisture resistance.
The present invention is further illustrated by the
following examples, but the invention is in no way
restricted to those examples.
141 2 1 00999
EXAMPLE
Example 1
[Preparation of solid titanium catalyst component (A)]
95.2 g of anhydrous magnesium chloride, 442 ml of
decane and 390.6 g of 2-ethylhexylalcohol were mixed and
heated at 130C for 2 hours to give a homogeneous solution.
Then, to the solution was added 21.3 g of phthalic
anhydride and they were mixed and stirred at 130C for 1
hour to dissolve the phthalic anhydride in the solution.
0 The thus obtained homogeneous solution was cooled to room
temperature, and then 75 ml of the homogeneous solution was
dropwise added to 200 ml of titanium tetrachloride kept at
-20C over a period of 1 hour. After the addition was
completed, the temperature of the resulting mixture liquid
lS was raised to 110C over a period of 4 hours. When the
temperature of the mixture liquid reached to 110C, 5.22 g
of diisobutyl phthalate (DIBP) was added to the mixture
liquid, and then resulting mixture was stirred at the same
temperature for 2 hours.
After the reaction was completed, a solid portion was
recovered from the reaction liquid by means of hot
filtration. The solid portion was suspended again in 275
ml of titanium tetrachloride, and the obtained suspension
was further heated at 110C for 2 hours. After the
reaction was completed, a solid portion was recovered again
by means of hot filtration. The solid portion was well
142 21 00999
washed with decane and hexane kept at 110C until no
titanium compound liberating in the solution was detected.
The solid titanium catalyst component (A) prepared as
above was stored as a decane slurry. A part of the slurry
S was dried to examine the catalyst composition. The catalyst
component (A) obtained had a composition comprising 2.4 %
by weight of titanium, 60 % by weight of chlorine, 20 % by
weight of magnesium and 13.0 % by weight of DIBP.
[Preparation of prepolymerized catalyst (B)]
Into a 2-liter autoclave equipped with a stirrer, 500
ml of purified hexane, 57.5 g of 3-methyl-1-butene, 50 mmol
of triethylaluminum, 50 mmol of triemethylmethoxysilane and
5.0 mmol Ti (in terms of titanium atom) of the above-
obtained solid titanium catalyst component (A) were charged
in a nitrogen atmosphere to perform a reaction for 2 hours.
The polymerization temperature in the autoclave was kept at
20C.
After the reaction was completed, the reactor was
purged with nitrogen, and a washing operation consisting of
removal of the supernatant liquid and addition of purified
hexane was carried out three times. Thereafter, the
obtained reaction liquid was suspended again using purified
hexane, and all of the resulting suspension was transferred
into a catalyst bottle to obtain a prepolymerized catalyst
(B). 5.7 g of poly-3-methyl-1-butene was produced based on
1 g of the solid titanium catalyst component (A).
`-- 21 00-999
143
[Polymerization]
Into a 2-liter autoclave, 750 ml of purified n-hexane
was charged, and further 0.75 mmol of triethylaluminum,
0.75 mmol of dicyclopentyldimethoxysilane (DCPMS) and 0.015
mmol Ti (in terms of titanium atom) of the above-obtained
prepolymerized catalyst (B) were charged at 60C in a
propylene atmosphere.
Further, 1200 ml of hydrogen was introduced into the
autoclave, and the temperature in the autoclave was raised
to 70C, followed by keeping the same temperature for 2
hours to perform a propylene polymerization. The pressure
during the polymerization was kept at 7 kg/cm2-G. After
the polymerization was completed, a slurry containing the
produced solid was filtered and separated into a white
powder and a liquid phase portion.
The yield of the white powder polymer was 303.2 g on
the dry basis, and the white powder polymer had a melt flow
rate (MFR) of 12.5 g/10 min and an apparent bulk specific
gravity of 0.45 g/ml. Further, the obtained white powder
was dissolved in decane for a time, and then gradually
cooled to obtain a powder. The amount of the boiled
heptane-insoluble component contained in this powder was
96.9% by weight and the crystallinity of the boiled
heptane-insoluble component was 71.0 %.
On the other hand, 2.0 g of a solvent-soluble polymer
was obtained by concentration of the above-obtained liquid
phase portion. Accordingly, the activity was 20,300 g-
~.
.~
21 00999
144
PP/mM-Ti, and the amount of the boiled heptane-insoluble
component contained in the whole polymer was 96.3 % by
weight.
The results are set forth in Table l.
Example 2
The procedure of the polymerization as in Example l
was repeated except that the polymerization temperature was
changed to 80C.
The results are set forth in Table l.
Example 3
The procedure of the polymerization as in Example l
was repeated except that the polymerization temperature was
changed to 90C.
The results are set forth in Table l.
Example 4
[Polymerization]
Into a 2-liter autoclave, 500 g of propylene and 6
liters of hydrogen were charged, and the temperature in the
autoclave was raised to 60C. Then, 0.6 mmol of
triethylaluminum, 0.6 mmol of dicyclopentyldimethoxysilane
(DCPMS) and 0.006 mmol Ti (in terms of titanium atom) of
the above-obtained prepolymerized catalyst (B) were charged
into the autoclave.
The temperature in the autoclave was raised to 70C,
followed by keeping the same temperature for 40 minutes to
perform a propylene polymerization. The reaction was
terminated by the addition of a small amount of ethanol.
. ,, .. , . ~ . ~ . . 1
. ~
145 21 00999
After the unreacted propylene was removed, a white powder
polymer was dried under a reduced pressure.
The results are set forth in Table 1.
Example 5
The procedure of the polymerization as in Example 1
was repeated except that the polymerization temperature was
changed to 80C.
The results are set forth in Table 1.
Comparative Example 1
The procedure of the polymerization as in Example 1
was repeated except that 0.075 mmol of
cyclopentyldimethyoxysilane was used instead of the DCPMS
and 500 ml of hydrogen was used.
The results are set forth in Table 1.
Comparative Example 2
The procedure of the polymerization as in Example 1
was repeated except that 0.075 mmol of
diphenyldimethoxysilane was used instead of the DCPMS and
700 ml of hydrogen was used.
The results are set forth in Table 1.
Comparative Example 3
[Preparation of solid titanium catalyst component (C)]
1.2 mol of diisoamylether was dropwise added to a
mixture of 500 ml of n-hexane and 0.5 mol of
diethylaluminum chloride at 25C over a period of 2 minutes
to perform a reaction for 10 minutes.
146 2 1 00999
A 2-liter reactor thoroughly purged with nitrogen was
charged with 4.0 mol of titanium tetrachloride, and the
temperature in the reactor was raised to 35C. To the
reactor, the above reaction solution was dropwise added
5 over a period 3 hours, followed by keeping the same
temperature for 30 minutes. Then, the temperature in the
reactor was raised to 75C and the reaction was further
performed for 1 hour. The resulting reactlon solution was
cooled to room temperature and the supernatant liquid was
removed, and then the thus produced solid was washed with 1
liter of hexane. The washing operation was further carried
out three times.
100 g of the obtained solid was suspended using 2
liter of n-hexane, and to the resulting suspension were
added 80 g of diisoamylether and 180 g of titanium
tetrachloride at room temperature over a period of 1 minute
to perform a reaction at 65C for 1 hour. After the
reaction was completed, the temperature was cooled to room
temperature and the supernatant was removed by decantation.
The thus produced solid was washed with 2 liters of hexane.
Then, the washing operation was further carried out three
times, to thereby obtain a solid titanium catalyst
component (C).
[Preparation of prepolymerized catalyst (D)]
Into a 2-liter autoclave equipped with a stirrer, 1
liter of purified hexane, 30 mmol of diethylaluminum
chloride and 3 g of the above-obtained solid titanium
147 2 1 00999
catalyst component (C) were charged in a nitrogen
atmosphere. Thereafter, 2 liters of hydrogen was
introduced into the autoclave and propylene was fed to the
reactor to perform a prepolymerization for 5 minutes. The
5 pressure during the reaction was kept at 5 kg/cm2-G.
After the reaction was completed, the unreacted
propylene and hydrogen were removed and the reactor was
purged with nitrogen, and a washing operation consisting of
removal of supernatant liquid and addition of purified
0 hexane was carried out three times, to thereby obtain a
prepolymerized catalyst (D). The thus obtained
prepolymerized catalyst (D) was suspended again using
purified decane and stored.
[Polymerization]
Into a 2-liter autoclave equipped with a stirrer, 750
ml of purified n-hexane was charged, and further 0.75 mmol
of diethylaluminum chloride, 0.75 mmol of p-toluic acid
methyl ester and 1.1 g of the above-obtained prepolymerized
catalyst (D) were charged at 60C in a propylene
atmosphere.
Further, 8 liters of hydrogen was introduced into the
autoclave, and the temperature in the autoclave was raised
to 70C, followed by keeping the same temperature for 4
hours to perform a propylene polymerization. The pressure
during the polymerization was kept at 7 kg/cm2-G. After
the polymerization was completed, 200 ml of methanol was
added to the resulting mixture and the temperature was
148 21 00999
raised to 80C. After 30 minutes, 1 ml of an aqueous
solution containing 20% of sodium hydroxide was added to
the resulting mixture and the unreacted gas was removed.
After the liquid phase was removed, the resulting
hexane slurry was washed with 300 ml of deionized water for
20 minutes and the aqueous phase was removed. Then, the
hexane slurry was filtered, and then washed and dried, to
thereby obtain a polypropylene powder.
The results are set forth in Table 1.
Table 1
Apparent Amount of
Activity MF~bulk - boiled Boiled heptane-
specific heptene-insoluble component
*1) gravity insoluble
component
g/10 (g/ml) ~wt%) Crystallinity [M5] [M3]
min (%)
Ex 120,300 12.5 0.45 96.3 75.0 0.992 0.0027
Ex.225,300 21.2 0.42 96.5 78.5 0.994 0.0025
Ex.325,500 33.4 0.40 96.9 79.3 0.995 0.0025
Ex.4 17,200 16.0 0.47 96.2 74.8 0.992 0.0029
Ex.5 22,700 23.5 0.40 96.6 78.9 0.994 0.0026
Comp
Ex.l 19,300 11.0 0.45 90.0 65.3 0.965 0.0036
Comp
Ex.2 20,000 13.8 0.45 90.9 65.0 0.966 0.0036
Comp
Ex.3 1,000 16.0 0.35 92.5 58.5 0.980 0.0017
*1) g-PP/mmol-Ti
., . - - .... ~11
2 1 00~99
149
Example 6
[Polymerization]
Into a 2-liter autoclave, 500 g of propylene and 17
liters of hydrogen was charged, and the temperature in the
S autoclave was raised to 60C. Then, 0.6 mmol of
triethylaluminum, 0.6 mmol of dicyclopentyldimethoxysilane
(DCPMS) and 0.006 mmol Ti (in terms of titanium atom) of
the above-obtained prepolymerized catalyst (B) were charged
into the autoclave. The temperature in the autoclave was
raised to 70C, followed by keeping the same temperature
for 40 minutes to perform a propylene homopolymerization.
After the hompolymerization was completed, a vent valve was
opened and the unreacted propylene was removed until the
pressure in the autoclave reached to atmospheric pressure.
lS After the removal was completed, ethylene and
propylene were copolymerized under conditions such that
ehtylene, propylene and hydrogen were fed into the
autoclave at 80N-liter/hr, 120N-liter/hr and 2N-liter/hr,
respectively. The vent opening degree of the autoclave was
controlled so that the pressure in the autoclave was kept
at 10 kg/cm2. The temperature in the autoclave was kept at
70C to perform a polymerization for 60 minutes. The
- polymerization reaction was terminated by the addition of a
small amount of ethanol and the unreacted gas in the
autoclave was purged out.
The yield of the white powder polymer was 143.3 g, and
the polymer had a melt flow rate (MFR) of 48 g/10 min and
21 00999
150
an apparent bulk specific gravity of 0.44 g/ml. The amount
of a decane-soluble component in the white powder polymer
was ll.4 % by weight and the intrinsic viscosity [~] of the
decane-soluble component was 3.7 dl/g.
S Further, the amount of the boiled heptane-insoluble
component in the decane-insoluble component was 94.4 % by
weight, the [Ms] value, [M3] value and crystallinity of the
boiled heptane-insoluble component were O.99l, 0.0035 and
73.2 %, respectively.
0 Exam~le 7
[Polymerization]
The procedure as in Example 6 was repeated except that
hydrogen was not used during the copolymerization.
The results are set forth in Table 2.
Example 8
[Polymerization]
The procedure as in Example 6 was repeated except that
the temperature of the propylene homopolymerization was
changed to 80C.
The results are set forth in Table 2.
Example 9
[Polymerization]
Into a 2-liter autoclave, 750ml of purified n-hexane
was charged, and further 0.75 mmol of triethylaluminum,
0.75 mmol of dicyclopentadimethoxysilane (DCPMS) and 0.015
mmol Ti ( in terms of titanium atom) of the above-obtained
-- 21 00999
151
prepolymerized catalyst (B) were charged at 60C in a
propylene atmosphere.
Then, 2700 ml of hydrogen was introduced into the
autoclave and the temperature in the autoclave was raised
to 70C, followed by keeping the same temperature for 2
hours to perform a propylene homopolymerization. The
pressure during the polymerization was kept at 7Kg/cm2-G.
After the homopolymerization was completed, the unreacted
gas was purged out until the pressure in the autoclave
reached to atmospheric pressure.
Thereafter, 120 ml of hydrogen was introduced, and
ethylene and propylene were copolymerized under conditions
such that a mixture gas of 64 mol% of propylene and 36 mol%
of ethylene were fed to perform a copolymerization at 70C
for 1 hour. The pressure during the polymerization was kept
at 2 Kg/cm2-G. After the reaction was completed, the
resulting slurry containing the produced solid was
filtered, to thereby obtain a white powder polymer.
The yield of the white powder polymer was 372.2g on
the dry basis, and the white powder polymer had a melt flow
rate (MFR) of 46 g/lOmin, and an apparent bulk specific
gravity of 0.45 g/ml. The amount of a decane-soluble
component in the white powder polymer was 12.0% by weight
and the intrinsic viscosity [~] of the decane-soluble
component was 3.9 dl/g.
Further, the amount of the boiled heptane-insoluble
component contained in the decane-insoluble component was
-- 21 00999
152
94.7% by weight, the [M5] value, [M3] value and
crystallinity of the boiled heptane-insoluble component
were 0.992, 0.0035 and 73.5%, respectively.
F.x~m~l e 10
[Polymerization]
The procedure as in Example 9 was repeated except that
hydrogen was not used during the copolymerization.
The results are set forth in Table 2.
Example 11
[Polymerization]
The procedure as in Example 9 was repeated except that
the propylene homopolymerization temperature was changed to
80C.
The results are set forth in Table 2.
Example 12
[Polymerization]
The procedure as in Example 9 was repeated except that
the propylene homopolymerization temperature was changed to
90C .
The results are set forth in Table 2.
Example 13
[Polymerization]
The procedure as in Example 7 was repeated except that
hexyltrimethoxysilane was used instead of
dicyclopentyldimethoxysilane.
The results are set forth in Table 2.
21 00999
153
Fxample 14
[Polymerization]
The procedure as in Example 13 was repeated except
that the propylene homopolymerization temperature was 80C.
The results are set forth in Table 2.
Comp~rative Fxample 4
The procedure as in Example 9 was repeated except that
0.075 mmol of diphenyldimethoxysilane was used instead of
DCPMS and 1600ml of hydrogen was used during the
0 homopolymerization.
The results are set forth in Table 2.
Comparative Example 5
The procedure of the polymerization as in Comparative
Example 4 was repeated except that hydrogen was not used
during the copolymerization.
The results are set forth in Table 2.
Comparative Example 6
[Preparation of solid titanium catalyst component (E)]
1.2 mol of diisoamylether was dropwise added to a
mixture of 500 ml of n-hexane and 0.5 mol of
diethylaluminum chloride at 25C over a period of 2 minutes
to perform a reaction for 10 minutes.
A 2-liter rector throughly purged with nitrogen was
charged with 4.0 mol of titanium tetrachloride, and the
temperature in the reactor was raised to 35C. To the
reactor, the above prepared reaction solution was dropwise
added over a period of 3 hours, followed by keeping the
154 21 00999
same temperature for 30 minutes. Then, the temperature in
the reactor was raised to 75C and the reaction was further
performed for 1 hour. The resulting reaction solution was
cooled to room temperature and the supernatant liquid was
removed. Then, the thus produced solid was washed with 1
liter of hexane. The washing operation was further carried
out three times.
lOOg of the obtained solid was suspended using 2 liter
of n-hexane, and to the resulting suspension were added 80
g of isoamylether and 180 g of titanium tetrachloride at
room temperature over a period of 1 minute to perform a
reaction at 65C for 1 hour. After the reaction was
completed, the temperature was cooled to room temperature
and the supernatant was removed by decantation. The thus
produced solid was washed with 2 liters of hexane. Then,
the washing operation was further carried out three times
to thereby obtain a solid titanium catalyst component (E).
[Preparation of prepolymerized catalyst (F)]
Into a 2-liter reactor equipped with a stirrer, 1
liter of purified hexane, 30 mmol of diethylaluminum
chloride and 3 g of the above-obtained solid titanium
catalyst component (E) were charged in a nitrogen
atmosphere. Thereafter, 2 liters of hydrogen was introduced
into the reactor and propylene was fed to the reactor to
perform a prepolymerization for 5 minutes. The pressure
during the reaction was kept at 5Kg/cm2-G.
2 ~ 00999
155
After the reaction was completed, the unreacted
propylene and hydrogen were removed and the reactor was
purged with nitrogen, and a washing operation consisting of
removal of the supernatant liquid and addition of purified
S hexane was carried out three times, to thereby obtain a
prepolymerized catalyst (F). The thus obtained
prepolymerized catalyst (F) was suspended again using
purified decane and stored.
[Polymerization]
Into a 2-liter autoclave equipped with stirrer, 750
ml of purified n-hexane was charged, and further 0.75 mmol
of diethylaluminum chloride, 0.75 mmol of p-toluic acid
methyl ester and 1.1 g of the above obtained prepolymerized
catalyst (F) were charged at 60C in a propylene
lS atmosphere.
Further, 18 liters of hydrogen was introduced into the
autoclave, and the temperature in the autoclave was raised
to 70C, followed by keeping the same temperature for 4
hours to perform a propylene polymerization. The pressure
during the polymerization was kept at 7Kg/cm2-G. After the
homopolymerization was completed, the unreacted gas was
purged out until the pressure reached to atmospheric
pressure.
Thereafter, 120 ml of hydrogen was introduced, and
ethylene and propylene were copolymerized under conditions
such that a mixture gas of 64 mol% of propylene and 36 mol%
of ethylene were fed to perform a copolymerization at 70C
2 1 00999
156
for 2 hours. The pressure during the polymerization was
kept at 2Kg/cm2-G. After the reaction was completed, 200ml
of methanol was added to the resulting mixture and the
temperature was raised to 80C. After 30 minutes, 1 ml of
an aqueous solution containing 20% of sodium hydroxide was
added to the resulting mixture and the unreacted gas was
removed.
After the liquid phase was removed, the resulting
hexane slurry was washed with 300 ml of deionized water for
20 minutes and the aqueous phase was removed. Then, the
hexane slurry was filtered, and then washed and dried, to
thereby obtain a white solid. The properties of the hexane
slurry were poor and a considerable white turbidity was
observed.
The results are set forth in Table 2.
-- 2l 00999
157
Table 2
Amount of
bolled
Apparent Decane- heptane-
Activity MFR bulk soluble insolublei Boiled heptane-
specifiC Component decane- in~oluble component
insoluble
component at
23C
g/mmol- g/10g/ml tlll Crystal-
Ti min wt% dl~g wt% llnity [Ms] tM31
Ex.623,900 480.4411.4 3.794.4 73.2 0.9910.0035
Ex.722,800 410.45 8.8 6.79S.0 73.0 0.9910.0036
Ex.826,700 520.42 9.3 3.995.8 74.0 0.9940.0032
Ex.924,800 460.4512.0 3.994.7 73-5 0.9920.0035
Ex.1024,100 400.46 9.5 6.694.9 73.3 0.9920.0031
Ex.1126,000 510.44 9.7 3.795.4 74.
Ex.1225,500 560.42 9.2 3.695.8 75.0 0.9950.0029
Ex.1321,800 45 0-45 8.0 6.394.6 72.1 0.9900.0035
Ex.1426,200 55 0-44 7.1 6.295.4 73.4 0.9930.0034
Comp
Ex.425,100 520.4513.0 2.390.8 66.7 0.9600.0036
Comp
Ex.523,700 430.46 9.2 4.391.1 66.3 0.9620.0038
Comp
Ex.61,200 340.2918.0 3.084.3 62.6 0.9780.0016
21 00999
-
158
F.xam~les 15 to 45 and Comparat;ve Example 7
To a propylene polymer having such properties that a
melt flow rate is 10 g/10 min (MFR:ASTM D1238, 230C, 2.16
kg load), and a boiled heptane-insoluble component therein
satisfies [Ms] of 0.992, [M3] of 0.0027 and a crystallinity
of 72.6%, various stabilizers as indicated in Table 3 were
added in an amount indicated in Table 3. The resulting
mixture was pelletized at 230C by means of an extruder
having a screw diameter of 45 mm~.
The thus obtained pellets were formed by means of a
commercially available T-die film forming machine equipped
with an extruder of 65 mm~ into a film of 420 mm in width
and 0.04 mm in thickness. At the time of film forming, the
resin temperature was 250C, the film forming speed was 20
m/min, and a draft ratio was 0.6.
MFR, heat aging resistance and weathering resistance
of the film obtained were evaluated.
The results are set forth in Table 4.
Estimation of the stabilizers of films are measured by
the following methods.
Thermal stability in the molding stage
MFR of films: The films shows better thermal stability
when the difference between the MFR of the
pellets and that of the film is smaller.
Tong-term heat stability
A film is aged at 100C in a gear oven, and a period
of time from the start of aging to the time when the
21 0099~
159
tensile elongation becomes 1/2 of that of the initial value
is measured.
The film has better heat-resistant and aging-resistant
properties when it shows a longer period of time.
5 Weathering Resistance
A film is irradiated with light for 500 hours by using
a sunshine weatherometer at a discharge voltage of 50 V and
a discharge current of 60 A, and with rain, and a retention
of tensile elongation thereof is measured.
0 The film has better weathering resistance when it
shows a larger retention of tensile elongation.
Table 3
Types of Stabilizers and Amounts added
(parts by weighttparts by weight-PP)
Phenolic Organic Thioether Hindered Metal Salts of HigherStabilizer Phosphite Stabilizer Amine Aliphatic Acid
Stabilizer Stabilizer
A B C D E F G H I J K L M
Ex.15 0.10 - 0.10 - - - - - - - - - -
Ex.16 - 0.10 - 0.10
Ex.17 0.10 - - - 0.10
Ex.18 - 0.10 - - 0.10
Ex.l9 0.10 - - - - - - 0.10
Ex.20 - 0.10 - - - - - 0.10
Ex.21 0.10 - - - - - - - - 0.10
Ex.22 0.10 - - - - - - - 0.10
Ex.23 - - 0.10 - 0.10
Ex.24 - - - 0.10 0.10
Ex.25 - - 0.10 - - - - 0.10
Ex.26 - - - 0.10 - - - 0.10
Ex.27 - - 0.10 - - - - - - 0.10
Ex.28 - - - 0.10 - - ~ - - 0.10
21 00999
160
Table 3 (Continued)
Types of Stabilizers and Amounts added
~parts by weight/parts by weight-PP)
Phenolic OrganicThioether Hindered Metal Salts of Higher
Stabilizer PhosphiteStabilizer Amine Aliphatic Acid
Stabilizer Stabilizer
A B C D E F G H I J K L M
Ex.29 - - - - 0.10 - - 0.10
Ex.30 - - - - - 0.10 - 0.10
Ex.31 - - - - - - 0.100.10
Ex.32 - - - - 0.10 - - - - 0.10
Ex.33 - - - - - 0.10 - - - 0.10
Ex.34 - - - - - - 0.10 - - 0.10
Ex.35 - - - - 0.10 - - 0.10 - 0.10
Ex.36 - - - - - - - 0.10 - 0.10
Ex.37 - - - - - - - - 0.100.10
Ex.38 - - - - - 0.100.100.10
Ex.39 - - - - - - - - - 0.10
Ex.40 - - - - - - - - - - 0.10
Ex.41 - - - - - - - - - - - 0.10
Ex.42
Ex.43 - - - - - - - - - 0.100.10
Ex.44 - - - - - - - - - 0.10 - 0.10
Ex.45 - - - - - - - - - 0.10 - - 0.10
Comp.
Ex.7 ~ ~ ~ ~ ~ ~ ~ ~ ~ ~-
The stabilizers used in the Examples are listed as
follows.
USF.D STABIT.IZERS
Phenol type Stabilizes
A: Stearyl ester of ~-(3,5-di-tert-butyl-4-
hydroxyphenyl)-propionic acid. (trade name; Irganox 1076,
from Nippon Ciba Geigy, Co.)
-- 21 00999
161
B: Tetrakis[methylene-3-(3,5-di-tert-butyl-4-
hydroxyphenyl)propionate]methane (trade name; Irganox 1010,
from Nippon Ciba Geigy, Co.)
Org~nophosphite type Stabilizers
C: Tris(2,4-di-tert-butylphenyl) phosphite (trade name;
Phosphite 168, from Nippon Ciba Geigy, Co.)
D: Tetrakis(2,4-d-tert-butylphenyl)-4,4'-biphenylene
diphosphonite (trade name; Sandostab P-EPQ, from Sandoz,
Co . )
Thioether type Stabilizers
E: Dilauryl thiodipropionate (trade name; Antiox L, from
Nippon Yusi, Co.)
F: Distearyl thiodipropionate (trade name: DSTP
~Yoshitomi", from Yoshitomi Pharmacy, Co.)
G: Pentaerythritol tetra ~-mercapto laurylthiopropionate
(trade name: Seenox 412S, from Shipro Chemical, Co.)
Hindered Amine type Stabilizers
H: Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (trade
name: Sanol LS770, from Sankyo, Co.)
I: Poly[[6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-
triazine-2,4-diyl][(2,2,6,6,-tetramethyl-4-
piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-
piperidyl)imino]] (trade name: Chimassorb 944LD, from
Nippon Ciba Geigy, Co.)
Metal Salts of Higher Aliphatic Acid
J: Calcium stearate
K: Calcium 12-hydroxystearate
162 21 00999
L: Magnesium Stearate
M: Calcium montanate
Table 4
Re~i~tance Weathering
MFR to heatre3iqtance
aging
Pellet Film (day) ~%)
Ex.lS 10.0 10.5 30 20
Ex.16 10.0 11.0 28 20
Ex.17 10.0 11.0 30 25
Ex.18 10.0 10.5 26 20
Ex.l9 10.0 11.0 28 25
Ex.20 10.0 11.0 30 30
Ex.21 10.0 10.5 35 30
Ex.22 10.0 10.0 35 30
Ex.23 10.0 11.0 70 25
Ex.24 10.0 10.5 80 30
Ex.25 10.0 10.5 100 25
Ex.26 10.0 11.0 120 25
Ex.27 10.0 10.0 120 35
Ex.28 10.0 10.0 120 30
Ex.29 10.0 11.5 45 20
Ex.30 10.0 11.5 50 25
Ex.31 10.0 12.0 50 25
Ex.32 10.0 11.5 50 25
Ex.33 10.0 12.5 55 30
Ex.34 10.0 11.0 55 30
Ex.35 10.0 10.5 70 40
Ex.36 10.0 13.0 150 50
Ex.37 10.0 12.0 220 55
Ex.38 10.0 12.0 250 70
Ex.39 10.0 12.0 25 25
Ex.40 10.0 12.5 25 25
Ex.41 10.0 13.0 30 25
Ex.42 10.0 13.5 25 25
Ex.43 10.0 11.5 35 30
Ex.44 10.0 11.5 40 35
Ex.45 10.0 12.0 35 30
Comp.Ex.715.0 29.0 13 10
s