JP2001098035A - Norbornene type addition copolymer having unsaturated bond and method for preparing norbornene type addition polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of addition polymerizing (a) a norbornene type monomer having a carbon-carbon unsaturated bond in addition to a norbornene ring with high activity as in the case of (b) another norbornene type monomer such as 2-norbornene, and norbornene copolymers obtained by copolymerizing the monomer (a) at any ratio. SOLUTION: Norbornene type monomers are polymerized 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.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel norbornene-based addition copolymer obtained by copolymerizing a norbornene-based monomer (a) having a carbon-carbon unsaturated bond other than a norbornene ring at an arbitrary composition ratio, The present invention relates to a novel method for producing a norbornene addition polymer suitable for producing the copolymer.

[0002]

2. Description of the Related Art Norbornene-based addition polymers have high heat resistance,
It is low in water absorption and excellent in electrical properties. In recent years, it has attracted attention as a polymer material for use in electric and electronic parts, but has a problem of low adhesion to metals and other materials. As a method for imparting adhesiveness, in addition polymerization, after polymerizing a norbornene-based monomer having a carbon-carbon unsaturated bond other than the norbornene ring (hereinafter sometimes referred to as monomer (a)) A method of modifying the unsaturated group to introduce a functional group is conceivable, but a monomer (a) having such an unsaturated bond may be used.
Has not yet been known how to efficiently copolymerize at an arbitrary composition ratio.

For example, (1) JP-A-3-205408, JP-A-4-63807, and International Publication WO
Japanese Patent Application Laid-Open No. 95/14048 describes a polymerization catalyst comprising a nickel or palladium compound having no alkyl group or aryl group and an organoaluminum compound. a)
It has been reported that a homo-addition polymer of 5-vinyl-2-norbornene and 5-ethylidene-2-norbornene is obtained in low yield, but specific examples of the production of the copolymer are shown. It has not been. (2) WO95 / 14048, Makromol. C
hem. RapidCommun. 13,455
-449 (1992), Macromolecule
s 29, 2755-2763 (1996) describes a method for polymerizing norbornene monomers using only an organic ion complex of nickel or palladium. In particular, Makromol. Chem. Rap
id Commun. 13, 455-459 (1
992) describes that dicyclopentadiene, which is the monomer (a), is polymerized at a low yield. However, there is no report of an example in which a copolymer was polymerized in the same manner as described above. (3) WO96 / 23010, WO98 / 12022,
WO98 / 47933 and others report that a catalyst having a neutral bidentate ligand having nitrogen or phosphorus on nickel or palladium polymerizes norbornene-based monomers. No examples of copolymerization have been reported.

According to the study of the present inventors, any of the polymerization catalysts described in the above (1), (2) and (3) can be obtained by using dicyclopentadiene, 5-vinyl-2-norbornene, When a monomer (a) such as ethylidene-2-norbornene and a norbornene-based monomer (b) having no carbon-carbon unsaturated bond other than a norbornene ring such as 2-norbornene are to be copolymerized, the polymerization activity is increased. In addition, the copolymerization ratio of the two is not sufficiently high, so that the introduction ratio of the monomer (a) into the polymer is extremely low, and it has been difficult to copolymerize at an arbitrary composition ratio.

[0005]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a novel norbornene-based monomer obtained by copolymerizing a norbornene-based monomer (a) having a carbon-carbon unsaturated bond in addition to a norbornene ring at an arbitrary ratio. An object of the present invention is to provide an addition copolymer. A second object is to provide a norbornene-based monomer (a) having a carbon-carbon unsaturated bond other than the norbornene ring.
Even in this case, it is an object of the present invention to provide a method of performing addition polymerization with high activity similarly to other norbornene-based monomers (b) such as 2-norbornene.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a neutral monodentate ligand such as phosphines and pyridines can be combined with an alkyl group or an aryl group. Using a polymerization catalyst obtained by mixing a Group 10 transition metal compound (A) with a Lewis acid (B) having the formula (I), a norbornene-based monomer having a carbon-carbon unsaturated bond other than the norbornene ring ( It has been found that when a) is polymerized, it is polymerized with extremely high activity.
-It has been found that the copolymer has extremely excellent copolymerizability with a norbornene-based monomer (b) having no unsaturated group such as norbornene, and the present invention has been completed.

Thus, according to the present invention, 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) an addition copolymer having a repeating unit content of 5 to 95 mol% derived from the monomer (a), and having a weight average molecular weight of 1,000 as polystyrene as measured by gel permeation chromatography. A norbornene-based addition copolymer having an unsaturated bond, characterized by having a molecular weight of from 1,000,000 to 1,000,000. Further, according to the present invention, a polymerization catalyst comprising a transition metal compound of Group 10 of the periodic table (A) having an alkyl group or an aryl group and a neutral electron-donating monodentate ligand, and a Lewis acid (B) And a method for producing a norbornene-based addition polymer, which comprises polymerizing a norbornene-based monomer using the method.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the present invention will be described below by dividing them into items.

(Norbornene-Based Addition Copolymer) The norbornene-based addition polymer of the present invention is a copolymer containing a repeating unit derived from a norbornene-based monomer (a) having a carbon-carbon unsaturated bond in addition to a norbornene ring. And represented by the general formula (1)

[0010]

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Wherein R ₁ is an alkenyl group having 2 to 20 carbon atoms having a carbon-carbon unsaturated bond;
₁ and R ₂ may be combined to form an alkylidene group having 1 to 20 carbon atoms. R _{2 to} R ₄ are a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R _{1 to} R ₄
May further have a functional group containing a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. Further, R ₁ and R ₄ may combine with each other to form a ring. m is 0 or 1. And a copolymer containing a repeating unit represented by the formula (1). In the present invention, the proportion of the repeating unit derived from the monomer (a) in the total repeating units of the polymer is from 5 mol% to 95 mol%, and can be arbitrarily selected depending on the purpose. In order to introduce a functional group and express a function,
0 mol% to 90 mol% is preferable, and 20 mol% to 80 mol% is more preferable.

The molecular weight of the norbornene-based addition polymer of the present invention is 1,000 to 1,000,000, preferably 5,000, in terms of polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography.
0 to 500,000. If the Mw is too small, the mechanical strength decreases, and if it is too large, the solution viscosity increases and handling becomes difficult.

The norbornene-based addition copolymer of the present invention comprises:
It is obtained by copolymerizing the monomer (a) and the monomer (b) with an optional composition, and if necessary, other copolymerizable monomers can also be copolymerized. .

(Norbornene-based monomer having a carbon-carbon unsaturated bond other than the norbornene ring (a)) Norbornene-based monomer having a carbon-carbon unsaturated bond other than the norbornene ring used for obtaining the addition polymer The body (a) has, for example, the general formula (2)

[0015]

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(Wherein R _{1 to} R ₄ and m are the same as those in the general formula (1)), and the bicyclo [2.2.1] wherein m in the general formula (2) is 0. Hept-2-enes,
m is 1 in tetracyclo [4.4.1 ^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, for example,
5-methylidenebicyclo [2.2.1] hept-2-ene, 5-ethylidenebicyclo [2.2.1] hept-2
-Ene, 5-vinylbicyclo [2.2.1] hept-2
Bicyclo [2.2.1] hept- having a carbon-carbon unsaturated bond in a linear or branched substituent such as -ene, 5-propenylbicyclo [2.2.1] hept-2-ene;
2-enes; tricyclo [4.3.1 ^2,5 . 0]-
Deca-3,7-diene (i.e., dicyclopentadiene), 5-cyclohexenylbicyclo [2.2.1] hept-2-ene, 5-cyclopentenylbicyclo [2.
2.1] Bicyclo [2.2.1] hept- having a carbon-carbon unsaturated bond such as hept-2-ene in the cyclic substituent.
2-enes; 8-methylidenetetracyclo [4.4.
^12,5 . ^17.10 . 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} . ^17.10 . Tetracyclo [4.4.1 ^2,5 .5] having a carbon-carbon unsaturated bond such as 0] -dodec-3-ene in a linear or branched substituent. ^17.10 . 0]
-Dodec-3-enes and the like, and among these, from the viewpoints of heat resistance and mechanical strength of the obtained polymer, ease of modification reaction, and the like, a carbon-carbon unsaturated bond is linear or branched. Preferred are bicyclo [2.2.1] hept-2-enes having a substituent and bicyclo [2.2.1] hept-2-enes having a carbon-carbon unsaturated bond in a cyclic substituent. -Ethylidenebicyclo [2.2.1] hept-2-ene, 5-vinylbicyclo [2.2.1] hept-2-ene, and dicyclopentadiene are most preferred.

(Norbornene-based monomer having no carbon-carbon unsaturated bond other than the norbornene ring (b)) The norbornene-based monomer (b) having no carbon-carbon unsaturated bond other than the norbornene ring is a non-volatile monomer. Bicyclo [2.2.1] hept-2-enes having no substituted or substituted carbon-carbon unsaturated groups, or unsubstituted or substituted carbon-
Tetracyclo [4.4.1] having no carbon unsaturated group
^2,5 . ^17.10 . Although 0] -dodec-3-enes can be used, bicyclo [2.2.1] hept-2-enes having high polymerization activity and being easily available are preferred.

Specific examples of the monomer (b) include, for example,
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 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 [2.2.1] hept-2-ene, 5 -Cyclohexyl having a linear or branched alkyl group such as -decylbicyclo [2.2.1] hept-2-ene.
2.1] hept-2-enes; tricyclo [4.3.
^12,5 . Bicyclo having a cyclic alkyl group such as 0] -dec-3-ene, 5-cyclohexylbicyclo [2.2.1] hept-2-ene and 5-cyclopentylbicyclo [2.2.1] hept-2-ene [2.2.1] hept-2-enes; tetracyclo [4.4.1 ^2,5 .
^17.10 . 0] -dodec-3-ene, 8-methyltetracyclo [4.4.1 ^2,5 . ^17.10 . 0] -dodec-3-ene, 8-ethyltetracyclo [4.4.1]
^2,5 . ^17.10 . 0] -dodec-3-ene and the like tetracyclo [4.4.1 ^2,5 . ^17.10 . 0] -dodec-3-enes; 5-phenylbicyclo [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-1,4,4
a, 9a- also referred tetrahydrofluorene), tetracyclo ^{[6.6.1 2,5.} 0 ^1,6 . 0 ^8,13 ]-
Tetradeca-3,8,10,12-tetraene (1,4
-Methano-1,4,4a, 5,10,10a-hexahydroanthracene); 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-chlorophenylbicyclo [2.2.1] hept-2
Bicyclo [2.2.1] hept-2-enes having a substituent containing a halogen atom such as -ene;

5-methoxycarbonylbicyclo [2.
2.1] Hept-2-ene, 5-ethoxycarbonylbi
Cyclo [2.2.1] hept-2-ene, 5-methyl-
5-methoxycarbonylbicyclo [2.2.1] hept
-2-ene, 5-methyl-5-ethoxycarbonylbis
Chromo [2.2.1] hept-2-ene, bicyclo [2.
2.1] Hept-5-enyl-2-methylpropione
G, bicyclo [2.2.1] hept-5-enyl-2-
Methyl octanoate, bicyclo [2.2.1] hept-
2-ene-5,6-dicarboxylic anhydride, 5-hydroxy
Cimethylbicyclo [2.2.1] hept-2-ene,
5,6-di (hydroxymethyl) bicyclo [2.2.
1] Hept-2-ene, 5,5-di (hydroxymethyl
L) bicyclo [2.2.1] hept-2-ene, 5-me
Toxibicyclo [2.2.1] hept-2-ene, 5-
Ethoxybicyclo [2.2.1] hept-2-ene, 5
-Phenoxybicyclo [2.2.1] hept-2-e
, 5,6-dicarboxybicyclo [2.2.1] hep
To-2-ene, 5-methoxycarbonyl-6-carboxy
Oxygen such as sibicyclo [2.2.1] hept-2-ene
Bicyclo [2.2.1] hep having a substituent containing an atom
To-2-enes; 5-cyanobicyclo [2.2.1]
Hept-2-ene, bicyclo [2.2.1] hept-2
A nitrogen atom such as -ene-5,6-dicarboxylic imide;
[2.2.1] hept-2 having substituted substituents
-Enes; 5-trimethylsilylbicyclo [2.2.
1] Hept-2-ene, 5-trimethoxysilylbisic
[2.2.1] Including silicon such as hept-2-ene
Bicyclo [2.2.1] hept-2-e having a substituent
8-chlorotetracyclo [4.4.1]^2,5.
1^7,10. 0] -dodec-3-ene, 8-chloromethyi
Letetracyclo [4.4.1^2,5. 1^7,10. 0]
-Dodeca-3-ene, 8-p-chlorophenyltetracy
Black [4.4.1^2,5. 1 ^7,10. 0] -dodeca
8- having a substituent containing a halogen atom such as 3-ene
Methylidenetetracyclo [4.4.1]^2,5. 1
^7,10. 0] -dodec-3-enes;

8-methoxycarbonyltetracyclo [4.4.1 ^2,5 . ^17.10 . 0] -dodeca-3-
Ene, 8-ethoxycarbonyltetracyclo [4.4.
^12,5 . ^17.10 . 0] -dodec-3-ene, 8-
Methyl-8-methoxycarbonyltetracyclo [4.
4.1 ^2,5 . ^17.10 . 0] -dodec-3-ene,
8-Hydroxymethyltetracyclo [4.4.
^12,5 . ^17.10 . 0] -dodec-3-ene), 8
-Methoxytetracyclo [4.4.1 ^2,5 . 1
^7,10 . 0] - tetracyclo having a substituent containing an oxygen atom, such as dodeca-3-ene ^{[4.4.1 2,5.} 1
^7,10 . 0] -dodec-3-enes; 8-cyanotetracyclo [4.4.1 ^2,5 . ^17.10 . 0] - tetracyclo having a substituent containing a nitrogen atom such as dodeca-3-ene ^{[4.4.1 2,5. 17.10} . 0] -dodec-3-enes; 8-trimethylsilyltetracyclo [4.4.1 ^2,5 . ^17.10 . 0] -dodeca-3
-Ene, 8-trimethoxysilyltetracyclo [4.
4.1 ^2,5 . ^17.10 . Tetracyclo [4. having a substituent containing silicon, such as [0] -dodec-3-ene;
4.1 ^2,5 . ^17.10 . 0] -dodec-3-ene and the like.

(Other Copolymerizable Monomers) Specific examples of other copolymerizable monomers that can be used in the present invention include, for example, JP-A Nos. Showa 6
Monocyclic cycloolefin monomers described in 4-66216, etc .; 1,3-cyclohexadiene, 1,3
Cyclic conjugated diene monomers described in JP-A-7-258318 such as cyclooctadiene; styrenes such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene and indene; 3-
Linear conjugated dienes such as 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 transition metal compound belonging to Group 10 of the periodic table (A) having an alkyl group or an aryl group and a neutral electron-donating monodentate ligand, and a Lewis catalyst. And acid (B). Here, the neutral electron-donating monodentate ligand is a ligand in which the ligand coordinates and binds to the central metal at one position and does not include a chelating ligand. . In the present invention, by using the catalyst, 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 can be obtained. The monomer (b) can be copolymerized at an arbitrary ratio and in a high yield, and the molecular weight of the obtained copolymer increases. Further, when a homopolymer of the monomer (a) is polymerized, the polymer can be obtained in a higher yield than a conventional catalyst.

Transition Metal Compound (A) Examples of the transition metal compound belonging to Group 10 of the periodic table in the compound (A) include nickel, palladium, and platinum. Among them, nickel and palladium are preferable from the viewpoint of polymerization activity.

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

[0026]

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

As the neutral electron donating ligand, any neutral electron donating compound capable of coordinating with the transition metal in one place can be used. Is preferably a compound having a Group 15 or 16 element of the periodic table. Elements of Group 15 of the periodic table include N, P, As, Sb, and the like, and elements of Group 16 include O, S, Se, and the like.
P, O and S are particularly preferred.

Specific examples of the neutral electron donating ligand include N-containing ligands such as amines, pyridines, nitriles, amides, isocyanides and the like.
Are ligands having phosphine, phosphinite, phosphite, etc., and ligands having O are oxygen, water, carbon monoxide, ethers, esters,
Examples of ligands having S, such as ketones, include sulfoxides, thioethers, and thiocyanates. Among these ligands,
Phosphines or pyridines are particularly preferred. Specific examples of the phosphines include phenylphosphine, diphenylphosphine, triphenylphosphine, tributylphosphine, tricyclohexylphosphine, methyldiphenylphosphine, dicyclohexylphosphine, dimethylphenylphosphine, diethylphenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tributylphosphine, and tributylphosphine. Examples thereof 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, and 2,6-lutidine.
Lutidine, 2,6-dimethoxypyridine, pyrazine,
2,3-diethylpyrazine, pyrizadine, pyrimidine,
Examples thereof include quinoline, quinaldine, quinazoline, quinoxaline, and phenazine.

The alkyl group of the compound (A) refers to a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms.
Specifically, a methyl group, an ethyl group, an n-propyl group, i
-Propyl group, n-butyl group, t-butyl group, n-hexyl group, cyclohexyl group and the like.
Further, a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms and having a substituent containing an oxygen atom, a nitrogen atom, a silicon atom and a halogen is also included. Specifically, a benzyl group,
Chloromethyl group, cyanomethyl group, methoxyethyl group,
Examples include a pentafluorocyclohexyl group and a trimethylsilylmethyl group. The aryl group refers to an aromatic group having 6 to 20 carbon atoms, and specifically includes a phenyl group, a naphthyl group, a methylphenyl group, a t-butylphenyl group, a chlorophenyl group, a methoxyphenyl group, a pentafluorophenyl group, and a methyl group. Examples thereof include a naphthyl group and a chloronaphthyl group.

Specific examples of such a transition metal compound (A)
Are listed below. In the examples of compounds, Ph is phenyl.
Group, Me is a methyl group, Et is an ethyl group, t-Bu is te
rt-butyl group, Cy is cyclohexyl group, CN is
An ano group and Py each represent pyridine. Pd (Me) (Cl) (PPh₃)₂, Pd (Me)
(Br) (PPh₃)₂, Pd (Me) (I) (PPh
₃)₂, Pd (Me) (I) (PMePh₂)₂, Pd
(T-Bu) (I) (PPh₃)₂, Pd (Ph)
(I) (PPh₃)₂, Pd (Ph) (I) (PMeP
h₂)₂, Pd (Ph) (I) (Py)₂, Pd (E
t) (Br) (PCy₃)₂, Pd (Ph) (Cl)
(MeCN)₂, Pd (Ph) (Cl) (PhC
N)₂, Pd (Ph) (I) [P (OMe)₃] ₂,
[Pd (Me) (Cl) (PPh₃)]₂, [Pd (M
e) (Cl) (Py)]₂, [Pd (Me) (Cl)
(MeCN)]₂, [Pd (Me) (Cl) (PhC
N)]₂, [Pd (Me) (Cl) (PCy₃)]₂,
Ni (Me) (Cl) (PPh₃)₂, Ni (Ph)
(I) (PPh₃)₂, Ni (Ph) (Cl) (PPh
₃)₂, Ni (Ph) (I) (Py)₂, Ni (Et)
(Br) (PCy₃)₂, Ni (Ph) (Cl) (Me
CN)₂, Ni (Ph) (Cl) (PhCN)₂, Ni
(Ph) (I) [P (OMe)₃]₂, [Ni (Me)
(Cl) (PPh₃)]₂, [Ni (Me) (Cl)
(Py)]₂, [Ni (Me) (Cl) (MeCN)]
₂, [Ni (Me) (Cl) (PhCN)]₂, [Ni
(Me) (Cl) (PCy₃)]₂To mention
it can.

The transition metal compound (A) is obtained by (1) a method of reacting a group 10 transition metal compound having a neutral monodentate ligand with an alkylating agent or an arylating agent to alkylate or arylate the compound. (2) a method in which a group 10 transition metal compound having an alkyl group or an aryl group and a bidentate or higher ligand is reacted with a neutral electron-donating monodentate ligand to cause coordination; A group 10 transition metal compound having only a bidentate or higher neutral ligand other than the electron-donating monodentate ligand and having no alkyl group or aryl group can be treated with an electron-donating monodentate ligand by alkylation. By reacting an agent or an arylating agent. Here, the bidentate or higher ligand is a neutral ligand that coordinates at two or more positions with respect to the central metal.

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

The Group 10 transition metal compound having a neutral electron donating monodentate ligand used in the above method (1) is
A compound in which b in the general formula (3) is 0, and specific examples thereof include Pd (Cl) ₂ (PPh ₃ ) ₂ and 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 (P
y) ₂ , Ni (Cl) ₂ (PhCN) ₂ , Ni (PPh
₃ ) _{4 and the} like.

The alkylating agent and the arylating agent to be used are the same as those described in Periodic Table 1 having an alkyl group or an aryl group.
Group 2, 12, 13, and 14 organometallic compounds can be given. Among them, organic lithium, organic magnesium,
Organozinc, organoaluminum and organotin are preferred, and organolithium, organoaluminum and organotin are particularly preferred.

Examples of the organic lithium include n-butyllithium, methyllithium, phenyllithium and the like. 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, diphenyl zinc and the like. Examples of the organic aluminum include trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, and methylaluminoxane. Examples of the organotin include tetramethyltin, tetra (n-butyl) tin, and tetraphenyltin. The addition amount of the alkylating agent or the arylating agent is 0.1 to 10 with respect to the Group 10 transition metal compound.
0 times is preferable, 0.2 to 50 times is more preferable, and 0.
5 to 20 times is particularly preferred. When the addition amount is 0.1 times or less, the polymerization activity is not improved, and when the addition amount is 100 times or more, a side reaction easily occurs.

The Group 10 transition metal compound having an alkyl group or an aryl group used in the method (2) is a ligand in which D in the general formula (3) is a neutral bidentate or higher. A compound, for example, a diene ligand.

Specific examples include bromo (methyl) (arene) palladium, chloro (phenyl) (arene) palladium, chloro (4-nitrophenyl) (arene) palladium, and 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-pentadiene)
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 (methyl) (norbornadiene) palladium, chloroethyl (ethylidene norbornene) palladium, dichloro (dicyclopentadiene) palladium,

Chloro (methyl) (arene) nickel, bromo (4-methoxyphenyl) (arene) nickel, bromo (4-nitrophenyl) (1,1-dimethylarene) 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) nickel, chloro (2-methylphenyl) (1,3-cyclohexadiene) nickel, chloro (methyl) (1,5-cyclooctadiene) nickel, chloro (2-cyanophenyl)
(Norbornadiene) nickel, chloro (3-methylphenyl) (vinyl norbornene) nickel, chloro (3
-Cyanophenyl) (ethylidene norbornene) nickel, chloro (methyl) (dicyclopentadiene) nickel and the like.

As the neutral electron donating monodentate ligand to be reacted with the above transition metal compound, the ligand described in the section of the above transition metal compound (A) is used. The addition amount of the neutral electron donating monodentate ligand is based on the Group 10 transition metal compound.
It is preferably 0.1 to 100 times, more preferably 0.2 to 50 times, and particularly preferably 0.5 to 20 times. The amount added is 0.
If it is less than 1 time, the polymerization activity is not improved, and if it is 100 times or more, side reactions tend to occur.

In the present invention, the transition metal compound used in the above method (3) is a compound of the formula (3) wherein b is 0,
Compounds in which D is a neutral bidentate or higher ligand. Specific examples include dichloro (arene) palladium, dibromo (1,1-dimethylarene) palladium, dichloro (1,2-butadiene) palladium, and 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 (vinyl) Norbornene) palladium, dichloro (ethylidene norbornene) palladium, dichloro (dicyclopentadiene) palladium, dichloro (arene) nickel, dibromo (1,1-dimethyla) Down) 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 (tetra Phenylcyclobutadiene) nickel, dichloro (1,3-cyclohexadiene) nickel, dichloro (1,4-cyclohexadiene) nickel, dichloro (1,5-cyclooctadiene) nickel, dibromo (norbornadiene) nickel, dichloro (vinylnorbornene) ) Nickel, nickel dichloro (ethylidene norbornene), nickel dichloro (dicyclopentadiene), and the like.

As the alkylating agent or arylating agent to be reacted, the same ones as described in the item (1) can be used.
As the neutral electron donating monodentate ligand, the same ones as in the above-mentioned transition metal compound (A) can be used. The order of the reaction is not particularly defined, and the amount to be added is the same as that in (1) and (2).

After the synthesis according to the methods (1) to (3), high activity is obtained with or without isolation of the reaction product. That is, an alkylating agent or an 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) The Lewis acid (B) used in the present invention is used for activating as a polymerization catalyst by interacting with the above-mentioned compound (A), and B, Al, Ti, Zn, Ge, Sn, S
Preferred is a compound having a metal element selected from b. From the viewpoint of activation, a compound having at least one halogen atom or oxygen atom directly bonded to the metal element, specifically having the metal element, Preference is given to halides, alkoxide compounds, aryl oxide compounds, hydroxides and oxides. Among them, a reaction product of organoaluminum and water, that is, an aluminoxane is also included.

Among these compounds, compounds having B, Al, and Ti are particularly preferable from the viewpoint of easy handling. Specifically, boron compounds having a halogen atom such as boron trifluoride, boron trichloride, and boron tribromide; boron compounds having an alkoxy group or an aryloxy group such as triethoxy boron; diethyl aluminum chloride, ethyl aluminum sesquioxide Aluminum compounds having a halogen atom such as chloride, ethylaluminum dichloride and aluminum trichloride; aluminoxanes such as methylaluminoxane, ethylaluminoxane, butylaluminoxane and chloroaluminoxane; and alkoxy or aryloxy groups such as triethoxyaluminum and triphenoxyaluminum. Aluminum compounds having a hydroxyl group such as aluminum hydroxide; titanium compounds such as titanium chloride (IV) and titanium (IV) bromide Titanium compounds having a gen atom; titanium compounds having an alkoxy group or an aryloxy group such as tetraisopropoxytitanium, trimethoxymonochloride and diethoxytitanium dichloride; and titanium compounds having a hydroxyl group such as hydroxytitanium trichloride and titanium hydroxide. Can be mentioned.

The above compounds include water, ether, ester,
Complexes in which a carboxylic acid or the like is coordinated 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 aqueous solution And a titanium chloride (IV) tetrahydrofuran complex.

(Polymerization method) In the polymerization reaction, the ratio of the transition metal compound (A) to the Lewis acid (B) can be appropriately selected depending on various conditions. / (B) is 1 / 0.5 to 1 / 10,00
0, preferably 1 / 0.8 to 1 / 5,000, more preferably 1/1 to 1,000. The polymerization reaction is started by mixing the three components of a norbornene monomer, a transition metal compound (A), and a Lewis acid (B). The order of mixing is not particularly limited, and the mixture of (A) and (B) may be added to and mixed with the norbornene-based monomer, or (B) may be added to the mixture of norbornene-based monomer and (A). May be added and mixed, or vice versa, but after mixing the catalyst components (A) and (B), it is preferable to leave the mixture at 10 ° C. or lower for 0.5 minutes or more, preferably at 5 ° C. It is more preferable to leave it for 0.5 minutes or more below. When (A) and (B) are mixed and reacted at a low temperature and left for a certain time at a low temperature, a stable catalyst system is obtained, a polymerization activity is improved, and a polymer having a relatively large molecular weight is easily obtained. This is because a polymer having a single peak molecular weight distribution is easily obtained.

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

In the present invention, the polymerization reaction may be carried out without a solvent, or may be carried out in a solvent. When a solvent is used, the solvent is not particularly limited as long as it does not affect the polymerization, but those generally used industrially are preferable. Specific examples of such a solvent include, for example, 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; nitromethane, nitrobenzene,
Nitrogen-containing hydrocarbons such as acetonitrile; diethyl ether
Ethers such as ter and tetrahydrofuran; solvents such as halogen solvents such as dichloromethane, chloroform, chlorobenzene and dichlorobenzene can be used. Among these solvents, aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic rings Group hydrocarbons are preferred.

When the polymerization is carried out in a solvent, the concentration of the norbornene-based monomer in the solution is preferably 1 to 50% by weight, more preferably 2 to 45% by weight, and particularly preferably 5 to 40% by weight. When the concentration of the monomer is 1% by weight or less, productivity is poor, and when the concentration 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.
The temperature is from -30C to 200C, preferably from 0C to 180C. The polymerization time is from 1 minute to 100 hours and is not particularly limited.

Further, as a method for adjusting the molecular weight of the obtained norbornene-based polymer, hydrogen or ethylene,
Α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene; and di-, tri-, and tetra-substituted olefins such as 4-methyl-1-pentene are used for norbornene monomers. The polymerization can be carried out by adding an appropriate amount of the compound (A), or by selecting the amounts of the transition metal compound (A) and the Lewis acid (B) and the polymerization temperature according to the purpose. The polymerization can be stopped by adding an excessive amount of a polymerization terminator such as an alcohol to the catalyst.

(Modification Reaction) Since the norbornene-based addition copolymer obtained in the present invention has a carbon-carbon unsaturated bond, for example, an epoxy group, a hydroxyl group, a carboxyl group, Functional groups such as a halogen group, a nitro group, an amino group, an acyl group, and 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) having a carbon-carbon unsaturated bond other than the norbornene ring.

[0054]

The present invention will be described more specifically below 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 a ¹ H-NMR spectrum. (3) The epoxy group introduction rate into the polymer was measured by an infrared absorption spectrum and a ¹ H-NMR spectrum. (4) The dielectric constant is 1M according to JIS K6911.
Hz. (5) The water absorption was measured using a disk-shaped test piece having a diameter of 50 mm and a thickness of 3 mm manufactured by a casting method according to JIS K7209. (6) The adhesion to metal was evaluated by performing a grid test on a cast film produced on a silicon wafer with copper according to JIS K5400. [Parts] and [%] in the examples are on a weight basis unless otherwise specified.

Example 1 (Polymerization) Pd (Ph) was placed in a glass reactor equipped with a stirrer.
(I) 0.1 part of (PPh ₃ ) ₂ was added, and subsequently 50 parts of dichloromethane and 200 parts of cyclohexane were added and dissolved. To this, 9.2 parts of dicyclopentadiene (DCP) and 15.8 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 the mixture was stirred in a temperature range of -10 ° C to 0 ° C for 20 minutes, and then subjected to a polymerization reaction at room temperature for 3 hours. . After the completion of the reaction, the polymerization reaction solution was poured into a large amount of acidic isopropanol hydrochloride to completely precipitate the polymer.
It dried under reduced pressure at 0 degreeC for 20 hours. The yield of the obtained polymer was 22.9 parts, and the molecular weight (in terms of polystyrene) was such that the number average molecular weight (Mn) = 63,900 and the weight average molecular weight (M
w) = 282,300. DCP / H in polymer
The NB composition ratio was 68/32 (mol / mol).

(Epoxy Modified) Obtained DCP / HNB
5 parts of the copolymer was dissolved in 160 parts of toluene, followed by m-
4 parts of 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.
It dried under reduced pressure for 0 hours. Epoxy modification ratio of unsaturated bond is 1
00%. (Cast film) 5 parts of the obtained epoxy-modified polymer was dissolved in 45 parts of xylene, applied on a silicon wafer with copper using a spinner, and then heated at 90 ° C. for 1 hour to form a crack having a thickness of 40 μm. No film was produced. The dielectric constant was 2.8, the water absorption was 0.08%, and the metal adhesion was good.

Example 2 (Polymerization) 9.2 parts of dicyclopentadiene (DCP) and 2
Example 1 was repeated except that 14.0 parts of dicyclopentadiene (DCP) and 8.1 parts of 2-hexyl-5-norbornene (HNB) were added instead of 15.8 parts of -hexyl-5-norbornene (HNB). The same experiment as in Example 1 was performed. The yield of the obtained polymer was 19.1 parts, and the molecular weight (in terms of polystyrene) was Mn = 113,900, Mw = 190,2.
00. The DCP / HNB composition ratio in the polymer is 3
8/62 (mol / mol). (Epoxy modification) In the same manner as in Example 1, epoxy modification was performed. The degree of epoxy modification of the unsaturated bonds 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 is 2.
5. The water absorption was 0.05%, and the metal adhesion was good.

Example 3 In 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 wt% ethylaluminum dichloride / cyclohexane solution was added to add 50 parts.
The polymerization reaction was carried out at ℃. After reacting for 2 hours, the polymerization reaction solution was poured into a large amount of isopropanol to completely precipitate the polymer. The polymer was separated by filtration, washed, 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 (in terms of polystyrene) was Mn = 3,700 and Mw = 16,800. The DCP / NB composition ratio in the polymer is 29/71
(Mol / mol).

Example 4 6 parts of dicyclopentadiene and 10 parts of 2-norbornene were replaced with 10 parts of dicyclopentadiene and 13.4 of 5-hexyl-2-norbornene (HNB).
The polymerization was carried out in the same manner as in Example 3, except that 7.8 parts of the 24.4 wt% ethyl aluminum dichloride / cyclohexane solution was replaced with 7.8 parts of a methyl aluminoxane / toluene solution (9.1 wt% Al). The yield of the obtained polymer was 23.0 parts, and the molecular weight (in terms of polystyrene)
Was Mn = 273,000 and Mw = 779,400. The DCP / HNB composition ratio in the polymer is 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. Obtained. A white polymer precipitated during the polymerization reaction. The yield of the polymer obtained is 20
And the yield was 100%, which was more than three times that of the conventional catalyst. Further, the polymer did not dissolve in a general solvent.

Comparative Example 1 Epoxy Modification Epoxy modification was carried out in the same manner as in Example 1 using the dicyclopentadiene homopolymer obtained in Example 5. Epoxy modification ratio of unsaturated bond is 10
It was 0%. (Cast film) An attempt was made to produce a cast film in the same manner as in Example 1. However, the film had countless cracks, a dielectric constant,
The water absorption could not be measured.

Example 6 In a glass reactor equipped with a stirrer,
Dichloro (1,5-cyclooctadiene) palladium 0.043 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 0.0% of triphenylphosphine dissolved in 10 parts of dichloromethane was added.
Forty parts were added. Next, 6 parts of dicyclopentadiene (DCP) and 10 parts of 2-norbornene (NB) dissolved in 200 parts of cyclohexane were added. Finally, a 24.4 wt% ethyl aluminum dichloride / cyclohexane solution 7.
8 parts were added and a polymerization reaction was carried out at 50 ° C. After reacting for 2 hours, the polymerization reaction solution was poured into a large amount of isopropanol to completely precipitate the polymer. The polymer was separated by filtration, washed, and dried under reduced pressure at 80 ° C. for 40 hours. The yield of the obtained polymer was 15.2, the molecular weight (in terms of polystyrene) was Mn = 24,500, and M
w = 62,100. The DCP / NB composition ratio in the polymer was 28/72 (mol / mol).

Comparative Example 2 Pd (Ph) (I) (PPh
The _{3) 2, Pd (Cl)} 2 ( except that instead of _{PPh 3) 2} was subjected to polymerization in the same manner as in Example 1. No polymer was obtained.

Comparative Example 3 Pd (Ph) (I) (PPh
₃ ) ₂ was replaced by Pd (Cl) ₂ (PPh ₃ ) ₂ and 10.0 parts of dicyclopentadiene (DCP) and 2-hexyl-
13.5 parts of 5-norbornene (HNB) are mixed with 6 parts of dicyclopentadiene (DCP) and 2-norbornene (NB) 1
Polymerization was carried out in the same manner as in Example 1 except that the amount was changed to 0 parts.
The yield of the obtained polymer was 0.5 part, and the molecular weight (in terms of polystyrene) was Mn = 4,200 and Mw = 14,600.
Met. The DCP / NB composition ratio in the polymer is 1/99
(Mol / mol).

Comparative Example 4 [Pd (Ph) (I) (PP
h _{3) 2]} a _{[Pd (CH 3 CN) 4} ] [ in place of the _{BF 4] 2,} polymerized in the same manner as in Example 1 except that no addition of methylaluminoxane / toluene solution is a Lewis acid went. No polymer was obtained.

Comparative Example 5 [Pd (Ph) (I) (PP
h ₃ ) ₂ ] [Pd (CH ₃ CN) ₄ ] [BF
₄ ] _{2 In place of} 0.14 parts, no methylaluminoxane / toluene solution was added and 10.0 parts of dicyclopentadiene (DCP) and 13.5 parts of 2-hexyl-5-norbornene (HNB) were added. Cyclopentadiene (D
Polymerization was carried out in the same manner as in Example 1 except that 6 parts of (CP) and 10 parts of 2-norbornene (NB) were used. The yield of the obtained polymer was 0.8 part, and the molecular weight (in terms of polystyrene)
Was Mn = 6,100 and Mw = 21,100.
The DCP / NB composition ratio in the polymer was 1/99 (mol / mol).

Comparative Example 6 [Pd (Ph) (I) (PP
h ₃ ) ₂ ] 0.1 part by the general formula (4)

[0068]

Embedded image

In place of 1.0 part of a palladium compound having a bidentate ligand represented by the following formula, 10.0 parts of dicyclopentadiene (DCP) and 13.5 parts of 2-hexyl-5-norbornene (HNB) were used. Dicyclopentadiene (DC
Polymerization was carried out in the same manner as in Example 1 except that 6 parts of P) and 10 parts of 2-norbornene (NB) were used. No polymer was obtained.

[0070]

According to the present invention, the norbornene-based monomer (a) having a carbon-carbon unsaturated bond in addition to the norbornene ring can be produced similarly to other norbornene-based monomers such as 2-norbornene. Active addition polymerization is possible. Further, according to the present invention, in addition to the norbornene ring,
A novel norbornene-based addition copolymer is obtained by copolymerizing the norbornene-based monomer (a) having a carbon unsaturated bond at an arbitrary ratio.

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Claims (4)

[Claims] 1. Addition of a norbornene monomer (a) having a carbon-carbon unsaturated bond other than the norbornene ring to a norbornene monomer (b) having no carbon-carbon unsaturated bond other than the norbornene ring A copolymer having a repeating unit content derived from the monomer (a) of 5 to 95 mol% and a weight-average molecular weight of 1,000 in terms of polystyrene as measured by gel permeation chromatography.
A norbornene-based addition copolymer having an unsaturated bond, which is from 1 to 1,000,000. 2. A polymerization catalyst comprising a transition metal compound of Group 10 of the periodic table (A) having an alkyl group or an aryl group and a neutral electron-donating monodentate ligand and a Lewis acid (B). A method for producing a norbornene-based addition polymer, comprising polymerizing a norbornene-based monomer. 3. The neutral electron-donating monodentate ligand contains a Group 15 or 16 element of the Periodic Table.
The manufacturing method as described. 4. A polymerization catalyst prepared by mixing the Group 10 transition metal compound (A) and the Lewis acid (B) and then leaving the mixture at 10 ° C. or lower for 0.5 minutes or more. Item 4. The production method according to item 2 or 3.