JP2788013B2 - Method for producing cyclic olefin random copolymer - Google Patents

Description

Description TECHNICAL FIELD [0001] The present invention relates to a method for producing a cyclic olefin-based random copolymer. More specifically, the present invention can reduce the content of polyethylene contained as impurities,
In addition, the present invention relates to a method for producing a cyclic olefin random copolymer capable of producing a cyclic olefin random copolymer having excellent transparency.

TECHNICAL BACKGROUND OF THE INVENTION A cyclic olefin random copolymer composed of ethylene and a specific bulky cyclic olefin is a synthetic resin in which optical properties, mechanical properties, thermal properties, and the like are balanced. Used in the field of optical materials such as disks and optical fibers.

However, when an optical memory disk is manufactured from such a cyclic olefin-based random copolymer, a very small number of read errors may occur. The present inventors have conducted intensive studies to reduce the reading error of the optical memory disk manufactured from the cyclic olefin-based random copolymer, and found that some of the reading errors were found in the cyclic olefin-based random copolymer. Was found to be caused by polyethylene contained as Therefore, the appearance of a method for producing a cyclic olefin random copolymer capable of reducing the content of polyethylene contained as an impurity is strongly desired.

By the way, such a cyclic olefin-based random copolymer, conventionally, ethylene and a cyclic olefin, in the presence of a catalyst formed from a soluble vanadium compound and an organoaluminum compound, hexane, a hydrocarbon such as heptane or the above cyclic olefin. It is produced by copolymerization using as a solvent. The present inventors have conducted intensive studies on a method for producing a cyclic olefin-based random copolymer having a reduced content of polyethylene contained as an impurity and excellent transparency, and the concentration of an organoaluminum compound supplied into a polymerization tank, The ratio between the concentration of the organoaluminum compound in the polymerization tank and the concentration of the vanadium compound supplied into the polymerization tank and the concentration of the vanadium compound in the polymerization tank may be set to a specific value or less. To complete the present invention.

Object of the Invention The present invention has been made in view of the prior art as described above, and can reduce the content of polyethylene contained as an impurity, and furthermore, has excellent transparency in a cyclic olefin-based random copolymer. It is an object of the present invention to provide a method for producing a cyclic olefin-based random copolymer that can be produced efficiently.

SUMMARY OF THE INVENTION A method for producing a cyclic olefin random copolymer according to the present invention comprises: (a) ethylene; and (b) the following formula [I] or [II]. (In the formula, n is 0 or 1, m is 0 or a positive integer, R ^{1 to} R ¹⁸ are each independently a hydrogen atom, a halogen atom or a hydrocarbon group, and R ^{15 to} R ¹⁸ May be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group).

[Wherein, l is an integer of 0 or 1 or more, and m and n
Is 0, 1 or 2, and R ^{1 to} R ¹⁵ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, and R ⁵ (or R ⁶ )
R ⁹ (or R ⁷ ) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be directly bonded without any group. And at least one cyclic olefin selected from the group consisting of unsaturated monomers represented by the following formulas, in the presence of a catalyst formed from a soluble vanadium compound and an organoaluminum compound, in a hydrocarbon-based solvent or When a cyclic olefin-based random copolymer is produced by copolymerization in a liquid phase composed of a cyclic olefin, the concentration of the organic aluminum compound supplied into the polymerization tank (C
_0Al ) and the concentration of the organoaluminum compound in the polymerization tank (C
_1Al) the ratio of the (C _0Al / C _1Al) and 11 or less, and a polymerization vanadium compound fed into the tank concentration (C _{0 v),} the ratio of the vanadium compound concentration (C _{1 v)} in a polymerization tank (C _0v /
C _1v ) is set to 3 or less.

According to the present invention, when copolymerizing ethylene and a cyclic olefin, the ratio of the concentration of the organic aluminum compound (C 0 _Al ) supplied into the polymerization tank to the concentration of the organic aluminum compound (C _1Al ) in the polymerization tank (C _{1 Al} ) C _0Al / C _1Al) was 11 or less, and the vanadium compound concentration supplied into the polymerization tank (C
And _{0 v),} since the ratio of the vanadium compound concentration in the polymerization vessel (C _{1 v)} the (C _0v / C _1v) and 3 or less, the content of polyethylene contained as an impurity is reduced, and excellent transparency A cyclic olefin-based random copolymer can be produced. Moreover, it is possible to efficiently prevent polyethylene from adhering to the polymerization vessel wall and the vicinity of the polymer outlet.

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

In the present invention, the cyclic olefin represented by the above general formula [I] or the general formula [II] and ethylene are
In a hydrocarbon mixed solvent or a liquid phase comprising the above-mentioned cyclic olefin, copolymerization is carried out in the presence of a catalyst comprising a vanadium compound and an organoaluminum compound which are soluble in the solvent to produce a cyclic olefin-based random copolymer. ing.

The cyclic olefin represented by the above formula used in the present invention [I], specifically, bicyclo [2,2,1] hept-2-ene derivatives, tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] -3-dodecene derivatives, hexacyclo [6,6,1,1 ^3.6, 1 ^10.13, 0 ^2.7, 0 ^9.14] -
4 Heputadensen derivatives, octacyclo [8,8,0,1 ^2.9, 1 ^4.7, 1 ^11.18, 1 ^13.16, 0
^3.8, 0 ^12.17] -5-docosene derivatives, pentacyclo [6,6,1,1 ^3.6, 0 ^2.7, 0 ^9.14] -4-hexadecene derivative, heptacyclo-5-icosene derivatives, heptacyclo-5-heneicosene derivatives, tricyclo [ 4,3,0,1 ^2.5] -3-decene derivatives, tricyclo [4,3,0,1 ^2.5] -3-undecene derivatives, pentacyclo [6,5,1,1 ^3.6, 0 ^2.7, 0 ^9.13] - 4-pentadecene derivatives, penta cyclopentadiene decadiene derivative, pentacyclo [4,7,0,1 ^2.5, 0 ^8.13, 1 ^9.12] -3-pentadecene derivatives, pentacyclo [7,8,0,1 ^3.6, 0 ^2.7, 1 ^10.17 , 0 ^11.16 , 1
^12.15] -4-eicosene derivatives, and Nonashikuro [9,10,1,1,4.7,0 ^3.8, 0 ^2.10, 0 ^12.21, 1
^13.20 , 0 ^14.19 , 1 ^15.18 ] -5-pentacocene derivative.

 Specific examples of such compounds are shown below.

Bicyclo [2,2,1] hept-2-ene 6-methylbicyclo [2,2,1] hept-2-ene 5,6-dimethylbicyclo [2,2,1] hept-2-ene 1-methylbicyclo [2,2,1] hept-2-ene 6-methylbicyclo [2,2,1] hept-2-ene 6-n-butylbicyclo [2,2,1] hept-2-ene 6-isobutylbicyclo [2,2,1] hept-2-ene Bicyclo [2,2,1] hept-2-ene derivatives such as 7-methylbicyclo [2,2,1] hept-2-ene; Tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] -3-dodecene 5,10-dimethyl-tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] -
3-dodecene 2,10-dimethyl-tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] -
3-dodecene 11,12-dimethyl-tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] -
3-dodecene 2,7,9- trimethyl tetracyclo [4,4,0,1 ^2.5, 1 ^7.10]
-3-dodecene 9-ethyl-2,7-dimethyltetracyclo [4,4,0,
1 ^2.5, 1 ^7.10] -3-dodecene 9-isobutyl-2,7-dimethyltetracyclo [4,4,0,1
^2.5, 1 ^7.10] -3-dodecene 9,11,12- trimethyl tetracyclo [4,4,0,1 ^2.5,
1 ^7.10 ] -3-Dodecene 9-ethyl-11,12-dimethyltetracyclo [4,4,0,1
^2.5, 1 ^7.10] -3-dodecene 9-isobutyl-11,12-dimethyltetracyclo [4,4,
0,1 ^2.5 , 1 ^7.10 ] -3-dodecene 5,8,9,10- tetramethyl cyclo [4,4,0,1 ^2.5, 1
^7.10 ] -3-Dodecene 8-methyl tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] -3
Dodecene 8-ethyl-tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] -3
Dodecene 8-propyl tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] -3
−Dodecene 8 hexyl tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] -3
−Dodecene 8 stearyl tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] -
3-dodecene 8,9-dimethyl-tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] -3
−Dodecene 8-methyl-9-ethyl tetracyclo [4,4,0,1 ^2.5, 1
^7.10 ] -3-Dodecene 8-chloro-tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] -3
Dodecene 8-bromo-tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] -3
Dodecene 8-fluoro-tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] -3
−Dodecene 8,9-dichloro-tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] -3
−Dodecene 8-cyclohexyl-tetracyclo [4,4,0,1 ^2.5,
1 ^7.10 ] -3-Dodecene 8 isobutyl tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] -
3-dodecene 8-butyl tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] -3
Dodecene 8 ethylidene tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] -
3-dodecene 8-ethylidene-9-methyltetracyclo [4,4,0,
1 ^2.5, 1 ^7.10] -3-dodecene 8-ethylidene-9-ethyltetracyclo [4,4,0,
1 ^2.5, 1 ^7.10] -3-dodecene 8-ethylidene-9-isopropyltetracyclo [4,4,
0,1 ^2.5 , 1 ^7.10 ] -3-dodecene 8-ethylidene-9-butyltetracyclo [4,4,0,
1 ^2.5, 1 ^7.10] -3-dodecene 8-n-propylidene-tetracyclo [4,4,0,1 ^2.5, 1
^7.10 ] -3-Dodecene 8-n-propylidene-9-methyltetracyclo [4,4,
0,1 ^2.5 , 1 ^7.10 ] -3-dodecene 8-n-propylidene-9-ethyltetracyclo [4,4,
0,1 ^2.5 , 1 ^7.10 ] -3-dodecene 8-n-propylidene-9-isopropyl tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] -3-dodecene 8-n-propylidene-9-butyltetracyclo [4,4,
0,1 ^2.5 , 1 ^7.10 ] -3-dodecene 8 isopropylidene tetracyclo [4,4,0,1 ^2.5, 1
^7.10 ] -3-Dodecene 8-isopropylidene-9-methyltetracyclo [4,4,
0,1 ^2.5 , 1 ^7.10 ] -3-dodecene 8-isopropylidene-9-ethyltetracyclo [4,4,
0,1 ^2.5 , 1 ^7.10 ] -3-dodecene 8 isopropylidene-9-isopropyl tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] -3-dodecene 8-isopropylidene-9-butyltetracyclo [4,4,
0,1 ^2.5, 1 ^7.10] -3-dodecene tetracyclo such [4,4,0,1 ^2.5, 1 ^7.10] -3-dodecene derivatives; Hexacyclo [6,6,1,1 ^3.6, 1 ^10.13, 0 ^2.7 0 ^9.14] -
4-heptadecene 12-methyl hexa cyclo [6,6,1,1 ^3.6, 1 ^10.13, 0 ^2.7,
0 ^9.14 ] -4-Heptadecene 12-ethyl hexa-cyclo [6,6,1,1 ^3.6, 1 ^10.13, 0 ^2.7,
0 ^9.14 ] -4-Heptadecene 12 isobutyl hexamethylene cyclo [6,6,1,1 ^3.6, 1 ^10.13, 0
^2.7, 0 ^9.14] -4-heptadecene 1,6,10-trimethyl-12-isobutylhexacyclo [6,
6,1,1 ^3.6, 1 ^10.13, 0 ^2.7 0 ^9.14] -4-heptadecene hexacyclo such as [6,6,1,1 ^3.6, 1 ^10.13, 0 ^2.7, 0
^9.14 ] -4-Heptadecene derivatives; Octacyclo [8,8,0,1 ^2.9, 1 ^4.7, 1 ^11.18, 1 ^13.16, 0
^3.8 , 0 ^12.17 ] -5-docosene 15 methyloctadecanoic cyclo [8,8,0,1 ^2.9, 1 ^4.7, 1 ^11.18,
1 ^13.16 , 0 ^3.8 , 0 ^12.17 ] -5-docosene 15 Ethyl octa cyclo [8,8,0,1 ^2.9, 1 ^4.7, 1 ^11.18,
1 ^13.16, 0 ^3.8, 0 ^12.17] -5-docosenoic octacyclo such as [8,8,0,1 ^2.9, 1 ^4.7, 1 ^11.18, 1
^13.16, 0 ^3.8, 0 ^12.17] -5-docosene derivatives; Pentacyclo [6,6,1,1 ^3.6, 0 ^2.7 0 ^9.14] -4-hexadecene 1,3-dimethyl-penta cyclo [6,6,1,1 ^3.6, 0 ^2.7,
0 ^9.14 ] -4-Hexadecene 1,6-dimethyl-penta cyclo [6,6,1,1 ^3.6, 0 ^2.7,
0 ^9.14 ] -4-Hexadecene 15,16-dimethylpentacyclo [6,6,1,1 ^3.6 , 0 ^2.7 , 0
^9.14] -4-hexadecene pentacyclo such [6,6,1,1 ^3.6, 0 ^2.7, 0 ^9.14] -4
-Hexadecene derivatives; Heptacyclo [8,7,0,1 ^2.9, 1 ^4.7, 1 ^11.17, 0 ^3.8, 0
^12.16 ] -5-Icocene Heptacyclo [8,7,0,1 ^2.9 , 1 ^4.7 , 1 ^11.18 , 0 ^3.8 , 0
^12.17 ] heptacyclo-5-icoecene derivatives or heptacyclo-5-heneicosene derivatives such as -5-heneicosene; Tricyclo [4,3,0,1 ^2.5] -3-decene 2-methyl-tricyclo [4,3,0,1 ^2.5] -3-decene 5-methyl - tricyclo [4,3,0,1 ^2.5] -3-tricyclo such decene [4,3,0,1 ^2.5] -3-decene derivatives; Tricyclo [4,4,0,1 ^2.5] -3-undecene 10-methyl - tricyclo [4,4,0,1 ^2.5] -3-tricyclo undecene [4,4,0,1 ^2.5] -3-undecene derivatives; Pentacyclo [6,5,1,1 ^3.6, 0 ^2.7 0 ^9.13] -4-pentadecene 1,3-dimethyl-pentacyclo [6,5,1,1 ^3.6 , 0 ^2.7 , 0
^9.13 ] -4-Pentadecene 1,6-dimethyl-penta cyclo [6,5,1,1 ^3.6, 0 ^2.7,
0 ^9.13 ] -4-Pentadecene 14,15-dimethylpentacyclo [6,5,1,1 ^3.6 , 0 ^2.7 , 0
^9.13] -4-pentadecene pentacyclo such [6,5,1,1 ^3.6, 0 ^2.7, 0 ^9.13] -4
-Pentadecene derivatives; Pentacyclo [6,5,1,1 ^3.6, 0 ^2.7, 0 ^9.13] 4,10 diene compounds such as penta decadiene; Pentacyclo [4,7,0,1 ^2.5, 0 ^8.13, 1 ^9.12] -3-pentadecene Methyl-substituted pentacyclo [4,7,0,1 ^2.5, 0 ^8.13, 1 ^9.12]
-3- pentadecene pentacyclo such [4,7,0,1 ^2.5, 0 ^8.13, 1 ^9.12] -3
-Pentadecene derivatives; Heptacyclo [7,8,0,1 ^3.6 , 0 ^2.7 , 1 ^10.17 , 0 ^11.16 , 1
^12.15 ] -4-Eicosene Dimethyl-substituted heptacyclo [7,8,0,1 ^3.6, 0 ^2.7,
Heptacyclo [7,8,0,1 ^3.6 , 0 ^2.7 , 1 ^10.17 , 0 ^10.17 , 0 ^11.16 , 1 ^12.15 ] -4-eicosene
^11.16 , 1 ^12.15 ] -4-Eicosene derivatives; Nonacyclo [9,10,1,1 ^4.7 , 0 ^3.8 , 0 ^2.10 , 0 ^12.21 , 1
^13.20 , 0 ^14.19 , 1 ^15.18 ] -5-pentacocene Trimethyl-substituted Nonashikuro [9,10,1,1 ^4.7, 0 ^3.8,
0 ^2.10 0 ^12.21, 1 ^13.20, 0 ^14.19, 1 ^15.18] -5-Nonashikuro such as pentacosenoic [9,10,1,1 ^4.7, 0 ^3.8 0 ^2.10,
0 ^12.21 , 1 ^13.20 , 0 ^14.19 , 1 ^15.18 ] -5-pentacocene derivative.

Specific examples of the cyclic olefin represented by the above formula [II] used in the present invention include the following compounds.

5-phenyl-bicyclo [2.2.1] hept-2-ene 5-methyl-5-phenyl-bicyclo [2.2.1] hept-2-ene 5-benzyl-bicyclo [2.2.1] hept-2-ene 5-tolyl-bicyclo [2.2.1] hept-2-ene 5- (ethylphenyl) -bicyclo [2.2.1] hept-
2-ene 5- (isopropylphenyl) -bicyclo [2.2.1] hept-2-ene 1,4-methano-1,4,4a, 9a-tetrahydrofluorene 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene Cyclopentadiene-acenaphthylene adduct 5- (α-naphthyl) -bicyclo [2.2.1] hept-2
−En 5- (acetoracenyl) -bicyclo [2.2.1] hept-
2-ene can be mentioned.

Further, as the polycyclic cyclic olefin represented by the above formula [I], specifically, the above compounds, or 1,4,5,8
-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-1,4,5,8-dimetano-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, 2,3-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-1,2,3,4,4
a, 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-dimetano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-
Isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-
Octahydronaphthalenes such as octahydronaphthalene can be exemplified.

The cyclic olefin represented by the formula [I] is obtained by converting a cyclopentadiene and a corresponding olefin into Diels-
It can be easily produced by Alder reaction.

In the present invention, when ethylene and a cyclic olefin are copolymerized, a catalyst formed from a soluble vanadium compound and an organoaluminum compound is used.

As the vanadium compound, specifically, the general formula VO (O
R) _a X _b or V (OR) _c X _d (where R is a hydrocarbon group, 0 ≦
a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0
≦ d ≦ 4, 3 ≦ c + d ≦ 4) vanadium compounds or their electron donor adducts are used. More specifically, VOCl ₃ , VO (OC ₂ H ₅ ) Cl ₂ , VO (OC ₂ H ₅ ) ₂ Cl, VO (O-iso-C ₃ H ₇ ) Cl ₂ , VO (OnC ₄ H ₉ ) Vanadium compounds such as Cl ₂ , VO (OC ₂ H ₅ ) ₃ , VOBr ₂ , VCl ₄ , VOCl ₂ , VO (OnC ₄ H ₉ ) ₃ and VCl ₃ .2OC ₈ H ₁₇ OH are used.

Further, as the electron donor that may be used when preparing the soluble vanadium catalyst component, alcohol,
Oxygen-containing electron donors such as phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, alkoxysilanes, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates Body and the like. More specifically, the number of carbon atoms such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropyl benzyl alcohol, etc. 18 alcohols having 6 to 6 carbon atoms which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, and naphthol;
20 phenols; ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, and benzoquinone; 15 aldehydes; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, dichlor Ethyl acetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, benzoate Cyclohexyl, phenyl benzoate, benzyl benzoate, methyl toluate,
Ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadic acid, diisosopropyl tetrahydrophthalate, diethyl phthalate, phthalate Carbon number 2 such as diisobutyl acid, di-n-butyl phthalate, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate, etc.
Organic acid esters having up to 30; acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride; methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole Ethers having 2 to 20 carbon atoms such as amide, diphenyl ether; acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide; methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline And amines such as tetramethylenediamine; nitriles such as acetonitrile, benzonitrile and tolunitrile; alkoxysilanes such as ethyl silicate and diphenyldimethoxysilane. Kill. Two or more of these electron donors can be used.

As the organoaluminum compound catalyst component, a compound having at least one Al-carbon bond in the molecule is used. For example, (i) a general formula R ¹ _m Al (OR ² ) _n H _p X _q (where R ¹ and R ² are hydrocarbon groups each having 1 to 15 carbon atoms, preferably 1 to 4, preferably 1 to 4, which may be the same or different, X is a halogen, m is 0 ≦ m ≦ 3, and n is 0 ≦ n <3, p is 0 ≦ n
<3, q is a number satisfying 0 ≦ q <3, and m + n + p
+ Q = 3 a is) an organoaluminum compound represented by, (ii) the general formula M ¹ AlR ¹ ₄ (wherein M ¹ is Li, Na, is K, R
¹ is the same as described above), and a complex alkylated product of a Group 1 metal and aluminum, and the like.

The following can be exemplified as the organoaluminum compound belonging to the above (i).

General formula R ¹ _m Al (OR ² ) _3-m (where R ¹ and R ² are the same as above. M is preferably 1.5
≦ m <3).

General formula R ¹ _m AlX _3-m (where R ¹ is the same as above; X is halogen, m is preferably 0 <m <3).

General formula R ¹ _m AlH _3-m (where R ¹ is the same as above, m is preferably 2 ≦ m <3).

General formula R ¹ _m Al (OR ² ) _n X _q (where R ¹ and R ² are the same as above. X is a halogen, 0 <
m ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3).

As the aluminum compound belonging to (i), more specifically, trialkylaluminum such as triethylaluminum and tributylaluminum, trialkenylaluminum such as triisopropenylaluminum,
In addition to dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide, alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide, the average composition represented by R ¹ _2.5 Al (OR ² ) _0.5 Having partially alkoxylated alkylaluminum, diethylaluminum chloride, dibutylaluminum chloride, dialkylaluminum halides such as diethylaluminum bromide, ethylaluminum sesquichloride, butylaluminum sesquichloride, alkylaluminum sesquibromide such as ethylaluminum sesquibromide , Ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum Partially halogenated alkyl aluminum such as alkyl aluminum dihalide such as minium dibromide, dialkyl aluminum hydride such as diethyl aluminum hydride, dibutyl aluminum hydride, etc.
Partially hydrogenated alkylaluminium, such as alkylaluminum hydrides such as ethylaluminum dihydride, propylaluminum dihydride, partially alkoxylated and halogenated, such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, ethylaluminum ethoxybromide Can be exemplified. Further, a compound similar to (i), for example, an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom may be used. As such a compound, specifically, (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ , (C ₄ H ₅ ) ₂ AlOAl (C ₄ H ₉ ) ₂ , And the like.

Compounds belonging to the above (ii) include LiAl (C ₂ H ₅ ) ₄ , L
iAl (C ₇ H ₁₅ ) _{4 and the} like can be exemplified. Among them, it is particularly preferable to use an alkyl aluminum halide, an alkyl aluminum dihalide or a mixture thereof.

In the present invention, when copolymerizing ethylene and the above-mentioned cyclic olefin, a hydrocarbon solvent can also be used. Such hydrocarbon solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, and kerosene and halogen derivatives thereof; cyclohexane, methylcyclopentane, and alicyclic hydrocarbons such as methylcyclohexane and the like. Halogen derivatives; aromatic hydrocarbons such as benzene, toluene and xylene, and halogen derivatives such as chlorobenzene are used.

In the present invention, ethylene and the cyclic olefin (general formula [I] or [II]) are copolymerized. If necessary, an α-olefin having 3 or more carbon atoms may be copolymerized. Α-olefins having 3 or more carbon atoms include, for example, propylene, 1-butene, 4-methyl,-
Α-olefins having 3 to 20 carbon atoms, such as 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. be able to.

In addition, another copolymerizable unsaturated monomer component can be copolymerized as needed within a range not to impair the object of the present invention. As such a copolymerizable unsaturated monomer, specifically, cyclopentene having less than an equimolar amount to the cyclic olefin component unit in the produced random copolymer,
Cyclohexene, 3-methylcyclohexene, cycloolefin such as cyclooctene, 1,4-hexadiene,
Non-conjugated such as 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene, 2-norbornene, 5-vinyl-2-norbornene Dienes and the like can be exemplified.

In producing a cyclic olefin-based random copolymer, the copolymerization reaction between ethylene and the above pentacyclopentadecenes (general formula [I]) or aromatic-containing cyclic olefins (general formula [II]) It is performed in a continuous manner.

In the present invention, the ratio (C _{0 Al} / C _{1 Al} ) of the concentration of the organic aluminum compound (C _OAl ) supplied into the polymerization tank to the concentration of the organic aluminum compound (C _1Al ) in the polymerization tank is 11 or less, preferably 9 to 9. 1 more preferably a 7 to 1, and the polymerization vanadium compound fed into the tank concentration (C _{0 v),} the ratio of the vanadium compound concentration (C _{1 v)} in a polymerization tank (C _0v / C _1v)
Is set to 3 or less, preferably 2.5 to 1, more preferably 2-1.

The soluble vanadium compound and the organoaluminum compound are usually supplied to a polymerization tank after being diluted with the hydrocarbon solvent or pentacyclopentadecenes or aromatic-containing cyclic olefins, respectively.

In the present invention, the ratio (Al / V) of aluminum atoms to vanadium atoms in the polymerization reaction system is desirably 2 or more, preferably 2 to 50, and particularly preferably 3 to 20.

In producing a cyclic olefin-based random copolymer, the concentration of the soluble vanadium compound in the copolymerization reaction system is usually 0.01 to 5 g atom / l, preferably 0.05 to 3 g atom / l as vanadium atom. l range.

Such a copolymerization reaction of ethylene and a cyclic olefin is carried out at a temperature of -50 to 100C, preferably -30 to 80C, more preferably -20 to 60C.

The reaction time (in the case of a continuous polymerization reaction, the average residence time of the polymerization reaction mixture) for performing the above copolymerization reaction varies depending on the type of the polymerization raw material, the concentration of the catalyst component, and the temperature, but is usually 5 minutes to 5 hours, preferably
The range is from 10 minutes to 3 hours. The pressure at which the copolymerization reaction is carried out is usually more than 0 and 50 kg / cm ² , preferably 0
Over 20 kg / cm ² . In the copolymerization, a molecular weight modifier such as hydrogen may be present in order to adjust the molecular weight of the obtained copolymer.

In producing a cyclic olefin-based random copolymer, the molar ratio of ethylene / cyclic olefin is 85/15 to 15 /
85, more preferably in the range of 40/60 to 85/15.

When a copolymerization reaction of ethylene and a cyclic olefin is performed as described above, a solution of a cyclic olefin-based random copolymer is obtained. The concentration of the cyclic olefin random copolymer contained in such a copolymer solution is usually in the range of 5 to 300 g / l, preferably 10 to 200 g / l.

The copolymer solution thus obtained is treated according to a conventional method to obtain a cyclic olefin-based random copolymer.

In the present invention, as described above, when copolymerizing ethylene with a cyclic olefin, the polymerization the organoaluminum compound supplied into the tank concentration (C _0Al), the organoaluminum compound concentration in the polymerization vessel and (C _1Al) the ratio of the (C _0Al / C _1Al)
11 or less, and the vanadium compound concentration (C _0v ) supplied to the polymerization tank and the vanadium compound concentration (C
_When the ratio (C _0v / C _1v ) to ( _v ) is not more than 3, the content of polyethylene contained in the obtained cyclic olefin random copolymer is reduced, and the transparency of the molded product obtained from the copolymer is reduced. Is improved. In addition, the amount of polyethylene adhering to the polymerization vessel wall and the vicinity of the copolymer outlet during polymerization can be significantly reduced.

In the present specification, polyethylene refers to not only a homopolymer of polyethylene but also a copolymer of ethylene and the above-mentioned cyclic olefin having an ethylene content of 90 mol% or more and having a crystal peak of 50 ° C or more by DSC measurement. Including coalescence.

As the cyclic olefin-based random copolymer thus obtained, a non-crystalline copolymer which does not have a DSC melting point and is measured by X-ray diffraction is preferable. Furthermore, the cyclic olefin-based random copolymer obtained by the method of the present invention usually has a molar ratio of ethylene / cyclic olefin of 95.
/ 5 to 30/70, preferably 90/10 to 40/60, more preferably 85/15 to 40/60. The glass transition point (Tg) of the cyclic olefin-based random copolymer is usually 10 to
240 ° C., preferably in the range of 20 to 200 ° C.

Effects of the Invention According to the present invention, when copolymerizing ethylene and a cyclic olefin, the concentration of the organic aluminum compound (C 0 _Al ) supplied into the polymerization tank and the concentration of the organic aluminum compound (C _1Al ) in the polymerization tank are determined. Ratio (C _{0 Al} / C _1Al ) is 11 or less, and the concentration of vanadium compound (C
And _{0 v),} since the ratio of the vanadium compound concentration in the polymerization vessel (C _{1 v)} the (C _0v / C _1v) and 3 or less, the content of polyethylene contained as an impurity is reduced, and excellent transparency A cyclic olefin-based random copolymer can be produced. Moreover, it is possible to efficiently prevent polyethylene from adhering to the polymerization vessel wall and the vicinity of the polymer outlet.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Diluted Example 1 [Catalyst _{preparation] VO (OC 2 H 5)} Cl 2 with cyclohexane, vanadium concentration was prepared vanadium catalyst is 18.6 mmol / l-cyclohexane. On the other hand, it was diluted with ethyl aluminum sesquichloride _{(Al (C 2 H 5)} 1.5 Cl 1.5) in cyclohexane was prepared organoaluminum catalyst the aluminum concentration is 164 mmol / l-cyclohexane.

[Polymerization] A polymerization vessel with a baffle plate and a stirrer having an inner diameter of 700 mm, a total volume of 570 l, and a reaction volume of 300 l, and a vertical multi-tube cooler having a heat transfer area of 19.4 m ² Withdrawing the polymerization solution from the bottom of the polymerization vessel with a stirrer, circulating the polymerization solution through the multitubular cooler, and returning to the polymerization vessel again, a circulation line,
Using a polymerization apparatus system having a circulation pump provided in a circulation line, ethylene; {Tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] -3-Dedosen} cyclic represented by olefin (hereinafter sometimes simply referred to tetracyclododecene.) And about 1 to butene-1.
The copolymerization reaction was continuously performed so as to contain 2 mol%. At the time of performing this reaction, the vanadium catalyst (V catalyst) prepared by the above-mentioned method is used to bring the V catalyst concentration in the polymerization vessel to 0.
It was fed into the polymerization reactor in such an amount as to give 35 mmol / l. In addition, the V catalyst concentration was adjusted in advance using cyclohexane as a polymerization solvent so that the V catalyst concentration immediately before being supplied to the polymerization reactor was 1.8 times the dilution factor of the catalyst concentration in the polymerization reactor.
The catalyst was diluted and supplied.

On the other hand, ethylaluminum sesquichloride as an organoaluminum compound and Al / V = 8.0 were supplied into the polymerization vessel in such an amount as to be 8.0. Moreover, the solution was diluted with cyclohexane as a polymerization solvent and supplied in advance so that the concentration immediately before being supplied to the polymerization vessel was 11 at a dilution ratio with respect to the concentration in the polymerization vessel. The location where these V catalyst and organoaluminum catalyst are supplied is near the tip of the upper stage blade of a stirrer equipped with two vertical disk turbine blades with a diameter of 0.25 m in two stages, where the stirring is strongest. It was done promptly.

Cyclohexane used as a polymerization solvent was supplied into the polymerization vessel at a rate of 233 kg / h. Ethylene at a rate of 2.69 kg / h,
Hydrogen gas as a molecular weight regulator was supplied to the gas phase in the polymerization reactor at a rate of 2.2 Nl / h. The polymerization liquid was vigorously stirred with a stirrer at a power of 4.4 kw / kL.

The temperature was controlled so that the polymerization temperature became 10 ° C. by circulating 25% by weight methanol water as a refrigerant between the jacket attached to the outside of the polymerization vessel and the shell of the multi-tube condenser. Nitrogen gas was introduced into the polymerization vessel to control the pressure so that the polymerization pressure was 1.0 kg / cm ² G.

The following method was used to clean the inner wall of the polymerization vessel. That is, a saucer (spray disk) having a partly opened hole was attached to the gas phase portion of the shaft connecting the stirrer and the stirring blade. In the spray disk, cyclohexane solvent was added in an amount of 30 kg / h, tetracyclododecene was added in an amount of 14.2 kg / h, and butene-1 was added in an amount of 0.41 kg / h.
While supplying in the amount of Kg / h, the shaft was rotated, and cyclohexane, tetracyclododecene and butene-1 were scattered from the hole of the spray disk by the centrifugal force generated by the rotation of the shaft, and sprayed on the inner wall of the polymerization vessel. . The sprayed tetracyclododecene, cyclohexane and butene-1 were mixed into the liquid phase along the inner wall.

When a copolymerization reaction of ethylene with tetracyclododecene and butene-1 was continuously performed under the above conditions, the concentration of the ethylene / tetracyclododecene / butene-1 copolymer was 4.0 to 4.3% by weight. A cyclohexane solution was obtained.

[Deashing] To a copolymer solution of ethylene and tetracyclododecene extracted from the polymerization vessel, boiler water at 80 ° C. and a NaOH solution having a concentration of 4% by weight as a pH regulator were added, and the copolymerization reaction was performed. At the same time, the catalyst residue remaining in the copolymer solution was removed (deashed) from the copolymer solution.

Once the copolymer solution after demineralization, the inner diameter is 900 mm,
Effective volume is stored in a stirred vessel is 1.0 m ^3, about by flowing cold water to the attached jacket outside the container 30
Cooled to 4040 ° C.

[Filtration] The thus obtained copolymer solution was supplied at a rate of 261 kg / h, nominally 13.5 mm in outer diameter, 28 mm in inner diameter and 1 m in length.
The mixture was supplied to a filter having 34 μm cotton wound filters (vertical type wind filter manufactured by Nippon Roki Co., Ltd.) and continuously filtered.

 Next, nominally 2 μm SUS 3 with an outer diameter of 25 mm and a length of 750 mm
04 layered metal mesh tube filter (Fujif
Filter type fresh plate made by ilter 15 filters)
261 Kg / h to the filter containing
Was.

In addition, nominal 0.3μm SUS with 61mm outer diameter and 510mm length
Using two filters each including three pleated filters made of 304 metal nonwoven fabric (PSP03 filter manufactured by Brunswick), the filters were connected in series, supplied at an amount of 261 kg / h, and continuously filtered.

[Precipitation] Acetone was added to the copolymer solution thus filtered to precipitate a copolymer, and the obtained copolymer was separated.

After extracting unreacted monomers from the obtained cyclic olefin-based random copolymer, the copolymer was separated, dried, pelletized, and dried.

When a cyclic olefin-based random copolymer was produced as described above, clogging of the filter medium was 9 days.

When an optical disc was manufactured from the obtained cyclic olefin-based random copolymer, a reading error considered to be caused by polyethylene contained in the substrate was caused by an optical disc manufactured from the copolymer obtained in Comparative Example 1 described later. Than was able to be reduced considerably.

Comparative Example 1 In Example 1, the same as Example 1 except that the Al catalyst concentration immediately before being supplied to the polymerization reactor was set to 60 times the catalyst concentration in the polymerization reactor, and the stirring power was slightly reduced. I made it.

When the cyclic olefin-based random copolymer was produced as described above, the clogging of the filter medium was 5 days.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C08F 4/60-4/70 C08F 2/00 C08F 10/02 C08F 210/02 C08F 32/00-32 / 08 C08F 232/00-232/08

Claims (1)

(57) [Claims] (1) (a) ethylene, and (b) the following formula [I] or [II] (In the formula, n is 0 or 1, m is 0 or a positive integer, R ^{1 to} R ¹⁸ are each independently a hydrogen atom, a halogen atom or a hydrocarbon group, and R ^{15 to} R ¹⁸ May be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group). [Wherein, l is an integer of 0 or 1 or more, and m and n
Is 0, 1 or 2, and R ^{1 to} R ¹⁵ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, and R ⁵ (or R ⁶ )
R ⁹ (or R ⁷ ) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be directly bonded without any group. And at least one cyclic olefin selected from the group consisting of unsaturated monomers represented by the following formulas, in the presence of a catalyst formed from a soluble vanadium compound and an organoaluminum compound, in a hydrocarbon-based solvent or In producing a cyclic olefin-based random copolymer by copolymerization in a liquid phase composed of a cyclic olefin, the concentration of the organic aluminum compound (C 0 _Al ) supplied to the polymerization tank and the concentration of the organic aluminum compound in the polymerization tank (C _1Al) and the ratio a (C _0Al / C _1Al) 11 or less and a polymerizable vanadium compound fed into the tank concentration (C _{0 v),} the ratio of the vanadium compound concentration (C _{1 v)} in the polymerization vessel (C _0v / C
_1v ) is 3 or less, a process for producing a cyclic olefin-based random copolymer.