JP2006016533A - Method for producing cyclic olefin copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a copolymerization catalyst system industrially more simply synthesizable and having high polymerization activity and high copolymerizability and to provide a method for producing a copolymer of an &alpha;-olefin and a cyclic olefin using the catalyst. <P>SOLUTION: A 2-20C &alpha;-olefin is copolymerized with at least one kind of cyclic olefin in the presence of the polymerization catalyst. Furthermore, the polymerization catalyst is composed of a transition metal compound (A) represented by formula (1) (wherein, M is a group 5 transition metal of the periodic table; X<SP>1</SP>and X<SP>2</SP>are each a hydrogen and a 1-20C alkyl group, an aryl group, an aralkyl group or a halogen; R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>s, R<SP>4</SP>, R<SP>5</SP>and R<SP>6</SP>s are each a hydrogen, a halogen or a 1-20C alkyl group, an aryl group or an aralkyl group; and m and n are each an integer of 0-3) and one or more kinds of activators (B) selected from an organoaluminumoxy compound or an organoboron compound. Thereby, the cyclic olefin copolymer is produced. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

  The present invention relates to a method for producing a copolymer comprising an α-olefin and a cyclic olefin. More specifically, the present invention relates to a method for efficiently producing a cyclic olefin copolymer using a copolymerization catalyst that is easy to synthesize and has high polymerization activity and high copolymerizability.

Since the copolymer of α-olefin and cyclic olefin is excellent in transparency, chemical resistance, water resistance and the like, various production methods have been proposed.
For example, a method using a so-called bridged metallocene catalyst comprising a transition metal complex having a bimolecular cyclopentadienyl skeleton bridged by silicon or a carbon atom and an aluminoxane compound (see, for example, Patent Documents 1 to 4), an amide A method for obtaining a copolymer of an olefin and a cyclic olefin using a crosslinked half-metallocene compound having a structure in which a donor molecule such as a group is crosslinked with a cyclopentadiene skeleton has been proposed (for example, see Patent Document 5). Yes.

All of these production methods use a bridged metallocene catalyst or a bridged half metallocene catalyst, and the synthesis of the transition metal compound used is complicated because there are many synthesis routes of 2 to 5 or more stages. There is a problem that it is difficult.
On the other hand, a method of copolymerizing an α-olefin and a cyclic olefin using a non-crosslinked half metallocene compound and an aluminoxane compound that are easy to synthesize has also been proposed (for example, see Patent Document 6). This is a method using one molecule of a cyclopentadienyl group having 1 to 3 substituents and a half metallocene compound having a hydrocarbon group or a diketonato group and an aluminoxane compound, but the polymerization activity is not sufficient.

In addition, a method for producing cyclic olefins using a transition metal compound used as a catalyst component in the present invention as a polymerization catalyst has also been proposed (see, for example, Patent Document 7), but the polymerization mode is ring-opening metathesis. This is not a method of copolymerizing an α-olefin and a cyclic olefin.
Therefore, development of a method for producing a cyclic olefin copolymer that is easy to synthesize and satisfies both high polymerization activity and high copolymerizability is desired.

Japanese Patent Laid-Open No. 3-45612 JP-A-6-271626 JP-A-6-271627 JP 2000-26518 A JP-A-11-504973 JP 2000-302811 A JP 2002-53647 A

  The present invention provides a method for producing a copolymer of an α-olefin and a cyclic olefin using a copolymerization catalyst that can be synthesized more easily for industrial use and has high polymerization activity and high copolymerizability. Objective.

  The present invention relates to a catalyst comprising one molecule of a ligand containing a specific aromatic amide skeleton, which is easy to synthesize, a transition metal compound in which at least one allyloxy group is coordinated to a metal, and an activator. -It has been made on the basis of the surprising fact that it has high polymerization activity and extremely excellent copolymerizability for copolymerization of olefin and cyclic olefin.

  That is, the present invention provides a copolymerization catalyst comprising a transition metal compound (A) represented by the following formula (1) and one or more activators (B) selected from organic aluminum oxy compounds or organic boron compounds. The present invention also relates to a method for producing a cyclic olefin copolymer, which comprises copolymerizing an α-olefin having 2 to 20 carbon atoms and at least one cyclic olefin. The cyclic olefin referred to here is represented by the following general formula (2).

(In the formula, M represents a transition metal of Group 5 of the periodic table. X ¹ and X ² may be the same or different, and each represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, or a halogen. R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different and each represents hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group. Any two or three may combine to form a ring, including rings having aromaticity including a conjugated double bond, and m and n are integers of 0 to 3. .)

(In the formula, R ^{7 to} R ¹⁸ may each independently be the same or different, and represent a hydrogen atom, a halogen atom, a hydrocarbon group optionally substituted with a halogen, a substituent containing oxygen, or a nitrogen atom. R ^{15 to} R ¹⁸ may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and R ¹⁵ And R ¹⁶ may form an alkylidene group, and n represents an integer of 0 to 2.)

  Furthermore, the present invention provides the transition metal compound represented by the general formula (1), wherein the transition metal represented by M is vanadium, and is represented by the α-olefin having 1 to 20 carbon atoms and the general formula (2). The present invention relates to a method for producing a copolymer with a cyclic olefin.

  INDUSTRIAL APPLICABILITY According to the present invention, a copolymerization catalyst that can be synthesized more easily for industrial use and has high polymerization activity and high copolymerizability, and more efficient α-olefin and cyclic olefin using the copolymerization catalyst. A method for producing a copolymer can be provided.

Hereinafter, the manufacturing method of the cyclic olefin copolymer in connection with this invention is demonstrated in detail.
The transition metal compound (A) of the copolymerization catalyst of α-olefin and cyclic olefin of the present invention is represented by the above formula (1). In the formula, M represents a transition metal of Group 5 of the periodic table. Vanadium is preferred. X ¹ and X ² may be the same or different and each represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group or a halogen. R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different and each represents hydrogen, halogen or an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group, Two or three may combine to form a ring. The ring includes those having aromaticity including a conjugated double bond. Preferably it consists of hydrogen or a C1-C20 alkyl group. m and n are integers of 0-3.

Specific examples of the alkyl group, aryl group, and alkyl, aryl, and aralkyl groups of X ¹ , X ² and R ^{1 to} R ⁶ in the formula (1) include methyl, ethyl, propyl, isopropyl, n- Butyl, isobutyl, t-butyl, sec-butyl, n-pentyl, isopentyl, 1-methylbutyl, 2-methylbutyl, 1,2-dimethylpropyl, neopentyl, n-hexyl, isohexyl, 1-methylpentyl, 2-methylpentyl , 3-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,

  1,1-ethylmethylpropyl, 1-ethylbutyl, 2-ethylbutyl, cyclohexyl, n-heptyl, isoheptyl, 4-methylhexyl, 3-methylhexyl, 2-methylhexyl, 1-methylhexyl, 1,1-dimethylpentyl 2,2-dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 1-ethylpentyl, 1- Propylbutyl, 2-ethylpentyl, 3-ethylpentyl, 1,1-ethylmethylbutyl, 1,1-diethylpropyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,4-dimethylpentyl,

  1-ethyl-2-methylbutyl, 1-ethyl-3-methylbutyl, 4-methylcyclohexyl, 3-methylcyclohexyl, cycloheptyl, 1,1,2-trimethylbutyl, 1,1,3-trimethylbutyl, 2,2 , 1-trimethylbutyl, 2,2,3-tylmethylbutyl, 3,3,1-trimethylbutyl, 3,3,2-trimethylbutyl, 1,1,2,2-tetramethylpropyl, n-octyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, isooctyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 1,1-dimethylhexyl, 2,2-dimethylhexyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 5,5- Methyl-hexyl,

  1,2-dimethylhexyl, 1,3-dimethylhexyl, 1,4-dimethylhexyl, 1,5-dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 3,4-dimethylhexyl, 2,5-dimethylhexyl, 3,5-dimethylhexyl, 1,1-methylethylpentyl, 1-ethyl-2-methylpentyl, 1-ethyl-3-methylpentyl, 1-ethyl-4-methylpentyl, 2 -Ethyl-1-methylpentyl, 2,2-ethylmethylpentyl, 3,3-ethylmethylpentyl, 2-ethyl-3-methylpentyl, 2-ethyl-4-methylpentyl, 3-ethyl-4-methylpentyl 3-ethyl-2-methylpentyl,

  1,1-diethylbutyl, 2,2-diethylbutyl, 1,2-diethylbutyl, 1,1-methylpropylbutyl, 2-methyl-1-propylbutyl, 3methyl-1-propylbutyl, 4-ethylcyclohexyl , 3-ethylcyclohexyl, 3,4-dimethylcyclohexyl, 1,1,2-trimethylpentyl, 1,1,3-trimethylpentyl, 1,1,4-trimethylpentyl, 2,2,1-trimethylpentyl, 2 , 2,3-trimethylpentyl, 2,2,4-trimethylpentyl, 3,3,1-trimethylpentyl, 3,3,2-trimethylpentyl, 3,3,4-trimethylpentyl, 1,2,3- Trimethylpentyl, 1,2,4-trimethylpentyl, 1,3,4-trimethylpentyl, 1,2,3-trimethylpentyl, 1 2,4-trimethylpentyl, 1,3,4-trimethylpentyl,

  1,1,2,2-tetramethylbutyl, 1,1,3,3-tetramethylbutyl, 1,1,2,3-tetramethylbutyl, 2,2,1,3-tetramethylbutyl, 1- Ethyl-1,2-dimethylbutyl, 2-ethyl-1,2-dimethylbutyl, 1-ethyl-2,3-dimethylbutyl, n-nonyl, isononyl, 1-methyloctyl, 2-methyloctyl, 3-methyl Octyl, 4-methyloctyl, 5-methyloctyl, 6-methyloctyl, 1-ethylheptyl, 2-ethylheptyl, 3-ethylheptyl, 4-ethylheptyl, 5-ethylheptyl,

  1,1-dimethylheptyl, 2,2-dimethylheptyl, 3,3-dimethylheptyl, 4,4-dimethylheptyl, 5,5-dimethylheptyl, 6,6-dimethylheptyl, 2-dimethylheptyl, 1,3 -Dimethylheptyl, 1,4-dimethylheptyl, 1,5-dimethylheptyl, 1,6-dimethylheptyl, 2,3-dimethylheptyl, 2,4-dimethylheptyl, 2,5-dimethylheptyl, 2,6- Dimethylheptyl, 3,4-dimethylheptyl, 3,5-dimethylheptyl, 3,6-dimethylheptyl, 4,5-dimethylheptyl, 4,6-dimethylheptyl, 5,6-dimethylheptyl,

  1,1,2-trimethylhexyl, 1,1,3-trimethylhexyl, 1,1,4-trimethylhexyl, 1,1,5-trimethylhexyl, 2,2,1-trimethylhexyl, 2,2,3 -Trimethylhexyl, 2,2,4-trimethylhexyl, 2,2,5-trimethylhexyl, 3,3,1-trimethylhexyl, 3,3,2-trimethylhexyl, 3,3,4-trimethylhexyl, 3, , 3,5-trimethylhexyl, 4,4,1-trimethylhexyl, 4,4,2-trimethylhexyl, 4,4,3-trimethylhexyl, 4,4,5-trimethylhexyl, 5,5,1- Trimethylhexyl, 5,5,2-trimethylhexyl, 5,5,3-trimethylhexyl, 5,5,4-trimethylhexyl,

  1,2,3-trimethylhexyl, 2,3,4-trimethylhexyl, 3,4,5-trimethylhexyl, 1,3,4-trimethylhexyl, 1,4,5-trimethylhexyl, 2,4,5 -Trimethylhexyl, 1,2,5-trimethylhexyl, 1,2,4-trimethylhexyl, 1,1-ethylmethylhexyl, 2,2-ethylmethylhexyl, 3,3-ethylmethylhexyl, 4,4- Ethylmethylhexyl, 5,5-ethylmethylhexyl, 1-ethyl-2-methylhexyl, 1-ethyl-3-methylhexyl, 1-ethyl-4-methylhexyl, 1-ethyl-5-methylhexyl, 2- Ethyl-1-methylhexyl, 3-ethyl-1-methylhexyl, 3-ethyl-2-methylhexyl, 1,1-diethylpentyl, 2,2-di Chirupenchiru, 3,3-diethyl-pentyl,

  1,2-diethylpentyl, 1,3-diethylpentyl, 2,3-diethylpentyl, 1,1-methylpropylpentyl, 2,2-methylpropylpentyl, 1-methyl-2-propylpentyl, n-decyl, Isodecyl, 1-methylnonyl, 2-methylnonyl, 3-methylnonyl, 4-methylnonyl, 5-methylnonyl, 6-methylnonyl, 7-methylnonyl, 1-ethyloctyl, 2-ethyloctyl, 3-ethyloctyl, 4-ethyloctyl, 5-ethyloctyl, 6-ethyloctyl, 1,1-dimethyloctyl, 2,2-dimethyloctyl, 3,3-dimethyloctyl, 4,4-dimethyloctyl, 5,5-dimethyloctyl, 6,6-dimethyl Octyl, 7,7-dimethyloctyl,

  1,2-dimethyloctyl, 1,3-dimethyloctyl, 1,4-dimethyloctyl, 1,5-dimethyloctyl, 1,6-dimethyloctyl, 1,7-dimethyloctyl, 2,3-dimethyloctyl, 2 , 4-dimethyloctyl, 2,5-dimethyloctyl, 2,6-dimethyloctyl, 2,7-dimethyloctyl, 3,4-dimethyloctyl, 3,5-dimethyloctyl, 3,6-dimethyloctyl, 3, 7-dimethyloctyl, 4,5-dimethyloctyl, 4,6-dimethyloctyl, 4,7-dimethyloctyl, 5,6-dimethyloctyl, 5,7-dimethyloctyl,

  n-undecyl, n-dodecyl, phenyl, benzyl, p-tolyl, m-tolyl, xylyl, mesityl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,4 , 6-trimethoxyphenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, naphthyl, 2-methoxyphenyl, 2-isopropoxyphenyl, 2-tert-butoxyphenyl, 2,6-ditertiary Butylphenyl, 2-methylphenyl, 2-isopropylphenyl, 2-tertiarybutylphenyl, 2-methyl-6-isopropylphenyl, 2-methyl-6-tertiarybutylphenyl, benzyl,

  (2-methylphenyl) methyl, (3-methylphenyl) methyl, (4-methylphenyl) methyl, (2,3-dimethylphenyl) methyl, (2,4-dimethylphenyl) methyl, (2,5-dimethyl) Phenyl) methyl, (2,6-dimethylphenyl) methyl, (3,4-dimethylphenyl) methyl, (3,5-dimethylphenyl) methyl, (2,3,4-trimethylphenyl) methyl, (2,3 , 5-trimethylphenyl) methyl, (2,3,6-trimethylphenyl) methyl, (2,4,5-trimethylphenyl) methyl, (2,4,6-trimethylphenyl) methyl, (3,4,5) -Trimethylphenyl) methyl, (2,3,4,5-tetramethylphenyl) methyl, (2,3,5,6-tetramethylphenyl) methyl, (pentamethyl) Phenyl) methyl, naphthylmethyl, etc. anthracenylmethyl the like

  In these hydrocarbon groups, a hydrogen atom may be optionally substituted with a halogen atom. Examples of the hydrocarbon group substituted with a halogen atom include trichloromethyl, trifluoromethyl, dichloromethyl, chloromethyl, o-chlorophenyl, pentafluorophenyl and the like. These may be used alone or in combination.

As a specific metal complex represented by the formula (1), for example, V (N-2,6-Me ₂ C ₆ H ₃ ) (O-2,6-Me ₂ C ₆ H ₃ ) Cl ₂ , ^{_{V (N-2,6-Me 2}} C 6 H 3) (O-2,6- i Pr 2 C 6 H 3) Cl 2, V (N-2,6-Me 2 C 6 H 3) (O _{-2,6-Ph 2 C 6 H 3} ) Cl 2 and _{V (N-2,6-Me 2} C 6 H 3) (O-2,6-t-Bu 2 -4-Me-C 6 H 3 ) Cl _{2 and the} like can be exemplified. These may be used alone or in combination.

  Examples of the organoaluminum oxy compound that can be used in the present invention include at least one compound among the organoaluminum oxy compounds represented by the following general formulas (3), (4), (5), and (6).

(In formula, R < ¹⁹ > -R < ²¹ > may be same or different, respectively, and a C1-C8 hydrocarbon group, n represents the integer of 1-50.)

(In formula, R < ²² > -R < ²⁴ > may be same or different, respectively, C1-C8 hydrocarbon group, n represents the integer of 1-50.)

(In the formula, R ²⁵ represents a hydrocarbon group having 1 to 8 carbon atoms, and n represents an integer of 1 to 50.)

(In formula, R < ²⁶ > -R < ²⁹ > may be same or different, respectively, C1-C8 hydrocarbon group, n represents the integer of 1-50.)

Specific examples of these organoaluminum oxy compounds include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, methylisobutylaluminoxane and the like. In particular, methylaluminoxane, isobutylaluminoxane, and methylisobutylaluminoxane can be preferably used. Two or more of these may be used in combination.
These organoaluminum oxy compounds may contain organoaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum.

Moreover, as an organic boron compound which can be used by this invention, at least 1 compound is mention | raise | lifted among the organic boron compounds shown by the following general formula (7) or (8).
(BR ³⁰ R ³¹ R ³² ) n (7)
(In the formula, R ^{30 to} R ³² may be the same or different and each represents a hydrocarbon group including a halogenated aryl group having 1 to 14 carbon atoms or a halogenated allyloxy group, and n represents an integer of 1 to 4. .)
^{Q (BR 33 R 34 R 35} R 36) n ··· (8)
(In the formula, Q is a quaternary amine, a quaternary ammonium salt, a carbocation, or a metal cation having a valence of +1 to +4, and R ^{33 to} R ³⁶ may be the same as or different from each other. A hydrocarbon group containing a halogenated aryl group or a halogenated allyloxy group, n represents an integer of 1 to 4.)

  Specific examples of the hydrocarbon groups of the general formulas (7) and (8) include phenyl, benzyl, p-tolyl, m-tolyl, xylyl, mesityl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl. 2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, naphthyl, o-isopropoxyphenyl, pentafluorophenyl, pentafluorobenzyl , Tetrafluorophenyl, tetrafluorotolyl and the like.

Specific examples of Q in the general formula (8) include pyridinium, 2,4-dinitro-N, N-diethylanilinium, p-nitroanilinium, 2,5-dichloroaniline, p-nitro-N, N-dimethylanilinium, quinolinium, N, N-dimethylanilinium, methyldiphenylammonium, N, N-diethylanilinium, 8-chloroquinolinium, trimethylammonium, tripropylammonium, triethylammonium, tributylammonium, triphenyl Examples include phosphonium, ammonium, triphenylmethyl, sodium, lithium, potassium, cesium, calcium, magnesium and the like.
Specific examples of these organic boron compounds include trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl). ) Borate and the like. Two or more of these may be used in combination. Most preferred is triphenylcarbenium tetrakis (pentafluorophenyl) borate.

Suitable catalysts for use in the present invention are (A) transition metal compounds and (B) one or more activators selected from alkylaluminumoxy compounds or organoboron compounds in any order and in any suitable process. Manufactured by combining with.
The catalyst composition ratio (molar ratio) between the component (A) and the component (B) is preferably (A) :( B) = 1: 0.01 to 1: 10000, more preferably 1: 100 to 1. : 3000.

  The catalyst may be prepared in advance by mixing it in a suitable solvent under an inert gas atmosphere such as nitrogen or argon, or in a reactor in which each component (A) and (B) is separately present in the monomer. And may be prepared in the reactor. Suitable solvents for preparing the catalyst include hydrocarbon solvents such as alkanes such as hexane and cyclohexane, and aromatic solvents such as toluene, benzene and ethylbenzene. Moreover, it is preferable to remove water and the like from these solvents in the pretreatment. The optimum catalyst preparation temperature is -20 ° C to 150 ° C.

  Examples of the α-olefin having 2 to 20 carbon atoms that can be used in the present invention include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene and the like. Can give.

  Moreover, as a cyclic olefin which can be used by this invention, it can represent with following General formula (2).

(In the formula, R ^{7 to} R ¹⁸ may each independently be the same or different, and represent a hydrogen atom, a halogen atom, a hydrocarbon group optionally substituted with a halogen, a substituent containing oxygen, or a nitrogen atom. R ^{15 to} R ¹⁸ may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and R ¹⁵ And R ¹⁶ may form an alkylidene group, and n represents an integer of 0 to 2.)

  Specific examples of the halogen atom of the general formula (2) and the hydrocarbon group which may be substituted with halogen include, for example, halogen groups such as fluorine, chlorine, bromine and iodine, chloromethyl group, bromomethyl group, and chloroethyl. Examples thereof include a halogen-substituted alkyl group having 1 to 20 carbon atoms such as a group and a halogen-unsubstituted alkyl group having 1 to 20 carbon atoms.

  Specific examples of the oxygen-containing substituent of the general formula (2) include alkoxy groups having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a phenoxy group, a methoxycarbonyl group, and an ethoxycarbonyl group. And an alkoxycarbonyl group having 1 to 20 carbon atoms.

  Furthermore, specific examples of the substituent containing a nitrogen atom in the general formula (2) include a C1-C20 alkylamino group such as a dimethylamino group and a diethylamino group, a cyano group, and the like. .

Specific examples of the cyclic olefin represented by the general formula (2) include bicyclo [2.2.1] hept-2-ene (hereinafter referred to as norbornene), 5-methylnorbornene, 5-ethylnorbornene, 5- Propyl norbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidenenorbornene, 5-vinylnorbornene, 5 -Chloronorbornene, 5-cyanonorbornene, 5-fluoronorbornene, 5,5-dichloronorbornene, 5,5,6-trifluoronorbornene, 5-methoxynorbornene, 5-dimethylaminonorbornene, 5,5,6-trifluoro -6-methylnorbornene Tricyclo ^[4.3.0.1 2.5] -3- decene, tricyclo ^[4.4.0.1 2.5] -3- undecene, tetracyclo [4.4.0.1 ^2.5. 1 ^7.10 ] -3-dodecene, 8-methyltetracyclo [4.4.0.1 ^2.5 . 1 ^7.10 ] -3-dodecene, 8-ethyltetracyclo [4.4.0.1 ^2.5 . 1 ^7.10 ] -3-dodecene, 8-propyltetracyclo [4.4.0.1 ^2.5 . 1 ^7.10 ] -3-dodecene, 8-butyltetracyclo [4.4.0.1 ^2.5 . 1 ^7.10 ] -3-dodecene, 8-isobutyltetracyclo [4.4.0.1 ^2.5 . 1 ^7.10 ] -3-dodecene, 8-ethylidenetetracyclo [4.4.0.1 ^2.5 . 1 ^7.10 ] -3-dodecene, 8-chlorotetracyclo [4.4.0.1 ^2.5 . 1 ^7.10 ] -3-dodecene, 8-cyanotetracyclo [4.4.0.1 ^2.5 . 1 ^7.10 ] -3-dodecene, 8-fluorotetracyclo [4.4.0.1 ^2.5 . 1 ^7.10 ] -3-dodecene, 8,8-dichlorotetracyclo [4.4.0.1 ^2.5 . 1 ^7.10 ] -3-dodecene, 8-methoxytetracyclo [4.4.0.1 ^2.5 . 1 ^7.10 ] -3-dodecene, 8-dimethylaminotetracyclo [4.4.0.1 ^2.5 . 1 ^7.10 ] -3-dodecene, 8,8,9-trifluorotetracyclo [4.4.0.1 ^2.5 . 1 ^7.10 ] -3-dodecene, 8,8,9-trifluoro-9-methyltetracyclo [4.4.0.1 ^2.5 . 1 ^7.10 ] -3-dodecene, pentacyclo [6.5.1.1 ^3.6 . 0 ^2.7 . 0 ^9.13 ] -4-pentadecene, pentacyclo [6.6.1.1 ^3.6 . 0 ^2.7 . 0 ^9.14 ] -4-hexadecene, hexacyclo [6.6.1.1 ^3.6 . 1 ^10.13 . 0 ^2.7 . 0 ^9.14 ] -4-heptadecene and the like. These cyclic olefins can be used alone or in combination of two or more. Among these cyclic olefins, norbornene, tricyclo [4.3.0.1 ^2.5 ] -3-decene, tricyclo [4.4.0.1 ^2.5 ] -3-undecene, tetracyclo [4. 4.0.1 ^2.5 . 1 ^7.10 ] -3-dodecene is preferred, and norbornene is particularly preferred.

The copolymerization method of the present invention can be carried out in any of bulk, solution, and slurry under the conditions of reduced pressure, atmospheric pressure, and increased pressure in the presence of monomers and a catalyst.
The temperature range suitable for carrying out the copolymerization is -30 ° C to 260 ° C, preferably 0 ° C to 200 ° C. The copolymerization may be performed in an inert gas atmosphere such as nitrogen or argon, or may be performed in an ethylene atmosphere, or a mixture of ethylene and / or α-olefins and the above inert gas. You can go under the atmosphere. Furthermore, hydrogen may be coexisted in addition to the above gas for molecular weight adjustment. Further, the catalyst component may be used by being supported on a suitable carrier such as alumina, magnesium chloride, or silica. If desired, a solvent can be used in the copolymerization. Suitable solvents for copolymerization include hydrocarbon solvents such as alkanes such as hexane and cyclohexane, and aromatic solvents such as toluene, benzene, and ethylbenzene.

A suitable amount of catalyst in the copolymerization is an amount giving [(product polymer weight) kg] / [catalyst (A) component 1 mol] = 10 kg / 1 mol to 1000000 kg / 1 mol of polymer. As a method for separating a polymer after copolymerization in the present invention, for example, a method of adding a polar solvent that becomes a poor solvent such as acetone or an alcohol mixed with an acid or an alkali to the copolymer solution to precipitate and recover the copolymer, Examples thereof include a method in which the reaction liquid is stirred into hot water and then distilled and recovered together with the solvent, or a method in which the solvent is distilled off by directly heating the reaction liquid.
In the method for producing a cyclic olefin copolymer of the present invention, each of the α-olefin monomer unit and the cyclic olefin monomer unit may be composed of two or more kinds of components, and is a ternary or quaternary copolymer. Is also possible.

  In the method for producing a cyclic olefin copolymer of the present invention, in addition to the above monomers, a cyclic olefin such as cyclohexene and cyclopentene, and an aromatic vinyl compound such as styrene can be copolymerized as a copolymerization monomer as necessary. It is.

  In the method for producing a cyclic olefin copolymer of the present invention, the composition in the cyclic olefin copolymer can be copolymerized in the range of 99 to 1 mol% of cyclic olefins to 1 to 99 mol% of α-olefins. Preferably it is 90-25 mol% of cyclic olefins with respect to 10-75 mol% of α-olefins.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
First, the measurement method will be described.
(1) Polymerization activity The polymerization activity was determined from the amount of polymer obtained after completion of the polymerization.
(2) Comonomer content in polymer The comonomer content in the polymer was determined by using ¹³ C-NMR spectrum according to Macromolecules, 33,8931 (2000).
(3) NMR measurement NMR measurement was carried out in a d ₆ -benzene / 1,2,4-trichlorobenzene (1/1 vol ratio) solution.
(4) Glass transition temperature (Tg) of polymer
The glass transition temperature (Tg) of the polymer was measured using a differential scanning calorimeter (DSC) at a temperature increase rate of 20 ° C./min in a nitrogen atmosphere.
(5) Molecular weight of polymer The molecular weight of the polymer was determined by the GPC method at 140 ° C. using o-dichlorobenzene as a measurement solvent by RI and calculated in terms of polystyrene.

[Production Example 1]
Synthesis example of V (N-2,6-Me ₂ C ₆ H ₃ ) (O-2,6-Me ₂ C ₆ H ₃ ) Cl ₂ (hereinafter, the metal complex is referred to as [metal complex-1])
2,6-Dimethylphenol (10.85 mmol) at −30 ° C. in a hexane solution (30 ml) containing V (N-2,6-Me ₂ C ₆ H ₃ ) Cl ₃ (3.0 g, 10.85 mmol). , 1.0 M dimethyl ether solution) was added dropwise over 15 minutes. The resulting reaction solution was slowly raised to room temperature while stirring and stirred overnight. The reaction solution was filtered, concentrated, and then recrystallized from hexane at −30 ° C. to obtain the target complex in a yield of 60%.
¹ H-NMR (CDCl ₃ ): δ 2.24 (s, 6H), 2.38 (s, 6H), 6.84 (m, 3H), 6.92 (m, 1H), 7.02 (m , 2H)
¹³ C-NMR (CDCl ₃ ): δ 16.9, 18.2, 125.5, 125.8, 127.4, 128.5, 129.7, 139.2, 168.8

[Production Example 2]
Synthesis example of V (CH ₂ Ph) ₂ (N-2,6-Me ₂ C ₆ H ₃ ) (O-2,6- ⁱ Pr ₂ C ₆ H ₃ ) 2])
2,6-Diisopropylphenol at −30 ° C. in a dichloromethane solution (25 ml) containing V (CH ₂ Ph) ₃ (N-2,6-Me ₂ C ₆ H ₃ ) (1.0 g, 2.25 mmol). A dichloromethane solution (5 ml) containing (402 mg, 2.25 mmol) was slowly added dropwise. The reaction solution was allowed to rise to room temperature while stirring, and further stirred for 40 hours, and the resulting reaction solution was concentrated. The target complex was obtained in a yield of 75% by recrystallizing the obtained solid using hexane.
¹ H-NMR (CDCl ₃ ): 1.32 (d, 12H), 2.97 (d, 10H), 3.20 (m, 2H), 7.23 (m, 16H)
¹³ C-NMR (CDCl ₃ ): 22.7, 27.1, 37.8, 37.9, 77.2, 120.6, 123.4, 125.9, 128.3, 128.4, 133 .6, 141.8, 150.0

[Example 1]
The inside was vacuum degassed and nitrogen-substituted 100 ml autoclave was used as white solid MAO (methylaluminoxane) (5 mmol in terms of Al, manufactured by Tosoh Akzo Co., Ltd .: PMAO-S with the solvent toluene and AlMe ₃ removed under vacuum. .) Was introduced. Next, 30 ml of a toluene solution of norbornene (concentration: 0.05 mol / l) distilled over Na and dehydrated and deoxygenated was charged. The internal temperature of the autoclave was kept at room temperature, and 2 ml of a toluene solution containing 0.5 μmol of [Metal Complex-1] was added to the autoclave. Immediately 0.8 MPa of ethylene gas was introduced to initiate the polymerization reaction. Polymerization was carried out for 10 minutes while maintaining the internal temperature and ethylene pressure of the autoclave. After completion of the polymerization, the content of the autoclave was transferred into a large amount of hydrochloric acid-methanol to precipitate a polymer.
Copolymerization activity = 3010 kg / mol · V · h.
From the GPC measurement, it was Mn = 7.6 × 10 ⁵ (Mw / Mn = 1.97).
It was Tg = -2.0 degreeC from DSC measurement.
^{From 13} C-NMR, the norbornene content in the copolymer was estimated to be 8.9 mol%.

[Example 2]
The inside was vacuum degassed and nitrogen-substituted 100 ml autoclave was used as white solid MAO (methylaluminoxane) (5 mmol in terms of Al, manufactured by Tosoh Akzo Co., Ltd .: PMAO-S with the solvent toluene and AlMe ₃ removed under vacuum. .) Was introduced. Next, 30 ml of a toluene solution (concentration: 0.1 mol / l) of norbornene distilled over Na and dehydrated and deoxygenated was charged. The internal temperature of the autoclave was kept at room temperature, and 2 ml of a toluene solution containing 0.5 μmol of [Metal Complex-1] was added to the autoclave. Immediately 0.8 MPa of ethylene gas was introduced to initiate the polymerization reaction. Polymerization was carried out for 10 minutes while maintaining the internal temperature and ethylene pressure of the autoclave. After completion of the polymerization, the content of the autoclave was transferred into a large amount of hydrochloric acid-methanol to precipitate a polymer.
Copolymerization activity = 2491 kg / mol · V · h.
From the GPC measurement, it was Mn = 6.4 × 10 ⁵ (Mw / Mn = 1.97).
From DSC measurement, it was Tg = 10.8 degreeC.
^{From 13} C-NMR, the norbornene content in the copolymer was estimated to be 13.2 mol%.

[Example 3]
The inside was vacuum degassed and nitrogen-substituted 100 ml autoclave was used as white solid MAO (methylaluminoxane) (5 mmol in terms of Al, manufactured by Tosoh Akzo Co., Ltd .: PMAO-S with the solvent toluene and AlMe ₃ removed under vacuum. .) Was introduced. Next, 30 ml of a norbornene toluene solution (concentration: 0.5 mol / l) distilled over Na and dehydrated and deoxygenated was charged. The internal temperature of the autoclave was kept at room temperature, and 2 ml of a toluene solution containing 2.5 μmol of [Metal Complex-1] was added to the autoclave. Immediately 0.8 MPa of ethylene gas was introduced to initiate the polymerization reaction. Polymerization was carried out for 10 minutes while maintaining the internal temperature and ethylene pressure of the autoclave. After completion of the polymerization, the content of the autoclave was transferred into a large amount of hydrochloric acid-methanol to precipitate a polymer.
Copolymerization activity = 367 kg / mol · V · h.
From the GPC measurement, it was Mn = 1.1 × 10 ⁵ (Mw / Mn = 1.85).
It was Tg = 69.3 degreeC from DSC measurement.
^{From 13} C-NMR, the norbornene content in the copolymer was estimated to be 32.9 mol%.

[Example 4]
The inside was vacuum degassed, and 30 ml of a toluene solution of norbornene (concentration: 0.1 mol / l) distilled and deoxygenated over Na in a 100 ml autoclave purged with nitrogen was charged. While maintaining the temperature constant in an ice bath of an autoclave, 0.25 ml of Et ₂ AlCl in n-hexane (Wako Pure Chemical Industries, concentration: 1 mol / l) was added, and then [Metal Complex-1] 2 ml of toluene solution containing 1.0 μmol of was added to the autoclave. Immediately 0.8 MPa of ethylene gas was introduced to initiate the polymerization reaction. Polymerization was carried out for 10 minutes while maintaining the internal temperature and ethylene pressure of the autoclave. After completion of the polymerization, the content of the autoclave was transferred into a large amount of hydrochloric acid-methanol to precipitate a polymer.
Copolymerization activity = 2308 kg / mol · V · h.
From the GPC measurement, it was Mn = 9.0 × 10 ⁵ (Mw / Mn = 1.80).
It was Tg = 0.0 degreeC from DSC measurement.
^{From 13} C-NMR, the norbornene content in the copolymer was estimated to be 9.6 mol%.

[Example 5]
The inside was vacuum degassed, and 30 ml of a toluene solution of norbornene (concentration: 0.1 mol / l) distilled and deoxygenated over Na in a 100 ml autoclave purged with nitrogen was charged. While keeping the temperature constant in an ice bath of an autoclave, 2 ml of a toluene solution containing 1.0 μmol: 1.2 μmol of [Metal Complex-2] and [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] Was added to the autoclave. Immediately 0.8 MPa of ethylene gas was introduced to initiate the polymerization reaction. Polymerization was carried out for 10 minutes while maintaining the internal temperature and ethylene pressure of the autoclave. After completion of the polymerization, the content of the autoclave was transferred into a large amount of hydrochloric acid-methanol to precipitate a polymer.
Copolymerization activity = 300 kg / mol · V · h.

  Although the present invention has been described in connection with the preferred embodiments, it should be understood that modifications and changes can be made without departing from the principles and scope of the invention as will be readily appreciated by those skilled in the art. And the modifications can be implemented within the scope of the present invention.

  According to the method of the present invention, it has become possible to industrially efficiently produce a novel cyclic olefin copolymer excellent in transparency and thermal stability.

Claims (3)

In the presence of a polymerization catalyst comprising a transition metal compound (A) represented by the following formula (1) and one or more activators (B) selected from organic aluminum oxy compounds or organic boron compounds, the number of carbon atoms is 2 to 20 A method for producing a cyclic olefin copolymer, comprising copolymerizing the α-olefin and at least one cyclic olefin.

(In the formula, M represents a transition metal of Group 5 of the periodic table. X ¹ and X ² may be the same or different, and each represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, or a halogen. R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different and each represents hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group. Any two or three may combine to form a ring, including rings having aromaticity including a conjugated double bond, and m and n are integers of 0 to 3. .) The method for producing a cyclic olefin copolymer according to claim 1, wherein the cyclic olefin is represented by the following general formula (2).

(In the formula, R ^{7 to} R ¹⁸ may each independently be the same or different, and represent a hydrogen atom, a halogen atom, a hydrocarbon group optionally substituted with a halogen, a substituent containing oxygen, or a nitrogen atom. R ^{15 to} R ¹⁸ may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and R ¹⁵ And R ¹⁶ may form an alkylidene group, and n represents an integer of 0 to 2.)   The process for producing a cyclic olefin copolymer according to claim 1 or 2, wherein M is vanadium in the transition metal compound (A) represented by the general formula (1).