JP2009035746A - Norbornene-based addition copolymer having unsaturated bond - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a norbornene-based addition copolymer obtained by copolymerizing (a) a norbornene-based monomer having a carbon-carbon unsaturated bond in addition to a norbornene ring. <P>SOLUTION: The norbornene-based addition copolymer including an unsaturated bond is obtained by addition copolymerizing (a) a norbornene-based monomer having a carbon-carbon unsaturated bond in addition to a norbornene ring and (b) a norbornene-based monomer having no carbon-carbon unsaturated bond in addition to a norbornene ring with the use of a polymerization catalyst composed of (A) a compound of a group 10 transition metal in the periodic table having an alkyl group or an aryl group and a neutral electron donative monodentate ligand and (B) a Lewis acid, in which the norbornene-based addition copolymer has 20-95 mol% repeating units content derived from monomers (a) and has a number average molecular weight of 16,800-1,000,000 when measured by the gel permeation chromatography in terms of polystyrene. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention, carbon in addition to the norbornene ring - about the norbornene addition copolymer obtained by addition copolymerization of norbornene-based monomer having a carbon unsaturated bond (a).

Norbornene-based addition polymers are excellent in heat resistance, low water absorption, and electrical properties, and have recently been attracting attention as polymer materials for use in electrical and electronic parts, but have the problem of low adhesion to metals and other materials. there were. As a method for imparting adhesion, a norbornene-based monomer having a carbon-carbon unsaturated bond in addition to the norbornene ring (hereinafter sometimes referred to as “ monomer (a) ” ) in addition polymerization is used. A method of introducing a functional group by modifying the unsaturated group after polymerization can be considered. A method of efficiently copolymerizing such a monomer (a) having an unsaturated bond at an arbitrary composition ratio is described below. Not yet known.

For example, (1) Patent Documents 1 to 3 describe a polymerization catalyst comprising a nickel or palladium compound having no alkyl group or aryl group and an organoaluminum compound. It has been reported that the homoaddition polymers of 5-vinyl-2-norbornene and 5-ethylidene-2-norbornene as (a) can be obtained in low yields. An example is not shown.
(2) Patent Document 3 and Non-Patent Documents 1 and 2 describe a method for polymerizing a norbornene-based monomer using only an organic ion complex of nickel or palladium. Is described that the monomer (a), dicyclopentadiene, is polymerized in a low yield, but no example of polymerizing the copolymer as described above has been reported.
(3) Patent Documents 4 to 6 and the like report that a catalyst having a neutral bidentate ligand having nitrogen and phosphorus on nickel or palladium polymerizes a norbornene monomer. No example of copolymerization of the monomer (a) has been reported.

JP-A-3-205408 JP-A-4-63807 WO95 / 14048 pamphlet WO96 / 23010 pamphlet WO98 / 12022 pamphlet WO98 / 47933 pamphlet Macromol. Chem. Rapid Commun. , 13, 455-459 (1992) Macromolecules, 29, 2755-2863 (1996).

However, according to the study by the present inventors, any of the polymerization catalysts described in the documents (1), (2), and (3) is dicyclopentadiene, 5-vinyl-2-norbornene, 5- When a norbornene monomer (a) such as ethylidene-2-norbornene and a norbornene monomer (b) having no carbon-carbon unsaturated bond other than the norbornene ring such as 2-norbornene are to be copolymerized, Since the polymerization activity was not sufficient and the copolymerization ratios differed greatly, the introduction rate of the monomer (a) into the polymer was extremely low, and it was difficult to copolymerize at an arbitrary composition ratio.

In the present invention, a norbornene monomer (a) having a carbon-carbon unsaturated bond other than the norbornene ring and a norbornene monomer (b) not having a carbon-carbon unsaturated bond other than the norbornene ring are arbitrarily added . An object is to provide a novel norbornene-based addition copolymer obtained by addition copolymerization in a proportion.

  As a result of intensive studies to solve the above problems, the present inventors have found that a neutral monodentate ligand such as phosphines and pyridines and a periodic table Group 10 transition metal having an alkyl group or an aryl group. When a norbornene monomer (a) having a carbon-carbon unsaturated bond in addition to the norbornene ring is polymerized using a polymerization catalyst obtained by mixing the compound (A) with a Lewis acid (B), the activity is extremely high. In addition, the present inventors have found that it is polymerized, and found that it is extremely excellent in copolymerizability with a norbornene monomer (b) having no unsaturated group such as 2-norbornene, thereby completing the present invention.

Thus, according to the present invention,
(I) A norbornene monomer (a) having a carbon-carbon unsaturated bond other than the norbornene ring and a norbornene monomer (b) having no carbon-carbon unsaturated bond other than the norbornene ring are substituted with an alkyl group. Alternatively, it can be obtained by addition copolymerization using a polymerization catalyst comprising a periodic table group 10 transition metal compound (A) having an aryl group and a neutral electron donating monodentate ligand and a Lewis acid (B). The addition copolymer to be obtained has a repeating unit content derived from the monomer (a) of 20 to 95 mol%, and a weight average molecular weight measured by gel permeation chromatography is 16,800 to 1, in terms of polystyrene. A norbornene-based addition copolymer having an unsaturated bond, and

(II) A norbornene monomer (a) having a carbon-carbon unsaturated bond other than the norbornene ring and a norbornene monomer (b) having no carbon-carbon unsaturated bond other than the norbornene ring are converted to an alkyl group. Alternatively, using a polymerization catalyst comprising an aryl group and a group 10 transition metal compound (A) having a neutral electron donating monodentate ligand and a Lewis acid (B), a polymerization temperature of 0 ° C. to 50 ° C. Gel Permeation Chromatography, which is an addition copolymer obtained by addition copolymerization at a polymerization time of 1 ° C. to 3 hours at a temperature of 20 ° C. and having a repeating unit content derived from the monomer (a) of 20 to 95 mol% A norbornene-based addition copolymer having an unsaturated bond is provided, characterized in that the weight average molecular weight measured by (1) is 16,800 to 1,000,000 in terms of polystyrene.

According to the present invention, carbon in addition to the norbornene ring - norbornene monomer (a) and carbon in addition to the norbornene ring having a carbon-carbon unsaturated bond - carbon unsaturated bond having no norbornene monomer and (b) A novel norbornene-based addition copolymer obtained by addition copolymerization at an arbitrary ratio is provided.

Preferred embodiments of the present invention will be described below by dividing into items.
(Norbornene addition copolymer)
The norbornene-based addition polymer of the present invention includes a norbornene-based monomer (a) having a carbon-carbon unsaturated bond other than the norbornene ring, and a norbornene-based monomer having no carbon-carbon unsaturated bond other than the norbornene ring. (B) (hereinafter sometimes referred to as “monomer (b)”), a periodic table Group 10 transition metal having an alkyl group or an aryl group and a neutral electron-donating monodentate ligand An addition copolymer obtained by addition copolymerization using a polymerization catalyst comprising a compound (A) and a Lewis acid (B), wherein the repeating unit content derived from the monomer (a) is 20 to 95 mol. The weight average molecular weight measured by gel permeation chromatography is 16,800 to 1,000,000 in terms of polystyrene.
As a representative example of the norbornene-based addition copolymer of the present invention , a general formula (1)

(In the formula, R ₁ is an alkenyl group having 2 to 20 carbon atoms having a carbon-carbon unsaturated bond, or R ₁ and R ₂ are combined to form an alkylidene group having 1 to 20 carbon atoms. R _{2 to} R ₄ may be a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group of R _{1 to} R ₄ may be a halogen atom, an oxygen atom, a nitrogen atom, It may have a functional group containing a sulfur atom or a silicon atom, and R ₁ and R ₄ may be bonded to each other to form a ring (m is 0 or 1). And a copolymer containing a repeating unit. In the present invention, the ratio of the repeating unit derived from the monomer (a) in the entire repeating unit of the polymer is 20 mol% to 95 mol%, and can be arbitrarily selected depending on the purpose. In order to introduce a functional group and develop a function , 20 mol% to 80 mol% is more preferable.

The molecular weight of the norbornene-based addition polymer of the present invention is 16,800 to 1,000,000, preferably 16,800 to 500,000 in terms of polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography. is there. If Mw is too small, the mechanical strength decreases, and if it is too large, the solution viscosity becomes high and handling becomes difficult.

(Monomer (a))
The monomer (a) is a monomer having a carbon-carbon unsaturated bond in addition to the norbornene ring. For example, the monomer (a) has the general formula (2).

_(Wherein, R 1 to R ₄ and m are the same as in formula (1).) The compound Ru indicated by like.
The compound represented by the general formula (2) includes bicyclo [2.2.1] hept-2-enes in which m in the general formula (2) is 0, and tetracyclo [4.4.1 in which m is 1. ^2,5 . 1 ^7,10 . 0] -dodec-3-enes, and any monomer can be used, but bicyclo [2.2.1] hept-2-enes having excellent copolymerization activity are used. Is preferred.

Specific examples of the monomer (a) include 5-methylidenebicyclo [2.2.1] hept-2-ene, 5-ethylidenebicyclo [2.2.1] hept-2-ene, and 5-vinyl. Bicyclo having a carbon-carbon unsaturated bond such as bicyclo [2.2.1] hept-2-ene, 5-propenylbicyclo [2.2.1] hept-2-ene as a linear or branched substituent [2.2.1] hept-2-enes; tricyclo [4.3.1 ^2,5 . 0] -deca-3,7-diene (ie dicyclopentadiene), 5-cyclohexenylbicyclo [2.2.1] hept-2-ene, 5-cyclopentenylbicyclo [2.2.1] hept-2 Bicyclo [2.2.1] hept-2-enes having a carbon-carbon unsaturated bond such as -ene as a cyclic substituent; 8-methylidenetetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene, 8-ethylidenetetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene, 8-vinyltetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene, 8-propenyltetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene or the like, a tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-enes and the like. Among these, from the viewpoint of heat resistance and mechanical strength of the resulting polymer, ease of modification reaction, etc., the carbon-carbon unsaturated bond is linear or Bicyclo [2.2.1] hept-2-enes having a branched substituent and bicyclo [2.2.1] hept-2-enes having a carbon-carbon unsaturated bond in a cyclic substituent are preferred. Most preferred are 5-ethylidenebicyclo [2.2.1] hept-2-ene, 5-vinylbicyclo [2.2.1] hept-2-ene, and dicyclopentadiene.

(Monomer (b))
The monomer (b) is a monomer having no carbon-carbon unsaturated bond other than the norbornene ring. As the monomer (b), bicyclo [2.2.1] hept-2-enes that are unsubstituted or have no carbon-carbon unsaturated group in the substituent, or carbon-carbon in the unsubstituted or substituted group Tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . Although 0] -dodec-3-enes can be used, bicyclo [2.2.1] hept-2-enes, which have high polymerization activity and are easily available, are preferred.

Specific examples of the monomer (b) include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2. 2.1] hept-2-ene, 5-butylbicyclo [2.2.1] hept-2-ene, 5-hexylbicyclo [2.2.1] hept-2-ene, 5-decylbicyclo [2] .2] bicyclo [2.2.1] hept- having a linear or branched alkyl group such as hept-2-ene, 5-decylbicyclo [2.2.1] hept-2-ene, etc. 2-enes; tricyclo [4.3.1 ^2,5 . Bicyclo having a cyclic alkyl group such as 0] -dec-3-ene, 5-cyclohexylbicyclo [2.2.1] hept-2-ene, 5-cyclopentylbicyclo [2.2.1] hept-2-ene [2.2.1] hept-2-enes; tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene, 8-methyltetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene, 8-ethyltetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene and the like tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] - dodeca-3-enes, etc.; 5-phenyl-bicyclo [2.2.1] hept-2-ene, tetracyclo ^{[6.5.1 2,5.} 0 ^1,6 . 0 ^8,13] - trideca -3,8,10,12- tetraene (1,4-methano -1,4,4a, also referred 9a- tetrahydrofluorene), tetracyclo ^{[6.6.1 2,5.} 0 ^1,6 . 0 ^8,13] - tetradec -3,8,10,12- tetraene (1,4-methano -1,4,4a, also referred to as 5,10,10a- hexa hydro anthracene) and the like; 5- chlorobicyclo [2 2.1] hept-2-ene, 5-chloromethylbicyclo [2.2.1] hept-2-ene, 5-bromomethylbicyclo [2.2.1] hept-2-ene, 5-p -Bicyclo [2.2.1] hept-2-enes having a substituent containing a halogen atom such as chlorophenylbicyclo [2.2.1] hept-2-ene;

5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-ethoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-methoxycarbonylbicyclo [2.2. 1] Hept-2-ene, 5-methyl-5-ethoxycarbonylbicyclo [2.2.1] hept-2-ene, bicyclo [2.2.1] hept-5-enyl-2-methylpropionate , Bicyclo [2.2.1] hept-5-enyl-2-methyloctanoate, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride, 5-hydroxymethylbicyclo [ 2.2.1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,5-di (hydroxymethyl) bicyclo [2.2. 1] Hept-2 Ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5-phenoxybicyclo [2.2.1] hept-2 Including oxygen atoms such as -ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-methoxycarbonyl-6-carboxybicyclo [2.2.1] hept-2-ene Bicyclo [2.2.1] hept-2-enes having a substituent; 5-cyanobicyclo [2.2.1] hept-2-ene, bicyclo [2.2.1] hept-2-ene- Bicyclo [2.2.1] hept-2-enes having a substituent containing a nitrogen atom such as 5,6-dicarboxylic imide; 5-trimethylsilylbicyclo [2.2.1] hept-2-ene, 5 -Trimethoxysilylbicyclo [2. .1] bicyclo having a substituent containing a silicon hept-2-ene [2.2.1] hept-2-enes; 8-chloro-tetracyclo ^{[4.4.1 2,5.} 1 ^7,10 . 0] -dodec-3-ene, 8-chloromethyltetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene, 8-p-chlorophenyltetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene having a substituent containing a halogen atom such as 8-methylidenetetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-enes;

8-methoxycarbonyltetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene, 8-ethoxycarbonyltetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene, 8-hydroxymethyltetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene), 8-methoxytetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene having a substituent containing an oxygen atom such as tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-enes; 8-cyanotetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene having a substituent containing a nitrogen atom such as tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-enes; 8-trimethylsilyltetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene, 8-trimethoxysilyltetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-ene and the like tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -dodec-3-enes and the like.

  The norbornene-based addition copolymer of the present invention is obtained by copolymerizing the monomer (a) and the monomer (b) with an arbitrary composition. Monomers can also be copolymerized.

(Other monomers that can be copolymerized)
Specific examples of other copolymerizable monomers that can be used in the present invention include monocyclic cyclic olefins such as cyclobutene, cyclopentene, cyclohexene, cyclooctene and the like described in JP-A No. 64-66216. Monomer; cyclic conjugated diene monomer described in JP-A-7-258318 such as 1,3-cyclohexadiene, 1,3-cyclooctadiene; styrene, α-methylstyrene, p- Examples include styrenes such as methylstyrene, p-chlorostyrene, and indene; chain conjugated dienes such as 1,3-butadiene and isoprene; vinyl ethers such as ethyl vinyl ether and isobutyl vinyl ether; and carbon monoxide. These monomers can be used independently or in combination of two or more.

(Polymerization catalyst)
The polymerization catalyst used in the present invention comprises a periodic table Group 10 transition metal compound (A) having an alkyl group or an aryl group, a neutral electron-donating monodentate ligand, and a Lewis acid (B). . Here, the neutral electron-donating monodentate ligand is a ligand in which the ligand is coordinate-bonded to the central metal at one position, and does not include a chelate ligand. . In the present invention, by using the catalyst, the monomer (a) and the monomer (b) can be copolymerized in a high yield, and the molecular weight of the resulting copolymer is increased. Furthermore, when the monomer (a) homopolymer is polymerized, the polymer is obtained in a higher yield than when a conventional catalyst is used .

Transition metal compound (A)
Examples of the periodic table Group 10 transition metal in the transition metal compound (A) include nickel, palladium, and platinum. Among these, nickel and palladium are preferable in terms of polymerization activity.

  The transition metal compound (A) used in the present invention is a Group 10 transition metal compound having an alkyl group or an aryl group and a neutral electron-donating monodentate ligand, and is represented by the general formula (3) Can do.

(In the formula, M represents a transition metal of Group 10 of the periodic table. D represents a neutral electron-donating monodentate ligand, and a plurality of D may be different from each other. Q represents an alkyl group or an aryl group. X represents an anionic ligand other than an alkyl group or an aryl group, a, b, and l represent an integer of 1 to 4, and c represents an integer of 0 to 4.)

  The neutral electron-donating ligand can be any neutral electron-donating compound that can be coordinated to the transition metal at one location. Compounds having Group 15 or Group 16 elements of the periodic table are preferred. The Group 15 element of the periodic table includes N, P, As, Sb, etc., and the Group 16 element includes O, S, Se, etc. Among them, N, P, O, and S are particularly preferable.

  Specific examples of the neutral electron-donating ligand include N-containing ligands such as amines, pyridines, nitriles, amides, isocyanides, and P-containing ligands. , Phosphines, phosphinites, phosphites, etc., as ligands having O, oxygen, water, carbon monoxide, ethers, esters, ketones, etc., as ligands having S, Examples thereof include sulfoxides, thioethers, thiocyanates, and the like. Of these ligands, phosphines or pyridines are particularly preferable. Specific examples of phosphines include phenylphosphine, diphenylphosphine, triphenylphosphine, tributylphosphine, tricyclohexylphosphine, methyldiphenylphosphine, dicyclohexylphosphine, dimethylphenylphosphine, diethylphenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tributylphosphine, Examples include furylphosphine, tri (paratoluenesulfonyl) phosphine, dichloroethylphosphine, chlorodiphenylphosphine, and tetraphenyldiphosphine. Examples of pyridines include pyridine, 2-bromopyridine, 2-benzylpyridine, 2-benzoylpyridine, 2,3-lutidine, 2,4-lutidine, 2,5-lutidine, 2,6-lutidine, 2,6- Examples thereof include dimethoxypyridine, pyrazine, 2,3-diethylpyrazine, pyrizazine, pyrimidine, quinoline, quinaldine, quinazoline, quinoxaline, and phenazine.

The alkyl group of the transition metal compound (A) represents a linear, branched, or cyclic hydrocarbon group having 1 to 20 carbon atoms. Specifically, a methyl group, an ethyl group, an n-propyl group, Examples include i-propyl group, n-butyl group, t-butyl group, n-hexyl group, cyclohexyl group and the like. Furthermore, the C1-C20 linear, branched, and cyclic hydrocarbon group which has a substituent containing an oxygen atom, a nitrogen atom, a silicon atom, and a halogen is also contained. Specific examples include a benzyl group, a chloromethyl group, a cyanomethyl group, a methoxyethyl group, a pentafluorocyclohexyl group, and a trimethylsilylmethyl group. The aryl group represents an aromatic group having 6 to 20 carbon atoms, specifically, a phenyl group, a naphthyl group, a methylphenyl group, a t-butylphenyl group, a chlorophenyl group, a methoxyphenyl group, a pentafluorophenyl group, a methyl group. A naphthyl group, a chloronaphthyl group, etc. can be mentioned.

Specific examples of such a transition metal compound (A) are given below. In the examples of the compounds, Ph represents a phenyl group, Me represents a methyl group, Et represents an ethyl group, t-Bu represents a tert-butyl group, Cy represents a cyclohexyl group, CN represents a cyano group, and Py represents pyridine.
Pd (Me) (Cl) (PPh ₃ ) ₂ , Pd (Me) (Br) (PPh ₃ ) ₂ , Pd (Me) (I) (PPh ₃ ) ₂ , Pd (Me) (I) (PMePh ₂ ) ₂ , Pd (t-Bu) (I) (PPh ₃ ) ₂ , Pd (Ph) (I) (PPh ₃ ) ₂ , Pd (Ph) (I) (PMePh ₂ ) ₂ , Pd (Ph) (I) (Py) ₂ , Pd (Et) (Br) (PCy ₃ ) ₂ , Pd (Ph) (Cl) (MeCN) ₂ , Pd (Ph) (Cl) (PhCN) ₂ , Pd (Ph) (I) [ P (OMe) ₃ ] ₂ , [Pd (Me) (Cl) (PPh ₃ )] ₂ , [Pd (Me) (Cl) (Py)] ₂ , [Pd (Me) (Cl) (MeCN)] _{2 , [Pd (Me) (Cl} ) (PhCN)] 2, [Pd (Me) (Cl) (PCy 3)] 2, _{i (Me) (Cl) (} PPh 3) 2, Ni (Ph) (I) (PPh 3) 2, Ni (Ph) (Cl) (PPh 3) 2, Ni (Ph) (I) (Py) 2 , Ni (Et) (Br) (PCy ₃ ) ₂ , Ni (Ph) (Cl) (MeCN) ₂ , Ni (Ph) (Cl) (PhCN) ₂ , Ni (Ph) (I) [P (OMe) ₃ ] ₂ , [Ni (Me) (Cl) (PPh ₃ )] ₂ , [Ni (Me) (Cl) (Py)] ₂ , [Ni (Me) (Cl) (MeCN)] ₂ , [Ni ( Me) (Cl) (PhCN)] ₂ , [Ni (Me) (Cl) (PCy ₃ )] _{2 and the} like.

The transition metal compound (A) comprises: (α) a method of reacting an alkylating agent or an arylating agent with a Group 10 transition metal compound having a neutral monodentate ligand, and alkylating or arylating the compound (β) A method in which a neutral electron-donating monodentate ligand is reacted with a group 10 transition metal compound having an alkyl group or aryl group and a bidentate or more ligand, and (γ) neutral electron donation An electron-donating monodentate ligand and an alkylating agent or aryl having a bidentate or more neutral ligand other than a neutral monodentate ligand and having no alkyl group or aryl group It can be obtained by a method of reacting an agent. Here, the bidentate or higher ligand is a neutral ligand that is coordinate-bonded at two or more locations with respect to the central metal.

  In addition, the transition metal compound synthesized and isolated and purified by a known method other than the above method can also be used.

The Group 10 transition metal compound having a neutral electron donating monodentate ligand used in the method (α) is a compound in which b in the general formula (3) is 0 . Specific examples thereof include Pd (Cl) ₂ (PPh ₃ ) ₂ , Pd (I) ₂ (Py) ₂ , Pd (OCOCH ₃ ) ₂ (Py) ₂ , Pd (Cl) ₂ (PhCN) ₂ , Pd ( PPh ₃ ) ₄ , Ni (Br) ₂ (PPh ₃ ) ₂ , Ni (I) ₂ (Py) ₂ , Ni (Cl) ₂ (PhCN) ₂ , Ni (PPh ₃ ) _{4 and the} like can be mentioned.

Examples of the alkylating agent and arylating agent used include Group 1, 2 , 12, 13, and 14 organometallic compounds having an alkyl group or an aryl group. Of these, organic lithium, organic magnesium, organic zinc, organic aluminum, and organic tin are preferable, and organic lithium, organic aluminum, and organic tin are particularly preferable.

  Examples of the organic lithium include n-butyl lithium, methyl lithium, and phenyl lithium. Examples of the organic magnesium include butylethylmagnesium, butyloctylmagnesium, dihexylmagnesium, ethylmagnesium chloride, n-butylmagnesium chloride, and allylmagnesium bromide. Examples of the organic zinc include dimethyl zinc, diethyl zinc, and diphenyl zinc. Examples of the organic aluminum include trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, methylaluminoxane and the like. Examples of the organic tin include tetramethyltin, tetra (n-butyl) tin, and tetraphenyltin.

  The addition amount of the alkylating agent or arylating agent is preferably 0.1 to 100 times, more preferably 0.2 to 50 times, and particularly preferably 0.5 to 20 times the Group 10 transition metal compound. . When the addition amount is 0.1 times or less, the polymerization activity is not improved.

The group 10 transition metal compound having an alkyl group or an aryl group used in the method (β) is a compound in which D in the general formula (3) is a neutral bidentate or higher ligand. For example, a diene ligand can be mentioned.

  Specific examples include bromo (methyl) (arene) palladium, chloro (phenyl) (arene) palladium, chloro (4-nitrophenyl) (arene) palladium, chloro (3-hydroxyphenyl) (arene) palladium, bromo ( 4-fluorophenyl) (1,1-dimethylallene) palladium, iodo (4-methoxyphenyl) (1,1-dimethylallene) palladium, chloro (t-butyl) (1,2-butadiene) palladium, iodo (3 -Methoxyphenyl) (1,2-butadiene) palladium, iodo (2-methoxyphenyl) (1,2-butadiene) palladium, chloroethyl (1,3-butadiene) palladium, chloro (2-cyanophenyl) (1,3 -Butadiene) palladium, bromo (2-methoxyphenyl) (1,2- Ntadiene) palladium, bromo (3-hydroxyphenyl) (1,3-pentadiene) palladium, chloro (methyl) (1,4-pentadiene) palladium, bromoethyl (isoprene) palladium, bromoethyl (cyclopentadiene) palladium, iodo (phenyl) (Tetraphenylcyclobutadiene) palladium, chloro (2-methylphenyl) (1,3-cyclohexadiene) palladium, chloro (phenyl) (1,4-cyclohexadiene) palladium, chloro (4-methylphenyl) (1,4 -Cyclohexadiene) palladium, dichloro (1,5-cyclooctadiene) palladium, chloro (methyl) (1,5-cyclooctadiene) palladium, chloroethyl (1,5-cyclooctadiene) palladium, bromo (me Le) (norbornadiene) palladium, chloroethyl (ethylidene norbornene) palladium, dichloro (dicyclopentadiene) palladium,

  Chloro (methyl) (allene) nickel, bromo (4-methoxyphenyl) (arene) nickel, bromo (4-nitrophenyl) (1,1-dimethylallene) nickel, chloro (4-methylphenyl) (1,2- Butadiene) nickel, dichlorobis (1,3-butadiene) nickel, chloro (3-hydroxyphenyl) (1,2-pentadiene) nickel, chloro (phenyl) (1,3-pentadiene) nickel, bromo (3-fluorophenyl) (1,3-pentadiene) nickel, iodo (2-cyanophenyl) (1,4-pentadiene) nickel, bromo (3-methoxyphenyl) (isoprene) nickel, chloro (phenyl) (cyclopentadiene) nickel, chloro (4 -Nitrophenyl) (tetraphenylcyclobutadiene) Kel, chloro (2-methylphenyl) (1,3-cyclohexadiene) nickel, chloro (methyl) (1,5-cyclooctadiene) nickel, chloro (2-cyanophenyl) (norbornadiene) nickel, chloro (3- And methyl (phenyl) (vinylnorbornene) nickel, chloro (3-cyanophenyl) (ethylidenenorbornene) nickel, and chloro (methyl) (dicyclopentadiene) nickel.

  As the neutral electron donating monodentate ligand to be reacted with the transition metal compound, the ligand described in the section of the transition metal compound (A) is used. The addition amount of the neutral electron donating monodentate ligand is preferably 0.1 to 100 times, more preferably 0.2 to 50 times, and 0.5 to 20 times the Group 10 transition metal compound. Is particularly preferred. When the addition amount is 0.1 times or less, the polymerization activity is not improved.

In the present invention, the transition metal compound used in the method (γ) is a compound in which b in the general formula (3) is 0 and D is a neutral bidentate or higher ligand. Specific examples include dichloro (arene) palladium, dibromo (1,1-dimethylallene) palladium, dichloro (1,2-butadiene) palladium, dichloro (1,3-butadiene) palladium, dichloro (1,2-pentadiene). Palladium, dibromo (1,3-pentadiene) palladium, dichloro (1,4-pentadiene) palladium, dibromo (isoprene) palladium, dibromo (cyclopentadiene) palladium, diiodo (tetraphenylcyclobutadiene) palladium, dichloro (1,3- Cyclohexadiene) palladium, dichloro (1,4-cyclohexadiene) palladium, dichloro (1,5-cyclooctadiene) palladium, dibromo (norbornadiene) palladium, dichloro (vinylnorbornene) paradiu Dichloro (ethylidenenorbornene) palladium, dichloro (dicyclopentadiene) palladium, dichloro (arene) nickel, dibromo (1,1-dimethylarene) nickel, dichloro (1,2-butadiene) nickel, dichloro (1,3-butadiene ) Nickel, dichloro (1,2-pentadiene) nickel, dibromo (1,3-pentadiene) nickel, dichloro (1,4-pentadiene) nickel, dibromo (isoprene) nickel, dibromo (cyclopentadiene) nickel, diiodo (tetraphenyl) Cyclobutadiene) nickel, dichloro (1,3-cyclohexadiene) nickel, dichloro (1,4-cyclohexadiene) nickel, dichloro (1,5-cyclooctadiene) nickel, dibromo (norbornadiene) Nickel, dichloro (vinyl norbornene) nickel, dichloro (ethylidene norbornene) nickel, dichloro (dicyclopentadiene) nickel, and the like.

As the alkylating agent or arylating agent to be reacted, the same ones as exemplified in the section (α) can be used. As the neutral electron donating monodentate ligand, the same ones as exemplified in the above-mentioned section of the transition metal compound (A) can be used. The order of reaction is not particularly limited, and the amount to be added is the same as the terms (α) and (β) .

After synthesis by the methods (α) to (γ) , high activity is exhibited whether or not the reaction product is isolated and produced. That is, an alkylating agent or arylating agent that is not bonded to a transition metal, or a neutral electron donating monodentate ligand may or may not be present.

Lewis acid (B)
Lewis acid used in the present invention (B) interacts with said compound (A), Ru is used to activate the polymerization catalyst. The Lewis acid (B), B, Al, Ti, Zn, Ge, Sn, a compound having a metal element selected from Sb is not preferable. From the viewpoint of activation, compounds having at least one halogen atom or oxygen atom directly bonded to the above metal element, specifically, halides, alkoxide compounds, aryloxide compounds, hydroxides having the above metal element And oxides are preferred. This also includes a reaction product of organoaluminum and water, that is, aluminoxane.

  Among these compounds, compounds having B, Al, and Ti are particularly preferable because of easy handling. Specifically, boron compounds having a halogen atom such as boron trifluoride, boron trichloride, boron tribromide; boron compounds having an alkoxy group or aryloxy group such as triethoxyboron; diethylaluminum chloride, ethylaluminum sesquioxide Aluminum compounds having halogen atoms such as chloride, ethylaluminum dichloride, aluminum trichloride; aluminoxanes such as methylaluminoxane, ethylaluminoxane, butylaluminoxane, chloroaluminoxane; alkoxy groups such as triethoxyaluminum and triphenoxyaluminum, or aryloxy groups Aluminum compound having a hydroxyl group, such as aluminum hydroxide; Ha, such as titanium chloride (IV), titanium bromide (IV) A titanium compound having a hydrogen atom; a titanium compound having an alkoxy group or an aryloxy group such as tetraisopropoxy titanium, trimethoxymonochloride, diethoxytitanium dichloride; a titanium compound having a hydroxyl group such as hydroxytitanium trichloride or titanium hydroxide Can be mentioned.

Moreover, the complex which water, ether, ester, carboxylic acid, etc. coordinated to the said compound can also be used. Specifically , boron trifluoride dihydrate, boron trifluoride diethyl ether complex, boron trifluoride tetrahydrofuran complex, boron trifluoride acetic acid (1: 2) complex, boron trichloride methyl sulfide complex, aluminum chloride Examples thereof include hydrates and titanium (IV) chloride tetrahydrofuran complexes.

(Polymerization reaction)
In the polymerization reaction, the use ratio of the transition metal compound (A) and the Lewis acid (B) can be appropriately selected according to various conditions. Usually, the molar ratio (A) / (B) is 1 /0.5 to 1 / 10,000, preferably 1 / 0.8 to 1 / 5,000, more preferably 1/1 to 1,000.

The polymerization reaction consists of the monomer (a) and the monomer (b), and other copolymerizable monomers that are optionally added (hereinafter collectively referred to as “norbornene monomers”). In some cases, the transition metal compound (A) and the Lewis acid (B) are mixed.

The order of mixing is not particularly limited, and the mixture of (A) and (B) may be added and mixed with the norbornene-based monomer, or the mixture of norbornene-based monomer and (A) (B) May be added and mixed , or vice versa, but after mixing the catalyst components (A) and (B), it is preferably left at 10 ° C or lower for 0.5 minute or longer, and 5 ° C or lower. It is more preferable to leave it for 0.5 minutes or more. (A) and (B) are mixed and reacted at a low temperature and allowed to stand for a certain period of time at a low temperature, a stable catalyst system is obtained, and a polymer having a relatively large molecular weight is easily obtained with improved polymerization activity. This is because it is easy to obtain a polymer having a single peak molecular weight distribution.

The polymerization catalyst is used in a molar ratio (transition metal in the polymerization catalyst: norbornene monomer) in a molar ratio, usually 1: 100 to 1: 2,000,000, preferably 1: 500. To 1,000,000, more preferably 1: 1,000 to 1: 500,000. If the amount of catalyst is too large, the operation becomes difficult when catalyst removal is necessary, and if the amount is too small, sufficient polymerization activity cannot be obtained.

In the present invention, the polymerization reaction may be performed without a solvent, or the polymerization may be performed in a solvent. When a solvent is used, it is not particularly limited as long as it does not affect the polymerization, but industrially general-purpose solvents are preferable. Specific examples of such a solvent include aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, Alicyclic hydrocarbons such as bicycloheptane, tricyclodecane, hexahydroindenecyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile; diethyl ether, Ethers such as tetrahydrofuran; halogen solvents such as dichloromethane, chloroform, chlorobenzene, dichlorobenzene ; and the like can be used . Among these, aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons are preferable.

  When the polymerization is carried out in a solvent, the concentration of the norbornene monomer is preferably 1 to 50% by weight, more preferably 2 to 45% by weight, and particularly preferably 5 to 40% by weight in the solution. When the concentration of the monomer is 1% by weight or less, productivity is poor, and when it is 50% by weight or more, the solution viscosity after polymerization is too high and subsequent handling becomes difficult.

The polymerization temperature is not particularly limited, but is generally -30 ° C to 200 ° C, preferably 0 ° C to 180 ° C, more preferably 0 ° C to 50 ° C.
The polymerization time is not particularly limited, but is generally 1 minute to 100 hours, preferably 1 minute to 3 hours.

Furthermore, the molecular weight of the norbornene-based polymer obtained can be adjusted. As a method of adjustment, hydrogen or ethylene, propylene, 1-butene, 1-pentene, 1-hexene, alpha-olefins such as 1-octene; such as 4-methyl-1-pentene, di-, tri-, tetrasubstituted Olefins ; and the like by adding an appropriate amount to the norbornene monomer, the amount of the transition metal compound (A) and the Lewis acid (B) used, and the polymerization temperature are selected according to the purpose. A method is mentioned. The polymerization can be stopped by adding an excessive amount of a polymerization terminator such as alcohol to the catalyst.

(Denaturation reaction)
Since the resulting norbornene-based addition copolymer has a carbon-carbon unsaturated bond, for example, by the method described in JP-A-6-172423 , an epoxy group, a hydroxyl group, a carboxyl group, a halogen group, a nitro group, an amino group A functional group such as an acyl group or a sulfone group can be introduced. The amount of the functional group to be introduced can be controlled by the copolymerization ratio of the monomer (a) .

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.
(1) The molecular weight was measured as a polystyrene equivalent value by gel permeation chromatography (GPC) using chloroform as a solvent.
(2) The monomer composition ratio of the polymer was measured by ¹ H-NMR spectrum.
(3) The epoxy group introduction rate into the polymer was measured by infrared absorption spectrum and ¹ H-NMR spectrum.
(4) The dielectric constant was measured at 1 MHz according to JIS K6911.
(5) The water absorption was measured according to JIS K7209 using a disk-shaped test piece having a diameter of 50 mm and a thickness of 3 mm manufactured by a casting method.
(6) adhesion to the metal, the cast film prepared on a copper with the silicon wafer according to JIS K5400, was evaluated by the cross-cut adhesion test.
In the examples, [part] and [%] are based on weight unless otherwise specified.

[Example 1]
(Polymerization) 0.1 part of Pd (Ph) (I) (PPh ₃ ) ₂ was added to a glass reactor equipped with a stirrer, and then 50 parts of dichloromethane and 200 parts of cyclohexane were added and dissolved. To this, 9.2 parts of dicyclopentadiene (DCP) and 15.8 parts of 2-hexyl-5-norbornene (HNB) were added and cooled to -10 ° C. Subsequently, 22.4 parts of a methylaluminoxane / toluene solution having an aluminum content of 9.1% was added and stirred for 20 minutes at a temperature range of −10 ° C. to 0 ° C., and then a polymerization reaction was performed at room temperature for 3 hours. . After completion of the reaction, the polymerization reaction solution was poured into a large amount of hydrochloric acid isopropanol to completely precipitate the polymer, washed by filtration, and dried under reduced pressure at 80 ° C. for 20 hours. The yield of the obtained polymer was 22.9 parts, and the molecular weight (polystyrene conversion) was number average molecular weight (Mn) = 63,900 and weight average molecular weight (Mw) = 282,300. The DCP / HNB composition ratio in the polymer was 68/32 (mol / mol).

(Epoxy modification)
5 parts of the obtained DCP / HNB copolymer was dissolved in 160 parts of toluene, and subsequently 4 parts of m-chloroperbenzoic acid was added and reacted at 90 ° C. for 3 hours. Thereafter, the reaction solution was poured into a large amount of isopropanol to completely precipitate the polymer, washed by filtration, and dried under reduced pressure at 40 ° C. for 20 hours. The epoxy modification rate of the unsaturated bond was 100%.
(Cast film)
5 parts of the resulting epoxy-modified polymer was dissolved in 45 parts of xylene, applied onto a silicon wafer with copper using a spinner, and then heated at 90 ° C. for 1 hour to form a 40 μm thick crack-free film. Produced. The dielectric constant was 2.8, the water absorption was 0.08%, and the metal adhesion was good.

[Example 2]
(polymerization)
Instead of 9.2 parts dicyclopentadiene (DCP) and 15.8 parts 2-hexyl-5-norbornene (HNB), 14.0 parts dicyclopentadiene (DCP) and 2-hexyl-5-norbornene (HNB) The same experiment as in Example 1 was performed except that 8.1 parts were added. The yield of the obtained polymer was 19.1 parts, and the molecular weight (polystyrene conversion) was Mn = 113,900 and Mw = 190,200. The DCP / HNB composition ratio in the polymer was 38/62 (mol / mol).
(Epoxy modification)
Epoxy modification was performed in the same manner as in Example 1. The epoxy modification rate of the unsaturated bond was 100%.
(Cast film)
In the same manner as in Example 1, a cast film having a thickness of 40 μm without cracks was produced. The dielectric constant was 2.5, the water absorption was 0.05%, and the metal adhesion was good.

[Example 3]
To a glass reactor equipped with a stirrer, 0.04 part of triphenylphosphine was added, followed by 0.04 part of chloromethyl (1,5-cyclooctadiene) palladium dissolved in 50 parts of dichloromethane. Next, 6 parts of dicyclopentadiene (DCP) and 10 parts of 2-norbornene (NB) dissolved in 200 parts of cyclohexane were added. Finally, 7.8 parts of a 24.4% by weight ethylaluminum dichloride / cyclohexane solution was added and the polymerization reaction was carried out at 50 ° C. After the reaction for 2 hours, the polymerization reaction solution was poured into a large amount of isopropanol to completely precipitate the polymer, washed by filtration, and dried under reduced pressure at 80 ° C. for 40 hours. The yield of the obtained polymer was 15.5 parts, and the molecular weight (polystyrene conversion) was Mn = 3,700 and Mw = 16,800. The DCP / NB composition ratio in the polymer was 29/71 (mol / mol).

[Example 4]
6 parts of dicyclopentadiene and 10 parts of 2-norbornene are replaced with 10 parts of dicyclopentadiene and 13.4 parts of 5-hexyl-2-norbornene (HNB), and 7.8 parts of a 24.4% by weight ethylaluminum dichloride / cyclohexane solution. Polymerization was carried out in the same manner as in Example 3 except that was replaced with a methylaluminoxane / toluene solution (9.1 wt% Al). The yield of the obtained polymer was 23.0 parts, and the molecular weight (polystyrene conversion) was Mn = 273,000 and Mw = 779,400. The DCP / HNB composition ratio in the polymer was 50/50 (mol / mol).

[Example 5]
Polymerization was carried out in the same manner as in Example 3 except that 6 parts of dicyclopentadiene and 10 parts of 2-norbornene were replaced with 20 parts of dicyclopentadiene to obtain a homopolymer of dicyclopentadiene. A white polymer precipitated during the polymerization reaction. The yield of the obtained polymer was 20 parts, and the yield was 100%, which was three times or more that when a conventional catalyst was used. Further, the polymer was not dissolved in a general solvent.

[Comparative Example 1]
(Epoxy modification)
Epoxy modification was performed in the same manner as in Example 1 using the dicyclopentadiene homopolymer obtained in Example 5. The epoxy modification rate of the unsaturated bond was 100%.
(Cast film)
An attempt was made to produce a cast film in the same manner as in Example 1. However, the film had numerous cracks, and the dielectric constant and water absorption rate could not be measured.

[Example 6]
To a glass reactor equipped with a stirrer, 0.043 part of dichloro (1,5-cyclooctadiene) palladium dissolved in 30 parts of dichloromethane at room temperature was added. Subsequently, 0.027 part of tetramethyltin dissolved in 10 parts of dichloromethane was added, and then 0.040 part of triphenylphosphine dissolved in 10 parts of dichloromethane was added. Next, 6 parts of dicyclopentadiene (DCP) and 10 parts of 2-norbornene (NB) dissolved in 200 parts of cyclohexane were added. Finally, 7.8 parts of a 24.4% by weight ethylaluminum dichloride / cyclohexane solution was added and the polymerization reaction was carried out at 50 ° C. After the reaction for 2 hours, the polymerization reaction solution was poured into a large amount of isopropanol to completely precipitate the polymer, washed by filtration, and dried under reduced pressure at 80 ° C. for 40 hours. The yield of the obtained polymer was 15.2, and the molecular weight (polystyrene conversion) was Mn = 24,500 and Mw = 62,100. The DCP / NB composition ratio in the polymer was 28/72 (mol / mol).

[Comparative Example 2]
Pd (Ph) (I) to _{(PPh 3) 2, Pd (} Cl) 2 was replaced by _{(PPh 3) 2} was subjected to polymerization in the same manner as in Example 1. A polymer was not obtained.

[Comparative Example 3]
Replacing Pd (Ph) (I) (PPh ₃ ) ₂ with Pd (Cl) ₂ (PPh ₃ ) ₂ , 10.0 parts of dicyclopentadiene (DCP) and 2-hexyl-5-norbornene (HNB) 13.5 Polymerization was conducted in the same manner as in Example 1 except that 6 parts of dicyclopentadiene (DCP) and 10 parts of 2-norbornene (NB) were used. The yield of the obtained polymer was 0.5 part, and the molecular weight (polystyrene conversion) was Mn = 4,200 and Mw = 14,600. The DCP / NB composition ratio in the polymer was 1/99 (mol / mol).

[Comparative Example 4]
[Pd (Ph) (I) (PPh ₃ ) ₂ ] was replaced with [Pd (CH ₃ CN) ₄ ] [BF ₄ ] ₂ except that a Lewis acid methylaluminoxane / toluene solution was not added. Polymerization was carried out in the same manner as in Example 1. A polymer was not obtained.

[Comparative Example 5]
Instead of 0.1 part of [Pd (Ph) (I) (PPh ₃ ) ₂ ] replaced by 0.14 part of [Pd (CH ₃ CN) ₄ ] [BF ₄ ] ₂ , no methylaluminoxane / toluene solution was added. Except that 10.0 parts of dicyclopentadiene (DCP) and 13.5 parts of 2-hexyl-5-norbornene (HNB) are replaced with 6 parts of dicyclopentadiene (DCP) and 10 parts of 2-norbornene (NB). Was polymerized in the same manner as in Example 1. The yield of the obtained polymer was 0.8 parts, and the molecular weight (polystyrene conversion) was Mn = 6,100 and Mw = 21,100. The DCP / NB composition ratio in the polymer was 1/99 (mol / mol).

[Comparative Example 6]
0.1 part of [Pd (Ph) (I) (PPh ₃ ) ₂ ] is added to the formula (4).

Dicyclo and that instead of the palladium compound 1.0 parts dicyclopentadiene (DCP) 10.0 parts of 2-hexyl-5-norbornene (HNB) 13.5 parts having bidentate ligand shown in Polymerization was conducted in the same manner as in Example 1 except that 6 parts of pentadiene (DCP) and 10 parts of 2-norbornene (NB) were used. A polymer was not obtained.

Claims (2)

  A norbornene monomer (a) having a carbon-carbon unsaturated bond other than the norbornene ring, and a norbornene monomer (b) having no carbon-carbon unsaturated bond other than the norbornene ring, an alkyl group or an aryl group And an addition copolymer obtained by addition copolymerization using a polymerization catalyst comprising a group 10 transition metal compound (A) having a neutral electron donating monodentate ligand and a Lewis acid (B). It is a polymer, the repeating unit content derived from the monomer (a) is 20 to 95 mol%, and the weight average molecular weight measured by gel permeation chromatography is 16,800 to 1,000,000 in terms of polystyrene. A norbornene-based addition copolymer having an unsaturated bond, characterized in that   A norbornene monomer (a) having a carbon-carbon unsaturated bond other than the norbornene ring, and a norbornene monomer (b) having no carbon-carbon unsaturated bond other than the norbornene ring, an alkyl group or an aryl group And a polymerization catalyst comprising a group 10 transition metal compound (A) and a Lewis acid (B) having a neutral electron donating monodentate ligand, a polymerization temperature of 0 ° C. to 50 ° C., polymerization Addition copolymer obtained by addition copolymerization in 1 minute to 3 hours, having a repeating unit content derived from monomer (a) of 20 to 95 mol%, measured by gel permeation chromatography A norbornene addition copolymer having an unsaturated bond, wherein the weight average molecular weight is 16,800 to 1,000,000 in terms of polystyrene.