JPS61221206A - Production of cycloolefin copolymer - Google Patents

Abstract

PURPOSE:To increase the copolymerization efficiency and polymerization activity of a cycloolefin and to narrow its MW distribution, by copolymerizing an alpha- olefin with a cycloolefin by using a catalyst comprising a specified transition metal compound and an aluminoxane. CONSTITUTION:An alpha-olefin is copolymerized with a cycloolefin in the presence of a catalyst comprising an aluminoxane and a compound of a transition metal selected from the elements of Groups IVb, Vb and VIb of the periodic table. Examples of said transition metal compounds include titanium, zirconium, hafnium, vanadium, chromium or the like compounds, among which titanium and zirconium compounds are preferable. The transition metal compound is preferably in a form of a compound having hydrocarbyl groups and/or halogenatoms. Examples of said aluminoxanes include organoaluminum compounds of formula I and II (wherein R is a hydrocarbyl group and m is an integer >=2).

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a method for producing a cyclic olefin copolymer.

More specifically, by copolymerizing an α-olefin and a cyclic olefin, the efficiency of copolymerizing the cyclic olefin is high.

Furthermore, the present invention relates to a method for efficiently producing a cyclic olefin copolymer having a narrow molecular weight distribution. - [Prior Art] Conventionally, a titanium-based catalyst consisting of a titanium compound and an organoaluminum compound has been used as a method for producing a cyclic olefin-based copolymer by copolymerizing an α-olefin such as ethylene with a cyclic olefin.

A method using a vanadium-based catalyst consisting of a vanadium compound and an organoaluminum compound is known.

Among these methods, in copolymerization using a titanium-based catalyst, cyclic olefins have poor reactivity compared to α-olefins such as ethylene, and copolymerization efficiency is low. Therefore, in order to expect copolymerization with α-olefin, it is necessary to add a large amount of cyclic olefin to one polymerization system. However, when a large amount of cyclic olefin is added, the catalytic activity is impaired and it also causes a decrease in the molecular weight of the copolymer, making it difficult to obtain a high molecular weight copolymer. Furthermore, side reactions such as ring-opening polymerization of cyclic olefins are likely to occur, and the resulting copolymer has a wide molecular weight distribution. On the other hand,
Copolymerization using vanadium-based catalysts has a higher cyclic olefin copolymerization efficiency than titanium-based catalysts, and the resulting copolymer has a narrower molecular weight distribution, but it generally has the drawback of extremely low polymerization activity.

In addition, a new highly active polymerization catalyst for olefin polymerization is disclosed in JP-A-58-19509, which discloses a catalyst comprising a transition metal compound and aluminoxane.

JP-A-59-95292, JP-A-60-3500
5, JP-A-60-35006, JP-A-60
This method has been proposed in Japanese Patent Laid-open No. 35007-35007, Japanese Patent Application Laid-Open No. 60-35008, etc. Among these prior art.

JP-A-58-19309, JP-A-60-3500
No. 5, JP-A-60-55006, JP-A-60
-35007 and JP-A-60-35008 disclose that the above-mentioned catalyst system can be applied to copolymerization of ethylene and α-olefin. There is no indication as to how to make the composite.

[Problem that the invention seeks to solve]

Therefore, in the field of producing cyclic olefin copolymers, there is a method that can efficiently produce cyclic olefin copolymers with high cyclic olefin copolymerization efficiency, excellent polymerization activity, and narrow molecular weight distribution. is strongly requested. Recognizing that the prior art in the field of producing cyclic olefin copolymers is in the above-mentioned situation, the present inventors have developed a cyclic olefin copolymer that has a high copolymerization efficiency of cyclic olefins, has excellent polymerization activity, and has a narrow molecular weight distribution. As a result of examining methods for producing olefin-based copolymers, the above objective was achieved by copolymerizing α-olefins and cyclic olefins in the presence of a catalyst consisting of 1M transfer metallized compound and a specific aluminoxane. This is what led us to the present invention.

[Means for solving the problem] and [Operation] The present invention is as follows.

(4) A compound of a transition metal selected from the group consisting of Groups ■b, Vb and ■b of the periodic table, and aluminoxane.

The gist of the invention is to produce a cyclic olefin copolymer characterized by copolymerizing an α-olefin and a cyclic olefin in the presence of a catalyst comprising:

The transition metal compound (A) as a catalyst component used in the process of the present invention is one of the group Ib, group Vb and group II of the periodic table.
A compound of a transition metal selected from the group consisting of group b,
For example, compounds such as titanium, zirconium, hafnium, vanadium, and chromium can be represented by N.
Among these transition metal compounds, titanium or zirconium compounds are preferred, and zirconium compounds are particularly preferred since they are highly active. A suitable form of the transition metal compound is preferably a compound having a hydrocarbon group or a compound having a hydrocarbon group and a halogen atom.

In particular, it preferably has at least one, particularly preferably two, hydrocarbon groups and preferably has at least one
A transition metal compound having halogen atoms, particularly preferably two halogen atoms. Specific examples of the hydrocarbon group include alkyl groups such as a methyl group, an ethyl group, a tert-butyl group, an isobutyl group, and a neopentyl group.

alkenyl groups such as isopfoubenyl group and 1-puntonyl group; cycloalkagenyl groups such as cyclopentagenyl group and methylcyclopentagenyl group;

Examples include aralkyl groups such as a benzyl group and a neophyl group, and among these hydrocarbon groups, a cycloalkagenyl group is preferred.

A cyclopentadienyl group is particularly preferred. Specific examples of the halogen atom include fluorine, chlorine, bromine, and iodine atoms. Furthermore, specific examples of transition metal compounds include bis(cyclopentadienyl)dimethyltitanium,
Bis(cyclopentadienyl) diethyl titanium, bis(
cyclopentagenyl) diisopropyl titanium, bis(
methylcyclopentadienyl) dimethyltitanium, bis(
cyclopentagenyl) methyltitanium monochloride, bis(cyclopentagenyl) ethyl titanium monochloride, bis(cyclopentagenyl) isopropyl titanium monochloride, bis(cyclopentagenyl) methyltitanium monopromide, bis(cyclopentagenyl) methyltitanium monochloride, pentagenyl) methyl titanium monoiodate, his(cyclopentagenyl)
Titanium compounds such as titanium difluoride, bis(cyclopentagenyl) titanium dichloride, bis(cyclopentagenyl) titanium dichloride, bis(methylcyclopentagenyl) titanium dichloride, bis(cyclopentagenyl) dimethylzirconium, bis (cyclopentagenyl)diethylzirconium, bis(methylcyclopentagenyl)diisopropylzirconium, bis(
cyclopentagenyl) methylzirconium monochloride, bis(cyclopentagenyl)ethylzirconium monochloride, bis(cyclopentagenyl)methylzirconium monobromide, bis(cyclopentagenyl)methylzirconium monochloride, bis(cyclopentagenyl)methylzirconium monochloride, pentagenyl) zirconium difluoride, bis(cyclopentagenyl) zirconium dichloride, bis(cyclopentagenyl) zirconium dichloride, bis(cyclopentagenyl) zirconium monochloride monohydride, bis(cyclopentagenyl) zirconium Zirconium compounds such as dichloride, bis(cyclopentagenyl)dimethylhafnium.

Hafnium compounds such as bis(cyclopentagenyl)methylhafnium monochloride, bis(cyclopentagenyl)no1fnium dichloride, bis(cyclopentagenyl)vanadium dichloride, bis(cyclopentagenyl)vanadium monochloride, etc. Examples include vanadium compounds.

Specifically, the general formula (1) or the general formula [lid] -R2A j? +OA ji9OA I R2 (1)C In the formula, R represents a hydrocarbon group and 1m represents an integer of 2 or more)
Examples include organoaluminum compounds represented by: In the aluminoxane, R is a methyl group,
Ethyl group, propyl group.

It is a hydrocarbon group such as a butyl group, preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

m is an integer of 2 or more, preferably 5 or more, particularly preferably 10 to 100. The following method can be exemplified as a method for producing the aluminoxane.

(1) A method of adding trialkylaluminium to a hydrocarbon medium suspension of a compound containing adsorbed water or a salt containing water of crystallization, such as sulfuric acid hydrate, aluminum sulfate hydrate, etc., and causing a reaction.

(2) A method in which water is allowed to act directly on trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or trihydrofuran.

Among these methods, method (1) is preferred.

Note that the aminooxane may contain a small amount of organometallic component.

Specifically, the α-olefins supplied to the polymerization reaction in the method of the present invention include ethylene, propylene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-
Examples include α-olefins having 2 to 20 carbon atoms, such as octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

In addition, specific examples of the cyclic olefins supplied to the polymerization reaction in the method of the present invention include cyclopropene, cyclopentene, cyclohexene, 3-methylcyclohexene, cycloheptene, cyclohexene, cyclodecene, cyclododecene, and cyclohexene. Monocycloalkenes such as decene, octasiphtetradecene, and cycloeicosene.

Norbornene% 5-methyl-2-norbornene, 5-
Ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5,
5.6-) Bicycloalkenes such as riftyl-2-norbornene, 2-bornene, 2.3.3a.

7L-trahydro-4,7-methano-1H-indene.

5a, 5, 6.7 &-trahydro 4,7-methano-
Tricycloalkenes such as IH-indene, 1,4,5
．． 8-dimethano-1,2,3,4,4a,5,8,8a
-In the presence of octahydronaphthalene, 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 + 3.414 a,
D I 8 + 8 &-octahydronaphthalene.

2-propyl-1,4,5,8-dimethano-1,2,5
,4゜4 a ,5 + 8-8 a-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,5,8.8&-octahydro Naphthalene, 2,3-dimethyl-1,4,5゜8-dimethano-1,2,3,4,4a, 5,8.8m-octahydronaphthalene, 2-methyl-3-ethyl-1,4, 5
,8-dimethano-1,2,3,4,4a ,5,8,8
a-Octahydronaphthalene, 2-〃Lower 1.4,5
．． 8-dimethano-1,2,3,4,4a,5,8,8a
-Octahydronaphthalene.

2-Bromo-1,4,5,8-dimethano-f 1213
-4-4 a s5, s, aa-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2
,3,4,4a,5.8,8a -octahydronaphthalene,2,3-dichloro-1,4゜5.8.8-dimethano-1,2,3,4,4a,5.8,8a - Child tracycloalkenes such as octahydronaphthalene.

Hexacyclo[6,6,,,13,6,11n,13.
02 order 7,09°14] hebutadecene-4, pentacyclo(8,8,1''.

14.7.111.1.8, o, o 3.8
, r312・17] Henikosen-5゜Octacyclo(
8, 8, 12・9, 14・7. , il・18.113・
160*0'8,012.17] Cyclic monoenes such as polycycloalkenes such as tococene-5, dicyclopentadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-norbornene, 1. 5-
Examples include cyclic polyenes such as cyclooctadiene, 5,8-entomefv hexahydronaphthalene, and alkylidenetetrahydroindene.

In the method of the present invention, the raw material olefin supplied to the polymerization reaction system is a mixture consisting of an α-olefin and a cyclic olefin. The content of the α-olefin in the polymerization raw material olefin is usually 1 to 90 mol%, preferably 2
The content of the cyclic olefin is usually 10 to 99 mol%, preferably t, < is 2.
It ranges from 0 to 98 mol%.

In the process of the invention, the olefin polymerization reaction is usually carried out in a hydrocarbon medium. Examples of the hydrocarbon medium include aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane, octadecane, cyclopenkune, methylcyclopenkune, and cyclohexane.

Alicyclic hydrocarbons such as cyclooctane, aromatic hydrocarbons such as benzene, toluene, and xylene, gasoline,
In addition to petroleum distillates such as kerosene and light oil.

The raw olefin also serves as a hydrocarbon medium. Among these hydrocarbon media, aromatic hydrocarbons are preferred.

In the method of the present invention, liquid phase polymerization methods such as suspension polymerization, solution polymerization, etc. are usually employed. The temperature during the polymerization reaction is usually -50 to 230" C1, preferably -30"
to 200°C.

When carrying out the method of the present invention by liquid phase polymerization, the proportion of the transition metal compound used is usually 10-8 to 10-2 gram atoms/12 as the concentration of transition metal atoms in one polymerization reaction system.
．． Preferably 10-7 to 10-3 grams / /
is within the range of In addition, the usage ratio of aluminoxane is 1
The concentration of aluminum atoms in the polymerization reaction system is usually 1
0-4 to 10-1 gram atoms/I1. It is preferably in the range of 10-3 to 50-2 gram atoms/l, and the ratio of aluminum atoms to transition metal atoms in the polymerization reaction system is usually 4 to 10, preferably 1.
It ranges from 0 to 106. The molecular weight of the copolymer can be adjusted by hydrogen and/or polymerization temperature.

In the method of the present invention, a cyclic olefin copolymer can be obtained by treating the polymerization reaction mixture after one polymerization reaction by a conventional method. The composition of the cyclic olefin copolymer is usually 20 to 996% of the α-olefin.
9 mole arc 1. Preferably 30 to 99.5 mol% and the cyclic olefin component is usually 0.1 to 80 mol%
, preferably in the range of 0.5 to 70 mol%. Further, the intrinsic viscosity [η] of the cyclic olefin copolymer measured in decalin at 165°C is usually 0.005 to 20 dl! /g, preferably 0.01 to 10 dl
/g, and its molecular weight distribution measured by gel permeation chromatography (APE) is usually 3 or less, preferably 2.5 or less. The degree of crystallinity determined by X-ray diffraction of the cyclic olefin co-electrode composite is usually in the range of 0 to 70%, preferably in the range of 0 to 65%.

〔Effect of the invention〕

According to the method of the present invention, a cyclic olefin copolymer having excellent monopolymerization activity and a narrow molecular weight distribution can be efficiently produced.

[Real #1 row] Next, one method of the present invention will be specifically explained using examples.

Example [Preparation of aluminoxane] A12 (
804) 3' 14H2037g and toluene 125ml
was charged to make a slurry. Also, toluene 125II
5 mol of trimethylaluminum Q diluted with Il was added dropwise at a temperature of 0 to -5°C. After the dropwise addition was completed, the temperature was raised to 40°C, and the reaction was continued at that temperature for 48 hours. Subsequently, solid-liquid separation was performed by filtration, and toluene was further removed from the separated liquid to obtain 17.5 g of white solid aluminoxane. The molecular weight determined by freezing point depression in benzene is 2000.
The m value of aluminoxane was 32. For polymerization, it was used after being redissolved in toluene.

[Overlapping]

500 mI with sufficient nitrogen substitution! After charging 250 J of luene (refined) and 2.5 g of norbornene into a glass autoclave, ethylene gas was circulated at bog/hr, and 20
Then, aluminoxane, which corresponds to 2.5 milligram atoms in terms of aluminum atoms, and toluene, which corresponds to 1.25 × 10 milligram atoms in terms of zirconium atoms, were dissolved in toluene. Polymerization was started by charging Zirconium dichloride. After polymerization was carried out at 20°C for 1 hour at normal pressure, the polymerization was stopped with isopropanol. The polymerization proceeded in a homogeneous solution state and one polymerization was completed. Absorption of ethylene was observed even after 1 hour.The polymer solution was added to a large amount of methanol/acetone mixture to precipitate the polymer, which was then dried under reduced pressure at 120°C overnight.The yield of the polymer after drying was 3.7 g. What is the activity per unit of zirconium?

It was 300 g polymer/milligram atom-Zr.

In addition, the ethylene content of this polymer, [η].

M w / M n and crystallinity are each 90 mol%
.

It was 2.53 dll/g, 2.03.2.1%.

Comparison row 1 800mII SUS with built-in 2.8kQ SUS pole (15mmφ) [Magnesium chloride 20 in the pot
g was added thereto and pulverized for 8 hours under a nitrogen atmosphere. Powder n'JI
Transfer to a Jtt 400ml flask, 12! [200 m# of titanium oxide was added and heated at 70-C for 2 hours. its diameter.

The pulverized product was separated and washed with decane until titanium tetrachloride was no longer detected in liquid E to obtain a titanium catalyst component. catalyst 1
9 mg of titanium atoms were supported in g.

[Overlapping]

Titanium catalyst equivalent to 5 X 10-3 milligram atoms in terms of flit atoms, 0.5 in terms of aluminum atoms
Polymerization was carried out in the same manner as in Example 1, except that triethylaluminum equivalent to milligram atoms was used and the polymerization was carried out for 60 minutes. Polymerization proceeded in a slurry state rather than a solution state. The obtained polymer had a molecular weight of 3.8 and an activity per titanium at position Ii.

760 g of polymer/milligram atom of T1.

The ethylene content was 99.9 mol% or more, and almost no norbornene was copolymerized.

Comparative Example 2 [Polymerization] Example 1 except that vanadyl monoethoxy dichloride, which is equivalent to 0.05 milligram atoms in terms of vanadium atoms, and ethylaluminum sesquichloride, which is equivalent to 0.5 milligram atoms in terms of aluminum atoms, were used. Polymerization was carried out in the same manner. Although the polymerization proceeded in a solution state, no absorption of ethylene was observed after one hour of polymerization. The polymer obtained was 4.0 g and the activity per unit vanadium was 80 g-polymer/milligram atom-V. In addition, the ethylene content of this polymer, [η].

M W 7 M n and crystallinity are each 89 mol%.

2.6sdI! /g, 2.45.1.5%.

Example 2 Polymerization was carried out in the same manner as in Example 1, except that 7.5 g of norbornene was used and the polymerization was carried out for 3 hours. Ethylene content, [η].

M + wk n and crystallinity are 72 mol% and 1, respectively.
．． 83dj7/g, 2.12,0% polymer 2.
3g was obtained. Activity per unit zirconium is 180g
-Polymer/milligram atom-Zr.

Example 3 Polymerization was carried out in the same manner as in Example 1, except that 2.5 g of 5-ethyl-2-norbornene was used in the polymerization of 'l[1. Ethylene content, [η), w/in and crystallinity are 91 mol- and 2.10 aJ/g, respectively.

3.5 g of 2.15.1.2% polymer were obtained. The activity per unit zirconium is 280g-polymer/
milligram atom-Zr.

Example 4 Example 10 Polymerization of 1,4,5,8-dimethano-1
, 2, 3, 4, 4 &, 5.8. Ethylene content, [η].

M　W　7M　n and crystallinity are each 96 mol%.

1.98 dlI/g, 2.20.40-polymer is 1
．． 88 was obtained. The activity per unit zirconium is 14
It was 0g-polymer/milligram atom-Zr.

Example 5 In Example 10 polymerization, 2-methyl-1,4°5.8
-dimethano-1*2+L'L4a, 5. Polymerization was carried out in the same manner as in Example 1, except that 2.5 g of L8a-octahydronaphthalene was used and the polymerization was carried out for 30 minutes. ethylene content,
[η), Mw/Mn and crystallinity are each 96 mol%
, 2.02 dl/g, 2.1 B, 45% of polymer is 1
．． 7g was obtained. Activity per rejected zirconium is 140
g-polymer/milligram atom-Zr.

Example 6 In Example 10 polymerization, 2-methyl-1,4°5.8
-dimethano-1,2,,3,,4,,4a, 5.8.8
Polymerization was carried out in the same manner as in Example 1, except that m-octahydronaphthalene was used at 1 CLg for 30 minutes. Ethylene content [η], M w 7M n and crystallinity are each 76 molar arc* 1-45 dl! /g-2J29,
0% polymer was added. The activity per unit zirconium is 90 g-polymer/milligram atom-Z
It was r.

Example 7 [Preparation of aluminoxane] K12 was added to a 200 ml flask that was sufficiently purged with argon.
(804)5 ・13 7.8 g of H2O and 3 toluene
0me was charged to make a slurry. Also, 25 toluene
100mmo trimethylaluminum diluted with a+f
It was added dropwise at a temperature of 0 to -5°C. After the dripping is finished,
The temperature was raised to 45°C, and the reaction was carried out at that temperature for one week. Subsequently, solid-liquid separation was performed by passing through, and toluene was further removed from the separated liquid, yielding 3.1 g of white solid aluminoxane!
Obtained. The molecular weight determined by freezing point depression in benzene was 2,650, and the m value of the aluminoxane was 44. For polymerization, it was used after being redissolved in toluene.

[Overlapping]

The aluminoxane synthesized in Example 7 was 2.5 milligram atoms in terms of aluminum atoms.

Using 2.5 g of norbornene, at 20°C for 2 hours.

Polymerization was carried out in the same manner as in Example 1, except that normal pressure polymerization was carried out. Ethylene content, [η), yw/Mn, and crystallinity are 92 mol-, 2,41 dlI/g, and 1.9 B, respectively.

7.6 g of 6.6% polymer was obtained. The activity per unit of zirconium was 610 g-polymer/milligram atom-Zr.

Example 8 Polymerization was carried out in the same manner as in Example 7, except that 7.5 g of 5-ethyl-2-norbornene was used. Ethylene content.

[η) 1MWMn and crystallinity are each 74 mol%.

1.79 dl/g 2.24.0% of polymer is 2.
2g was obtained. The activity per unit of zirconium was 180 polymers/milligram atom of Zr.

Example 9 In the polymerization of Example 7, bis(cyclopentadienyl)zirconium monochloride monohydride was used instead of bis(cyclopentadienyl)zirconium dichloride at a concentration of 2.5X i O-2miQ in terms of zirconium atoms.
Polymerization was carried out in the same manner as in Example 7 except that gram atoms were used. Ethylene content.

[η), Mw/Mn and crystallinity are each 91 molar width.

3.3 g of 1.98aj7/g, 2.20.2.6% polymer was obtained. Activity per unit zirconium is 1
30 g of polymer/milligram atom of Zr.

Example 10 [Preparation of aluminoxane] A was added to a 2001111 flask that had been sufficiently purged with argon.
12 (804), -14H, 207,4g and toluene 2
5mJ? 90 mmol of trimethylaluminum diluted with
g) Lin-normal octylaluminum 10 mmol of mixed alkyl aluminum was added dropwise at a temperature of 0 to -5°C. After dropping, the temperature was raised to 40℃, and at that temperature it was heated to 48℃.
Allowed time to react. Subsequently, solid-liquid separation was performed once, and the separated liquid was used for polymerization as an aluminoxane solution.

[Overlapping]

The aluminoxane synthesized in Example 10 contained 2.5 milligram atoms in terms of aluminum atoms and 2.5 norbornene in terms of aluminum atoms.
Example 1 was carried out in the same manner as in Example 1, except that the polymerization was carried out at normal pressure at 20° C. for 2 hours. Ethylene content, [η), Mw,
/Mn and crystallinity are each 91 mol%, 2.12
dl/g, 2.31, 2.1g of 4.2% polymer
Obtained. The activity per unit of zirconium was 170 g-polymer/milligram atom-Zr.

Example 11 [Polymerization] After charging 250 mj+ of purified toluene and 2.5 g of 5-ethylidene-2-norbornene into a glass autoclave with an internal volume of 500 mj7, ethylene was introduced at 60 g/hr at %20°C. It was held for 10 minutes. Thereafter, the aluminoxane synthesized in Example 7, which corresponds to 2.5 milligram atoms in terms of aluminum atoms, and the bis(cyclopentadienyl)zirconium, which corresponds to 1.25X10-2 milligram atoms in terms of zirconium atoms. Dichloride was charged to start polymerization.

Polymerization was carried out at 20° C. for 1 hour at normal pressure. The subsequent operations were performed in the same manner as in Example 1. Ethylene content.

[η) 1Mw/Mn and crystallinity are each 92 mol%
, 2.05dl1g, 1.97.0.8 3.1g of the rumored polymer was obtained. The activity per unit of zirconium was 250 g-polymer/milligram atom-Zr.

The iodine value was 59.

Example 12 [Polymerization] Using a IIt continuous polymerization reactor, purification and toluene were
00 mj'/hr, aluminoxane synthesized in the same manner as in Example 7, 2.5 milligram atoms/hr in terms of aluminum atoms, bis(cyclopentagenyl)zirconium dichloride, 5X1 in terms of zirconium atoms.
Ethylene is continuously fed at a rate of 0.0" 11 g atoms/hr and simultaneously in one polymerization vessel at a rate of 1201/hr,
Continuously feeding propylene at a rate of 801/hr and 5-ethylidene-2-fulbornene at a rate of 1 g/hr, polymerization temperature 20"G, atmospheric pressure, residence time 1 hour.

Polymerization was carried out under conditions such that the polymer concentration was 19 g/l.

The resulting polymer solution was treated in the same manner as in Example 1. The polymerization activity of the catalyst was 1900 g-polymer concentration II y Lamb atoms-Zr, ethylene content 82 mol%, [η)
1.53dj7/g, crystallization +12.1%, Mw/Mn
1.92. A rubbery polymer with an iodine number of 12 was obtained.

Example 13 [Polymerization] Polymerization was carried out in the same manner as in Example 12, except that dicyclopentadiene was continuously supplied at a rate of 1 g/hr instead of 5-ethylidene-2-norbornene. went. The polymer concentration is 16g7g, and the polymerization activity of the catalyst is 1600t<-polymer/milligram atom-
It was Zr. Ethylene content of produced polymer, [η],
The A conversion f%j, Mw/Mn and iodine value are each 83
Mol(,1,51dJ?/g.

2.6 arc, 1.99.8 Example 14 [Polymerization] In Example 120 polymerization, 5-ethyl-2-norbornene was used instead of 5-ethylidene-2-norbornene.
Polymerization was carried out in the same manner as in Example 12, except that the mixture was supplied continuously at a rate of /hr. Polymer concentration is 25g/I! and the polymerization activity of the catalyst was 2500 perpolymer/milligram atom-Zr. Ethylene content of the resulting polymer,
Propylene content 1 [η], crystallinity and M w/M n are each 81 mol%.

17 mol%, 1.65 dl! /g, 0.3 arc, 1.
It was 89.

Example 15 [Polymerization] Polymerization was carried out in the same manner as in Example 12, except that in the polymerization of Example 120, 1801 t/hr of butene was supplied instead of propylene and the polymerization was carried out at 0°C. The polymer concentration is 10 g/l and the polymerization activity of the catalyst is 1000x-
Polymer/milligram atom-zr. Ethylene content of the produced polymer, [η].

Crystallinity* Mw/Mn and iodine value are each 78
mob%, 4.12al/g, O<, 1.95.13
Met.

Example 16 [Polymerization] II! Purified toluene was produced using a continuous polymerization reactor of 500
J/hr, the aluminoxane synthesized in the same manner as in Example 7 was converted into an aluminum atom of 5.0 mg atom/hr.
hr, bis(cyclopentagenyl)zirconium dichloride was continuously supplied at a rate of 1 x 10-2 milligram atoms/hr in terms of zirconium atoms, and ethylene 40j? /hr, propylene 16
01/hr and 5-ethyl-2-norbornene 1g/hr
Continuously supplying at a ratio of r, polymerization temperature 45"C1 normal pressure
Polymerization was carried out under conditions such that the residence time was 1 hour and the polymer concentration was 11 t/l.

Water was added to the resulting polymer solution for deashing, toluene was removed, and the solution was dried under reduced pressure at 120"C for 12 hours.

The polymerization activity of the catalyst is 1100 g-polymer/milligram atom-Zr, and the ethylene content is <56 mol, [η]0
．． 12611g, crystallinity 0%, Mw/Mn 2.0
A liquid polymer No. 7 was obtained.

Claims (1)

[Claims] (1) In the presence of a catalyst consisting of (A) a transition metal compound selected from the group consisting of Groups IVb, Vb and VIb of the periodic table, and (B) aluminoxane, A method for producing a cyclic olefin copolymer, characterized by copolymerizing it with a cyclic olefin.