JP2653773B2 - Production of cyclic polyene copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a cyclic polyene copolymer. More specifically, ethylene, 1-butyl
The present invention relates to a method for efficiently producing a cyclic polyene copolymer having a high molecular weight distribution and a high molecular weight distribution by copolymerizing ten and a cyclic polyene.

[0002]

BACKGROUND OF THE INVENTION Conventionally, a method for producing a cyclic olefin-based copolymer by copolymerizing an α-olefin such as ethylene and a cyclic olefin such as a cyclic monoene or a cyclic polyene has been proposed by using a titanium compound and an organoaluminum compound. A method using a titanium-based catalyst, and a vanadium-based catalyst comprising a vanadium compound and an organoaluminum compound is known.

[0003] Among these methods, in copolymerization using a titanium-based catalyst, cyclic olefins have lower reactivity and lower copolymerization efficiency than α-olefins such as ethylene. In order to expect copolymerization, 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 further, the molecular weight of the copolymer is reduced, which makes it difficult to obtain a high molecular weight copolymer. Further, there is a disadvantage that a side reaction such as a ring-opening polymerization reaction of a cyclic olefin is apt to accompany, and the resulting copolymer has a wide molecular weight distribution. On the other hand, in copolymerization using a vanadium catalyst,
Compared with titanium-based catalysts, the copolymerization efficiency of cyclic olefins is higher and the molecular weight distribution of the resulting copolymer is narrower, but generally has the drawback of extremely low polymerization activity.

Further, catalysts comprising a transition metal compound and an aluminoxane as a new highly active polymerization catalyst in the olefin polymerization method are disclosed in JP-A-58-19309, JP-A-59-95292, and JP-A-60-95292. 35005
JP, JP-A-60-35006, JP-A-60-
No. 35007, Japanese Patent Application Laid-Open No. 60-35008, and the like. Among these prior arts, JP-A-58-19309, JP-A-60-35005, JP-A-60-35006, and JP-A-60-35
007 and JP-A-60-35008 describe that the catalyst system can be applied to copolymerization of ethylene and α-olefin, but all of them produce a cyclic olefin copolymer. Nothing is shown on how to do this.

Accordingly, in the field of the production of cyclic olefin copolymers, it is necessary to efficiently produce a cyclic olefin copolymer having a high copolymerization efficiency of a cyclic olefin, a high polymerization activity, and a narrow molecular weight distribution. There is a strong demand for a method that can do this. The present inventors have recognized that the prior art in the field of producing cyclic olefin-based copolymers is in the above-described situation, and has a high cyclic polyene copolymerization efficiency, is further excellent in polymerization activity, and has a narrow molecular weight distribution. As a result of examining a method capable of producing a polyene-based 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 It has been found that the above object can be achieved by copolymerizing ethylene, 1-butene and a cyclic polyene in the presence of, and the present invention has been achieved.

[0006]

SUMMARY OF THE INVENTION The process for producing a cyclic polyene copolymer according to the present invention comprises: (A) a compound having a cyclopentadienyl group of a transition metal selected from the group consisting of titanium, zirconium, hafnium and vanadium; ) aluminoxane, in the presence of a catalyst consisting of, d
It is characterized by copolymerizing styrene , 1-butene and cyclic polyene.

[0007]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the method for producing the cyclic polyene copolymer according to the present invention will be specifically described.

FIG. 1 shows an example of a process for preparing a catalyst used in the method of the present invention. The method for producing the cyclic polyene-based copolymer according to the present invention includes: (A) a compound having a cyclopentadienyl group of a transition metal selected from the group consisting of titanium, zirconium, hafnium, and vanadium (hereinafter referred to as “transition metal compound” is.), and (B) aluminoxane, in the presence of a catalyst consisting of, e
Tylene, 1-butene and cyclic polyene are copolymerized.

The transition metal compound (A) as a catalyst component used in the method of the present invention can be exemplified by a transition metal compound selected from the group consisting of titanium, zirconium, hafnium and vanadium. Among the transition metal compounds, compounds of titanium or zirconium are preferable, and zirconium compounds are particularly preferable because of high activity.

Preferred forms of the transition metal compound include:
Compounds having a hydrocarbon group or compounds having a hydrocarbon group and a halogen atom are preferred, in particular having preferably at least one, particularly preferably two, hydrocarbon groups and preferably at least one, particularly preferably two, It is a transition metal compound having two halogen atoms. As the hydrocarbon group, specifically, methyl group, ethyl group, n-
Butyl, sec-butyl, tert-butyl, isobutyl, alkyl such as neopentyl, alkenyl such as isopropenyl, 1-butenyl, cyclopentadienyl, methylcyclopentadienyl, etc. Examples thereof include an aralkyl group such as a cycloalkadienyl group, a benzyl group and a neophyl group. Among these hydrocarbon groups, a cycloalkadienyl group is preferred, and a cyclopentadienyl group is particularly preferred. Specific examples of the halogen atom include a fluorine, chlorine, bromine and iodine atom.

Further, as the transition metal compound, specifically, bis (cyclopentadienyl) dimethyltitanium, bis (cyclopentadienyl) diethyltitanium, bis (cyclopentadienyl) diisopropyltitanium, bis (methylcyclopentadienyl) ) Dimethyl titanium, bis (cyclopentadienyl) methyl titanium monochloride, bis (cyclopentadienyl) ethyl titanium monochloride, bis (cyclopentadienyl) isopropyl titanium monochloride, bis (cyclopentadienyl) methyl titanium mono Bromide, bis (cyclopentadienyl) methyltitanium monoiodide, bis (cyclopentadienyl) titanium difluoride, bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) titanium dibromide, Titanium compounds such as bis (methylcyclopentadienyl) titanium diiodide; bis (cyclopentadienyl) dimethyl zirconium, bis (cyclopentadienyl) diethyl zirconium, bis (methylcyclopentadienyl) diisopropyl zirconium, bis ( Cyclo (pentadienyl) methyl zirconium monochloride, bis (cyclopentadienyl) ethyl zirconium monochloride, bis (cyclopentadienyl) methyl zirconium monobromide, bis (cyclopentadienyl) methyl zirconium monoiodide, bis (cyclo (Pentadienyl) zirconium difluoride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) Zirconium compounds such as zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium diiodide; bis (cyclopentadienyl) dimethylhafnium, bis (cyclopentadienyl) methylhafnium monochloride, bis (cyclopentadienyl) A) Hafnium compounds such as hafnium dichloride, and vanadium compounds such as bis (cyclopentadienyl) vanadium dichloride and bis (cyclopentadienyl) vanadium monochloride.

The aluminoxane (B) as a catalyst component used in the method of the present invention is specifically represented by the general formula [I] or the general formula [II]:

[0013]

Embedded image

(Wherein, 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, and a butyl group, preferably a methyl group and 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, copper sulfate hydrate or aluminum sulfate hydrate, and reacted. (2) A method in which water is allowed to directly act on trialkylaluminum in a medium such as benzene, toluene, ethyl ether, and tetrahydrofuran.

Among these methods, the method (1) is preferable. The aluminoxane may contain a small amount of an organic metal component. Α- olefin supplied to the polymerization reaction in the method of the present invention, ethylene
Len and 1-butene.

The cyclic polyene supplied to the polymerization reaction in the method of the present invention is specifically dicyclopentadiene, 5-methylene-2-norbornene, 5-ethylidene-
Examples thereof include cyclic polyenes such as 2-norbornene, 5-norbornene, 1,5-cyclooctadiene, 5,8-endomethylenehexahydronaphthalene, and alkylidenetetrahydroindene.

The process for producing a cyclic polyene copolymer of the present invention can be applied to the copolymerization of an α-olefin with the following cyclic monoene. Production conditions similar to those for producing a cyclic polyene-based copolymer can be employed.

Examples of such cyclic monoenes include monocycloalkenes such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, 3-methylcyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, tetracyclodecene, octacyclodecene, and cycloeicosene. Norbornene, 5-methyl-2-norbornene, 5-ethyl-2-
Bicycloalkenes such as norbornene, 5-isobutyl-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,
Tricycloalkenes such as 5,6,7a-tetrahydro-4,7-methano-1H-indene; 1,4,5,8-dimetano-1,2,3,4,4a, 5,8,8a-octa Hydronaphthalene, 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-1,4,5,8,8-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 and 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 ] dococene-5 and the like.

In the method of the present invention, the starting olefin supplied to the polymerization reaction system is a mixture of ethylene, 1-butene and a cyclic polyene. The content of the ethylene and 1-butene in the olefin for polymerization is usually in the range of 1 to 90 mol%, preferably 2 to 80 mol%, and the content of the cyclic polyene is usually 10 to 99 mol%.
Preferably it is in the range of 20 to 98 mol%.

In the method of the present invention, ethylene, 1-butene
The polymerization reaction of the hydrocarbon and cyclic polyene is usually carried out in a hydrocarbon medium. Specific examples of the hydrocarbon medium include aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane, and octadecane; alicyclics such as cyclopentane, methylcyclopentane, cyclohexane, and cyclooctane. In addition to hydrocarbons, aromatic hydrocarbons such as benzene, toluene, and xylene, petroleum fractions such as gasoline, kerosene, and light oil, olefins as raw materials also serve as hydrocarbon media. Among 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 at the time of the polymerization reaction is usually in the range of -50 to 230 ° C, preferably -30 to 200 ° C.

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

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

[0024]

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

[0025]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

[0026]

[Reference Example 1] [Preparation of aluminoxane] Al ₂ O 3 was placed in a 200 ml flask sufficiently purged with argon.
(SO ₄ ) 7.8 g of ₃ · 13H ₂ O and 30 ml of toluene were charged to form a slurry. In addition, 100 mmol of trimethylaluminum diluted with 25 ml of toluene was added to 0-
It was added dropwise at a temperature of 5 ° C. After completion of the dropping, 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 filtration, and toluene was further removed from the separated liquid to obtain 3.1 g of aluminoxane as a white solid. The molecular weight determined by freezing point depression in benzene was 2650, and the m-value of aluminoxane was 44. For polymerization, it was used after re-dissolving in toluene.

[Polymerization] In a glass autoclave having an internal volume of 500 ml, purified toluene 250 ml and 5-ethylidene-2-norbornene 2.5
g, ethylene was passed through at 60 liters / hr,
It was kept at 20 ° C. for 10 minutes. Thereafter, 1.25 × 10 5 in terms of aluminoxane and zirconium atoms equivalent to 2.5 milligram atoms in terms of aluminum atoms.
Bis (cyclopentadienyl) zirconium dichloride corresponding to ^-2 milligram atoms was charged to initiate polymerization.
The polymerization was carried out at 20 ° C. for 1 hour at normal pressure. Thereafter, the polymer solution was added to a large amount of a mixed solution of methanol / acetone to precipitate a polymer and dried overnight at 120 ° C. under reduced pressure. The ethylene content, [η], Mw / Mn and crystallinity were 92
3.1 g of a 2.0% dl / g, 1.97, 0.8% polymer by mole% was obtained. The activity per unit zirconium was 250 g-polymer / milligram atom-Zr. The iodine value was 59.

[0028]

REFERENCE EXAMPLE 2 [Polymerization] Using a 1-liter continuous polymerization reactor, purified toluene was used at 500 ml / hr, and aluminoxane synthesized in the same manner as in Reference Example 1 was converted to aluminum atom at 2.5 mg atom / hr. , Bis (cyclopentadienyl) zirconium dichloride is continuously supplied at a rate of 5 × 10 ⁻³ milligram atoms / hr in terms of zirconium atoms, and 120 l / hr of ethylene, 80 l / hr of propylene and 5-Ethylidene-2-norbornene is continuously supplied at a rate of 1 g / hr, and the polymerization temperature is 20
Polymerization was carried out at a temperature of 1 ° C., normal pressure, and a residence time of 1 hour, under the conditions of a polymer concentration of 19 g / liter. The resulting polymer solution is
The same treatment as in Reference Example 1 was performed. The polymerization activity of the catalyst is 1900
g-polymer / milligram atom-Zr, a rubbery polymer having an ethylene content of 82 mol%, [η] of 1.53 dl / g, a crystallinity of 2.1%, Mw / Mn of 1.92 and an iodine value of 12 was obtained. Was.

[0029]

Except that Reference Example 3] The [Polymerization] dicyclopentadiene instead of 5-ethylidene-2-norbornene in the polymerization of Example 2 was continuously fed at a rate of 1 g / hr, the same polymerization as in Reference Example 2 went. The polymer concentration was 16 g / l and the polymerization activity of the catalyst was 1600 g-polymer / milligram atom-Zr
Met. The ethylene content, [η], crystallinity, Mw / Mn and iodine value of the resulting polymer were 83 mol%, respectively.
1.51 dl / g, 2.6%, 1.99, and 8.

[0030]

Example 1 [Polymerization] In the polymerization of Reference Example 2 , butene was used instead of propylene.
Polymerization was carried out in the same manner as in Reference Example 2 except that the polymerization was carried out at 0 ° C. at a supply rate of −80 L / hr. The polymer concentration was 10 g / liter and the polymerization activity of the catalyst was 1000
g-polymer / milligram atom-Zr. Ethylene content of product polymer, [η], crystallinity, Mw / Mn
And the iodine value are respectively 78 mol%, 4.12 dl /
g, 0%, 1.95, 13.

[0031]

Reference Example 4 In the polymerization of Reference Example 2 , bis (cyclopentadienyl) hafnium dichloride was replaced with bis (cyclopentadienyl) zirconium dichloride in an amount of 5 × 10 ⁻² milligram atoms / hr in terms of hafnium atoms, and aluminoxane. Reference Example except that was continuously supplied at a rate of 10 milligram atoms / hr in terms of aluminum atoms.
Polymerization was carried out in the same manner as in Example 2 . The polymer concentration during polymerization is 2
The polymerization activity of the catalyst was 240 g-polymer / milligram atom-Hf. The ethylene content of the produced polymer is 84 mol%, and [η] is 1.64 d.
l / g and Mw / Mn were 2.2.

[0032]

Reference Example 5 In the polymerization of Reference Example 2 , bis (methylcyclopentadienyl) dimethyltitanium was substituted for bis (cyclopentadienyl) zirconium dichloride in an amount of 5 × 10 ⁻² milligram atoms / hr in terms of titanium atoms. Polymerization was carried out in the same manner as in Reference Example 2 except that xane was continuously supplied at a rate of 10 mg atoms / hr in terms of aluminum atoms. The polymer concentration during polymerization is 14 g
/ Liter and the polymerization activity of the catalyst was 140 g-polymer / milligram atom-Ti. The ethylene content of the produced polymer is 80 mol%, and [η] is 1.44 dl /
g and Mw / Mn were 2.4.

[0033]

[Reference Example 6] [Preparation of aluminoxane] Al ₂ O 3 was placed in a 400 ml flask sufficiently purged with argon.
Was (SO _{4) 3} · 14H ₂ was charged with O37g and toluene 125ml slurry. Then, 0.5 mol of trimethylaluminum diluted with 125 ml of toluene was added to 0 to -5.
It was added dropwise at a temperature of ° C. After completion of the dropwise addition, the temperature was raised to 40 ° C., and the reaction was carried out 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 aluminoxane as a white solid. The molecular weight determined by freezing point depression in benzene was 2,000, and the m-value of aluminoxane was 32. For polymerization, it was used after re-dissolving in toluene.

[Polymerization] After charging 250 ml of purified toluene and 2.5 g of norbornene into a 500 ml glass autoclave sufficiently purged with nitrogen, ethylene gas was passed at 60 l / hr.
It was kept at 20 ° C. for 10 minutes. Then, bis (cyclopentadienyl) zirconium dichloride dissolved in toluene, equivalent to aluminoxane equivalent to 2.5 mg atoms in terms of aluminum atoms, and 1.25 × 10 ^-2 mg atoms in terms of zirconium atoms, was mounted. And polymerization was started. After 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 observed even after 1 hour of the polymerization. The polymer solution was added to a large amount of a mixed solution of methanol / acetone to precipitate a polymer, which was dried overnight at 120 ° C. under reduced pressure. The polymer yield after drying was 3.7 g, and the activity per unit zirconium was 300 g-polymer / milligram atom-Zr. The ethylene content, [η], Mw / Mn and crystallinity of this polymer were 9
0 mol%, 2.33 dl / g, 2.03 and 2.1%.

[0035]

In the polymerization of Reference Example 7 Reference Example 6, except that the norbornene using 7.5g, was carried out for 3 hours polymerization, Reference Example 6
Polymerization was carried out in the same manner as described above. Ethylene content, [η], Mw /
Mn and crystallinity are respectively 72 mol%, 1.83 d
2.3 g of 1 / g, 2.12, 0% polymer were obtained. The activity per unit zirconium was 180 g-polymer / milligram atom-Zr.

[0036]

In the polymerization of Reference Example 8 Reference Example 6, except that 5-ethyl-2-norbornene was used 2.5g, was performed in the same manner as in polymerization Example 6. The ethylene content, [η], Mw / Mn and crystallinity were 91 mol%, 2.10 dl / g, respectively.
3.5 g of 2.15, 1.2% polymer were obtained. The activity per unit zirconium was 280 g-polymer / milligram atom-Zr.

[0037]

REFERENCE EXAMPLE 9 In the polymerization of Reference Example 6 , 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene was used.
Polymerization was performed in the same manner as in Reference Example 6 , except that 5 g was used and polymerization was performed for 30 minutes. The ethylene content, [η], Mw / Mn and crystallinity were respectively 96 mol%, 1.98 dl / g, and 2.
1.8 g of 20, 40% polymer were obtained. The activity per unit zirconium was 140 g-polymer / milligram atom-Zr.

[0038]

Reference Example 10 In the polymerization of Reference Example 6 , 2-methyl-1,2-methyl-1,
References except that polymerization was performed for 30 minutes using 2.5 g of 4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene.
Polymerization was carried out as in Example 6 . Ethylene content, [η], M
w / Mn and crystallinity are respectively 96 mol% and 2.02
1.7 g of dl / g, 2.18, 45% polymer were obtained. The activity per unit zirconium was 140 g-polymer / milligram atom-Zr.

[0039]

Reference Example 11 In the polymerization of Reference Example 6 , 2-methyl-1,
Reference Example 6 except that 10 g of 4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene was used and polymerized for 30 minutes.
Polymerization was carried out in the same manner as described above. Ethylene content, [η], Mw /
Mn and crystallinity are 76 mol% and 1.45 dl, respectively.
/ G, 2.29, 0%, 1.1 g of polymer was obtained.
The activity per unit zirconium was 90 g-polymer / milligram atom-Zr.

[0040]

REFERENCE EXAMPLE 12 Reference Example 6 was repeated except that the aluminoxane synthesized in Example 6 was subjected to atmospheric pressure polymerization at 20 ° C. for 2 hours using 2.5 mg of an aluminum atom and 2.5 g of norbornene at 20 ° C. Polymerization was performed in the same manner. 7.6 g of a polymer having an ethylene content, [η], Mw / Mn and crystallinity of 92 mol%, 2.41 dl / g, 1.98 and 3.6%, respectively, were obtained. The activity per unit zirconium was 610 g-polymer / milligram atom-Zr.

[0041]

Reference Example 13 In the polymerization of Reference Example 12 , 5-ethyl-2
- participation, except that norbornene was subjected to polymerization using a 7.5g
Polymerization was carried out in the same manner as in Example 12 . Ethylene content,
2.2 g of a polymer having [η], Mw / Mn and crystallinity of 74 mol%, 1.79 dl / g, 2.24 and 0%, respectively, were obtained. The activity per unit zirconium is 18
0 g-polymer / milligram atom-Zr.

[0042]

REFERENCE EXAMPLE 14 In the polymerization of Reference Example 12 , bis (cyclopentadienyl) zirconium monochloride monohydride was used instead of bis (cyclopentadienyl) zirconium dichloride in an amount of 2.5 × in terms of zirconium atom.
Polymerization was carried out in the same manner as in Reference Example 12 , except that 10 ^-2 milligram atoms were used. Ethylene content, [η], Mw / Mn
And a crystallinity of 91 mol%, 1.98 dl /
g, 2.20, 2.6% of the polymer 3.3 g were obtained. The activity per unit zirconium was 130 g-polymer / milligram atom-Zr.

[0043]

[Reference Example 15] [Preparation of aluminoxane] Al ₂ O 3 was placed in a 200 ml flask sufficiently purged with argon.
(SO ₄₎ a ₃ · 14H _{2 O7.4g} and mixed alkyl aluminum diluted trimethylaluminum 90mmol and tri-n-octyl aluminum 10mmol in 25ml of toluene was added dropwise to a temperature of 0 to-5 ° C.. After completion of the dropwise addition, the temperature was raised to 40 ° C., and the reaction was carried out at that temperature for 48 hours. Subsequently, the mixture was filtered to perform solid-liquid separation, and the separated liquid was used as an aluminoxane solution for polymerization.

[Polymerization] The aluminoxane synthesized in Reference Example 15 was converted to an aluminum atom in an amount of 2.5 milligram atoms in terms of aluminum atom and norbornene 2.5.
with g, except that for 2 hours atmospheric pressure polymerization at 20 ° C., ginseng
Performed in the same manner as in Example 6 . Ethylene content, [η], Mw /
Mn and crystallinity are 91 mol% and 2.12 dl, respectively.
/ G, 2.31 and 4.2% of polymer 2.1 g were obtained.

The activity per unit zirconium is 170 g-
Polymer / milligram atom-Zr.

[0046]

REFERENCE EXAMPLE 16 [Polymerization] Using a 1 liter continuous polymerization reactor, purified toluene was 500 ml / hr, and aluminoxane synthesized in the same manner as in Reference Example 12 was 2.5 mg atom / hr in terms of aluminum atom. , Bis (cyclopentadienyl) zirconium dichloride in 5 × 10 ^{-3 in} terms of zirconium atom
The reactor was continuously supplied at a rate of milligram atoms / hr, and continuously supplied at a rate of 120 liters / hr of ethylene, 80 liters / hr of propylene and 1 g / hr of 5-ethyl-2-norbornene simultaneously in a polymerization reactor. Temperature 20
Polymerization was carried out under the conditions of ° C., normal pressure, residence time of 1 hour and polymer concentration of 25 / liter. The resulting polymer solution is
The same treatment as in Reference Example 6 was performed. The polymerization activity of the catalyst is 2500
g-polymer / milligram atom-Zr. The ethylene content, propylene content, [η], crystallinity and Mw / Mn of the resulting polymer were 81 mol%, 17 mol%, 1.65 dl / g, 0.3% and 1.89, respectively.

[0047]

[Reference Example 17] [Polymerization] Using a 1 liter continuous polymerization reactor, 5
Aluminoxane synthesized in the same manner as in Reference Example 12 was 5.0 ml / hr in terms of aluminum atom, and bis (cyclopentadienyl) zirconium dichloride was 1 × 10 ⁻² mg atom in terms of zirconium atom. / Hr, and continuously feed 40 l / hr of ethylene, 160 l / hr of propylene and 5-ethyl-2-norbornene 1 in the polymerization reactor.
g / hr, and the polymerization was carried out under the conditions of a polymerization temperature of 45 ° C., normal pressure, residence time of 1 hour and a polymer concentration of 11 g / l. Water was added to the resulting polymer solution for decalcification, and then toluene was removed, followed by drying under reduced pressure at 120 ° C. for 12 hours. The polymerization activity of the catalyst was 1100 g-polymer / milligram atom-Zr, ethylene content 56 mol%, [η] 0.12 dl / g, crystallinity 0%, Mw / M
A liquid polymer having n2.07 was obtained.

[Brief description of the drawings]

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

Continuation of the front page (56) References West German Patent Application Publication 3240382 (DE, A) H. REICHERT & W. GEISELER, "POLYMER RECTION ENGINEERI NG, 1983, HANSER PUBLI SHERS, P. 208-220 MAKROMOLEKULAR C CEMIE.

Claims (1)

(57) [Claims] 1. A (A) a titanium, zirconium, hafnium, a compound having a cyclopentadienyl group transition metals selected from the group consisting of vanadium, and (B) aluminoxane, in the presence of a catalyst consisting of ethylene A method for producing a cyclic polyene-based copolymer, comprising copolymerizing 1-butene and a cyclic polyene.