Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1999-05-20
2001-10-09
Wu, David W. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S348600, C526S160000, C526S161000, C526S916000, C526S131000, C526S336000, C526S283000, C502S152000, C502S155000
Reexamination Certificate
active
06300447
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an ethylene-&agr;-olefin-nonconjugated polyene random copolymer, a composition comprising said copolymer and a process for producing said copolymer. More precisely, the present invention relates to an ethylene-&agr;-olefin-nonconjugated polyene random copolymer having a wide molecular weight distribution and superior in processability, a composition comprising said copolymer and a process for producing said copolymer.
2. Description of Related Art
Because of their good performances such as good heat resistance, good weathering resistance, good ozone resistance and the like, ethylene-&agr;-olefin-nonconjugated polyene random copolymers have used in wide application as automobile materials, building materials, industrial materials, cable materials and the like. The copolymers have conventionally been produced using vanadium catalysts.
The copolymers obtained by using these catalysts, however, had a narrow molecular weight distribution and are inferior in processability. As a means for improving these defects, for example, a process has been proposed in which a multi-step polymerization vessel is used to form a polymer having varied molecular weight and a different composition. Actually, however, a polymer having a desired molecular weight distribution and composition could not be easily obtained. In addition, the process had a problem that the productivity of the reaction vessel was very low due to the necessity of limiting the ratio of polymers produced in respective polymerization step-vessels.
Recently, on the other hand, numerous processes for producing ethylene-&agr;-olefin-nonconjugated polyene random copolymers have been proposed using highly reactive metallocene catalysts. These processes, however, had also a defect that the polymer produced by these processes had a very narrow molecular weight distribution like the polymers obtained with the conventional vanadium catalysts and thus their processability was greatly problematic.
Under these circumstances, the purpose of the invention is to provide an ethylene-&agr;-olefin-nonconjugated polyene random copolymer having a wide molecular weight distribution and superior inprocessability, a composition comprising said copolymer and a process for producing said copolymer.
SUMMARY OF THE INVENTION
The present invention relates to an ethylene-&agr;-olefin-nonconjugated polyene random copolymer obtained by polymerizing the following components (a), (b) and (c) in the presence of a catalyst comprising a transition metal complex having at least one cyclopentadienyl skeleton and satisfying the conditions (1), (2), (3) and (4):
(a) ethylene,
(b) &agr;-olefin having 3 to 20 carbon atoms, and
(c) one or more nonconjugated polyene containing a nonconjugated polyene in which at least one or more hydrogen atoms are respectively bound to all of carbon atoms having a double bond;
(1) the molar ratio of a unit derived from ethylene to a unit derived from &agr;-olefin in the copolymer being 95/5 to 20/80,
(2) the iodine value is 0 to 50 (g/100 g polymer,)
(3) the intrinsic viscosity [&eegr;] measured in xylene at 70° C. is 0.5 to 10 dl/g, and
(4) the Q value (weight average molecular weight/ number average molecular weight) measured by gel permeation chromatography (GPC) is 3.0 or more.
The present invention also relates to a copolymer composition comprising said copolymer of the invention and all or part of a softening agent, a reinforcing agent and a vulcanizing agent.
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, (a) is ethylene.
In the present invention, (b) is &agr;-olefin having 3 to 20 carbon atoms.
As the &agr;-olefin, a mixture of two or more monomers can be used simultaneously. Specific examples of the &agr;-olefin include linear olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and the like, branched olefins such as 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene and the like, vinylcyclohexane and so on. Preferred compounds are propylene and 1-butene. Particularly preferred one is propylene.
In the present invention, (c) is a nonconjugated polyene in which at least one or more hydrogen atoms are respectively bound to all of carbon atoms having a double bond.
As a nonconjugated polyene (c) in which at least one or more hydrogen atoms are respectively bound to all of carbon atoms having a double bond can be used linear or cyclic nonconjugated dienes and nonconjugated polyene monomers. Specific examples include 1,4-hexadiene, 1,5-hexadiene, 1,5-heptadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,7-nonadiene, 1,8-nonadiene, 1,8-decadiene, 1,9-decadiene, 1,12-tetradecadiene, 1,13-tetradecadiene, 3-methyl-1,4-hexadiene, 3-methyl-1,5-hexadiene, 3-ethyl-1,4-hexadiene, 3-ethyl-1,5-hexadiene, 3,3-dimethyl-1,4-hexadiene, 3,3-dimethyl-1,5-hexadiene, 5-vinyl-2-norbornene, 2,5-norbornadiene, 7-methyl-2,5-norbornadiene, 7-ethyl-2,5-norbornadiene, 7-propyl-2,5-norbornadiene, 7-butyl-2,5-norbornadiene, 7-pentyl-2,5-norbornadiene, 7-hexyl-2,5-norbornadiene, 7,7-dimethyl-2,5-norbornadiene, 7-methyl-7-ethyl-2,5-norbornadiene, 7-chloro-2,5-norbornadiene, 7-bromo-2,5-norbornadiene, 7-fluoro-2,5-norbornadiene, 7,7-dichloro-2,5-norbornadiene, 1-methyl-2,5-norbornadiene, 1-ethyl-2,5-norbornadiene, 1-propyl-2,5-norbornadiene, 1-butyl-2,5-norbornadiene, 1-chloro-2,5-norbornadiene, 1-bromo-2,5-norbornadiene, 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene and the like. In addition, examples include cyclic dienes having structural formulae shown below:
In the present invention, these polyenes can be used independently or in combination thereof. Particularly, norbornadiene derivatives, which are particularly cyclic polyenes having strained cyclic structure such as norbornadiene, dicyclopentadiene or vinyl norbornene are preferred. When these compounds are used, the molecular weight distribution can be widened by the addition of a relatively small amount.
More preferred one is dicyclopentadiene, which is advantageous in that the molecular weight distribution can be widened by the smallest amount.
As (c) in the present invention, other polyenes may be co-used in order to control physical properties. In these other polyene, it is not necessary that at least one or more hydrogen atoms be respectively bound to all of carbon atoms having a double bond. Specific examples of these polyenes include 5-ethylidene-2-norbornene, 5-propylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, and polyene compounds illustrated in JP 10-7735 A, JP 9-40586 A, JP 9-188724 A and the like. Preferably, 5-ethylidene-2-norbornene is used.
The copolymer of the invention is a copolymer obtained by polymerizing the components (a), (b) and (c) described above in the presence of a catalyst comprising a transition metal complex having at least one cyclopentadienyl skeleton.
As the transition metal complex above, any complex illstrated in JP 9-169878 A, JP 9-87313 A, JP 9-12635 A, and JP 8-301934 A are available, but transition metal complexes (A) represented by the following chemical formula [I]-[III] are preferred.
The copolymer of the present invention is suitably obtained by using a catalyst comprising the following (A), (B) and/or (C).
(A): at least one transition metal complex represented by the following formula [I], [II] or [III]:
wherein M
1
represents a transition metal atom of group IV in the Periodic Table of the Elements; A represents an atom of group XVI in the Periodic Table of the Elements; J represents an atom of group XIV in the Periodic Table of the Elements; Cp
1
represents a group having a cyclopentadiene type anion skeleton; X
1
, X
2
, R
1
, R
2
, R
3
, R
4
, R
5
and R
6
independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group, or a
Johoji Hirofumi
Kuwabara Toshiyuki
Ogawa Atsuko
Fitch Even Tabin & Flannery
Harlan R.
Sumitomo Chemical Company Limited
Wu David W.
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