CA1312695C

CA1312695C - Cyclo-olefinic random copolymer, olefinic random copolymer, and process for producing cyclo-olefinic random copolymers

Info

Publication number: CA1312695C
Application number: CA000560207A
Authority: CA
Inventors: Naoshi Ishimaru; Toshiyuki Tsutsui; Akinori Toyota; Norio Kashiwa
Original assignee: Mitsui Petrochemical Industries Ltd
Current assignee: Mitsui Chemicals Inc
Priority date: 1987-03-02
Filing date: 1988-03-01
Publication date: 1993-01-12
Anticipated expiration: 2010-01-12
Also published as: CN88101641A; US5003019A; KR910009376B1; DE3853843D1; EP0283164A2; US5008356A; EP0283164A3; EP0283164B1; DE3853843T2; KR890013064A; CN1017804B

Abstract

ABSTRACT OF THE DISCLOSURE
A cyclo-olefinic random copolymer composed of an alpha-olefin component having 3 to 20 carbon atoms and a cyclo-olefin component, (i) said copolymer containing 5 to 99 mole% of recurring units derived from said alpha-olefin component having 3 to 20 carbon atoms and 1 to 95 mole% of recurring units derived from said cyclo-olefin component, and (ii) said copolymer having an intrinsic vis-cosity [?], measured in decalin at 135 °C, of from 0.01 to 10 dl/g; and an olefinic random copolymer composed o (A) an olefin component having 3 to 20 carbon atoms and (B) a cyclic polyene component and as required, (C) a cyclo-olefin component, (i) said copolymer containing S to 99 mole% of recurring units derived from said alpha-olefin component (A) having 3 to 20 carbon atoms and 1 to 95 mole% of recurring units derived from said cyclic polyene component SB) and 0 to 90 mole% of recurring units derived from said cyclo-olefin component (C), and (ii) said copolymer having an intrinsic vis-cosity [?], measured in decalin at 135 °C, of from 0.01 to 10 dl/g; and a process for production thereof. Also provided is a process for producing a cyclo-olefinic random copolymer, which comprises copolymerizing an alpha-olefin and a cyclo-olefin in the presence of a catalyst formed from (A) a compound of a transition metal of Group IVB of the periodic table having as a ligand a multi-dentate coordination compound in which at least two con-jugated cycloalkadienyl groups or substituted products thereof are bonded via a lower alkylene group, and (B) an aluminoxane.

Description

~312$~

BACKGROUND OF THE INVENTION
1. Field of the Invention This invention relates to a novel cyclo-olefinic random copolymer. More specifically, the invention has for its object the provision of a cyclo-olefinic random copolymer having excellent transparency, thermal stability, heat aging resistance, chemical resistance, solvent resistance, dielectric properties and mechanical properties and a narrow molecular weight distribution and a narrow composition distribution.
This invention also relates to a novel olefinic random copolymer. More specifically, the invention has for its object the provision of an olefinic random co-polymer containing a carbon--carbon unsaturated bond in its side chain which has excellent transparency, thermal stability, heat aging resistance, chemical resistancer solvent resistan~e, dielec~ric properties and mechanical properties and a narrow molecular weiyht distribution and -a narrow composition distribution.
This invention further relates to a process for producing a cyclo-olefinic random copolymer by copoly-merizing an alpha-olefin and a cyclo-olefin in the pre-sence of a highly active polymerization catalyst. More specifically, the invention relates to a process for 2~ producing a cyclo-olefinic random copolymer which com-prises copolymerizing an alpha-olefin and a cyclo-olefin in the presence of a catalyst comprising a spe ific tran-sition metal compound and an aluminoxane.
2. Description of the Prior Art - Known processes for producing cyclo-olefinic copolymers by copolymeri~ing alpha-olefins such as ethylene and cyclo-olefins involve the use of ~itanium-containing catalysts comprising titanium compounds and ~' ~$~2$~j organoaluminum compounds or vanadium-containing ca~alysts comprising vanadium compounds and organoaluminum com-pounds.
In a copolymerization process using a titanium-containing catalyst, a cyclo-vlefin has lower reactivity than an alpha-olefin such as ethylene and the copoly-merization efficiency is low. In order, therefore, to expect production of a copolymer of the cyclo-olefin with the alpha-olefin, it is necessary to add the cyclo-olefin in a large quantity to the polymerization system. The presence of a large quantity of the cyclo-olefin reduces the activity of the catalyst and may result in a decrease in the molecular weight of the resulting copolymer. It is difficult therefore to obtain a high-molecular-weight copolymer. Moreover, this process has the defect that side-reactions such as the ring-opening polymeri~ation of the cyclo-olefin tend to occur, and the resulting polymer has a broad molecular weight distribution~ On the other hand, in a copolymeri~ation process using a vanadium-containing catalyst, the copolymerization efficiency ofthe cyclo-olefin is higher than in the ~ase of using the titanium-containing catalyst and the resulting copolymer has a narrow molecular weight distribution. But it has the defect that the polymerization activity is generally very low.
Catalysts comprising transition metal compounds and aluminoxanes are proposed as highly active poly-merization catalysts for olefins in, for example, Japanese Laid-Open Patent Publications Nos. 19309/lg83, 95292~1984, 35005/1985, 35006~1985 t 35007/1985 and 35008/1985. Of these, Japanese Laid-Open Patent Publications Nos. 19309 1983, 35005/1985, 35006/1985, 35007/1985 and 35008/1985 describe that these catalyst systems can be applied to the copolymerization of ethylene with other alpha-olefins.
35 With regard to the production of cyclo-olefinic co-polymers, 3apanese Laid-Open Patent Publication No.

221206/1986 discloses a catalyst comprising a transition metal compound and an aluminoxane with regard to the production of a copolymer of an alpha-olefin and a cyclo-olefin. This catalyst, however, has low polymerization activity, and is difficult of giving the copolymer in good yields.
It is generally known that by using Ziegler-type catalysts comprising a combination of titanium or vanadium compounds and organoaluminum compounds, binary copolymers f ethylene with cyclo-olefins or ternary copolymers of ethylene, alpha-olefins such as propylene or l-butene and cyclo-olefins are obtainedO However, no example has been known in which an alpha-olefin having 3 to 20 carbon atoms was copolymerized with a cyclo-olefin in the absence of ethylene with a 2iegler-type catalyst. Naturally, no such copolymer has been reported so far.
Polycarbonate, poly~methyl methacrylate) and polyethylene terephthalate have been known as synthetic resins having excellent transparency. For example, poly-carbonate is a resin haviny excellent thermal stability,heat aging resistance and impact strength in addition to -excellent transparency, but have the disadvantage of being inferior in chemical resistance and susceptible to attack by strong alkalies~ Poly(~ethyl methacrylate) is suscep-tible to attack by ethyl acetate, acetone and toluene, isswollen in ether and has low thermal stability. Poly-ethylene terephthalate has excellent thermal stability and mechanical properties, but is susceptible to attack by strong acids or alkalies and liable to undergo hydrolysis.
Many polyolefins widely used as general-purpose resins have excellent chemical resistance, solvent resist-ance and mechanical properties, but poor thermal stability Moreover, they have poor transparency because of their crystalline nature. Generally, the transparency of poly-olefins is improved by adding a nucl~ating agent and thereby finely dividing their crystalline structure, or by 12 `,3 ~ r3 quenching them to stop growth of crystals. The effects of such techniques, however, have not proved to be entirely satisfactory. Rather, the addition of a third comp~nent such as a nucleating agent is likely to reduce the in-herent excellent properties of the polyolefins. Thequenching method requires a large-sized apparatus, and with a reduction in crystallinity, the polyolefins are likely to be degraded in thermal stability and rigidity.
With regard to the copolymerization of ethylene with bulky comonomers, U~ S. Patent No. 2,883,372, for example, discloses a copolymer of ethylene and 2,3-dihydrodicyclopentadiene. This copolymer has an excellent balance between rigidity and transparency, but poor thermal stability because its glass transition temperature is about 100 C. A copolymer of ethylene and 5 ethyl-idene-2-norbornene has similar defects.
Japanese Patent Publication Nou 14910/1971 proposes a homopolymer of 1j4,5,8-dimethano~
1,2,3,4,4a,5,8,8a-octahydro-naphthalene. This polymer, however, has poor thermal stability and heat aging re-sistance.
Japanese Laid-Open Patent Publication No.
1~7728/1983 proposes a homopolymer of 1~4,5,8-dimethano-1,2,3,4,4a~5,8,8a-octahydronaphthalene or a copolymer of the above cyclo-olefin and a norbornene-type comonomer.
It is clear from this patent document that these co-polymers are ring-opened polymers. These ring-opened polymers have poor thermal stability and heat aging re-sistance because they contain an unsaturated bond in the main polymer chain.
Japanese Laid-Open Patent Publications Nos.
168708/1985, 98780/1986, 115912/lg86~ 115916/1986, 1~0816/1986, 95906/1986 and 95905~1986 disclose that olefinic random copolymers of ethylene and specific bulky cyclo-olefins have a good balance in thermal stability, heat aging resistance, chemical resistance, solvent `3 3 ~

resistance, dielectric properties and mechanical proper-ties while having transparency, and exhibit excellent performance in the field of optical materials such as optical memory discs and optical fibers. These copolymers contain ethylene copolymerized therein, and in order to impart good thermal stability, a large amount of a cyclo-olefin must be copolymerized. Reaction of such copolymers with maleic anhydride or the like to impart polar property to these copolymers usually requires the use of peroxides.
This causes cleavage of the main chain and results in a reduction in molecular weight. It is desired therefore to provide olefinic random copolymers which in spite of a low cyclo-olefin content, have excellent thermal stability and can be modified without using peroxides.
SUMMARY OF THE INVENTION
It is an object of ~his invention to provide a novel cyclo-olefinic random copolymer which has excellent transparency, thermal stability, heat aging resistance, chemical resistance, solvent resistance~ dielectric pro-perties and mechanical properties and a narrow molecularweight distribution and a narrow composition distributi~n and which possesses excellent thermal stability eYen when its cyclo-olefin content is smallO
Another object of this invention is to provide a novel olefinic random copolymer which has excellent transparency, thermal stability, heat aging resistance, chemical resistance, solvent resistance, dielectric pro-perties and mechanical properties and a narrow molecular weight distribution and a narrow composition distribution~
possesses excellent thermal stability even when its cyclo-olefin content is small, and which has a carbon-carbon unsaturated bond capable of reacting with maleic anhydride or the like in its side chain, and which can be modified easily according to various purposes.
Still another obejct of this invention is to provide a process Eor producing a cyclo~olefinic copolymer having a narrow molecular weight distribution with excel-lent polymerization activity and a high copolymerization efficiency of the cyclo-olefin.
The above objects are achieved in accordance with this invention by a cyclo-olefinic random copolymer composed of an alpha-olefin component having 3 to 20 carbon atoms and a cyclo-olefin component, (i) said copolymer containing 5 to 99 mole% of recurring units derived from said alpha-olefin component having 3 to 20 carbon atoms and 1 to 95 mole% of recurring units derived from said cyclo-olefin component, and ~ ii) said copolymer having an intrinsic vis-cosity [~] 9 measured in decalin at 135 C, of from 0.01 to 10 dl/g, The above objects are also achieved in accord-ance with this invention hy an olefinic random copolymer composed of t~) an olefin component having 3 to 20 carbon atoms and ~B) a cyclic polyene component and as required~
tC) a cyclo-olefin component, (i) said copolymer containing 5 to 99 mole% of recurring units derived from said alpha-olefin component ~A) having 3 to 20 carbon atoms and 1 to 95 molP% of recurring units derived from said cyclic polyene component (B~ and 0 to 90 mole~ of recurring units derived from said cyclo-olefin component tC), and (ii) said copolymer having an intrinsic vis-cosity ~7], measured in decalin at 135 C, of from 0.01 to 10 dl/g.

3~ The above objects are also achieved in accord-ance with this invention by a process for producing a cyclo-olefinic random copolymer, which comprises co-polymerizing an alpha-olefin and a cyclo-olefin in the presence of a catalyst formed from ~A) a compound of a transition metal of Group IVB of the periodic table having as a ligand a multi-dentate coordination compound in which at least two con-jugated cycloalkadienyl groups or substituted products thereof are bonded via a lower alkylene group, and (B) an aluminoxane.
5 DETAILED DESCRIPTI0~1 OF THE PRE:FERRED EMBODIMENTS
The present inventors made investigations for a novel cyclo-olefinic random copolymer which has excellent transparency, thermal stability, heat aging resistance, chemical resistance, solvent resistance, dielectric pro-perties and mechanical properties and a narrow molecularweight distribution and a narrow composition distribution and which possesses excellent thermal stability even when its cyclo-olefin content is ~mall. These investigations have now led to the discovery that a novel cyclo-olefinic random eopolymer having the aforesaid properties can be obtained by copolymerizing an alpha-olefin having 3 to 20 carbon atoms with a cyclo-olefin in the presence of a catalyst formed from a zirconium catalyst and an alumi-noxane under specific conditions.
Aceording to this invention, there is provided a cyclo-olefinic random copolymer composed of an alpha- -olefin component having 3 to 20 carbon atoms and a cy~lo-olefin component, (i) said copolymer containing 5 to 99 mole% of recurring units derived from said alpha-olefin component having 3 to 20 carbon atoms and 1 to 95 mole% of recurring units derived from said cyclo-ole~in component, and (ii) said copolymer having an in~rinsic vis-cosity [~1, measured in decalin at 135 C, of from 0.01 to 10 dl/g The cyclo-olefinic random copolymer of this invention is a cyclo-olefinic random copolymer composed of an alpha-olefin component having 3 to 20 carbon atoms and a cyclo-olefin component.
The cyclo-olefin component is a cyclo-olefin represented by the following general formula 1I ], [II ~ Or ~ 3 ~

[III], and in the cyclo-olefinic random copolymer of this invention, the cyclo-olefin component forms a structure represented by the general formula [IV~, lV] or lVI].

~ [I]

S ~ ~-R )C III3 I~-R )d 1III~

In the formulae, a and b are an interger of O or more, c and d are an integer of 3 or more~ and each of to R10 represents a hydrogen atom, a halogen atom or a hydrocarbon group.

[IV~

~ 0~c [V]

~ ~ [VI~
¦ ( -C-R Id In the formulae, a, b, c, d, and Rl to R10 are as defined above.
In the production of the cyclo-olefinic random copolymer of this invention, examples of the C3-C~o alpha-olefin used as a material include propylene, 1-butene, l-hexene, 4-methyl-1-pentene, l-octene, l-decene, l-dodecene, l-tetradecene, l-hexadecene, l-octadecene and l-eicosene.
The cyclo-olefin used 2S another material in the production of the cyclo-olefinic random copolymer of this invention is at least one cyclo-olefin selected from the group of unsaturated monomers represented by general formulae tIl, [II~ and rIII].
Cyclo-olefins repre~ented by general formula [I~

may be easily produced by condensing cyclopentadienes with the corresponding olefins in accordance with the Diels-Alder reaction. Cyclo-olefins represented by general formula ~II3 can be easily produced likewise by condensing cyclopentadienes with ~he corresponding cyclo-olefins in accordance with the Diels-Alder reaction.
Specific examples of the cyclo-olefins of general formula ~I] include octahydronaphthalenes such as 1,4,5,8-dimethano-1,2,3,4,4a~5,8,8a-octahydro-1 0 naphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-propyl-1,4,5,8-dimethano-1,2,3,4,4a,5t8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a,5,B,8a-octahydronaphthalene, 2-stearyl-1,4,5,8-dimethano~1,2,3,4,4a,5~8,8a-octahydronaphthalene, 2,3-dimethyl-].~4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-methyl-3-ethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene/
2-chloro-1,4,5,8-dimethano-1,2~3,4,4a,5,8,8a-octahydronaphthalene, 2-bromo-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-n-butyl-1,4~5,8-dimethano-1,2,3,4,4a~5,8,8a-octahydronaphthalene, and 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, and;
the compounds described in Table 1 below.

~t~

Table 1 Chemical fonmula Chemical name 3 ~ 5 bicyclo12,2,1]hept-2-ene H3 6-methylbicyclo[2,2,1]-hept--CH3 5,6-dimethylbicyclol2,2,1]-H3 hept-2-ene CH
l-;ethylbicyelol2,2,1]-hept~

. . _ __ H5 6~ethylbicyclo~2,2,1]-hept-~_ 4H9 6-n-butylbieyelol2,2/l]-hept-.
. ~ C4H9 6-i-butylbieyclo~2,2,1]-hept-_ _ _ _ ~
H3 7-methylbicyclo[2,2,1~-hept-2~ 1 llO 5,10~dimethyltetraeyelo-2,5,17~l]-3_dodecen i - to be eontinued -Table 1 (continued?
Chff~cal formula Chemi~al name ,_ ~

2,10-dimethyltetracyclo-[~,4,o,l2,5,11~10~~3'dodecene I / t \ ~ ~ 11,12~imethyltetracyclo--c~ [4,4,0,1 ' ,1 ' ]-3-dodecene . ._ 3 CH3 2,7,9-trImethyltetracyclo-. ~ 14,4,0~12~5,17~l~_3_dodecene ~3 . _. . ~

C2~ 9-ethyl-2,7_dImethyltetra->1 ~ cyclot~,4,0,1 ' ,1 ' 1-3-dodeoene .. _ _ . ,~

CH2cH(cH332 9-isobutyl-2,7-dimethyltetra-~I ~ cyclot4,~,0,12~5,17~10]_~_ , ~ dodecene . .

9,11,12-trimethyltetracy~lo--C~3~ ~ t~,~,o,l2,5,17,10~-3_dOdecene \/\ /
.. _ 2H5 9-ethyl-11,12-dimethyltetra-I ~ I ~ cyclol4,4,0,12'5,17'1 ~-3-_ dodecene - ~ to be contLnued -~ e3 ~.f~ 3 Table 1 (continued) _ ~ .
C~nical form~la Ch~nical name _ _ _ /~ /~ C~12CH(C~3)~
f' ~ 1~ 9~ utyl~ 12~imethyl~.-tetra~Clo [4 ,4 ,0 ,12 ~5 ,17 3~odecene _ _ ~CH3 5, 8, 9 ,10-tetramethyltetra->~ ~yclot4,4"o,l2'5,17~1]_3_ CE~3 dodeoene CE13 .
_ ~

4 ~ 12 h~Xa~:lol6~6~lJl3~5 110~13 5¢~.11 o2,7 o9~l4~ eptad~ene .
. . __ ___ _ C~3 12~th~1hexacy~10 16 r6 ~3. 9 13~ 110,13 o2~7 o9tl~l_4_ heptadeoene -__ _ . _ _ _ C ~ 12~ ylhexa~yclot6,6,1, 2 5 13~6,~ 3~o2~7~o9~l4] 4 ~S'~ )~ ~ ~6' heptadecene .

CH(CB3)~ 12-isobutyIhexacyclot6,6,1, 13'~ 0~l3~o2r7 o9~14~ 4 hepkade oene ._ ~ ~ C~(C~3)2 1,6,10-trimethyl-12-isobutyl-I`l~ }~exacyclOt6,6,1,13,6,110,13 j ~ C~3 02'7,09'14]-4-hepkadecene - to be eont~nued -Table 1 (continued) _ _ Ch~nical fQn~la Ch~nical nane ~/~octacyclo- [ g ~8 ~l2 ~ 4 ~7, ,113'16,o,o3,8 ol~, _ .
~CH3 15-methyloctacyclo- [ 8 ,8 ~
12,~ 5~113'16,0,~3~, ~/~c~H515~thyloctacyclo- 18 ,8 ,1~ '9, -- - ol2 ,~ 5~ ,1 3 16 ,o lo3 ,8, Specific examples of the cyclo-olefins o general formula ~II3 are compounds shown in Table 2 below.

:~ 3 .~. 2 ~

Table 2 Chemical ormula Chemical name ,.. ~

¢ ~ tricyclo[4,3,0,12'5]-3-decene CH
2-methyltricyclo[4,3,0,12'5]-3_decene 5-methyltricyclo[4,3,0,12'5]-CH3 _ _ _ _ 8 tricyclol4,4,0,12'5]-3-decene 10-methyltricyclo-t4,4,0,1 '5]-3_decene 3 3 1,3~dimethylpentacyclo-~/~ [6,6,1,13~6 ,o2~7 ,o9~14~
~ ~ 4-hexadecene _ 1,6-dimethylpentacyclo-~6,6,l,l3r6,o2~7~o9~l4] 4 CH3 hexadecene .
- to be continued -Table 2 (continued?
_ ~
Chenical fonmula Chemical name . _ 15,16~dimethylpentacyclo-I I )~ [6,6,1,13r6,o2~7,o9~
\ 1 / ~ 4-hexadecene ~ 12 pentaCyclol6~5~ 3~6 ,o2 ~7 5 ~ 7 ~ 11 09~13]-4-pentadecene _ . ._ ~
ÇH3 C~l3 1,3-di~ethylpentacyclo-[615,l,l3f6,o2~7 o~,l3 4-pentadecene . ... _. ~

,'~ ~ 1,6~dLmethylpentacyclo-11 >I >I I [6,s,l,l3~6~02~7,ng,l3]-4 pentadecene . . . . . _ ___ 14,15-dimetylpentacyclo-)qc~3 -c~31 l t6,5,1,13~6,o~,7~ 9,13] 4 pentadecene .... .... __ ..... _ _ _ 3 2 1 1 ~ pentacyclot6,6,1,13'~,0~'7, SW~J 11 o9'14]-4-he~

_ ~ 1 17 heptacyclot8,7,1,12'9,14'7, 61 ~ ~4 111'l7,o~o3~8~ol2~l6~ 5 7 8 9 1111213 eicosene - to be continued -~ c~

Table 2 (continued?
_ . . n _ .
Chemical fo~la Chemical name .

~ ~ 1 ~ 15 pe~tacyclo~8r8,12'9,14'7, 6[ ~ >1 Jl4 lll'l8to~o3~8,0l2,l7]
7 8 9 10 111213 5-heneicosene Specific examples of the cyclo-olefins of general formula [III] include cyclopentene, 3-methyl-cyclopentene, 4-methylcyclopentene9 3!4-dimethylcyclo-pentene, 3,5-dimethylcyclopentene, 3-chlorocyclopentene, cyclohexene, 3-methylcyclohexene, 4-methylcyclohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene and cyclo-heptene.
The cyclo-olefinic random copolymer o~ this invention contains 5 to ~9 mole%~ preferably 15 to 95 mole~, especially preferably 30 to 90 mole%, of recurring units derived from the alpha~olefin component having 3 to 20 carbon atoms, and 1 to 95 mole%, preferably 5 ~o 95 mole%~ especially preferably 10 to 70 mole%, of recurring units derived from the cyclo-olefin component. The re~
curring units derived from the C3-C20 alpha-olefin com-ponent and the recurring units derived from the cyclo-olefin component are arranged at random to form a sub-stantially linear cyclo-olefinic random copolymer~ That the cyclo-olefinic random copolymer of this invention is substantially linear can be ascertained by the fact that the copolymer completely dissolves in decalin at 135 C.
The intrinsic viscosity t~], measured in decalin at 135 C, of the cyclo-olefinic random copolymer of this invention is 0.01 to 10 dl/g, preferably 0.05 to 7 dl/g, especially preferably 0.1 to 5 dl/g.
The molecular-weight distribution ~Mw~Mn) of the cyclo-olefinic random copolymer of this invention, mea-sured by gPl permeation chromatography (GPC), is usually 3 ~3 not more than 4, preferably not more than 3.5, especially preferably not more than 3.
The cyclo-olefinic random copolymer of this invention has a glass transition temperature (Tg) of 10 to 240 C, preferably 20 to 200 C.
The cyclo-olefinic random copolymer of this invention can be produced by polymerizing the alpha-olefin having 3 to 20 carbon atoms with a predetermined amount of the cyclo-olefin in the presence of a catalyst formed from 1~ (A) a zirconium compound having as a ligand at least two indenyl or substituted indenyl groups or partially hydrogenated groups thereof being bonded via an alkylene group such as an ethylene group, and (B) an aluminoxane.
The zirconium compound may have at least two indenyl or substituted indenyl groups or partially hydrogenated groups thereof, preferably two indenyl groups, two substituted indenyl groups, or two partially hydrogenated groups thereof~
Specific examples of the above zirconium com-pound include ethylenebis(indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium monochloride mOnohydrider ethylenebis(indenyl~ethoxyzirconium chloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)ethoxy-zirconium chloride, ethylenebis(indenyl)dimethylzirconium, ethylenebis(indenyl3diethylzirconium, ethylenebis(indenyl)diphenylzirconium, ethylenebis(indenyl3dibenzylzirconium, ethylenebis~indenyl)methylzirconium monobromide, ethylenebis(indenyl~ethylzirconium monochloride, ethylenebis(indenyl)benzylzirconium mono-chloride, ~ 3 ~

ethylenebis(indenyl)methylzirconium mono-chloride, ethylenebistindenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dibromide, ethylenebis(4,5,6,7~tetrahydro-1-indenyl~-dimethylzirconium, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)-ethylzirconium ethoxide, ethylenebis~4,5,6,7-tetrahydro-1-indenyl)- 0 zirconium dichloride~
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)-zirconium dibromide, ethylenebis(4-methyl-1-indenyl)zirconium dichloride, ethylenebis~5-methyl-1-indenyl)zirconium dichloride, ethylenebis(6-methyl-1-indenyl)zirconium dichloride, ethylenebi~7-methyl-1-indenyl~zirconium 0 dichloride~
ethylenebis~5-methoxy-1 indenyl)zirconium dichloride, ethylenebis(2,3-dimethyl-1-indenyl)zirconium dichloride, ethylenebis~4,7-dimethyl-1-indenyl)zirconium dichloride, ethylenebist4,7-dimethoxy-1-indenyl)zirconium dichloride, ethylenebistindenyl)zirconium dimethoxide, ethylenebis~indenyl)zirconium diethoxide, ethylenebis(indenyl~methoxyzirconium chloride, ethylenebis(indenyl3ethoxyzirconium chloride, ethylenebis(indenyl)methylzircQnium ethoxide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)-zirconium dimethoxide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)-zirconium diethoxide, :~ 3~2$~1 ethylenebis~4,5,6,7-~etrahydro-1-indenyl)-methoxyzirconium chloride, ethylenebis(4~5,6,7-tetrahydro-1-indenyl)-methylzirconium ethoxide, methylenebis(indenyl~zirconium dichloride, methylenebis(indenyl)dimetbyl~irconium, methylenebis(4,5,6,7~tetrahydro-1-indenyl)-zirconium dichloride, propylenebis(indenyl)zirconium dichloride, propylenebis(indenyl)dimethylzirconi~m, and propylenebis(4,5,6,7-tetrahydro-1-indenyl)~
zirconium dichloride.
The aluminoxane used as component (b) of the catalyst may be, for example, an organoaluminum compound represented by the following general formula [VII] or tVIII~

R2Al~ 1 ~ O-AlR2 1VII~
R

m~2 lVIII]

wherein R represents a hydrocarbon group such as a methyl, ethyl, n-propyl, isopropyl~ n-butyl or isobutyl group~ preferably the methyl, ethyl or isobutyl group, especially preferably the methyl group, m is an integer of 2 or more, preferably 5 or mor~.
The aluminoxane may be produced, for example, by the following method (1) or (2~.
The aluminoxane of general formula lVII] or [VIII] may be formed of mixed oxyaluminum units ~Al~
R

having different hydrocarbon groups. In ~his caset the 30 aluminoxane preerably has at least an oxymethyl aluminum ~ 3 '~ 2~

unit ~OAl~ in a proportion of at least 30 mole%, prefer-C~13 ably at least 50 mole~, especially preferably at least 70 mole%.
~1) A trialkyl aluminum or a mixture of at least two trialkyl aluminums is added to, and reacted with, a suspension of a compound containing water of adsorption or a salt containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate or cerous chloride hydrate in a hydrocarbon medium.
~ 2) Water is caused to act directly upon a trialkyl aluminum or a mixture of at least two trialkyl aluminums in a medium such as benzene, toluene, ethyl ether or tPtrahydrofuranO
The method ~ preferred~ The aluminoxane may permissibly contain small amounts of organometallic components.
The catalyst ingredient ~A) or catalyst in-gredients (A) and (B) may be used as supported on a 20 carrier. The carrier may be, for example, an inorganic compound such as silica or alumina, or an organic polymeric compound such as polyethylene or polypropylene.
It has been found in accordance with this invention that by copolymerizing the C3-C20 alpha~olefin 25 with the cyclo-oleEin in specific proportions using the above catalyst system, a copolymer having properties not hitherto proposed can be obtained. This copolymerization may be carried out in a liquid phase or in a vapor phase, preferably in the liquid phase. Copolymerization in the liquid phase is usually carried out in a hydrocarbon medium. Examples of the hydrocarbon medium are aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane and octadecane, alicyclic hydrocarbons such as cyclopentane, methyl-cyclopentane, cyclohexane and cyclooctane, aromatic ~s~

hydrocarbons such as benzene, toluene and xylene, and petroleum fractions such as gasoline, kerosene and light oil. The starting olefin may also be used as the hydro-carbon medium. The aromatic hydrocarbons are especially preferred as the hydrocarbon medium.
The temperature in the polymerization- reaction in the process of this invention is usually -50 to 230 C, preferably -30 to 200 C.
The proportion of the zirconium compound used in carrying out the process of this invention in the liquid phase is usually 10 8 to 10 2 gram-atom/D ~ preferably 10 7 to 10 3 gram-atom/~, as the concentration of the æirconium atom in the polymerization reaction system. The propor-tion of the aluminoxane is usually 10 4 to 10 1 gram-atom/Q, preferably 103 to 5 x 10 2 gram atom/~, as theconcentration of the aluminum atom in the polymerization reaction system. The ratio of the aluminum ato~ to the t~ansition metal atom in the polymerization system is usually from 4 to 107, preferably from 10 to 10~. The molecular weight of the copolymer can be adjusted by USiQ9 hydrogen, and/or adjusting the polymerization temperature.
The present inventors also made investigations for a novel olefinic random copolymer which has excellent transparency, thermal stability, heat aging resistance, chemical resistance, solvent resistance, dielectric pro-perties and mechanical properties and a narrow molecular weight distribution and a narrow composition distribution, possesses excellent thermal stability even when its cyclo-olefin content is small, and which has a carbon-carbon unsaturated bond capable of reacting with maleic anhydride or the like in its side chain and can be modified easily according to various purposes. These investigations have led to the discovery that a novel olefinic random co-polymer can be obtained by copolymerizing an alpha-olefin 3s having 3 to 20 carbon atoms and a cyclic polyene and as required, a cyclo-olefin in the presence of a catalyst formed from a zirconium catalyst and an aluminoxane under specific conditions.
Thus, according to another aspect of this invention there is provided an olefinic random copolymer composed of ~A) an olefin component having 3 to 20 carbon atoms and (B) a cyclic polyene component and as required, (C) a cyclo-olefin component, (i) said copolymer containing 5 to 99 mole% of recurring units derived from said alpha-olefin component (A) having 3 to 20 carbon atoms and 1 to 95 mole% of recurring units derived from said cyclic polyene component (B) and 0 to 90 mole% of recurring units derived from said cyclo-olefin component ~C3, and (ii) said copolyemr having an intrinsic viscotiy [~], measured in decalin at 135C~ of from 0.01 to 10 dl/g.
The olefinic random copolymer in this embodiment is composed of ~A) an alpha-olefin component having 3 to 20 carbon atoms and ~B) a cyclic polyene and as required, (C) a cyclo-olefin component. The cyclo-olefin component ~C) is the same cyclo-olefin component of general formula [I]l ~II] or ~ given hereinabove. As in the aforesaid cyclo-olefinic random copolymer, the cyclo-olefin com-ponent forms the structure represented by general formula tIV], [V~ or tVIl given hereinabove.
Specific examples of the alpha-olefin used as a starting material in the production of th~ olefinic random copolymer of this invention may be those given herein-above .
Specific examples of the cyclic polyene (B) used as a starting material in the production of the olefinic random copolymer of this invention are 1,3-cyclopentadiene, 1,3-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cyclo-heptadiene, 1,3-cycloheptadiene, dicyclopentadiene, di-cyclohexadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornen~, 5-vinyl-2-norbornene, 5-isopropylidene-2-2~ 3~

- 2~ -norbornene, methylhydroindene, 2,3-diisopropylidene-5-norbornene r ~-ethylidene-3-isopropylidene-5-norbornene, and ~-propenyl-2,5-norbornadiene.
The olefinic random copolymer of this invention contains 5 to 99 mole%, preferably 15 to 95 mole%, es-pecially preferably 30 to 90 mole%, of recurring units derived from the alpha-olefin component (A), 1 to 95 mole%, preferably 5 to 85 mole%, especially preferably 10 to 70 mole%, of recurring units derived from the cyclo-olefin component (B), and 0 to 90 mole~, preferably 2 to80 mole~l especially preferably 5 to 70 mole%, of re-curring units derived from the cyclo-olefin component tC).
These recurring units derived from the components ~A), tB) and ~C) are arranged at random to form a substantially linear olefinic random copolymerO That the olefinic random copolymer of this invention is ~ubstantially linear and has no gelled crosslinked structure can be ascertained from the act that the copolymer completely dissolves in decalin at 135 C.
The in~rinsic viscosity ~1, measured in decalin at 135 C, of the olefinic random copolymer of this invention is 0.01 to 10 dl/g, preferably 0.05 to 7 dl~g, especially preferably 0.1 to 5 dl/g.
The molecular-weight distribution (Mw~Mn~ of the olefinic random copolymer of this invention, measured by gel permeation chromatography (GPC), is usually not more than 4, preferably not more than 3.5, especially prefer-ably not more than 3.
The olefinic random copolymer of this invention 3~ can be produced by polymerizing an alpha-olefin having 3 to 20 carbon atoms and the cyclic polyene and as required, a predetermined amount of the cyclo-olefin in the presence of a catalyst formed from (A) a zirconium compound having as a ligand at least two indenyl or substituted indenyl groups or partially hydrogenated groups thereof being bonded via an alkylene group such as an e~hylene group, and ~B) an aluminoxane.
Examples of the zirconium compound and the aluminoxane may be the same as given hereinabove with regard to the production of the cyclo-olefnic random copolymer.
The catalyst ingredient (A) or catalyst ingre-dients (A~ and (B) may be used as supported on a carrier~
Examples of the carrier are inorganic compounds such as silica and alumina and organic polymeric compounds such as polyethylene and polypropylene.
It has been found in accordance with this invention that by copolymerizing ~he C3-C20 alpha-olefin and the cyclic polyene and optionally the cyclo-olefin in specific proportions using the above catalyst system, a copolymer having properties not hitherto proposed can be obtained. This copolymerization may be carried out in a liquid phase or in a vapor phase, preferably in the liquid phase. Copolymerization in the liquid phase is usually carried out in a hydrocarbon medium. Examples of the hydrocarbon medium are aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane and octadecane, alicyclic hydro-carbons such as cyclopentane, methylcyclopentane, cyclo-hexane and cyclooctanef aromatic hydrocarbons such as benzene, toluene and xylene, and petroleum fractions such as gasoline, kerosene and light oil. The starting olefin may also be used as the hydrocarbon medium. The aromatic hydrocarbons are especially preferred as the hydrocarbon medium.
The temperature in the polymerization reaction in the process of this invention is usually -50 to 230 C, preferably -30 to 200 C.
The proportion of the zirconium compound used in carrying out the process of this invention in the liquid ~ 3~i - ~6 -phase s usually 10 8 to 10 2 gram-atom~, preferably 10 7 to 10 gram-atom/~, as the concentration of ~he zirconium atom in the polymerization reaction system. The propor-tion of the aluminoxane is usually 10 4 to 10 1 gram-atom~, preferably 10 3 to 5 x 10 2 gram-atom/~, as the concentration of the aluminum atom in the polymerization reaction system. The ratio of the aluminum atom to the transition metal atom in the polymerization system is usually from ~ to 107, preferably from 10 to 106. The molecular weight of the copolymer can be adjusted by using hydrogen, and/or adjusting the polymerization temperatureO
The cyclo-olefinic random copolymer and the olefinic random copolymer provided by this invention have excellent transparency, thermal stability, heat aging resistance, chemical resistance, solvent resistance~
dielectric properties and mechanical properties and a narrow molecular weight distribution and a narrow com-position distribution, and possess excellent homogeneity.
Because of their excellent properties, they find a wide variety of applications. For example, those having a low molecular weight can be used as synthetic waxes in candles, impregnants for match splints, paper treating agents7 sizes, rubber antioxidants, water-proofing agents for corrugated boards, agents for retarding the effect of chemical fertilizers, heat storing agents, binders for ceramics, paper capaci~ors, electrical insulators for electrical wires and cables, neutron decelerating agents, textile treating aids, water-repellents for build-ing materials, protective agents for paint coatings, lusterants, thixotropy-imparting agents, agents for im-parting hardening to the cores of penciles and crayons, carbon ink bases, electrophotographic toners, lubricants and mold releasing agents for molding of synthetic resins, resin coloring agents, hot-melt adhesives and lubricating greases. Those having a high molecular-weight are useful in optical applications as optical lenses, optical discs, c`~

- ~7 -optical fibers and windowpanes, electrical applications as water tanks for electrical irons, electric ovens, base plates for liq~id crystal display, printed circuit boards, high-frequency circuit boards, and transparent conductive sheets or films, medical applications as injecting syringes, pipettes and animal gages, chemical applications or in other fields as housings of various measuring in-struments, camera bodies, films, and helmets.
Those containing not more than about 20 mole% of recurring units from the cyclo-olefin component may be used in fields where their shape memorizing property is utilized, such as vibration controlling materials or tubes. Specifically, they may be used as joints of irregularly-shaped pipes, laminating materials for the inside and outside parts of pipes and rods, clamping pins for optical fiber connectors, plaster bandages~ con-tainers, automobile bumpers, various space blocking materials, and vibration con~rol materials (soundproof materials) or medical tubes in the form of laminates with metallic surface materials.
The novel olefinic random-copolymer of this invention can be easily cured or modified since it con-tains a carbon-carbon unsaturated bond in its side chain~
In the field of producing cyclo-olefinic co polymers, it has been strongly desired to develop a process which can produce cyclo-olefinic copoly~ers having a narrow molecular weight distribution efficiently with a high copolymerizing efficiency of cyclo-olefins and ex-cellent polymerization activity. The present inven~ors recognized that the prior art in the field of producing cyclo-olefinic copolymers was as stated above, and worked on a process which can produce a cyclo-olefinic copolymer having a narrow molecular weight distribution with a high copolymerization efficiency of the cyclo-olefin and excel-lent polymerization activity. This work has now led tothe discovery that the aforesaid object can be achieved by ~ 3 ~

copolymeri~ing an alpha-olefin and a cyclo-olefin in the presence of a catalyst composed of a compound of a tran-sition metal of Group IVB of the periodic table having a specific coordination compound as a ligand and an alumi~
noxane.
Thus, according to still another aspect of this invention, th~-~e~ is provided a process for producing a cyclo-olefinic random copolymer, which comprises co-polymerizing an alpha-olefin and a cyclo-olefin in the presence of a catalyst formed from (A) a compound o~ a transition metal of Group IVB of the periodic table having as a ligand a multi-dendate coordination compound in which at least two con-jugated cycloalkadienyl groups or substituted products thereof are bonded via a lower alkylene group, and ~ B) an aluminoxane.
The catalyst used in the process of this invention is formed from tA) a compound of a transition metal of Group IVB of the periodic table and (B) an aluminoxane.
~ The transition metal compound ~A~ used as a catalyst ingredient in the process of thi~ invention is a compound of a transition metal of Group I~B of the periodic table which has as a ligand a multidentate co-ordina$ion compound in which at least two conjugated cycloalkadienyl groups or substituted groups thereof are bonded via a lower alkylene group. The compound of the transition metal of Group IV~ of the periodic table are selected from titanium, zirconium and hafnium compounds.
Titanium and zirconium are preferred as the transition metal in the catalyst ingredient (A), zirconium being especially preferred.
For example, the Group IVB transition metal compound ~A) is represented by the ollowing general formula [IX]

~3 r~---- 2\ Me / ~ [IX]

wherein R represents a lower alkylene group, and Rl and R2 represent a conjugated cycloalkadienyl group or a substituted group thereof, R3 and R4 represent a cyclo-alkadienyl group, an aryl group, an alkyl group, anaralkyl group, a cycloalkyl group, a halogen atomr a hydrogen atom, ORa, SRb, NR2, or Pd2, R~, Rb, Rc and Rd represents a hydrocarbon group such as an alkyl, cyclo-alkyl, aryl or aralkyl group, or a silyl group, and the Rc groups and Rd groups m~y be linked to form a ring.
The lower alkylene group may be~ for example~
a methylene, ethylene, propylene or butylene group.
Examples of the conjugated cycloalkadienyl group includ~ a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, a dimethylcyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, and a fluorenyl group. Examples of the alkyl group are methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, 2-ethyl- -hexyl, decyl and oleyl groupsO The aryl group may be, for example, a phenyl or tolyl group. The aralkyl groups may be, for example, a benzyl or neophyl group. Examples of the cycloalkyl group include cyclopentyl~ cyclohe~yl, cyclooctyll norbornyl and bicyclononyl groups and alkyl-substituted groups thereof. The hydrocarbon group may also include unsa~urated aliphatic groups such as vinyl, allyl, propenyl, isopropenyl and l-butenyl groups, and unsaturated alicyclic groups such as a cyclohexenyl group.
The halogen atom may be for example fluorine, chlorine or bromine.
The zirconium compounds includef for example, the indenyl-type zirconium compounds exemplified here-inabove, and the following compounds.
E~hylenebis(cyclopentadienyl)zirconium mono-chloride monohydride, - 3~ -ethylenebis~cyclopentadienyl)zirconium di-chloride, ethylenebis(cyclopentadienyl)methylzirconium monochloride, ethylenebis~cyclopentadienyl~dimethylzirconium, ethylenebis(cyclopentadienyl)diphenylzirconium, methylenebis~cyclopentadienyl)zirconium di-chloride, methylenebis(cyclopentadienyl)dimethylzirconium, propylenebis(cyclopentadienyl)zirconium di-chloride, ethylenebis(fluorenyl)zirconium dichloride, ethylenebis(fluorenyl)dimethylzirconium, ethylenebis~fluorenyl)diphenylzirconiumr methylenebis(fluorenyl)zirconium dichloride, methylenebis~fluorenyl)dimethylzirconium, and propylenebistfluorenyl~zirconium dichloride.
Examples of the titanium compounds include e~hylenebis(indenyl)titanium dichloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)-titanium dichloride, ethylenebis(cy~lopentadienyl~titanium di-chloride, methylenebis(cyclopentadienyl)titanium di-5 Chloride, propylenebis(cyclopentadienyl)titanium di-chloride, methylenebis(indenyl)titanium dichloride, methylenebis(4,5,6,7-tetrahydro-1-indenyl)-0 titanium dichloride,propylenebis(indenyl)titanium dichloride, ethylenebis(fluorenyl)titanium dichloride, and propylenebis~fluorenyl)titanium dichloride.
Examples of the hafnium compounds include the following compounds.
Ethylenebis(cyclopentadienyl)hafnium dichloride, 2 ~

methylenebis(cyclopentadienyl)hafnium di~
chloride, propylenebis~cyclopentadienyl)hafnium di-chloride, methylenebis(indenyl)hafnium dichloride, methylenebis(4,5,6,7-tetrahydro-1-indenyl)-hafnium dichloride, propylenebis(indenylihafnium dichloride, ethylenebis(indenyl)hafnium dichloride, and ethylenebis(4,5,6~7-tetrahydro-1-indenyl3hafnium dichloride.
The aluminoxane used as the catalyst ingredient (B) may be, for example, the oeganoaluminum compounds of general formulae [VII] and [VIII~ which are exemplified lS hereinabove.
The catalyst ingredient ~A) or the catalyst ingredients tA) and (B) may be used as supported on a carrier. The carrier may b~, for example, an inorganic compound such as silica or alumina, or an organic poly-meric compound such as polye hylene or polypropylene.
Specific examples of C2-C20 alpha-olefins which are used in the polymerization reaction in accordance with the process of this invention include, ethylene, propylene, l-butene, l-hexene, 4-methyl-1-pentene, 1-octene, l-decene, l-octadecene and l-eicosene.
Specific exampl~s of the cyclo-olefin to be supplied to the polymerization reaction in accordance with the process of this invention inolude cyclic monoenes, for example monocycloalkenes such as cyclopropene, cyclo-butene, cyclopentene, cyclohexene, 3-methylcyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, tetracyclodecene, oc~acyclodecene and cycloeicosene, bicycloalkenes such as norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5~6-dimethyl-2-norbornene, and 5,5,6-trimethyl-2-norbornene, tricycloalkenes such as 2,3,3a,7a-tetrahydro-4,7~methano-3 ~

lH-indene and 3a,5,6,7a-tetrahydro-4,~-methano-1~1-indene, tetracycloalkenes such as 1,4,5,8-dimethano-1,~,3,4,4a,5,8,8a-octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3r4,4a,5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydro-naphthalene, 2-propyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-stearyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydro-naphthalene, 2-methyl-3-ethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-chloro-1y4,5,8-dimethano-1,2,3,4,4a,5r8,8a-octahydronaphthalene, 2~
bromo-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydro-naphthalene, 2-fluoro-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, and 2,3-dichloro-1,4,5~8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene; polycycloalkenes such as hexacyclo[6,6,1,13'6,11'l3,02'7,09'~4]-heptadecene-4, pentacyclo[8,8,12'9~14'7,1 1~18,~
~0 0,03'8,012'17]heneicosene-5, otacyclol8,8,12'9, 14~7 111,18 1l3rl6~o~3~8~ol2tl7ldecocene-5;
and cyclic polyenes such as dicyclopentadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 1,5-cyclooctadiene, 5,8-endomethylenehexahydronaphthalene and alkylildenetetrahydroindenes.
In the process of this invention, a mixture of the alpha-olefin and the cyclo-olefin is fed into the polymerization reaction system as a starting material.
The content of the alpha-olefin in the mixture is usually 1 to 90 mole~, preferably 2 to 80 mole%, and the content of the cyclo-olefin is usually 10 to ~9 mole%, preferably 20 to 98 mole%.
In the process of this invention, the poly-merization is usually carried out in a hydrocarbon medium.
Examples of the hydrocarbon medium are aliphatic hydro-carbons such as butane, isobutane, pentane, hexane, ~ 3 ~

octane, decane, dodecane, hexadecane and octadecane, alicyclic hydro_arbons such as cyclopentane, methyl-cyclopentane, cyclohexane and cyclooctane, aromatic hydrocarbons such as benzene, toluene and xylene, and petroleum fractions such as gasoline, kerosene and light oil. The starting olefin may also be used as the hydro-carbon medium. The aromatic hydrocarbons are especially preferred as the hydrocarbon medium.
In the process of this invention, a liquid phase polymerization method such as suspension polymerization and solution polymerization and a vapor-phase polymeri-zation method are usually employed. The temperature in the polymerization reaction is usually -50 to 230 C, preferably -30 to 200 C.
The proportion of the transition metal compound used in carrying out the process of this invention in the liquid phase is usually 10 8 to 10 2 gram-atom/~, preferably 10 7 to 10 3 gram-atom~Rr as the concentration of the transition metal atom in the polymerization reac-tion system. The proportion of the aluminoxane is usually - 1~ 4 to 10 1 gram-atom/~, preferably 103 to 5 x 10 2 gram-atom~, as the concentration of the aluminum atom in the polymerization reaction system. The ratio of the aluminum atom to the transiton metal atom in the poly-merization system is usually from 4 to 107, preferably from 10 to 106. The molecular weight of the copolymer can be adjusted by using hydrogen, and/or adjusting the poly-merization temperature.
In the process of this invention, a cyclo-olefinic copolymer is obtained by working up the poly-merization reaction mixture after the polymerization reaction by conventional methods. The resulting cyclo-olefinic copolymer is usually composed of 20 to 99.9 mole~, preferably 30 to 99.5 mole%, of the alpha-olefin component and 0.1 to 80 mole%, preferably 0.5 to 70 mole~, of the cyclo-olefin component. The intrinsic viscosity .3 e.

~ 3~ -[7, . measured in decalin at 135 C, of the cyclo-olefinc copolymer is usually 0.005 to 20 dl~g, preferably 0.01 to 10 dl~g. Its molecular wei~ht distribution measured by gel permeation chromatography is usually not more than 3, preferably not more than 2.5.
The process of this invention can produce a cyclo-olefinic random copolymer having a narrow molecular weight distribution with excellent polymerization activity.
The following examples speci~ically illustrate the cyclo-olefinic random copolymer and the olefinic random copolymer of this invention.
The properties of the copolymers obtained in the following examples were measured by the following methods.
Copolymer composition _(mole~
The conten~ of units derived from the cyclo-olefin component in the eopolymer was measured by 13C-NMR
~200 megaher~).
Intrinsic viscosity [~1 Measured by an Vbbelohde viscometer at 135 C.
Molecular wei~ht distribution (Mw~Mn) Measured by the GPC method.
Glass transition tempeeature (TG) Measured by a dynamic mechanical analyzer (DMA) (made by E. I. du Pont de Nemours ~ Co.)O

Preparation of ethylenebis~indenyl)zirconium dichloride Tetrahydrofuran (60 ml~ was fed into a 200 ml fully nitrogen-purged glass flask, and then cooled to -78 C. Zirconium tetrachloride (4.9 g) was introduced into the flask. The mixture was gradually heated to 60 C
and stirred for 1 hour at this temperature to form a solution. Subsequently, a solution of 21 millimoles of bis(indenyl)ethane lithium salt in 50 ml of tetrahydro-furan was added, and the mixture was stirred at 60 C for ci - 3s -1 hour. The mixture was further stirred for 12 hours at 25 QC. Under reduced pressure, tetrahyrofuran was removed to form a solid. The solid was washed with methanol, and dried under reduced pressure to give 2.19 of ethylene-bis(indenyl)zirconium dichloride Preparation of an aluminoxane A12(SO4)3-14H2O (37 g) and 125 ml of toluene were introduced into a 400 ml fully nitrogen-purged flask, and ccoled to 0 C. Trimethyl aluminum (500 millimoles) diluted with 125 ml of toluene was added dropwise. The mixture was heated to 40 C, and treated at this tem-perature for 10 hours. After the reaction, the reaction mixture was filtered. By removing toluene from the filtrate, 13 9 of aluminoxane as a white solid was ob-tained. The aluminoxane had a molecular weight of 930when i~ was determined by freezing point depression in benzene. The _ value of the aluminoxane in the catalyst ingredient (B) was 14. For polymerization, ~he alu~i-noxane was used as a solution in toluene.
Polymerization A 1000 ml fully nitrogen-purged glass autoclave was charged with 500 ml of purified toluene and 15 g of tetracyclododecene, and propylene gas was passed through it at a rate of 60 liters/hrO The flask was maintained at 20 C for 10 minutes. Subsequently, 5 mg-atom as the aluminum atom of the aluminoxne and 0.5 x 10 ~ mg-atom, as the zirconium atom, of ethylenebis(indenyl)zirconium dichloride in toluene were introduced into the autoclave, and the polymerization was started~ The polymerization was carried out at 20 C for 2 hours under atmospheric pressure, and then stopped by adding isopropanol. The polymerization proceeded in a homogeneous solution, and after the 2-hour polymerization, absorption of propylene was observed. The polymer solution was added to a large amount of a mixture of methanol and acetone to precipitate the polymer The polymer was dried overnight under reduced pressure at 120 C. After drying, the amount of the copolymer yielded was 601 9. The activity per unit amount of zirconium was 60 g of polymer/mg Zr atom-hr.
The resulting copolymer contained 75 mole% of propylene, and had an intrinsic viscosity [~] of 0.09 dl/g, a mol-ecular weight distribution of 1.48, and a glass transition temperature of 78 C.

Example 1 was repeated except that the co-polymerization conditions indicated in Table 3 were employed. The properties of the resulting polymers are also shown in Table 3.

3 :l 2 . _ _ . _ _ __ ~ a~ ~ o ~ ~al ~ . ~ Ct) i~ c~ ~ er ~ ~ u~ O ~r o 1~:
~ __ _ _ _ o~ 5~ a~
~ ~ o o o o o o o o o 3 J-q~ _ _ ~ y a~ Cd~ In O ~ C
C ~ ~ C
o ,. ~ _ _ ~ ~ d' ~ D ~ ~) _~ ~ ~ ~
_ _ ~ O
~~s ~ e ~ ~c ~
~ N J~ O
_ _ _ .
.
~1 ~ OO O O .
--~¦ ~ ~ ~ O ~ r ~ n N ~ C e ~ O
;~ ~} _ __ ~ f ~ ~P ~V~ Oz ~ = ~ C~ V V 11~
~ ._ ~ o ~ ~ u~ ô o o C~ C o~ ~ o J::~ ~ u N ~1 V L~ _ _ _ ~ 3 3 1~ 1I C
3~ ~ ~ 'j~; . c't = c t = ~. ',00 ~z~o<il ~
0~ _ ~ '_ ~ o40~
~ ~ JJ t: ~ ~ 8 ~
.1 ,~ .1 <1)-- O c ~ ~ ~ _ = = = c-~ O e~

o _ _ _ _ ~ ~ ~ C ~
al ,î ~
_ _ __ .

~ 2 ~3~ ~

Polymeri~ation A 1000 ml fully nitrogen-p~rged glass autoclave was charged with 500 ml of purified toluene and 15 g of 5-ethylidene-2-norbornene, and propylene gas was passed through it at a rate of 60 liters/hr. The flask ~as maintained at 20 C for 10 minutes. Subsequently, 5 mg-atom as the aluminum atom of the aluminoxane and 0.5 x 10 ~ mg-atom, as the zirconium atom, o ethylenebis-(indenyl)zirconium dichloride dissolved in toluene wereintroduced into the autoclave, and the polymeri~ation was started. The polymerization was carried out at 20 C for 4 hours under atmospheric pressure, and then stopped by adding isopropanol. The polymerization proceeded in a homogeneous solution, and after the 4-hour polymerization, absorption of propylene was observed. The polymer solu-tion was added to a large amount of a mixture of methanol and acetone to precipitate the polymer. The polymer was dried overnight under reduced pressure at 120 C. After drying, the amount of the cvpolymer yielded was 2.2 g.
The resulting copolymer contained 66 mole% of propylene, and had an intrinsic viscosity [7] 0.16 dl/g~ and a mol-ecular weight distribution of 1.4].

Example 10 was repeated except that the co-polymerization conditions indicated in Table 4 were em-ployed. The properties of the resulting polymers are also shown in Table 4.

~`2~

_ , ,. =

1:~
,~,_ ~ ~ ~ ~ ~ o ~~` ~ _~ o _~ -.
~ _ , o o o o o o o o .c o~
o CO ,~ ,1 o 1~
U~ _ . .. _ . -, ~ O C C dP
~ ~ ~ g ~ ~ .
~ ~ ~ o 1` .~ r oo a~
3~ _ o ~C' .c ~ S ~r r e e e e e c 7~
. -~ a . O E3 ~rl ~ ~ ~ ~ ~ ~ e c ~ ~ e ~1 ~ ,~, e~ _ v ~, C. O O
~: ~ ~ ~ ~ ,~ ~ n a V ~ Y,~ ~ ~ . ~ U ,~

JNJ ~ ~q ~ ~
.~ . ~ ~
~0 ~ YVY~ ~ e ~ ~ C ~ ~ ~ o C

V . _ _ ~ ~ C r ~ C 1~ V

_ _ _ ~ n E~ O
s ~ ~
o ~ 3 ~ ~

o~
X ~ . .

~3~,~l3~

-- ~0 --Polymerization A 1000 ml fully nitrogen-purged glass autoclave was charged with 250 ml of purified toluene and 7.5 g of tetracyclododecene, and ethylene gas was passed through it at a rate o 60 liters/hr. The flask was maintained at 20 C for 10 minutes7 Subsequently, 2.5 mg-atom as the aluminum atom of the aluminoxane and 2~5 x 10 2 mg-atom, as the zirconium atom, of ethylenebis(indenyl)zirconium dichloride in toluene were introduced into the autoclave, and the polymerization was started. The polymerization was carried out at 20 C for 30 minutes under atmospheric pressure, and then stopped by adding isopropanol. The polymerization proceeded in a homogeneous solution, and after the 30-minute polymerization, absorption of ethylene was observed. The polymer solution was added to a large amount of a mixture of methanol and acetone to precipitate the polymer. The polymer was dried overnight under re-duced pressure at 120 C. A~ter drying, the amount of the copolymer yielded was 16.6 g~ The activity per unit amount o zirconium was 1~300 g of polymer~mg Zr atom-hr.
The resulting copolymer contained 90 mole% of ethylene~
and had an intrinsic viscosity ~] of 2035 dl/g and a molecular weight distribution of 2.03.

Example 18 was repeated except that 7 5 5 9 of 2-methyl~1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydro-naphthalene was used instead of the tetracyclododecene.
There was obtained 15.1 g of a copolymer having an ethylene content of 92 mole%, a molecular weight dis-tribution of 2.20 and an intrinsic viscosity of 2.43 dl/g.
The activity per unit amount of zirconium was 1,200 g of polymer/mg Zr atom-hr.

Example 18 was repeated except that 7.5 9 of 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a,5~8,8a-octa-hydronaphthalene was used instead of the tetracyclo-dodecene. There was obtained 13.7 g of a copolymer having an ethylene content of 93 mole%, a molecular weight dis-tribution of 2.15 and an intrinsic viscosity t~] of 2.46 dl/g. The activity per unit amount of zirconium was 1,100 g of polymer/mg Zr atom-hr.

Example 18 was repeated except that 3.5 9 of 5-methyl-2-norbornene was used instead of the tetracyclo-dodecene. There was obtained 9.4 g of a copolymer havingan ethylene content of 82.3 mole%, a molecular weight distribution of 2.07 and an intri~sic viscosity 1~] of 2.86 dl~g. The activity per unit amount of zirconium was 750 g of polymer/mg Zr atom-hr.

Example 18 was repeated except that 7~5 g of 5 methyl-2-norbornene was used instead of the tetracyclo-dodecene. There was obtained 15.6 9 of a copolymer having an ethylene content of 74.8 mole% 7 a molecular weight 2~ distribution of 2011 and an intrinsic viscosity 1~] of 2.18 dl~g. The activity per unit amount of zirconium was 630 g of polymer/mg Zr atom~hr.

Example 18 was repeated except that 7.5 g of norborn~ne was used instead of the tetracyclododeceneO
There was obtained 8.1 9 of a copolymer having an ethylene content of 74 mole%, a molecular weight distribution of 2.32 and an intrinsic viscosity ~] of 2.15 dl/g. The activity per unit amount of zirconium was 650 g of polymer~mg ~r atom-hr~

Example 18 was repeated except that 7.5 g of 5-ethylidene-2-norbornene was used instead of the tetra-cyclododecene. There was obtained 7.1 g of a copolymer having an ethylene content of 76.5 mole %~ a molecular weight distribution of 2.14 and an intrinsic viscosity [~3 ~ ,t,~

- ~2 -of 2.21 dl/y. The activity per unit amount of æirconium was 570 g of polymer~mg-Zr atom-hr A 1000 ml fully nitrogen-purged glass autoclave was charged with 500 ml of purified toluene and 15 g of tetracyclododecene, and propylene gas was passed through it at a rate of 60 liters/hr. The flask was maintained at 20 C for 10 minutesO Subsequently, 5 mg-atom as the aluminum atom of the aluminoxane and 0O5 x 10 2 mg atom, as the zirconium atom, of ethylenebis(indenyl)~irconium dichloride in toluene were introduced into the autoclave, and the polymerization was started. The polymerization was carried out at 20 C for 2 hours under atmospheric pressure, and then stopped by adding isopropanol. The polymerization proceeded in a homogeneous solution, and after the 2-hour polymerization, absorption o propylene was observed. The polymer solution was added to a large amount of a mixture of methanol and acetone to precipitate the polymerO The polymer was dried overnight under re~
duced pressure at 120 C. After drying, the amount of the ~ copolymer yielded was 6.1 9. The ac ivity per unit amount of zirconium was 60 9 of polymer/mg Zr atom-hr. The resulting copolymer contained 75 mole% of propylene, and had an intrinsic viscosity [~] o~ OOO9 dl~g and a mol-ecular weight distribution of 1.48.

Example 25 was repeated except that the amount of purified toluene was changed to 250 ml, 15 9 or 5-methyl-l~pentene was used instead of the tetracyododecene and 250 ml of 4-methyl-1-pentene was used instead of propylene, and the polymerization was carried out at 20 C
for 3 hours. There was obtained 0.6 g of a copolymer having a 4-methyl-1-pentene content of 97 mole%, an in-trinsic viscosity 17] of 0.13 dl/g and a molecular weight 3s distribution of 1.30~

Claims

1. A cyclo-olefinic random copolymer composed of an alpha-olefin component having 3 to 20 carbon atoms and a cyclo-olefin component, (i) said copolymer containing 5 to 99 mole% of recurring units derived from said alpha-olefin component having 3 to 20 carbon atoms and 1 to 95 mole% of recurring units derived from said cyclo-olefin component, and (ii) said copolymer having an intrinsic vis-cosity [?], measured in decalin at 135 °C, of from 0.01 to 10 dl/g.

2. The cyclo-olefinic random coopolymer of claim 1 which contains 15 to 95 mole% of units derived from said alpha-olefin component and 5 to 35 mole% of units derived from said cyclo-olefin.

3. The cyclo-olefinic random coopolymer of claim 1 which contains 30 to 90 mole% of units derived from said alpha-olefin component and 10 to 70 mole% of units derived from said cyclo-olefin.

4. The cyclo-olefinic random copolymer of claim 1 which has an intrinsic viscosity [?], measured in decalin at 135 °C, of 0.05 to 7 dl/g.

5. The cyclo-olefinic random copolymer of claim 2 which has an intrinsic viscosity [?], measured in decalin at 135 °C, of 0.05 to 7 dl/g.

6. The cyclo olefinic random copolymer of claim 3 which has an intrinsic viscosity [?], measured in decalin at 135 °C, of 0.05 to 7 dl/g.

7. The cyclo-olefinic random copolymer of claim 1 which has an intrinsic viscosity [?], measured in decalin at 135 °C, of 0.5 to 5 dl/g.

8. The cyclo-olefinic random copolymer of claim 2 which has an intrinsic viscosity [?], measured in decalin at 135 °C, of 0.5 to 5 dl/g.

9. The cyclo-olefinic random copolymer of claim 3 which has an intrinsic viscosity [?], measured in decalin at 135 °C, of 0.5 to 5 dl/g.

10. The cyclo-olefinic random copolymer of claim 7 wherein the alpha-olefin component is a component selected from propylene and 4-methyl-1-pentene components, and the cyclo-olefin component is a component selected from tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, norbornene and 5-methyl-2-norbornene components.

11. The cyclo-olefinic random copolymer of claim 8 wherein the alpha-olefin component is a component selected from propylene and 4-methyl-1-pentene components, and the cyclo-olefin component is a component selected from tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, norbornene and 5-methyl-2-norbornene components.

12. The cyclo-olefinic random copolymer of claim 9 wherein the alpha-olefin component is a component selected from propylene and 2-methyl-1-pentene components, and the cyclo-olefin component is a component selected from tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, norbornene and 5-methyl-2-norbornene components.

13. An olefinic random copolymer composed of (A) an olefin component having 3 to 20 carbon atoms and (B) a cyclic polyene component and as required, (C) a cyclo-olefin component, (i) said copolymer containing 5 to 99 mole% of recurring units derived from said alpha-olefin component (A) having 3 to 20 carbon atoms and 1 to 95 mole% of recurring units derived from said cyclic polyene component (B) and 0 to 90 mole% of recurring units derived from said cyclo-olefin component (C), and (ii) said copolymer having an intrinsic vis-cosity [?]; measured in decalin at 135 °C, of from 0.01 to 10 dl/g.

14. The olefinic random copolymer of claim 13 which contains 15 to 95 mole% of units derived from the alpha-olefin component (A), 5 to 85 mole% of units derived from the cyclic polyene component, and 2 to 80 mole% of the cyclo-olefin component.

15. The olefinic random copolymer of claim 13 which contains 30 to 90 mole% of units derived from the alpha-olefin component (A), 10 to 70 mole% of units derived from the cyclic polyene component, and 5 to 70 mole% of the cyclo-olefin component.

16. The olefinic random copolymer of claim 13 which has an intrinsic viscosity [?], measured in decalin at 135 °C, of 0.05 to 7 dl/g.

17. The olefinic random copolymer of claim 14 which has an intrinsic viscosity [?], measured in decalin at 135 °C, of 0.05 to 7 dl/g.

18. The olefinic random copolymer of claim 15 which has an intrinsic viscosity [?], measured in decalin at 135 °C, of 0.05 to 7 dl/g.

19. The olefinic random copolymer of claim 13 which has an intrinsic viscosity [?], measured in decalin at 135 °C, of 0.5 to 5 dl/g.

20. The olefinic random copolymer of claim 14 which has an intrinsic viscosity [?], measured in decalin at 135 °C, of 0.5 to 5 dl/g.

21. The olefinic random copolymer of claim 15 which has an intrinsic viscosity [?], measured in decalin at 135 °C, of 0.5 to 5 dl/g.

22. The olefinic random copolymer of claim 19 wherein the alpha-olefin component (A) is a propylene component, the cyclic polyene component (B) is a component selected from 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene components, and the cyclo-olefin component (C) is a component selected from tetracyclodecene and norbornene components.

23. The olefinic random copolymer of claim 20 wherein the alpha-olefin component (A) is a propylene component, the cyclic polyene component (B) is a component selected from 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene components, and the cyclo-olefin component (C) is a component selected from tetracyclodecene and norbornene components.

24 The olefinic random copolymer of claim 21 wherein the alpha-olefin component (A) is a propylene component, the cyclic polyene component (B) is a component selected from 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene components, and the cyclo-olefin component (C) is a component selected from tetracyclodecene and norbornene components.

25. A process for producing a cyclo-olefinic random copolymer, which comprises copolymerizing an alpha-olefin and a cyclo-olefin in the presence of a catalyst formed from (A) a compound of a transition metal of Group IVB of the periodic table having as a ligand a multi-dentate coordination compound in which at least two con-jugated cycloalkadienyl groups or substituted products thereof are bonded via a lower alkylene group, and (B) an aluminoxane.

26. The process of claim 25 wherein the transition metal compound is a zirconium compound containing as a ligand at least two indenyl groups or substituted indenyl groups or partially hydrogenated groups thereof which are bonded via an alkylene group.

27. The process of claim 26 wherein the aluminoxane is an organoaluminum compound represented by the general formula [VII]

[VIII]

wherein R represents a hydrocarbon group, and m represents an integer of at least 2.

28. The process of claim 27 wherein R is a methyl, ethyl or isobutyl group, and m is an integer of at least 5.

29. The process of claim 27 wherein R is a methyl group and m is an integer of 5 to 50.

30. The process of claim 26 wherein the transition metal compound is ethylenebis(indenyl)zirconium di-chloride.

31. The process of claim 27 wherein the alpha-olefin is selected from ethylene, propylene and 4-methyl-1-pentene, and the cyclo-olefin is selected from tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 5-methyl-2-norbornene, norbornene and 5-ethylidene-2-norbornene.

32. The process of claim 28 wherein the alpha-olefin is selected from ethylene, propylene and 4-methyl-1-pentene, and the cyclo-olefin is selected from tetracyclododecene, 2-methyl 1,4,5,8-dimethano-1,2r3,4,4a,5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1.2,3,4,4a,5,8,8a-octahydronaphthalene, 5-methyl-2-norbornene, norbornene and 5-ethylidene-2-norbornene

33. The process of claim 30 wherein the alpha-olefin is selected from ethylene, propylene and 4-methyl-1-pentene, and the cyclo-olefin is selected from tetrasyslododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,B-dimethano-1,2t3,4,4a,5,8,8a-octahydronaphthalene, 5-methyl-2-norbornene, norbornene and 5-ethylidene-2-norbornene.