163
What is claimed is:
1. 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 [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,
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 %;
[M5]= <IMG>
...(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;
[M3]= <IMG>
...(2)
164
wherein
[Pmmrm] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each
a propylene unit,
[Prmrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prmmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit, and
165
[Pw] is absorption intensity of all methyl groups
in a propylene unit.
2. The propylene polymer as claimed in claim 1, which
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
<IMG>
, M is carbon or silicon, R1 and R are each a
hydrocarbon group, and R3 is hydrogen or a hydrocarbon group.
3. A propylene block copolymer composed of:
a crystalline polypropylene portion which may
comprise constituent units derived from ethylene and/or an
olefin of 4 to 10 carbon atoms in an amount of 0 to 20 % by
mol, and
a low-crystalline or non-crystalline copolymer
portion which contains two or more kinds of constituent units
derived from an olefin of 2 to 20 carbon atoms, and
the block copolymer comprising, in total,
constituent units derived from propylene in an amount of 50
to 98 % by mol, constituent units derived from ethylene
and/or an olefin of 4 to 10 carbon atoms in an amount of 50
to 2 % by mol, and optionally, constituent units derived from
165a
a diene compound having 4 to 20 carbon atoms in an amount of
not more than 5 % by mol,
wherein the propylene block copolymer has 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
following formula (1A) using absorption intensity [Pmmmm],
[Pw], [S.alpha..gamma.], [S.alpha..delta.+] and [T.delta.+.delta.+] in a 13C-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], [S.alpha..gamma.], [S.alpha..delta.+] and
166
[T.delta.+.delta.+] in a 13C-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
%;
<IMG>
...(1A)
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,
[S.alpha..gamma.] 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 .gamma. position,
[S.alpha..delta.+] 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 .alpha. position and the
other is situated at the .delta. position or farther than the .delta.
position, and
167
[T.delta.+.delta.+] 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 .delta. position or
farther than the .delta. position and the other is also situated
at the .delta. position or farther than the .delta. position;
<IMG>
...(2A)
wherein
[Pmmrm] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each
a propylene unit,
[Prmrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
168
[Prmmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit, and
[Pw], [S.alpha..gamma.], [S.alpha..delta.+] and [T.delta.+.delta.+] have the same meanings
as defined in the above formula (1A).
4. The propylene block copolymer as claimed in
wherein claim 3, which 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
<IMG>
, M is carbon or silicon, R1 and R2 are each a
hydrocarbon group, and R3 is hydrogen or a hydrocarbon
group.
5. A process for 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:
169
[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 (ii)
wherein X is a cycloalkyl group, an aryl group or
<IMG>
, 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:
<IMG> (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;
170
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.
6. A process for preparing a propylene polymer,
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 (ii)
wherein X is a cycloalkyl group, an aryl group or
171
<IMG>
, 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:
<IMG> (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 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)
contained in the prepolymerized catalyst.
172
7. A process for preparing a propylene block
copolymer, which comprises a first polymerization stage for
homopolymerizing propylene or copolymerizing propylene with
ethylene and/or .alpha.-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 .alpha.-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,
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
<IMG>
, M is carbon or silicon, R1 and R are each a
hydrocarbon group, and R3 is hydrogen or a hydrocarbon
group;
[II] the organometallic catalyst component (b); and
173
[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
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.
3. A propylene polymer composition comprising:
[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 [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,
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 %;
and
174
[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;
<IMG>
...(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;
<IMG>
...(2)
wherein
[Pmmrm] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
175
[Pmrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each
a propylene unit,
[Prmrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prmmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit, and
[Pw] is absorption intensity of all methyl groups in a
propylene unit.
9. The propylene polymer composition as claimed in
claim 8, wherein the propylene polymer 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
176
<IMG>
, M is carbon or silicon, R1 and R2 are each a hydrocarbon
group, and R3 is hydrogen or a hydrocarbon group.
10. A propylene polymer composition comprising:
[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 [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,
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%;
[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
176a
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;
[M5]= <IMG> ... (1)
177
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;
[M3]= <IMG> ...(2)
wherein
[Pmmrm] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each
a propylene unit,
[Prmrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
178
[Prmmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit, and
[Pw] is absorption intensity of all methyl groups in a
propylene unit.
11. The propylene polymer composition as claimed in
claim 10, wherein the propylene polymer 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
<IMG>
, M is carbon or silicon, R1 and R2 are each a
hydrocarbon group, and R3 is hydrogen or a hydrocarbon
group.
12. A propylene polymer composition comprising:
[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,
179
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,
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 %;
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;
<IMG>
...(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;
180
<IMG>
...(2)
wherein
[Pmmrm] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each
a propylene unit,
[Prmrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prmmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
181
units represented by <IMG> in which ? and ? are each a
propylene unit, and
[Pw] is absorption intensity of all methyl groups in a
propylene unit.
13. The propylene polymer composition as claimed in
claim 12, wherein the propylene polymer 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
<IMG>
, M is carbon or silicon, R1 and R are each a
hydrocarbon group, and R3 is hydrogen or a hydrocarbon
group.
14. A propylene polymer composition comprising:
[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 [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,
182
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 %;
[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
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;
<IMG>
...(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;
183
<IMG>
...(2)
wherein
[Pmmrm] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each
a propylene unit,
[Prmrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prmmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
184
units represented by <IMG> in which ? and ? are each a
propylene unit, and
[Pw] is absorption intensity of all methyl groups in a
propylene unit.
15. The propylene polymer composition as claimed in
claim 14, wherein the propylene polymer 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
<IMG>
, M is carbon or silicon, R1 and R2 are each a
hydrocarbon group, and R3 is hydrogen or a hydrocarbon
group.
16. A propylene polymer composition comprising:
[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 [M5] obtained from the following
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,
185
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 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 %;
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;
<IMG>
...(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;
<IMG>
...(2)
wherein
[Pmmrm] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
186
propylene unit,
[Pmrmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prmmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each
a propylene unit,
[Prmmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by IMG> in which ? and ? are each a
propylene unit,
[Prrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit, and
[Pw] is absorption intensity of all methyl groups in a
propylene unit.
17. The propylene polymer composition as claimed in
claim 16, wherein the propylene polymer contains 10 -
10,000 ppm of polymer comprising constituent units derived
187
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
<IMG>
, M is carbon or silicon, R1 and R2 are each a
hydrocarbon group, and R3 is hydrogen or a hydrocarbon
group.
18. A propylene polymer composition comprising:
[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 in the range of 0.1 to 500 g/10 min,
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,
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 %;
188
[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;
[M5]= <IMG> ...(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;
[M3]= <IMG> ...(2)
wherein
[Pmmrm] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
189
[Pmrmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each
a propylene unit,
[Prmrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prmmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
propylene unit, and
[Pw] is absorption intensity of all methyl groups in a
propylene unit.
19. The propylene polymer composition as claimed in
claim 18, wherein the propylene polymer contains 10 -
10,000 ppm of polymer comprising constituent units derived
190
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
<IMG>
,M is carbon or silicon, R1 and R are each a
hydrocarbon group, and R3 is hydrogen or a hydrocarbon
group.
20. A propylene polymer composition comprising:
[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 [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,
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 %;
and
191
[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;
[M5]= <IMG> ...(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;
[M3]= <IMG> ...(2)
wherein
[Pmmrm] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
192
[Pmrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each
a propylene unit,
[Prmrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prmmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit, and
[Pw] is absorption intensity of all methyl groups in a
propylene unit.
21. The propylene polymer composition as claimed in
claim 20, wherein the propylene polymer 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
. 193
<IMG>
, M is carbon or silicon, R1 and R2 are each a
hydrocarbon group, and R3 is hydrogen or a hydrocarbon
group.
22. A propylene polymer composition comprising:
[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 following
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 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 %;
[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;
194
<IMG>
...(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;
<IMG>
...(2)
wherein
[Pmmrm] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each
a propylene unit,
195
[Prmrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prmmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit, and
[PW] is absorption intensity of all methyl groups in a
propylene unit.
23. The propylene polymer composition as claimed in
claim 22, wherein the propylene polymer 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
<IMG>
, M is carbon or silicon, R1 and R are each a
hydrocarbon group, and R3 is hydrogen or a hydrocarbon
group.
196
24. A propylene polymer composition comprising:
[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 [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,
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 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 %;
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;
<IMG>
...(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
197
[Pw] is absorption intensity of all methyl groups in a
propylene unit;
<IMG>
...(2)
wherein
[Pmmrm] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each
a propylene unit,
[Prmrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prmmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
198
[Prrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit, and
[Pw] is absorption intensity of all methyl groups
in a propylene unit.
25. The propylene polymer composition as claimed in
claim 24, wherein the propylene polymer contains 10 - 10,000
ppm of polymer comprising constituent units derived from a
compound represented by the following (i) or (ii):
H2C=CH-X (i)
H2C=CH-CH2-X (ii)
wherein X is a cycloalkyl group, an aryl group or
<IMG>
, M is carbon or silicon, R1 and R are each a
hydrocarbon group, and R3 is hydrogen or a hydrocarbon group.
26. A propylene polymer composition comprising:
[A2] a propylene block copolymer composed of:
a crystalline polypropylene portion which may
comprise constituent units derived from ethylene and/or an
olefin of 4 to 10 carbon atoms in an amount of 0 to 20 % by
mol, and
a low-crystalline or non-crystalline copolymer
portion which contains two or more kinds of constituent units
derived from an olefin of 2 to 20 carbon atoms, and
198a
the block copolymer comprising, in total,
constituent units derived from propylene in an amount of 50
to 98 % by mol, constituent units derived from ethylene
and/or an olefin of 4 to 10 carbon atoms in an amount of 50
to 2 % by mol, and optionally, constituent units derived from
a diene compound having 4 to 20 carbon atoms in an amount of
not more than 5 % by mol,
wherein the propylene block copolymer has such
properties that:
a melt flow rate [MFR] of the 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 formula (1A) using absorption intensity [Pmmmm],
[Pw],
199
[s.alpha..gamma.], [s.alpha..delta.+] and [T.delta.+.delta.+] in a 13C-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], [S.alpha..gamma.], [s.alpha..delta.+] and
[T.delta.+.delta.+] in a 13C-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
[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;
<IMG>
... (1A)
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 methyl groups in a
propylene unit,
[s.alpha..gamma.] 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
200
secondary carbons one is situated at the a position and the
other is situated at the .gamma. position,
[s.alpha..delta.+] 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 .delta. position or farther than the .delta.
position, and
[T.delta.+.delta.+] 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 .delta. position or
farther than the .delta. position and the other is also situated
at the .delta. position or farther than the .delta. position;
<IMG>
...(2A)
wherein
[Pmmrm] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
201
[Pmrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each
a propylene unit,
[Prmrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prmmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit, and
[Pw], [s.alpha..gamma.], [s.alpha..delta.+] and [T.delta.+.delta.+] have the same meanings
as defined in the above formula (lA).
27. The propylene polymer composition as claimed in
claim 26, wherein the propylene block copolymer 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
202
<IMG>
, M is carbon or silicon, R and R are each a
hydrocarbon group, and R is hydrogen or a hydrocarbon group.
28. A propylene polymer composition comprising:
[A2] a propylene block copolymer composed of:
a crystalline polypropylene portion which may
comprise constituent units derived from ethylene and/or an
olefin of 4 to 10 carbon atoms in an amount of 0 to 20 % by
mol, and
a low-crystalline or non-crystalline copolymer
portion which contains two or more kinds of constituent units
derived from an olefin of 2 to 20 carbon atoms, and
the block copolymer comprising, in total,
constituent units derived from propylene in an amount of 50
to 98 % by mol, constituent units derived from ethylene
and/or an olefin of 4 to 10 carbon atoms in an amount of 50
to 2 % by mol, and optionally, constituent units derived from
a diene compound having 4 to 20 carbon atoms in an amount of
not more than 5 % by mol,
wherein the propylene block copolymer has such
properties that:
a melt flow rate (MFR) of the 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
202a
following formula (1A) using absorption intensity [Pmmmm],
[Pw], [S.alpha..gamma.], [.alpha..delta.+] and [T.delta.+.delta.+] in a 13C-NMR spectrum of a
boiled heptane-insoluble component contained in the 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], [S.alpha..gamma.], [[S.alpha..delta.+] and
[T.delta.+.delta.+] in a 13C-NMR spectrum of a boiled heptane-insoluble
component contained in the copolymer is in the range of
0.0020 to 0.0050, and
a crystallinity of a boiled heptane-insoluble
component contained in the copolymer is not less that 60 %;
203
[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
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
stablizer 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;
<IMG>
.. (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 methyl groups in a
propylene unit,
[S.alpha..gamma.] 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 .alpha. position and the
other is situated at the .gamma. position,
[s.alpha..delta.+] 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 .alpha. position and the
204
other is situated at the .delta. position or farther than the .delta.
position, and
[T.delta.+S.delta.] 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 .delta. position or
farther than the .delta. position and the other is also situated
at the .delta. position or farther than the .delta. position;
<IMG>
...(2A)
wherein
[Pmmrm] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each
a propylene unit,
[Prmrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
205
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prmmr] is absorptlon intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
lPrrrrl is absorption intensity of methyl groups
present in the third unit among continuous five propylene
unlts represented by <IMG> in which ? and ? are each a
propylene unit, and
[Pw], [s.alpha..gamma.], [s.alpha..delta.+] and [T.delta.+.delta.+] have the same meanings
as defined in the above formula (1A).
29. The propylene polymer composltion as claimed in
clalm 28, whereln the propylene block copolymer contains 10
- 10,000 ppm of polymer comprising constituent units
derlved from a compound represented by the followlng
formula (1) or (ii):
H2C-CH - X (i)
H2C-CH-CH2-X (ii)
wherein X is a cycloalkyl group, an aryl group or
<IMG>
M is carbon or silicon, R1 and R2 are each a
hydrocarbon group, and R3 is hydrogen or a hydrocarbon
group.
30. A propylene polymer composition comprising:
206
[A2] a propylene block copolymer composed of:
a crystalline polypropylene portion which may
comprise constituent units derived from ethylene and/or an
olefin of 4 to 10 carbon atoms in an amount of 0 to 20 % by
mol, and
a low-crystalline or non-crystalline copolymer
portion which contains two or more kinds of constituent units
derived from an olefin of 2 to 20 carbon atoms, and
the block copolymer comprising, in total,
constituent units derived from propylene in an amount of 50
to 98 % by mol, constituent units derived from ethylene
and/or an olefin of 4 to 10 carbon atoms in an amount of 50
to 2 % by mol, and optionally, constituent units derived from
a diene compound having 4 to 20 carbon atoms in an amount of
not more than 5 % by mol,
wherein the propylene block copolymer has such
properties that:
a melt flow rate (MFR) of the 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 formula (1A) using absorption intensity [Pmmmm],
[Pw], [S.alpha..gamma.], [S.alpha..delta.+] and [T.delta.+.delta.+] in a 13C-NMR spectrum of a
boiled heptane-insoluble component contàined in the copolymer
is in the range of 0.970 to 0.995,
a pentad tacticity [M3] obtained from the following
formula (2A) using absorption intensity lPmmrm], [Pmrmr],
[Pmrrr], [Prmrr], [Prmmr], [Prrrr], [Pw], [S.alpha..gamma.], [S.alpha..delta.+ ] and
206a
[T.delta.+.delta.+] in a 13C-NMR spectrum of a boiled heptane-insoluble
component contained in the copolymer is in the range of
0.0020 to 0.0050, and
a crystallinity of a boiled heptane-insoluble
component contained in the copolymer is not less that 60 %;
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;
[M5]= <IMG> ... (1A)
wherein
207
[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 methyl groups in a
propylene unit,
[S.alpha..gamma.] 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 .alpha. position and the
other is situated at the .gamma. position,
[s.alpha..gamma.] 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 .alpha. position and the
other is situated at the .delta. position or farther than the .delta.
position, and
[T.delta.+.delta.+] 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 .delta. position or
farther than the .delta. position and the other is also situated
at the .delta. position or farther than the .delta. position;
<IMG>
...(2A)
wherein
208
[Pmmrm] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each
a propylene unit,
[Prmrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prmmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit, and
[Pw], [S.alpha..gamma.], [S.alpha..delta.+] and [T.delta.+.delta.+] have the same meanings
as defined in the above formula (1A).
209
31. The propylene polymer composition as claimed in
claim 30, wherein the propylene block copolymer 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
<IMG>
, M is carbon or silicon, R1 and R2 are each a
hydrocarbon group, and R3 is hydrogen or a hydrocarbon group.
2. A propylene polymer composition comprising:
[A2] a propylene block copolymer composed of:
a crystalline polypropylene portion which may
comprise constituent units derived from ethylene and/or an
olefin of 4 to 10 carbon atoms in an amount of 0 to 20 % by
mol, and
a low-crystalline or non-crystalline copolymer
portion which contains two or more kinds of constituent units
derived from an olefin of 2 to 20 carbon atoms, and
the block copolymer comprising, in total,
constituent units derived from propylene in an amount of 50
to 98 % by mol, constituent units derived from ethylene
and/or an olefin of 4 to 10 carbon atoms in an amount of 50
to 2 % by mol, and optionally, constituent units derived from
a diene compound having 4 to 20 carbon atoms in an amount of
209a
not more than 5 % by mol,
wherein the propylene block copolymer has such
properties that:
a melt flow rate (MFR) of the 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 formula (1A) using absorption intensity [Pmmmm],
[Pw], [S.alpha..gamma.], [S.alpha..delta. ] and [T.delta.+.delta.+ ] in a 13C-NMR spectrum of a
boiled heptane-insoluble component contained in the 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], [S.alpha..gamma.], [S.alpha..gamma.] and
210
[T.delta.+.delta.+] in a 13C-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
%;
[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 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 based on 100 parts by weight of the propylene block
copolymer:
<IMG>
... (1A)
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 methyl groups in a
propylene unit,
[S.alpha..gamma.] is absorption intensity of such secondary
carbons that are present in a main chain and out of two
211
kinds of tertiary carbons positioned nearest to said
secondary carbons one is situated at the .alpha. position and the
other is situated at the .gamma. position,
[S.alpha..delta.+] 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 .alpha. position and the
other is situated at the .delta. position or farther than the .delta.
position, and
[T.delta.+.delta.+] 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 .delta. position or
farther than the .delta. position and the other is also situated
at the .delta. position or farther than the .delta. position;
[M3]= <IMG> ...(2A)
wherein
[Pmmrm] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
212
[Pmrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each
a propylene unit,
[Prmrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prmmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prrrr] is absorption intensity of methyl groups
present in the third unit amonq continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit, and
[Pw], [S.alpha..gamma.], [S.alpha..delta.+] and [T.delta.+.delta.+] have the same meanings
as defined in the above formula (1A).
33. The propylene polymer composition as claimed in
claim 32, wherein the propylene block copolymer 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
213
<IMG>
, M is carbon or silicon, R1 and R are each a
hydrocarbon group, and R3 is hydrogen or a hydrocarbon group.
34. A propylene polymer composition comprising:
[A2] a propylene block copolymer composed of:
a crystalline polypropylene portion which may
comprise constituent units derived from ethylene and/or an
olefin of 4 to 10 carbon atoms in an amount of 0 to 20 % by
mol, and
a low-crystalline or non-crystalline copolymer
portion which contains two or more kinds of constituent units
derived from an olefin of 2 to 20 carbon atoms, and
the block copolymer comprising, in total,
constituent units derived from propylene in an amount of 50
to 98 % by mol, constituent units derived from ethylene
and/or an olefin of 4 to 10 carbon atoms in an amount of 50
to 2 % by mol, and optionally, constituent units derived from
a diene compound having 4 to 20 carbon atoms in an amount of
not more than 5 % by mol,
wherein the propylene block copolymer has such
properties that:
a melt flow rate (MFR) of the 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 [H5] obtained from the
213a
following formula (1A) using absorption intensity [Pmmmml,
[Pw], [S.alpha..gamma.], [S.alpha..delta.+] and [T.delta.+.delta.+] in a 13C-NMR spectrum of a
boiled heptane-insoluble component contained in the 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], [Pmrmrl,
[Pmrrr], [Prmrr], [Prmmr], [Prrrr], [Pw], [S.alpha..gamma.], [S.alpha..delta.+] and
[T.delta.+T.delta.+] in a 13C-NMR spectrum of a boiled heptane-insoluble
component contained in the copolymer is in the range of
0.0020 to 0.0050, and
a crystallinity of a boiled heptane-insoluble
component contained in the copolymer is not less that 60 %;
and
214
[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 propylene block copolymer;
<IMG>
... (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 methyl groups in a
propylene unit,
[S.alpha..gamma.] 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 .alpha. position and the
other is situated at the .gamma. position,
[S.alpha..delta.+] 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 .alpha. position and the
other is situated at the .delta. position or farther than the .delta.
position, and
[T.delta.+.delta.+] 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
215
tertiary carbons one is situated at the .delta. position or
farther than the .delta. position and the other is also situated
at the .delta. position or farther than the .delta. position;
<IMG>
...(2A)
wherein
[Pmmrm] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each
a propylene unit,
[Prmrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prmmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
216
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit, and
[Pw], [S.alpha..gamma.], [S.alpha..delta.+] and [T.delta.+.delta.+] have the same
meanings as defined in the above formula (1A).
35. The propylene polymer composition as claimed in
claim 34, wherein the propylene block copolymer 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
<IMG>
, M is carbon or silicon, R1 and R are each a
hydrocarbon group, and R3 is hydrogen or a hydrocarbon group.
36. A propylene polymer composition comprising:
[A2] a propylene block copolymer composed of:
a crystalline polypropylene portion which may
comprise constituent units derived from ethylene and/or an
olefin of 4 to 10 carbon atoms in an amount of 0 to 20 % by
216a
mol, and
a low-crystalline or non-crystalline copolymer
portion which contains two or more kinds of constituent units
derived from an olefin of 2 to 20 carbon atoms, and
the block copolymer comprising, in total,
constituent units derived from propylene in an amount of 50
to 98 % by mol, constituent units derived from ethylene
and/or an olefin of 4 to 10 carbon atoms in an amount of 50
to 2 % by mol, and optionally, constituent units derived from
a diene compound having 4 to 20 carbon atoms in an amount of
not more than 5 % by mol,
wherein the propylene block copolymer has such
properties that:
a melt flow rate [MFR] of the copolymer at 230°C
under a load of 2.16 kg is in the range of 0.1 to 500 g/10
min,
217
a pentad isotacticity [M5] obtained from the following
formula (1A) using absorption intensity [Pmmmm], [Pw],
[S.alpha..gamma.], [S.alpha..delta.+] and [T.delta.+.delta.+] in a 13C-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], [S.alpha..gamma.], [S.alpha..delta.+] and
[T.delta.+.delta.+] in a 13C-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
[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;
<IMG>
... (1A)
wherein
218
[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 methyl groups in a
propylene unit,
[S.alpha..gamma.] 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 .gamma. position,
[S.alpha..delta.+] 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 .delta. position or farther than the .delta.
position, and
[T.delta.+.delta.+] 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 .delta. position or
farther than the .delta. position and the other is also situated
at the .delta. position or farther than the .delta. position;
[M3]= <IMG>
...(2A)
wherein
219
[Pmmrm] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each
a propylene unit,
[Prmrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prmmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit, and
[Pw], [S.alpha..gamma.], [S.alpha..delta.+] and [T.delta.+.delta.+] have the same meanings
as defined in the above formula (1A).
220
37. The propylene polymer composition as claimed in
claim 36, wherein the propylene block copolymer 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
<IMG>
, M is carbon or silicon, R1 and R2 are each a
hydrocarbon group, and R3 is hydrogen or a hydrocarbon group.
38. A propylene polymer composition comprising:
[A2] a propylene block copolymer composed of:
a crystalline polypropylene portion which may
comprise constituent units derived from ethylene and/or an
olefin of 4 to 10 carbon atoms in an amount of 0 to 20 % by
mol, and
a low-crystalline or non-crystalline copolymer
portion which contains two or more kinds of constituent units
derived from an olefin of 2 to 20 carbon atoms, and
the block copolymer comprising, in total,
constituent units derived from propylene in an amount of 50
to 98 % by mol, constituent units derived from ethylene
and/or an olefin of 4 to 10 carbon atoms in an amount of 50
to 2 % by mol, and optionally, constituent units derived from
a diene compound having 4 to 20 carbon atoms in an amount of
220a
not more than 5 % by mol,
wherein the propylene block copolymer has such
properties that:
a melt flow rate (MFR) of the 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 formula (1A) using absorption intensity [Pmmmm],
[Pw], [S.alpha..gamma.], [S.alpha..delta.+] and [T.delta.+.delta.+] in a 13C-NMR spectrum of a
boiled heptane-insoluble component contained in the 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], [S.alpha..gamma.], [S.alpha..delta.+] and
221
[T.delta.+.delta.+] in a 13C-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
[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;
<IMG>
... (1A)
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 methyl groups in a
propylene unit,
[S.alpha..gamma.] 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 .gamma. position,
[s.alpha..delta.+] 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
222
secondary carbons one is situated at the .alpha. position and the
other is situated at the .delta. position or farther than the .delta.
position, and
[T.delta.+.delta.+] 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 .delta. position or
farther than the .delta. position and the other is also situated
at the .delta. position or farther than the .delta. position;
<IMG>
...(2A)
wherein
[Pmmrm] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each
a propylene unit,
[Prmrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
223
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prmmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit, and
[Pw], [S.alpha..gamma.], [S.alpha..delta.+] and [T.delta.+.delta.+] have the same meanings
as defined in the above formula (1A).
39. The propylene polymer composition as claimed in
claim 38, wherein the propylene block copolymer 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
<IMG>
, M is carbon or silicon, R1 and R2 are each a
hydrocarbon group, and R3 is hydrogen or a hydrocarbon
group.
40. A propylene polymer composition comprising:
224
[A2] a propylene block copolymer composed of:
a crystalline polypropylene portion which may
comprise constituent units derived from ethylene and/or an
olefin of 4 to 10 carbon atoms in an amount of 0 to 20 % by
mol, and
a low-crystalline or non-crystalline copolymer
portion which contains two or more kinds of constituent units
derived from an olefin of 2 to 20 carbon atoms, and
the block copolymer comprising, in total,
constituent units derived from propylene in an amount of 50
to 98 % by mol, constituent units derived from ethylene
and/or an olefin of 4 to 10 carbon atoms in an amount of 50
to 2 % by mol, and optionally, constituent units derived from
a diene compound having 4 to 20 carbon atoms in an amount of
not more than 5 % by mol,
wherein the propylene block copolymer has such
properties that:
a melt flow rate (MFR) of the 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 formula (1A) using absorption intensity [Pmmmm],
[Pw], [S.alpha..gamma.], [S.alpha..delta.+] and [T.delta.+.delta.+] in a 13C-NMR spectrum of a
boiled heptane-insoluble component contained in the 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], [S.alpha..gamma.], [S.alpha..delta.+] and
224a
[T.delta.+.delta.+] in a 13C-NMR spectrum of a boiled heptane-insoluble
component contained in the copolymer is in the range of
0.0020 to 0.0050, and
a crystallinity of a boiled heptane-insoluble
component contained in the copolymer is not less that 60 %;
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; 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;
225
[M5]= <IMG>
... (1A)
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 methyl groups in a
propylene unit,
[S.alpha..gamma.] 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 .alpha. position and the
other is situated at the .gamma. position,
[S.alpha..delta.+] 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 .alpha. position and the
other is situated at the .delta. position or farther than the .delta.
position, and
[T.delta.+.delta.+] 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 .delta. position or
farther than the .delta. position and the other is also situated
at the .delta. position or farther than the .delta. position;
226
[M3]= <IMG>
...(2A)
wherein
[Pmmrm] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each
a propylene unit,
[Prmrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prmmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
227
units represented by <IMG> in which ? and ? are each a
propylene unit, and
[Pw], [S.alpha..gamma.], [S.alpha..delta.+] and [T.delta.+.delta.+] have the same
meanings as defined in the above formula (1A).
41. The propylene polymer composition as claimed in
claim 40, wherein the propylene block copolymer 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
<IMG>
, M is carbon or silicon, R1 and R are each a
hydrocarbon group, and R3 is hydrogen or a hydrocarbon group.
42. A propylene polymer composition comprising:
[A2] a propylene block copolymer composed of:
a crystalline polypropylene portion which may
comprise constituent units derived from ethylene and/or an
olefin of 4 to 10 carbon atoms in an amount of 0 to 20 % by
mol, and
a low-crystalline or non-crystalline copolymer
portion which contains two or more kinds of constituent units
derived from an olefin of 2 to 20 carbon atoms, and
227a
the block copolymer comprising, in total,
constituent units derived from propylene in an amount of 50
to 98 % by mol, constituent units derived from ethylene
and/or an olefin of 4 to 10 carbon atoms in an amount of 50
to 2 % by mol, and optionally, constituent units derived from
a diene compound having 4 to 20 carbon atoms in an amount of
not more than 5 % by mol,
wherein the propylene block copolymer has such
properties that:
a melt flow rate [MFR] of the 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 formula (1A) using absorption intensity [Pmmmm],
[Pw], [S.alpha..gamma.], [S.alpha..delta.] and [T.delta.+.delta.+] in a 13C-NMR spectrum of a
boiled
228
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], [S.alpha..gamma.], [s.alpha..delta.+] and
[T.delta.+.delta.+] in a 13C-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
[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;
<IMG>
... (1A)
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 methyl groups in a
propylene unit,
[s.alpha..gamma.] 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
229
secondary carbons one is situated at the .alpha. position and the
other is situated at the .gamma. position,
[S.alpha..delta.+] 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 .alpha. position and the
other is situated at the .delta. position or farther than the .delta.
position, and
[T.delta.+.delta.+] 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 .delta. position or
farther than the .delta. position and the other is also situated
at the .delta. position or farther than the .delta. position;
<IMG>
...(2A)
wherein
[Pmmrm] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Pmrmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
230
[Pmrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each
a propylene unit,
[Prmrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prmmr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit,
[Prrrr] is absorption intensity of methyl groups
present in the third unit among continuous five propylene
units represented by <IMG> in which ? and ? are each a
propylene unit, and
[Pw], [S.alpha..gamma.], [S.alpha..delta.+] and [T.delta.+.delta.+] have the same meanings
as defined in the above formula (1A).
43. The propylene polymer composition as claimed in
claim 42, wherein the propylene block copolymer 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
231
<IMG>
, M is carbon or silicon, R1 and R2 are each a
hydrocarbon group, and R3 is hydrogen or a hydrocarbon group.
44. The propylene polymer as claimed in claim 2,
wherein X in the formulae (i) and (ii) is cyclopentyl,
cyclohexyl, cycloheptyl, phenyl, tolyl, xylyl, naphthyl or a
group of the formula
<IMG>
where M is carbon or silicon, R1 and R2 are each
independently C1-4alkyl, phenyl, naphthyl or norbornyl and R3
is hydrogen, C1-4alkyl, phenyl, naphthyl or norbornyl.
45. The propylene polymer as claimed in claim 2,
wherein the compound of the formula (i) or (ii) is 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-1-hexene, 3-ethyl-1-hexene,
allylnaphthalene, allylnorbornene, styrene, dimethylstyrene,
vinylnaphthalene, allyltoluene, allylbenzene,
vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, or
allyltrialkylsilane.
46. The propylene polymer as claimed in claim 2,
wherein the compound of the formula (i) or (ii) is 3-methyl-
1-butene, 3-methyl-1-pentene or 3-methyl-1-hexene.
232
47. The propylene polymer as claimed in claim 2,
wherein the compound of the formula (i) or (ii) is
vinylcyclohexane, allyltrimethylsilane, styrene or
dimethylstyrene.
48. The propylene polymer block copolymer as claimed in
claim 4, wherein X is the formulae (i) and (ii) is
cyclopentyl, cyclohexyl, cycloheptyl, phenyl, tolyl, xylyl,
naphthyl or a group of the formula
<IMG>
where M is carbon or silicon, R1 and R2 are each
independently C1-4alkyl, phenyl, naphthyl or norbornyl and R3
is hydrogen, C1-4alkyl, phenyl, naphthyl or norbornyl.
49. The propylene polymer as claimed in claim 48,
wherein the compound of the formula (i) or (ii) is 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-1-hexene, 3-ethyl-1-hexene,
allylnaphthalene, allylnorbornene, styrene, dimethylstyrene,
vinylnaphthalene, allyltoluene, allylbenzene,
vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, or
allyltrialkylsilane.
50. The propylene polymer as claimed in claim 48,
wherein the compound of the formula (i) or (ii) is 3-methyl-
1-butene, 3-
233
methyl-1-pentene or 3-methyl-1-hexene.
51. The propylene polymer as claimed in claim 48, wherein
the compound of the formula (i) or (ii) is vinylcyclohexane,
allyltrimethylsilane, styrene or dimethylstyrene.
52. The propylene polymer as claimed in claim 1, 2, 44, 45,
46 or 47, which is propylene homopolymer having at least 90% by
weight of the boiled heptane-insoluble component; and wherein the
boiled heptane-insoluble component has a crystallinity of not less
than 60%.
53. The propylene block copolymer as claimed in claim 3, 4,
48, 49, 50 or 51, which consists of:
a crystalline polypropylene portion which is
composed essentially of constituent units derived from propylene
and 0 to 20 mol% of constituent units derived from ethylene or
C4-10.alpha.-olefin,
a low-crystalline or non-crystalline copolymer
portion composed essentially of two or more kinds of constituent
units derived from at least two members selected from the group
consisting of ethylene, propylene and C4-20.alpha.-olefin,
wherein the constituent units derived from
propylene are contained in an amount of 60 to 97 mol% and the
constituent units derived from ethylene or C4-10.alpha.-olefin are
contained in an amount of 40 to 3 mol%.
234
54. The propylene block copolymer as claimed in claim 53,
which contains at least 85% by weight of the boiled heptane-
insoluble component in a 23°C-decane-soluble portion; and wherein
the boiled heptane-insoluble component has a crystallinity of not
less than 60%.
55. The propylene polymer composition as claimed in any one
of claims 26 through 43, wherein the propylene block copolymer
[A2] consists of:
a crystalline polypropylene portion which is
composed essentially of constituent units derived from propylene
and 0 to 20 mol% of constituent units derived from ethylene or
C4-10.alpha.-olefin,
a low-crystalline or non-crystalline copolymer
portion composed essentially of two or more kinds of constituent
units derived from at least two members selected from the group
consisting of ethylene, propylene and C4-20.alpha.-olefin,
wherein the constituent units derived from
propylene are contained in an amount of 60 to 97 mol% and the
constituent units derived from ethylene or C4-10.alpha.-olefin are
contained in an amount of 40 to 3 mol%.
56. The propylene polymer composition as claimed in claim
55, wherein the propylene block copolymer [A2] which contains at
least 85% by weight of the boiled heptane-insoluble component in a
235
23°C-decane-soluble portion; and wherein the boiled heptane-
insoluble component has a crystallinity of not less than 60%.
57. The propylene polymer composition as claimed in any
one of claims 8 through 25, wherein the propylene polymer
[A1] is propylene homopolymer having at least 90% by weight
of the boiled heptane-insoluble component; and the boiled
heptane-insoluble component has a crystallinity of not less
than 60%.
58. The process as claimed in claim 5, 6 or 7, wherein
X in the formulae (i) and (ii) is cyclopentyl, cyclohexyl,
cycloheptyl, phenyl, tolyl, xylyl, naphthyl or a group of the
formula
<IMG>
where M is carbon or silicon, R1 and R are each
independently C1-4alkyl, phenyl, naphthyl or norbornyl and R3
is hydrogen, C1-4alkyl, phenyl, naphthyl or norbornyl.
59. The process as claimed in claim 58, wherein the
compound of the formula (i) or (ii) is 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-1-hexene, 3-ethyl-1-hexene,
allylnaphthalene, allylnorbornene, styrene, dimethylstyrene,
vinylnaphthalene, allyltoluene, allylbenzene,
vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, or
236
allyltrialkylsilane.
60. The process as claimed in claim 58, wherein the
compound of the formula (i) or (ii) is 3-methyl-1-butene,
3-methyl-1-pentene or 3-methyl-1-hexene.
61. The process as claimed in claim 58, wherein the
compound of the formula (i) or (ii) is vinylcyclohexane,
allyltrimethylsilane, styrene or dimethylstyrene.
62. The process of claim 58 wherein:
the organometallic catalyst component (b) is a
trialkylaluminum; and
the silicon compound [III] is represented by
the formula:
Ra n-Si-(ORb)4-n (III)
(wherein n is 1, 2 or 3;
Ra is cyclopentyl, alkyl substituted-
cyclopentyl, cyclopentenyl, alkyl substituted-
cyclopentenyl, cyclopentadienyl or alkyl
substituted-cyclopentadienyl, and
Rb is C1-4alkyl).
63. The process of claim 52, wherein the silicon
compound [III] is dicyclo-pentyldimethoxysilane.
