JPH0713084B2 - Method for producing cyclic olefin copolymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a process for producing a cyclic olefin copolymer.
More specifically, it relates to a method for efficiently producing a cyclic olefin-based copolymer having a high copolymerization efficiency of the cyclic olefin and a narrow molecular weight distribution by copolymerizing α-olefin and the cyclic olefin.

[Conventional technology]

Conventionally, as a method for producing a cyclic olefin copolymer by copolymerizing α-olefin such as ethylene and a cyclic olefin, a titanium catalyst comprising a titanium compound and an organoaluminum compound, a vanadium compound comprising a vanadium compound and an organoaluminum compound. Methods using catalysts are known.

Among these methods, in copolymerization using a titanium-based catalyst, cyclic olefin has poor reactivity as compared with α-olefin 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 the 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. Further, there are disadvantages that side reactions such as ring-opening polymerization reaction of cyclic olefins are likely to occur and the resulting copolymer has a wide molecular weight distribution. On the other hand,
Copolymerization using a vanadium-based catalyst has a higher copolymerization efficiency of cyclic olefin and a narrower molecular weight distribution of the resulting copolymer than a titanium-based catalyst, but generally has a drawback that the polymerization activity is extremely small.

Further, a catalyst comprising a transition metal compound and aluminoxane as a new highly active polymerization catalyst in the olefin polymerization method is disclosed in JP-A-58-19309, JP-A-59-95292, and JP-A-60-35005. , JP-A-60-35006,
It has been proposed in Japanese Patent Laid-Open Nos. 60-35007 and 60-35008. Among these prior arts, JP-A-58
-19309, JP60-35005, JP60-35
JP-A-006, JP-A-60-35007, JP-A-60-35008
The publication describes that the catalyst system can be applied to the copolymerization of ethylene and α-olefin, but neither of them shows anything about a method for producing a cyclic olefin copolymer. .

[Problems to be solved by the invention]

Therefore, in the field of producing a cyclic olefin copolymer, the copolymerization efficiency of the cyclic olefin is high, further excellent in polymerization activity, it is possible to efficiently produce a cyclic olefin copolymer having a narrow molecular weight distribution. There is a strong demand for methods. The present inventors have recognized that the prior art in the field of producing cyclic olefin copolymers is in the above-mentioned situation, and the cyclic olefin has high copolymerization efficiency, excellent polymerization activity, and a narrow molecular weight distribution. As a result of examining a method capable of producing an olefin copolymer, a catalyst comprising a compound having a cyclopentadienyl group of a transition metal selected from the group consisting of titanium, zirconium, hafnium and vanadium and a specific aluminoxane The present invention has been achieved by finding that the above object can be achieved by copolymerizing α-olefin and cyclic olefin in the presence of

[Means for Solving Problems] and [Operation] The present invention provides (A) a compound having a cyclopentadienyl group of a transition metal selected from the group consisting of titanium, zirconium, hafnium and vanadium, and (B) The gist of the invention is the production of a cyclic olefin copolymer, which comprises copolymerizing α-olefin and cyclic olefin in the presence of a catalyst comprising aluminoxane.

FIG. 1 shows the steps for preparing the catalyst used in the method of the present invention.

Examples of the transition metal compound (A) as a catalyst constituent used in the method of the present invention include transition metal compounds selected from the group consisting of titanium, zirconium, hafnium and vanadium. Among them, titanium or zirconium compounds are preferable,
A zirconium compound is particularly preferable because it has high activity. As a suitable form of the transition metal compound, a compound having a hydrocarbon group or a compound having a hydrocarbon group and a halogen atom is preferable, and particularly preferably at least one, particularly preferably two hydrocarbon groups are contained. And, it is preferably a transition metal compound having at least one, and particularly preferably two halogen atoms. As the hydrocarbon group, specifically, a methyl group, an ethyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group,
Alkyl group such as neopentyl group, isopropenyl group,
Examples thereof include an alkenyl group such as a 1-butenyl group, a cyclopentadienyl group, a cycloalkadienyl group such as a methylcyclopentadienyl group, an aralkyl group such as a benzyl group and a neophyl group, and the like. Of the hydrogen groups, a cycloalkadienyl group is preferable,
The cyclopentadienyl group is particularly preferred. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Further, as the transition metal compound, specifically, bis (cyclopentadienyl) dimethyl titanium,
Bis (cyclopentadienyl) diethyl titanium, bis (cyclopentadienyl) diisopropyl titanium, bis (methylcyclopentadienyl) dimethyl titanium, bis (cyclopentadienyl) methyl titanium monochloride,
Bis (cyclopentadienyl) ethyl titanium monochloride, bis (cyclopentadienyl) isopropyl titanium monochloride, bis (cyclopentadienyl) methyl titanium monobromide, bis (cyclopentadienyl) methyl titanium monoiodide, bis (Cyclopentadienyl) titanium difluoride, bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl)
Titanium compounds such as titanium dibromide, bis (methylcyclopentadienyl) titanium diiodide, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diethylzirconium, bis (methylcyclopentadienyl) diisopropyl Zirconium, bis (cyclopentadienyl) methylzirconium monochloride, bis (cyclopentadienyl) ethylzirconium monochloride, bis (cyclopentadienyl) methylzirconium monobromide, bis (cyclopentadienyl) methylzirconium monoiodide , Bis (cyclopentadienyl) zirconium difluoride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopepylene Zirconium compounds such as tadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium diiodide, bis (cyclopentadienyl) dimethylhafnium, bis (cyclopentadienyl) methylhafnium monochloride, bis (cyclopenta) Examples thereof include hafnium compounds such as dienyl) hafnium dichloride, and vanadium compounds such as bis (cyclopentadienyl) vanadium dichloride and bis (cyclopentadienyl) vanadium monochloride.

Specific examples of the aluminoxane (B) as a catalyst constituent used in the method of the present invention include general formula [I] or general formula [II] (In the formula, R represents a hydrocarbon group and m represents an integer of 2 or more). In the aluminoxane, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group or 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 in which a trialkylaluminum is added to a hydrocarbon medium suspension such as a compound containing adsorbed water or a salt containing water of crystallization, for example, a copper sulfate hydrate or an aluminum sulfate hydrate to react.

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

Among these methods, the method (1) is preferable. The aminooxane may contain a small amount of organic metal component.

As the α-olefin which is supplied to the polymerization reaction in the method of the present invention, specifically, ethylene, propylene, 1-butene, 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, 1-eicosene.

Further, as the cyclic olefin which is supplied to the polymerization reaction in the method of the present invention, specifically, cyclopropene, cyclobutene, cyclopentene, cyclohexene, 3-methylcyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, tetracyclodecene, octacyclo Monocycloalkenes such as decene and cycloeicosene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-
Binoralkene such as 2-norbornene, 5,6-dimethyl-2-norbornene, 5,5,6-trimethyl-2-norbornene and 2-bornene, 2,3,3a, 7a-tetrahydro-4,7-methano- 1H-indene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene and other tricycloalkenes, 1,4,5,8-dimethano-1,2,3,4,4a, 5 In addition to 2,8,8a-octahydronaphthalene, 2-methyl-1,4,5,8-
Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,
8a-octahydronaphthalene, 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-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-fluoro-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- tetra cycloalkenes such octahydronaphthalene, hexacyclo [6,6,1,1 ^3,6, 1 ^10,13, 0 ^2,7,
0 ^9,14] heptadecene -4 pentacyclo [8,8,1 ^2,9, 1
^4,7, 1 ^{11, 18,} 0, 0 ^3,8, 0 ^12,17] henicosenoic -5, octacyclo [8,8,1 ^2,9, 1 ^4,7, 1 ^{11, 18,} 1 ^{13, 16} , 0,0 ^3,8 ,
[0 ^12,17 ] Cyclic monoenes such as polycycloalkenes such as docosene-5, dicyclopentadiene, 5-methylene-
2-norbornene, 5-ethylidene-2-norbornene, 5-norbornene, 1,5-cyclooctadiene, 5,8
Examples thereof include cyclic polyenes such as endomethylene hexahydronaphthalene and alkylidene tetrahydroindene.

In the method of the present invention, the raw material olefin supplied to the polymerization reaction system is a mixture of α-olefin and cyclic olefin. The content of the α-olefin in the raw material for polymerization olefin is usually in the range of 1 to 90 mol%, preferably 2 to 80 mol%, and the content of the cyclic olefin is usually 10 to 99 mol%, preferably It is in the range of 20 to 98 mol%.

In the method of the present invention, the olefin polymerization reaction is usually carried out in a hydrocarbon medium. Specific examples of the hydrocarbon medium include butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane, octadecane, and other aliphatic hydrocarbons, cyclopentane, methylcyclopentane, cyclohexane, cyclooctane, and other alicyclic groups. In addition to hydrocarbons, aromatic hydrocarbons such as benzene, toluene, and xylene, petroleum fractions such as gasoline, kerosene, and light oil, olefin as a raw material also serves as a hydrocarbon medium. Of these hydrocarbon media, aromatic hydrocarbons are preferred.

In the method of the present invention, a liquid phase polymerization method such as a suspension polymerization method or a solution polymerization method is usually employed. The temperature during the polymerization reaction is usually -50 to 230 ° C, preferably -30 to 200.
It is in the range of ° C.

The ratio of the transition metal compound used when the method of the present invention is carried out by the liquid phase polymerization method is usually 10 ⁻⁸ to 10 ⁻² g atom / as the concentration of the transition metal atom in the polymerization reaction system, preferably 10 ^-7 to 10 ^-3 gram atom / range. Also,
The proportion of aluminoxane used is usually 10 ^-4 to 10 ^-1 gram atom /, preferably 10 ^-3 to 5 × 10 ^-2 gram atom / as the concentration of aluminum atoms in the polymerization reaction system.
And the ratio of aluminum atom to transition metal atom in the polymerization reaction system is usually 4 to 10 ⁷ , preferably 10 to 10 ⁶ . The molecular weight of the copolymer can be adjusted by hydrogen and / or the polymerization temperature.

In the method of the present invention, a cyclic olefin copolymer is obtained by treating the polymerization reaction mixture after completion of the polymerization reaction by a conventional method. The composition of the cyclic olefin copolymer is such that the α-olefin component is usually 20 to 99.9 mol%, preferably 30 to 99.5 mol% and the cyclic olefin component is usually 0.1 to 80 mol%, preferably 0.5 to 70%. It is in the range of mol%. The intrinsic viscosity [η] of the cyclic olefin copolymer measured in decalin at 135 ° C.
Is usually 0.005 to 20 dl / g, preferably 0.01 to 10 d
It is in the range of 1 / g, and the molecular weight distribution measured by gel permeation chromatography (GPC) is usually 3 or less, preferably 2.5 or less. The degree of crystallinity of the cyclic olefin copolymer determined by X-ray diffraction is usually 0 to 70%, preferably 0 to 65%.

〔The invention's effect〕

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

〔Example〕

Next, the method of the present invention will be specifically described with reference to examples.

Practical example [Preparation of aluminoxane] Al ₂ (SO ₄ ) was added to a 400 ml flask that had been thoroughly purged with argon.
37 g of ₃ · 14H ₂ O and 125 ml of toluene were charged into a slurry. 0.5 mol of trimethylaluminum diluted with 125 ml of toluene was added dropwise thereto at a temperature of 0 to -5 ° C. After the dropping was completed, the temperature was raised to 40 ° C. and the reaction was performed at that temperature for 48 hours. Subsequently, solid-liquid separation is performed by filtration, and toluene is further removed from the separated liquid to obtain 17.5 g of a white solid aluminoxane.
Got The molecular weight determined by freezing point depression in benzene was 2000, and the m value of aluminoxane was 32.
It was redissolved in toluene and used for the polymerization.

[Polymerization] Purified toluene (250 ml) and norbornene (2.5 g) were charged into a 500 ml glass autoclave sufficiently replaced with nitrogen, ethylene gas was passed at 60 / hr, and the mixture was kept at 20 ° C for 10 minutes. Then, aluminoxane equivalent to 2.5 mg of aluminum atom and bis (cyclopentadienyl) zirconium dichloride dissolved in toluene corresponding to 1.25 × 10 ^-2 mg of zirconium atom were charged and polymerized. Started. After carrying out the polymerization at 20 ° C. for 1 hour under normal pressure, the polymerization was stopped with isopropanol. The polymerization proceeded in a uniform solution state, and absorption of ethylene was recognized even after 1 hour of the polymerization. Add the polymer solution to a large amount of a methanol / acetone mixture to precipitate the polymer and allow it to stand overnight.
It was dried under reduced pressure at 0 ° C. The polymer yield after drying was 3.7 g, and the activity per unit zirconium was 300 g polymer /
It was milligram atom-Zr. The ethylene content, [η], w / n and crystallinity of this polymer are
It was 90 mol%, 2.33 dl / g, 2.03, 2.1%.

Comparative Example 1 Magnesium chloride 20g was placed in an 800 ml SUS pot containing a 2.8 kg SUS ball (15 mmφ) and placed under a nitrogen atmosphere.
Crushed for 8 hours. The ground product was transferred to a 400 ml flask, 200 ml of titanium tetrachloride was added, and the mixture was heated at 70 ° C for 2 hours. Then, the pulverized product was separated and washed with decane until titanium tetrachloride was not detected in the liquid to obtain a titanium catalyst component. 9 mg of titanium atoms were supported on 1 g of the catalyst.

[Overlap]

Polymerization was carried out in the same manner as in Example 1 except that a titanium catalyst equivalent to 5 × 10 ⁻³ mg of titanium atom was used and triethylaluminum equivalent to 0.5 mg of atom of aluminum was used for 30 minutes. Ivy. The polymerization proceeded in a slurry state instead of a solution state. The polymer obtained was 3.8 g, and the activity per unit titanium was 760 g.
-Polymer / milligram atom-Ti, the ethylene content was 99.9 mol% or more, and norbornene was hardly copolymerized.

Comparative Example 2 [Polymerization] Polymerization was carried out in the same manner as in Example 1 except that vanadyl monoethoxy dichloride corresponding to 0.05 mg of vanadium atom and ethylaluminum sesquichloride corresponding to 0.5 mg of aluminum atom were used. I went. Although the polymerization proceeded in a solution state, absorption of ethylene was not recognized after 1 hour of the polymerization. The obtained polymer was 4.0 g, and the activity per unit vanadium was 80 g-
Polymer / milligram atom-V. The ethylene content, [η], w / n and crystallinity of this polymer were 89 mol%, 2.68 dl / g, 2.45 and 1.5%, respectively.

Example 2 In the polymerization of Example 1, 7.5 g of norbornene was used,
Polymerization was carried out in the same manner as in Example 1 except that the polymerization was carried out for 3 hours. Polymers with ethylene content, [η], w / n and crystallinity of 72 mol%, 1.83dl / g.2.12 and 0% are 2.3%, respectively.
g got. The activity per unit zirconium was 180 g-polymer / milligram atom-Zr.

Example 3 Polymerization was performed in the same manner as in Example 1 except that 2.5 g of 5-ethyl-2-norbornene was used in the polymerization of Example 1.
Polymers with ethylene content, [η], w / n and crystallinity of 91 mol%, 2.10 dl / g, 2.15 and 1.2% respectively 3.5 g
Was obtained. The activity per unit zirconium was 280 g-polymer / milligram atom-Zr.

Example 4 1,4,5,8-dimethano-1,2,3,4,4 in the polymerization of Example 1
Polymerization was performed in the same manner as in Example 1 except that 2.5 g of a, 5,8,8a-octahydronaphthalene was used and polymerization was performed for 30 minutes. As a result, 1.8 g of a polymer having ethylene content, [η], w / n and crystallinity of 96 mol%, 1.98 dl / g, 2.20 and 40% respectively was obtained. The activity per unit zirconium is 140 g-polymer /
It was milligram atom-Zr.

Example 5 In the polymerization of Example 1, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene was added.
Polymerization was performed in the same manner as in Example 1 except that 2.5 g was used and the polymerization was performed for 30 minutes. 1.7 g of a polymer having ethylene content, [η], w / n and crystallinity of 96 mol%, 2.02 dl / g, 2.18 and 45% respectively was obtained. The activity per unit zirconium is 14
It was 0 g-polymer / milligram atom-Zr.

Example 6 In the polymerization of Example 1, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene was converted to 1
Polymerization was performed in the same manner as in Example 1 except that 0 g was used and the polymerization was performed for 30 minutes. Polymers with ethylene content [η], w / n and crystallinity of 76 mol%, 1.45 dl / g, 2.29 and 0% respectively
1.1g was obtained. The activity per unit zirconium was 90 g-polymer / milligram atom-Zr.

Example 7 [Preparation of aluminoxane] Al ₂ (SO ₄ ) was added to a 200 ml flask which was sufficiently purged with argon.
He was charged with ₃ · 13H ₂ O 7.8g and toluene 30ml was slurried. 100 mmol of trimethylaluminum diluted with 25 ml of toluene was added dropwise thereto at a temperature of 0 to -5 ° C. After the completion of dropping, the temperature was raised to 45 ° C. and the reaction was carried out at that temperature for 1 week. Subsequently, solid-liquid separation was performed by filtration, and toluene was further removed from the separated liquid to obtain 3.1 g of a white solid aluminoxane. The molecular weight obtained by freezing point depression in benzene is
It was 2650, and the m value of aluminoxane was 44. In the polymerization, it was redissolved in toluene and used.

[Overlap]

Polymerization was performed in the same manner as in Example 1 except that 2.5 mg of aluminoxane synthesized in Example 7 in terms of aluminum atom and 2.5 g of norbornene were used and polymerization was carried out at 20 ° C. for 2 hours under normal pressure. Ethylene content, [η], w / n
And crystallinity of 92 mol%, 2.41 dl / g, 1.98, and 3.
7.6 g of 6% polymer was obtained. The activity per unit zirconium was 610 g-polymer / milligram atom-Zr.

Example 8 Polymerization was performed in the same manner as in Example 7 except that 7.5 g of 5-ethyl-2-norbornene was used in the polymerization of Example 7. 2.2 g of a polymer having ethylene content, [η], w / n and crystallinity of 74 mol%, 1.79 dl / g 2.24 and 0% respectively was obtained. 18 activity per unit zirconium
It was 0 g-polymer / milligram atom-Zr.

Example 9 In the polymerization of Example 7, bis (cyclopentadienyl) zirconium monochloride was used instead of bis (cyclopentadienyl) zirconium dichloride in an amount of 2.5 × 10 ^-2 mg of zirconium atom. Was polymerized in the same manner as in Example 7. Ethylene content, [η], w / n and crystallinity
As a result, 3.3 g of a polymer having 91 mol%, 1.98 dl / g, 2.20 and 2.6% was obtained. The activity per unit zirconium was 130 g-polymer / milligram atom-Zr.

Example 10 [Preparation of aluminoxane] Al ₂ (SO ₄ ) was added to a 200 ml flask thoroughly purged with argon.
₃ · 14H ₂ O 7.4g and trimethylaluminum 90mmol and tri-n-octyl aluminum diluted with toluene 25ml
10 mmol of mixed alkylaluminum was added dropwise at a temperature of 0 to -5 ° C. After the dropping was completed, the temperature was raised to 40 ° C. and the reaction was performed at that temperature for 48 hours. Next, pass the solid-liquid separation,
The separated liquid was used for polymerization as an aluminoxane solution.

[Overlap]

The procedure of Example 1 was repeated, except that 2.5 mg of aluminoxane synthesized in Example 10 in terms of aluminum atom and 2.5 g of norbornene were used and polymerization was carried out at 20 ° C. for 2 hours under normal pressure. 2.1 g of a polymer having ethylene content, [η], w / n and crystallinity of 91 mol%, 2.12 dl / g, 2.31 and 4.2% respectively was obtained. The activity per unit zirconium was 170 g-polymer / milligram atom-Zr.

Example 11 [Coupling] Purified toluene 2 was added to a glass autoclave having an internal volume of 500 ml.
After charging 50 ml and 2.5 g of 5-ethylidene-2-norbornene, ethylene was passed through at 60 / hr and kept at 20 ° C. for 10 minutes. Thereafter, aluminoxane synthesized in Example 7 corresponding to 2.5 mg of aluminum atoms and bis (cyclopentadienyl) zirconium dichloride corresponding to 1.25 × 10 ^-2 mg of zirconium atoms were converted. Charge and start the polymerization. The polymerization was carried out at 20 ° C. for 1 hour at normal pressure. The subsequent operation was performed in the same manner as in Example 1. 3.1 g of a polymer having ethylene content, [η], w / n and crystallinity of 92 mol%, 2.03 dl / g, 1.97 and 0.8% respectively was obtained. The activity per unit zirconium is
250 g-polymer / milligram atom-Zr. The iodine value was 59.

Example 12 [Polymerization] Using the continuous polymerization reactor of 1, purified toluene was added at 500 ml /
hr, aluminoxane synthesized in the same manner as in Example 7 was 2.5 mg atom / hr in terms of aluminum atom, and bis (cyclopentadienyl) zirconium dichloride was 5 × 10 ⁻³ mg atom / hr in terms of zirconium atom. It is continuously fed with ethylene in the polymerization vessel at the same time.
120 / hr, propylene 80 / hr and 5-ethylidene-2
-Norbornene was continuously fed at a rate of 1 g / hr, and polymerization was carried out under the conditions of a polymerization temperature of 20 ° C, normal pressure, residence time of 1 hour and polymer concentration of 19 g / hr. The resulting polymer solution was treated as in Example 1. The polymerization activity of the catalyst is 1900 g-polymer / milligram atom-Zr, ethylene content 82 mol%, [η] 1.53 dl / g, crystallinity 2.1%, w / n 1.92,
A rubbery polymer with an iodine value of 12 was obtained.

Example 13 [Polymerization] Polymerization was carried out in the same manner as in Example 12 except that dicyclopentadiene was continuously fed at a rate of 1 g / hr instead of 5-ethylidene-2-norbornene in the polymerization of Example 12. Ivy. The polymer concentration is 16 g /, and the polymerization activity of the catalyst is 16
00 g-polymer / milligram atom-Zr. The ethylene content, [η], crystallinity, w / n and iodine value of the produced polymer were 83 mol%, 1.51 dl / g, 2.6% and 1.9, respectively.
It was 9 and 8.

Example 14 [Polymerization] 5-ethyl-2-norbornene was replaced by 1 g / hr in place of 5-ethylidene-2-norbornene in the polymerization of Example 12.
Polymerization was performed in the same manner as in Example 12 except that the mixture was continuously fed at the rate of. The polymer concentration was 25 g /, and the polymerization activity of the catalyst was 2500 g-polymer / milligram atom-Zr. Ethylene content of the produced polymer, propylene content,
[Η], crystallinity and w / n are 81 mol% and 17 respectively.
It was mol%, 1.65dl / g, 0.3%, and 1.89.

Example 15 [Polymerization] In the polymerization of Example 12, butene-180 / hr was supplied instead of propylene, and the polymerization was performed at 0 ° C.
Polymerization was carried out in the same manner as in Example 12. Polymer concentration is 10 g /
The polymerization activity of the catalyst was 1000 g-polymer / milligram atom-Zr. Ethylene content of the produced polymer,
[Η], crystallinity, w / n and iodine value are 78 respectively.
mol%, 4.12 dl / g, 0%, 1.95, 13.

Example 16 [Polymerization] Using the continuous polymerization reactor of 1, purified toluene was added at 500 ml / h.
The ratio of aluminoxane synthesized in the same manner as in Example 7 was 5.0 mg atom / hr in terms of aluminum atom, and bis (cyclopentadienyl) zirconium dichloride was 1 × 10 ^-2 mg atom / hr in terms of zirconium atom. It is continuously fed with ethylene in the polymerization vessel at the same time.
40 / hr, 160 / hr of propylene and 1 g / hr of 5-ethyl-2-norbornene were continuously supplied at a polymerization temperature of 45
Polymerization was carried out under conditions of a temperature of 0 ° C., atmospheric pressure, a residence time of 1 hour, and a polymer concentration of 11 g /. Water was added to the produced polymer solution for deashing, toluene was removed, and vacuum drying was carried out at 120 ° C. for 12 hours. The polymerization activity of the catalyst was 100 g-polymer / milligram atom-Zr, ethylene content 56 mol%, [η] 0.12 dl /
A liquid polymer with g, 0% crystallization and w / n 2.07 was obtained.

Example 17 Bis (cyclopentadienyl) in the polymerization of Example 12
Bis (cyclopentadienyl) hafnium dichloride instead of zirconium dichloride was continuously supplied at a rate of 5 × 10 ^-2 mg / hr in terms of hafnium atom and 10 mg / hr in terms of aluminum atom. Polymerization was performed in the same manner as in Example 12.
The polymer concentration during the polymerization was 24 g /, and the polymerization activity of the catalyst was 240 g-polymer / milligram atom-Hf. The produced polymer has an ethylene content of 84 mol% and [η] is 1.
64dl / g and Mw / Mn were 2.2.

Example 18 Bis (cyclopentadienyl) in the polymerization of Example 12
Instead of zirconium dichloride, bis (methylcyclopentadienyl) dimethyltitanium was used as a titanium atom of 5
Polymerization was performed in the same manner as in Example 12 except that x10 ^-2 mg / hr and aluminoxane were continuously supplied at a rate of 10 mg / hr in terms of aluminum atom. The polymer concentration during the polymerization was 14 g /, and the polymerization activity of the catalyst was 140 g-polymer / milligram atom-Ti. The polymer produced has an ethylene content of 80 mol% and [η] of 1.44.
dl / g and Mw / Mn were 2.4.

[Brief description of drawings]

FIG. 1 is an explanatory view showing a preparation process of a catalyst used in the method of the present invention.

Claims (1)

[Claims] 1. In the presence of a catalyst comprising (A) a compound having a cyclopentadienyl group of a transition metal selected from the group consisting of titanium, zirconium, hafnium and vanadium, and (B) an aluminoxane, -A method for producing a cyclic olefin-based copolymer, which comprises copolymerizing an olefin and a cyclic olefin.