JP2003292586A - Norbornene ring opened polymer, hydrogenated substance of norbornene ring opened polymer and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a norbornene ring opened polymer (ring opened polymer) obtained by carrying out ring opening metathesis polymerization of a norbornene monomer (2) having a specific functional group and a method for producing the ring opened polymer, the ring opened polymer and a hydrogenated substance of the norbornene ring opened polymer (hydrogenated substance) obtained by hydrogenating the ring opened polymer and a method for producing the hydrogenated substance. <P>SOLUTION: The ring opened polymer has a repeating unit (1) (wherein, R<SP>1</SP>to R<SP>4</SP>denote each a hydrogen atom, a 1-10C alkyl group or the like; Y denotes a methylene group or the like; and m denotes 0 or 1) in the molecule and 1,000-1,000,000 weight-average molecular weight measured by a gel permeation chromatography. The method for producing the ring opened polymer is provided. The hydrogenated substance is obtained by hydrogenating ≥50% of double bonds in the ring opened polymer. The method for producing the hydrogenated substance is provided. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a ring-opening polymer obtained by ring-opening polymerization of a norbornene-based monomer having an alkoxycarbonyl group (carboxyl group) and an alkoxycarbonylalkyl group (carboxyalkyl group) as substituents. The present invention relates to a combination, a hydride of the ring-opening polymer, and a method for producing these.

[0002]

2. Description of the Related Art Recently, a ring-opening polymer of a norbornene-based monomer having a functional group as a substituent (hereinafter, also referred to as "functional group-containing norbornene-based monomer") and a hydride thereof have a heat resistance, It has been attracting attention as a functional group-containing polymer having excellent electrical properties and low water absorption. Further, the polymer has excellent adhesion to inorganic materials such as metal and glass, and is also excellent in compatibility with organic materials such as antioxidants, plasticizers, ultraviolet absorbers, colorants, curing agents, flame retardants, It is expected to be used for a wide range of composite materials.

Conventionally, as a production example of a functional group-containing polymer, for example, by a Diels-Alder addition reaction of cyclopentadiene and an olefin having a functional group such as acrylic acid ester, methacrylic acid ester, acrylonitrile, maleic anhydride, and maleimide. A method is known in which the obtained norbornene-based monomer having a functional group as a substituent at both the 5-position or 6-position or the 5- or 6-position is subjected to ring-opening polymerization using a metathesis reaction catalyst ( JP-A-50-58200, JP-B-60-43
365 publication, Polymer Vol. 39, Num
ber39, No. 5, pp1007-1014,19
1998, Macromolecules. , Volume 33,
6239, 2000 etc.).

As another method for producing a functional group-containing polymer, a norbornene-based monomer having a functional group at both the 5-position or 6-position, or at both the 5-position and cyclopentadiene is added by Diels-Alder addition. There is known a method of ring-opening polymerization of reacted tetracyclododecenes having a functional group as a substituent at the 8-position or 9-position, or at both of the 8- and 9-positions in the presence of a metathesis polymerization catalyst (Japanese Patent Laid-Open No. Hei 10-1999) 1
-132626, WO01 / 42332, etc.).

However, in these methods,
Since the functional group-containing norbornene-based monomer used as a starting material has low polymerization reactivity, there is a problem that a large amount of polymerization catalyst is required to obtain a ring-opening polymer in good yield. Further, since the functional group-containing norbornene-based monomer has a lower polymerization reactivity than the norbornene-based monomer having no functional group, even if an attempt is made to copolymerize them, a large amount of the functional group-containing norbornene-based monomer is used. In addition to the requirement, there were cases where a copolymer having a desired composition ratio and molecular weight could not be obtained.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems of the prior art, and is a norbornene-based monomer containing a functional group that is easily available and has high polymerization reactivity. Provided are a norbornene-based ring-opening polymer obtained by ring-opening polymerization of a polymer and a method for producing the same, and a hydrogenated norbornene-based ring-opening polymer obtained by hydrogenating the norbornene-based ring-opening polymer and a method for producing the same. Is an issue.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that an alkoxycarbonyl group (carboxyl group) and an alkoxycarbonylalkyl group (carboxyalkyl group) are substituted with a substituent. As a specific norbornene-based monomer having as, by metathesis ring-opening polymerization in the presence of a metathesis reaction catalyst, it is possible to efficiently obtain the desired norbornene-based ring-opening polymer,
Further, they have found that a hydrogenated product of a ring-opening polymer can be efficiently obtained by hydrogenating the obtained ring-opening polymer, and have completed the present invention.

Thus, according to the first aspect of the present invention, the compound represented by the formula (1)

[0009]

[Chemical 3]

(In the formula, R ^{1 to} R ⁴ each independently represent a functional group containing a hydrogen atom or a hetero atom, or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, Y has 1 carbon atom which may have a substituent.
Represents an alkylene group of 5 and m is 0 or 1. ) Is a norbornene-based ring-opening polymer having a repeating unit represented by the formula (1), and has a weight average molecular weight of 1,000 to 1 determined by gel permeation chromatography.
There is provided a norbornene-based ring-opening polymer characterized by having a number of 1,000,000.

In the norbornene ring-opening polymer of the present invention, in the repeating unit represented by the above formula (1), the group represented by C (═O) OR ⁴ in the above formula (1) is in an exo position. It is preferable that the ratio of the repeating unit in is not less than 70 mol%.

According to a second aspect of the present invention, equation (2)

[0013]

[Chemical 4]

(Wherein R ^{1 to} R ⁴ , Y and m have the same meanings as described above), and a norbornene-based monomer represented by the following formula:
Provided is a method for producing a norbornene-based ring-opening polymer, which comprises performing ring-opening metathesis polymerization in the presence of a metathesis reaction catalyst.

In the production method of the present invention, as the norbornene-based monomer represented by the above formula (2), the group represented by the formula: C (═O) OR ⁴ in the above formula (2) is exo. It is preferable to use a monomer containing 70 mol% or more of the monomer at the position. Further, it is preferable to use a ruthenium carbene complex catalyst as the metathesis reaction catalyst.

According to a third aspect of the present invention, a norbornene-based ring-opening polymer hydride obtained by hydrogenating a carbon-carbon double bond of the norbornene-based ring-opening polymer of the present invention, wherein the double bond is A hydrogenated norbornene-based ring-opening polymer is provided, wherein 50% or more of the hydrogenated product is hydrogenated.

According to a fourth aspect of the present invention, the norbornene-based ring-opening polymer is characterized in that the carbon-carbon double bond of the norbornene-based ring-opening polymer of the present invention is hydrogenated in the presence of a hydrogenation catalyst. A method for producing a combined hydride is provided.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION 1) Norbornene-based monomer, 2) Norbornene-based ring-opening polymer and method for producing the same, 3) Norbornene-based ring-opening polymer hydride and method for producing the same. It will be described in detail separately.

1) Norbornene Monomer In the present invention, the norbornene monomer represented by the above formula (2) is used as a raw material for production. In the formula (2), R ^{1 to} R ⁴ each independently represent a hydrogen atom- or hetero atom-containing functional group or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom.

Examples of the hydrocarbon group having a hetero atom-containing functional group or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom include, for example, 1 to 10 carbon atoms.
And alkyl groups, cycloalkyl groups having 3 to 8 carbon atoms, phenyl groups and the like.

Heteroatoms are group 15 or group 16 of the periodic table.
Group atom, eg, N, O, P, S, As, Se
An atom etc. are mentioned. Examples of the halogen atom include F, Cl, Br and I atoms.

Specific examples of the functional group containing a hetero atom or the alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom include a methyl group, an ethyl group and n.
-Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-
C1-C1 having no substituents such as pentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group
An alkyl group of 0;

Methoxymethyl group, ethoxymethyl group, 2
-C1-10 alkyl group substituted with a functional group containing an oxygen atom such as methoxyethyl group, 3-methoxypropyl group, 4-methoxybutyl group; methylthiomethyl group, ethylthiomethyl group, 2-methylthioethyl Group, an alkyl group having 1 to 10 carbon atoms substituted with a functional group containing a sulfur atom such as a 3-methylthiopropyl group and a 4-methylthiobutyl group;

An alkyl group having 1 to 10 carbon atoms substituted with a functional group containing a nitrogen atom such as a dimethylaminomethyl group, a diethylaminomethyl group and a 2-dimethylaminoethyl group;
Fluoromethyl group, chloromethyl group, bromomethyl group,
Difluoromethyl group, dichloromethyl group, difluoromethyl group, trifluoromethyl group, trichloromethyl group,
2,2,2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group, perfluoropentyl group and the like, an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom; and the like. To be

Examples of the functional group containing a hetero atom or the cycloalkyl group having 3 to 8 carbon atoms which may be substituted with a halogen atom include cyclopropyl group and 2-
Chlorocyclopropyl group, 2-methylcyclopropyl group, cyclopentyl group, 2-methylcyclopentyl group,
Examples thereof include a 3-fluorocyclopentyl group, a 3-methoxycyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, a 4-chlorocyclohexyl group and the like.

Examples of the functional group containing a hetero atom or the phenyl group which may be substituted with a halogen atom include, for example, a phenyl group, a 4-methylphenyl group and a 4 group.
-Chlorophenyl group, 2-chlorophenyl group, 3-methoxyphenyl group, 2,4-dimethylphenyl group and the like can be mentioned.

Among these, R ¹ and R ² are each independently a hydrogen atom or a C ¹ -C 1 having no substituent.
It is preferably 10 alkyl groups, and particularly preferably both are hydrogen atoms. Further, R ³ and R ⁴ are each independently a hydrogen atom or a carbon atom having no substituent.
It is preferably an alkyl group of 10 to 10, more preferably at least one of R ^{3 and} R ⁴ is a hydrogen atom, and particularly preferably both are hydrogen atoms.

Y is C 1 which may have a substituent.
Represents the alkylene group of ~ 5. The alkylene group having 1 to 5 carbon atoms which may have a substituent is specifically represented by the formula: (C
It is a group represented by r ¹ r ² ) _n . In the formula, r ¹ and r ² are not particularly limited as long as they are groups bonded to carbon atoms and inactive to the ring-opening polymerization of the norbornene-based monomer.

Examples of r ¹ and r ² include a hydrogen atom,
C1-C6 alkyl group having no substituent, C1-C6 alkyl group substituted by a halogen atom, C1-C6 alkyl group substituted by an alkoxy group, and alkylthio group-substituted Alkyl group having 1 to 6 carbon atoms, alkyl group having 1 to 6 carbon atoms substituted with amino group or substituted amino group, alkoxy group having 1 to 6 carbon atoms, halogen atom, phenyl optionally having substituent (s) Groups and the like. Among these, r ¹ and r ² are each independently independent of each other because of easy availability and high polymerization reactivity.
It is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, which does not have a substituent, and particularly preferably both are hydrogen atoms.

N represents an integer of 1 to 5, n is preferably 3 or less, and more preferably 1. When n is 2 or more,
The groups represented by the formula: Cr ¹ r ² may be the same or different.

In the norbornene-based monomer represented by the above formula (2), m represents 0 or 1, and synthesis and purification are easy, and a target ring-opening polymer can be efficiently obtained. From the viewpoint of the above, it is preferable that m is 0.

In the norbornene-based monomer represented by the above formula (2), the formula: C (=
The proportion of the monomer in which the group represented by O) OR ⁴ is in the exo position is preferably 70 mol% or more, more preferably 80 mol% or more. A ring-opening polymer can be obtained more efficiently by using a compound in which the group represented by the formula: C (═O) OR ⁴ contains a large amount of monomers in the exo position.

A specific example of the norbornene-based monomer represented by the above formula (2) is a norbornene-based monomer in which m is 0: 5-carboxy-5-carboxymethyl-
2-norbornene, 5-carboxy-5- (2'-carboxy) ethyl-2-norbornene, 5-carboxy-
Norbornenes having two carboxylic acid groups such as 5- (3′-carboxy) propyl-2-norbornene and 5-carboxy-5-carboxymethyl-6-methyl-2-norbornene;

5-carboxy-5-methoxycarbonylmethyl-2-norbornene, 5-carboxy-5-ethoxycarbonylmethyl-2-norbornene, 5-carboxy-5-n-propoxycarbonylmethyl-2-norbornene, 5-carboxy -5-isopropoxycarbonylmethyl-2-norbornene, 5-carboxy-5
n-butoxycarbonylmethyl-2-norbornene, 5
-Carboxy-5-tert-butoxycarbonylmethyl-3-norbornene, 5-carboxy-5- (2'-
Methoxycarbonyl) ethyl-2-norbornene, 5-
Carboxy-5- (2'-ethoxycarbonyl) ethyl-2-norbornene, 5-carboxy-5- (3'-methoxycarbonyl) propyl-2-norbornene, 5-
Carboxy-5-carboxymethyl-6-methyl-2-
Norbornene,

5-methoxycarbonyl-5-carboxymethyl-2-norbornene, 5-ethoxycarbonyl-
5-carboxymethyl-2-norbornene, 5-n-propoxycarbonyl-5-carboxymethyl-2-norbornene, 5-isopropoxycarbonyl-5-carboxymethyl-2-norbornene, 5-n-butoxycarbonyl-5-carboxy Methyl-2-norbornene, 5
-Tert-butoxycarbonyl-5-carboxymethyl-2-norbornene, 5-methoxycarbonyl-5-
(2'-carboxy) ethyl-2-norbornene, 5-
Ethoxycarbonyl-5- (2'-carboxy) ethyl-2-norbornene, 5-methoxycarbonyl-5-
(3'-carboxy) propyl-2-norbornene, 5
-Ethoxycarbonyl-5- (2'-carboxy) propyl-2-norbornene, 5-methoxycarbonyl-5
Norbornenes having a carboxylic acid group such as-(4'-carboxy) butyl-2-norbornene and an ester group;

5-methoxycarbonyl-5-methoxycarbonylmethyl-2-norbornene, 5-ethoxycarbonyl-5-methoxycarbonylmethyl-2-norbornene, 5-methoxycarbonyl-5-ethoxycarbonylmethyl-2-norbornene, 5- Ethoxycarbonyl-5-ethoxycarbonylmethyl-2-norbornene,
5-n-propoxycarbonyl-5-methoxycarbonylmethyl-2-norbornene, 5-isopropoxycarbonyl-5-methoxycarbonylmethyl-2-norbornene, 5-n-butoxycarbonyl-5-methoxycarbonylmethyl-2-norbornene, 5-tert-butoxycarbonyl-5-methoxycarbonylmethyl-2-
Norbornene, 5-methoxycarbonyl-5- (2'-
Methoxycarbonyl) ethyl-2-norbornene, 5-
Ethoxycarbonyl-5- (2'-methoxycarbonyl) ethyl-2-norbornene, 5-methoxycarbonyl-5- (2'-ethoxycarbonyl) ethyl-2-norbornene, 5-ethoxycarbonyl-5- (2'-ethoxy) Carbonyl) ethyl-2-norbornene, 5-methoxycarbonyl-5- (3′-methoxycarbonyl)
An ester group such as propyl-2-norbornene, 5-ethoxycarbonyl-5- (3′-methoxycarbonyl) propyl-2-norbornene, 5-methoxycarbonyl-5- (4′-methoxycarbonyl) butyl-2-norbornene is used. Norbornenes having two; and the like.

Examples of the tetracyclododecenes in which m is 1 include compounds in which cyclopentadiene is added to the norbornene-based monomer.

The norbornene-based monomer represented by the above formula (2) can be easily produced, for example, as follows.

[0039]

[Chemical 5]

(In the formula, R ^{1 to} R ⁴ and Y have the same meanings as described above.) That is, in the norbornene-based monomer represented by the formula (2), a norbornene-based monomer in which m is 0 is used. Body (2-1)
Can be obtained by a Diels-Alder addition reaction of cyclopentadiene (3) with an olefin compound (4). According to this reaction, the formula: C (= O) OR ⁴
The monomer (2-1) in which the group represented by
Those containing 0 mol% or more, preferably 80 mol% or more are preferable because they can be easily obtained.

The tetracyclododecenes (2-2) in which m is 1 include the norbornene-based monomer (2-1) obtained by the Diels-Alder addition reaction and cyclopentadiene (3). It can be obtained by the Diels-Alder addition reaction of (the following reaction formula).

[0042]

[Chemical 6]

(In the formula, R ^{1 to} R ⁴ and Y have the same meanings as described above.) In any reaction, the reaction solution is separated by a known method such as distillation, column chromatography or recrystallization. Purification by a purifying means to obtain the target formulas (2-1) and (2-
The norbornene-based monomer represented by 2) can be efficiently isolated.

2) Norbornene ring-opening polymer and method for producing the same The norbornene ring-opening polymer of the present invention has a repeating unit derived from the norbornene monomer represented by the above formula (1) in the molecule. . The ratio of the repeating units derived from the norbornene-based monomer to all the repeating units can be arbitrarily selected depending on the purpose of producing the polymer, but it is a balance between heat resistance, electrical characteristics, low water absorption and adhesion, and compatibility. Considering the above, 1 to 90% is preferable, and 1 to 80% is more preferable. The ratio of the repeating unit represented by the formula (1) contained in the norbornene ring-opening polymer to all the repeating units is, for example, ¹ H-NMR of the obtained ring-opening polymer.
It can be determined by measuring the spectrum.

The weight average molecular weight of the norbornene ring-opening polymer is not particularly limited, but it is usually 1,000 to 1,000.
50,000, preferably 3,000 to 500,000,
It is more preferably 5,000 to 50,000. The weight average molecular weight (Mw) of the ring-opening polymer is a value determined as a polystyrene conversion value by gel permeation chromatography (GPC).

In the norbornene ring-opening polymer of the present invention, among the repeating units represented by the above formula (1), the group represented by C (═O) OR ⁴ in the above formula (1). The proportion of the repeating unit in the exo position is preferably 70 mol% or more, more preferably 80 mol% or more.

The norbornene ring-opening polymer of the present invention is
(i) 1 of the norbornene-based monomer represented by the above formula (2)
(Iii) a homopolymer of two or more of the norbornene-based monomers represented by the formula (2). ) Formula (2)
And at least one norbornene-based monomer represented by
It may be obtained by copolymerizing a norbornene-based monomer with any other copolymerizable monomer.

Other optional monomers used in (iii) above include, for example, 2-norbornene and 5-methyl-
2-norbornene, 5-ethyl-2-norbornene, 5
-Ethylidene-2-norbornene, 5-phenyl-2-
Norbornene, 5-cyclohexyl-2-norbornene, 5-cyclohexenyl-2-norbornene, dicyclopentadiene, 1,4-methano-1,4,4a, 9a
-Tetrahydrofluorene, tetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ]-
3-dodecene, 8-ethyltetracyclo [4.4.0.
1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethylidene tetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ]-
Norbornene-based monomer having no substituent such as 3-dodecene or having a hydrocarbon group as a substituent; 5-methoxycarbonyl-2-norbornene, 5-methyl-5-
Methoxycarbonyl-2-norbornene, 2-norbornene-5,6-dicarboxylic acid anhydride, 2-norbornene-5,6-dicarboxylic acid imide, 8-methoxycarbonyltetracyclo [4.4.0.12,5.17] , 10]-
3-dodecene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-
Monocyclic cyclic olefins such as cyclopentene and cyclooctene; cyclic diolefins such as cyclohexadiene, cycloheptadiene and cyclooctadiene; and the like. Among them, norbornene-based monomers having no substituent or having a hydrocarbon group as a substituent are preferable because a copolymer having a desired composition ratio and molecular weight can be easily obtained.

The norbornene-based ring-opening polymer of the present invention is produced by subjecting at least one norbornene-based monomer represented by the above formula (2) to ring-opening metathesis polymerization in the presence of a metathesis reaction catalyst. be able to.

The metathesis reaction catalyst is any transition metal compound of Groups 4 to 8 of the periodic table, as long as it is a catalyst for ring-opening metathesis polymerization of the norbornene-based monomer represented by the above formula (2). But it's okay. For example, Orfin M
ethathesis and Metathesis P
Olymerization (KJ Ivinand
J. C. Mol, Academic Press, S
ring-opening metathesis reaction catalysts as described in an Diego 1997) can be used.

Examples of the ring-opening metathesis reaction catalyst include (a) a ring-opening metathesis polymerization catalyst obtained by combining a transition metal compound with an alkylating agent or a Lewis acid which functions as a cocatalyst, and (b) Periodic Tables 4 to 8 Group transition metal-carbene complex catalysts, (c) metallacyclobutane complex catalysts and the like can be mentioned. These metathesis reaction catalysts can be used alone or in combination of two or more. Among these, it is preferable to use a transition metal-carbene complex catalyst of Group 4 to 8 of the periodic table of the above (b) because it does not require a cocatalyst and has high activity. Use is particularly preferred.

Specific examples of the transition metal halogen compound (a) include MoBr ₂ , MoBr ₃ , MoBr ₄ ,
MoCl ₄ , MoCl ₅ , MoF ₄ , MoOCl ₄ , M
molybdenum halides such as oOF ₄ ; WBr ₂ , W
Cl ₂ , WBr ₄ , WCl ₄ , WCl ₅ , WCl ₆ , W
F ₄ , WI ₂ , WOBr ₄ , WOCl ₄ , WOF ₄ , W
Examples thereof include tungsten halides such as Cl ₄ (OC ₆ H ₄ Cl ₂ ) ₂ ; vanadium halides such as VOCl ₃ and VOBr ₃ ; titanium halides such as TiCl ₄ and TiBr ₄ .

Specific examples of the organometallic compound functioning as a cocatalyst include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, triphenylaluminum, tribenzylaluminum,
Organic aluminum compounds such as di-n-butyl aluminum monochloride, diethyl aluminum monochloride, diethyl aluminum monoiodide, diethyl aluminum monohydride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, methylaluminoxane and isobutylaluminoxane;

Tetramethyltin, diethyldimethyltin, tetraethyltin, dibutyldiethyltin, tetrabutyltin, tetraoctyltin, trioctyltin fluoride, trioctyltin chloride, trioctyltin bromide, trioctyltin iodide, dibutyltin difluoride. Organotin compounds such as bismuth, dibutyltin dichloride, dibutyltin dibromide, dibutyltin diiodide, butyltin trifluoride, butyltin trichloride, butyltin tribromide, butyltin triiodide;

Organolithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium and phenyllithium; organic sodium compounds such as n-pentyl sodium; methylmagnesium iodide, ethylmagnesium bromide, methylmagnesium bromide, n-propyl magnesium bromide, t
-Organomagnesium compounds such as butylmagnesium chloride and arylmagnesium chloride; Organozinc compounds such as diethylzinc; Organocadmium compounds such as diethylcadmium; Trimethylboron, triethylboron, tri-n-butylboron, triphenylboron, tris (per) Organoboron compounds such as fluorophenyl) boron, N, N-dimethylanilinium tetrakis (perfluorophenyl) borate and trityltetrakis (perfluorophenyl) borate; and the like.

Transition metal of Groups 4 to 8 of the periodic table (b) above
As the carbene complex catalyst, for example, a tungsten alkylidene complex catalyst, a molybdenum alkylidene complex catalyst,
Examples thereof include a rhenium alkylidene complex catalyst and a ruthenium carbene complex catalyst.

Of the above-mentioned tungsten alkylidene complex catalyst
As a specific example, W (N-2,6-Prⁱ _TwoC₆H_Three)
(CHBu^t) (OBu^t)_Two, W (N-2,6-Pr
ⁱ _TwoC₆H_Three) (CHBu^t) (OCMe_TwoC
F_Three)_Two, W (N-2,6-Prⁱ _TwoC₆H_Three) (CH
Bu^t) (OCMe (CF_Three)_Two)_Two, W (N-2,6
-Pr ⁱ _TwoC₆H_Three) (CHCMe_TwoPh) (OB
u^t)_Two, W (N-2,6-Prⁱ _TwoC₆H_Three) (CH
CMe_TwoPh) (OCMe_TwoCF_Three)_Two, W (N-2,
6-Prⁱ _TwoC₆H_Three) (CHCMe_TwoPh) (OCM
e (CF_Three)_Two)_TwoEtc.

Specific Examples of Molybdenum Alkylidene Complex Catalyst
As Mo (N-2,6-Pr ⁱ _TwoC₆H_Three) (C
HBu^t) (OBu^t)_Two, Mo (N-2,6-Prⁱ
_TwoC ₆H_Three) (CHBu^t) (OCMe_TwoCF_Three)_Two,
Mo (N-2,6-Prⁱ _TwoC₆H_Three) (CHBu^t)
(OCMe (CF_Three)_Two)_Two, Mo (N-2,6-Pr
ⁱ _TwoC₆H_Three) (CHCMe_TwoPh) (OBu^t)_Two,
Mo (N-2,6-Prⁱ _TwoC₆H_Three) (CHCMe_Two
Ph) (OCMe_TwoCF_Three)_Two, Mo (N-2,6-P
rⁱ _TwoC₆H_Three) (CHCMe_TwoPh) (OCMe (C
F_Three)_Two)_Two, Mo (N-2,6-Prⁱ _TwoC₆H_Three)
(CHCMe_TwoPh) (BIPHEN), Mo (N-
2,6-Prⁱ _TwoC₆H_Three) (CHCMe_TwoPh) (B
INO) (THF) and the like.

Specific examples of the rhenium alkylidene complex catalyst include Re (CBu ^t ) (CHBu ^t ) (O-2,6
_{^{-Pr i 2 C 6 H 3)}} 2, Re (CBu t) (CHBu
^t ) (O-2-Bu ^t C ₆ H ₄ ) ₂ , Re (CBu ^t ).
(CHBu ^t ) (OCMe ₂ CF ₃ ) ₂ , Re (CBu
^t ) (CHBu ^t ) (OCMe (CF ₃ ) ₂ ) ₂ , Re
(CBu ^t ) (CHBu ^t ) (O-2,6-Me ₂ C ₆
H ₃ ) _{2 and the} like.

In the above formula, Pr ⁱ is an isopropyl group, B ⁱ
The u ^t is tert- butyl group, Me represents a methyl group, Ph
Is a phenyl group and BIPHEN is 5,5 ', 6,6'-
Tetramethyl-3,3'-di-tert-butyl-1,
The 1'-biphenyl-2,2'-dioxy group was replaced with BINO.
Is a 1,1'-dinaphthyl-2,2'-dioxy group, T
HF represents tetrahydrofuran, respectively.

Further, specific examples of the ruthenium carbene complex catalyst include compounds represented by the following formula (A) or formula (B).

[0062]

[Chemical 7]

In the above formulas (A) and (B), = CR ⁵ R ⁶
And = C = CR ⁵ R ⁶ are carbene compounds containing a carbene carbon of the reaction center. R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom, and these carbene The compound may or may not contain heteroatoms. L ¹ represents a carbene compound containing a hetero atom, L ²
Represents a carbene compound containing a hetero atom or any neutral electron-donating compound.

Here, a carbene compound containing a hetero atom and
Is a compound containing a carbene carbon and a heteroatom
Say. L¹And L^TwoBoth L¹Is a heteroatom-containing
It is a ruben compound, and the carbene carbon contained in these is
Is a ruthenium metal atom directly bonded to the
Groups containing children are attached. L^ThreeAnd L^FourRespectively
It independently represents any anionic ligand. Also, R⁵,
R⁶, L¹, L^Two, L ^ThreeAnd L^Four2 pieces, 3 pieces, 4 pieces,
5 or 6 are bound to each other to form a multidentate chelating ligand
May be formed. Also, as a specific example of a hetero atom,
May include N, O, P, S, As, Se atoms and the like.
it can. Among these, stable carbene compounds were obtained.
In view of the above, N, O, P, S atoms and the like are preferable, and N source
Children are particularly preferred.

In the above formulas (A) and (B),
On (anionic) ligand L^Three, L ^FourFrom the central metal
A ligand that has a negative charge when pulled apart, for example
For example, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.
Halogen atom; diketonate group, alkoxy group, aryl
Hydrocarbons containing oxygen such as ruoxy and carboxyl groups
Group; set by halogen atom such as cyclopentadienyl chloride group
Examples include a substituted alicyclic hydrocarbon group and the like. This
Among them, halogen atom is preferable, and chlorine atom is more preferable.
preferable.

When L ² is a neutral electron-donating compound,
L ² may be any ligand as long as it has a neutral charge when separated from the central metal. Specific examples thereof include carbonyls, amines, pyridines, ethers, nitriles, esters, phosphines, thioethers, aromatic compounds, olefins, isocyanides, thiocyanates and the like. Among these, phosphines and pyridines are preferable, and trialkylphosphines are more preferable.

Examples of the ruthenium complex catalyst represented by the general formula (A) include benzylidene (1,3-dimesityl imidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-
Dimesitylimidazolidin-2-ylidene) (3-methyl-2-butene-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-octahydrobenzimidazole-2-ylidene) (tri Cyclohexylphosphine)
Ruthenium dichloride, benzylidene [1,3-di (1
-Phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-2,3-
Dihydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,3
4-triphenyl-2,3,4,5-tetrahydro-1
H-1,2,4-triazole-5-ylidene) ruthenium dichloride, (1,3-diisopropylhexahydropyrimidine-2-ylidene) (ethoxymethylene)
A ruthenium carbene complex in which a hetero atom-containing carbene compound such as (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesitylimidazolidine-2-ylidene) pyridine ruthenium dichloride and a neutral electron donating compound are bonded;

Benzylidenebis (1,3-dicyclohexylimidazolidin-2-ylidene) ruthenium dichloride, benzylidenebis (1,3-diisopropyl-4)
-Imidazoline-2-ylidene) ruthenium carbene complex in which two hetero atom-containing carbene compounds such as ruthenium dichloride are bonded;

Examples of the ruthenium complex catalyst represented by the general formula (B) include (1,3-dimesitylimidazolidine-2-ylidene) (phenylvinylidene) (tricyclohexylphosphine) ruthenium dichloride, (T-Butylvinylidene) (1,3-diisopropyl-4-imidazoline-2-ylidene) (tricyclopentylphosphine) ruthenium dichloride, bis (1,3-dicyclohexyl-4-imidazoline-2-
Ylidene) phenylvinylidene ruthenium dichloride and the like. In addition, specific examples of the metallacyclobutane complex (c) include titanacyclobutanes and the like.

The amount of the metathesis reaction catalyst used is a molar ratio of the monomer to the catalyst, and the catalyst: monomer = 1: 100 to.
1: 2,000,000, preferably 1: 500 to 1:
1,000,000, more preferably 1: 1,000-
It is 1: 500,000. If the amount of catalyst is more than the above molar ratio, it may be difficult to remove the catalyst, and if it is too small, sufficient polymerization activity may not be obtained.

The ring-opening polymerization of the norbornene type monomer using the metathesis reaction catalyst can be carried out in a solvent or without a solvent. When the hydrogenation reaction is carried out as it is without isolating the produced polymer after completion of the polymerization reaction, it is preferable to polymerize in a solvent.

The solvent used is not particularly limited as long as it dissolves the produced polymer and does not inhibit the polymerization reaction. Examples of the solvent used include n-pentane and n-
Aliphatic hydrocarbons such as hexane and n-heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane,
Alicyclic hydrocarbons such as hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene, acetonitrile, propionitrile and benzonitrile; diethyl ether Ethers such as tellurium, tetrahydrofuran, dioxane; ketones such as acetone, ethyl methyl ketone, cyclopentanone, cyclohexanone; esters such as methyl acetate, ethyl acetate, ethyl propionate, methyl benzoate; chloroform, dichloromethane, Halogenated hydrocarbons such as 1,2-dichloroethane, chlorobenzene, dichlorobenzene and trichlorobenzene; and the like. Among these, it is preferable to use aromatic hydrocarbons, alicyclic hydrocarbons, ethers, ketones or esters.

The concentration of the norbornene-based monomer in the solvent is
It is preferably 1 to 50% by weight, more preferably 2 to 45% by weight, still more preferably 5 to 40% by weight. When the concentration of the norbornene-based monomer is less than 1% by weight, the productivity of the polymer may be deteriorated, and when it exceeds 50% by weight, the viscosity after the polymerization is too high and the subsequent hydrogenation becomes difficult. There is.

The metathesis reaction catalyst may be dissolved in a solvent and added to the reaction system, or may be added as it is without being dissolved. Examples of the solvent for preparing the catalyst solution include the same solvents as those used for the polymerization reaction.

Further, in the polymerization reaction, a molecular weight modifier may be added to the reaction system in order to adjust the molecular weight of the polymer. As the molecular weight modifier, α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; styrenes such as styrene and vinyltoluene; ethers such as ethyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; Halogen-containing vinyl compounds such as allyl chloride; oxygen-containing vinyl compounds such as allyl acetate, allyl alcohol, and glycidyl methacrylate; nitrogen-containing vinyl compounds such as acrylonitrile and acrylamide can be used. A polymer having a desired molecular weight can be obtained by using 0.1 to 100 mol% of a molecular weight modifier with respect to the norbornene-based monomer represented by the formula (2).

The polymerization temperature is not particularly limited, but is usually -1.
00 ° C to + 200 ° C, preferably -50 ° C to +180
C., more preferably -30.degree. C. to + 160.degree. C., and further preferably 0.degree. C. to + 140.degree. The polymerization time is usually 1 minute to 100 hours and can be appropriately adjusted depending on the progress of the reaction.

3) Hydrogenated Norbornene Ring-Opening Polymer and Process for Producing the Same The hydrogenated norbornene ring-opening polymer of the present invention is obtained by hydrogenating the carbon-carbon double bond of the norbornene ring-opening polymer of the present invention. It is a thing. In the norbornene-based ring-opening polymer hydride of the present invention, the proportion of hydrogenated carbon-carbon double bonds (hydrogenation rate) is usually 50% or more, and preferably 70% or more from the viewpoint of heat resistance. , 80% or more is more preferable, and 90% or more is still more preferable.

The hydrogenation rate of the hydrogenated norbornene ring-opening polymer is, for example, ¹ H-N of the norbornene ring-opening polymer.
It can be determined by comparing the peak intensity derived from the carbon-carbon double bond in the MR spectrum with the peak intensity derived from the carbon-carbon double bond in the ¹ H-NMR spectrum of the hydride.

The hydrogenation reaction of the norbornene ring-opening polymer is carried out, for example, by saturating the carbon-carbon double bond in the main chain of the norbornene ring-opening polymer with hydrogen gas in the presence of a hydrogenation catalyst. This can be done by converting to a bond.

The hydrogenation catalyst to be used is not particularly limited, such as a homogeneous catalyst and a heterogeneous catalyst, and those generally used for hydrogenating olefin compounds can be appropriately used.

Examples of the homogeneous catalyst include cobalt acetate and triethylaluminum, nickel acetylacetonate and triisobutylaluminum, a combination of titanocene dichloride and n-butyllithium, zirconocene dichloride and sec-butyllithium, tetrabutoxytitanate and dimethylmagnesium. Ziegler-based catalyst consisting of a combination of a transition metal compound such as

Ruthenium carbene complex catalyst described in the above-mentioned ring-opening metathesis reaction catalyst, dichlorotris (triphenylphosphine) rhodium, JP-A-7-2929,
JP-A-7-149823, JP-A-11-109460,
JP-A-11-158256, JP-A-11-193332
3, a noble metal complex catalyst comprising a ruthenium compound described in JP-A-11-109460 and the like.

Examples of the heterogeneous catalysts include catalysts in which a metal such as nickel, palladium, platinum, rhodium or ruthenium is supported on a carrier such as carbon, silica, diatomaceous earth, alumina or titanium oxide. More specifically, for example, nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina and the like can be used. These hydrogenation catalysts can be used alone or in combination of two or more kinds.

Among these, the carbon-carbon double bond in the polymer can be selectively hydrogenated without causing a side reaction such as modification of the functional group contained in the norbornene ring-opening polymer, It is preferable to use a noble metal complex catalyst such as rhodium or ruthenium and a palladium-supported catalyst such as palladium / carbon, and more preferable to use a ruthenium carbene complex catalyst or a palladium-supported catalyst.

The above-mentioned ruthenium carbene complex catalyst is
It can be used as a ring-opening metathesis reaction catalyst and a hydrogenation catalyst. In this case, the ring-opening metathesis reaction and the hydrogenation reaction can be carried out continuously.

When the ring-opening metathesis reaction and the hydrogenation reaction are continuously carried out using a ruthenium carbene complex catalyst, a vinyl compound such as ethyl vinyl ether or a catalyst modifier such as α-olefin is added to the catalyst. A method in which the hydrogenation reaction is started after activating is also preferably used. Furthermore, it is also preferable to employ a method of adding a base such as triethylamine or N, N-dimethylacetamide to improve the activity.

The hydrogenation reaction is usually carried out in an organic solvent. The organic solvent can be appropriately selected depending on the solubility of the produced hydride, and the same organic solvent as the polymerization solvent can be used. Therefore, after the polymerization reaction, the hydrogenation catalyst can be added to the reaction solution or the filtrate obtained by separating the ring-opening metathesis reaction catalyst from the reaction solution without changing the solvent to carry out the reaction.

The hydrogenation reaction conditions may be appropriately selected depending on the type of hydrogenation catalyst used. The amount of hydrogenation catalyst used is usually 0.01 per 100 parts by weight of the ring-opening polymer.
-50 parts by weight, preferably 0.05-20 parts by weight, more preferably 0.1-10 parts by weight. The reaction temperature is generally -10 ° C to + 250 ° C, preferably -10 ° C to +21.
It is 0 ° C, more preferably 0 ° C to + 200 ° C. -10
If the temperature is lower than 0 ° C, the reaction rate becomes slow, while if it exceeds 250 ° C, a side reaction tends to occur. The pressure of hydrogen is usually 0.
01 to 10.0 MPa, preferably 0.05 to 8.0 M
Pa, more preferably 0.1 to 5.0 MPa. If the hydrogen pressure is less than 0.01 MPa, the hydrogenation rate is slow, and if it exceeds 10.0 MPa, a high pressure reactor is required.

The hydrogenation reaction time is appropriately selected to control the hydrogenation rate. The reaction time is usually 0.1 to 50
The time range is such that 50% or more, preferably 70% or more, more preferably 80% or more, most preferably 90% or more of the main chain carbon-carbon double bonds in the polymer can be hydrogenated. it can.

The norbornene ring-opening polymer and hydride obtained as described above are excellent in heat resistance and electric characteristics. Therefore, heat-resistant optical component materials such as plastic lenses, spherical lenses, aspherical lenses, copier lenses, video camera converter lenses, optical disk pickup lenses, vehicle parts lenses, etc .; semiconductor encapsulation materials, semiconductor underfilm materials, It can be suitably used for applications such as semiconductor protective film material, liquid crystal encapsulating material, circuit base material, circuit protective material, flattening film material, and electronic component material such as electric insulating film material.

[0091]

EXAMPLES Next, the present invention will be described in more detail by way of examples. The present invention is not limited to the examples below. The parts and% in the examples and comparative examples are based on weight unless otherwise specified.

(1) Weight average molecular weight The weight average molecular weight (Mw) is determined by gel permeation chromatography (GP) of ring-opening polymer or hydride.
It was measured by C) and converted into polystyrene. (2) Monomer composition ratio and hydrogenation ratio The composition ratio of the copolymer and the hydrogenation ratio (%) of the hydride are ¹
It was determined by 1 H-NMR spectrum measurement. (3) Polymerization conversion rate The polymerization conversion rate (%) was determined by measurement by gas chromatography.

Production Example 1 5-carboxy-5-carboxy
Production of dimethyl-2-norbornene A glass reactor equipped with a stirrer was charged with 90 parts of dioxane, 50 parts of itaconic acid and 30 parts of cyclopentadiene, and stirred at reflux temperature for 5 hours. The solvent was removed under reduced pressure, water was added to the residue, and the obtained precipitate was dried to obtain white crystals. ¹ H
-By NMR measurement, this crystal was found to be 5-carboxy-5-
Carboxymethyl-2-norbornene (corresponding to a compound in which R ^{1 to} R ⁴ are all hydrogen atoms, Y is a methylene group, and m is 0 in the formula (2)) and is directly bonded to the 5-position of the norbornene ring. It was confirmed that 80% of the carboxyl groups were in the exo position.

Production Example 2 5-carboxy-5-methoxy
Production of carbonylmethyl-2-norbornene 50 parts of itaconic acid was added to itaconic acid monomethyl ester 55
Crystals were obtained in the same manner as in Production Example 1 except that parts were replaced.
^{According to 1} H-NMR measurement, this was found to be 5-carboxy-
5-methoxycarbonylmethyl-2-norbornene (in the formula (2), R ¹ , R ² and R ⁴ are hydrogen atoms, R ³
Is a methyl group, Y is a methylene group, and m is 0. ), And it was confirmed that 80% of the carboxyl groups directly bonded to the 5-position of the norbornene ring were in the exo-position.

Production Example 3 5-Carboxy-2-norbol
Manufacture of Nene, except that 50 parts of itaconic acid was replaced with 27 parts of acrylic acid
Crystals were obtained in the same manner as in Production Example 1. ^{By 1} H-NMR measurement, it was confirmed that this was 5-carboxy-2-norbornene, and 10% of the carboxyl group directly bonded to the 5-position of the norbornene ring was in the exo position.

Example 1 5-carboxy-5-carboxy
Production of Ring-Opening Polymer of Cimethyl-2-norbornene Tetrahydrofuran (T
HF) 300 parts, 5-carboxy-5 obtained in Production Example 1
Carboxymethyl-2-norbornene (CCMN) 30
Parts and 0.7 parts of 1-hexene as a chain transfer agent were added, and then heated to 80 ° C. 3. A THF solution (0.162% by weight solution) of benzylidene (1,3-dimesitylimidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, which is a polymerization catalyst, was added thereto.
5 parts was added, and the mixture was heated with stirring at 80 ° C. for 3 hours to obtain a polymer solution. When a part of the polymer solution was collected and analyzed,
The polymerization conversion rate was 99% or more, and the weight average molecular weight (Mw) (in terms of polystyrene) was 18,000. Also, ¹ H
-By NMR measurement, it was confirmed that this polymer was a ring-opening polymer having the structure of formula (1).

Example 2 Tetracyclo [4.4.0.1]
^2,5 . 1 ^7,10 ] dodec-3-ene and 5-carboxy
Ring opening with ci-5-carboxymethyl-2-norbornene
Production of Copolymer As a monomer, tetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] dodec-3-ene (TCD) (15 parts) and 5-carboxy-5-carboxymethyl-obtained in Production Example 1
2-norbornene (CCMN) 18.4 parts (monomer composition: TCD / CCMN = 50/50 (mol / mol)) was used, except that the amount of 1-hexene used was 0.16 parts. Polymerization was carried out in the same manner as in Example 1. The polymerization conversion rate was 98%, the monomer composition ratio in the obtained ring-opening copolymer was TCD / CCMN = 50/50 (mol / mol), and the weight average molecular weight (Mw) was 34,400.

Example 3 Tetracyclo [4.4.0.1]
^2,5 . 1 ^7,10 ] dodec-3-ene and 5-carboxy
Ring opening with ci-5-carboxymethyl-2-norbornene
Manufacture of Copolymer Hydride To an autoclave equipped with a stirrer, the entire amount of the polymer solution obtained in Example 2 was added, the inside of the autoclave was replaced with nitrogen, and then 1.38 parts of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride, And a hydrogenation catalyst solution prepared by dissolving 1.3 parts of ethyl vinyl ether in 13 parts of toluene were added, and the hydrogen pressure was 4.5 MPa at 160 ° C.
Hydrogenation was carried out for an hour. The hydrogenation reaction liquid was poured into a large amount of methanol to completely precipitate solids. The solid content is collected by filtration,
After washing, it was dried under reduced pressure at 70 ° C. for 12 hours to obtain a hydrogenated ring-opening polymer. The weight average molecular weight (Mw) of this product is 1
It was confirmed by ¹ H-NMR that the carboxy group was completely preserved and that the hydrogenation rate was 99% or more.

Example 4 Tetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] dodec-3-ene and 5-carboxy
Ci-5-methoxycarbonylmethyl-2-norbornene
Production of ring-opening copolymer with tetracyclo [4.4.0.1 ^2,5 .
15 parts of 1 ^7,10 ] dodec-3-ene (TCD) and 19.7 parts of 5-carboxy-5-methoxycarbonylmethyl-2-norbornene (CMCMN) obtained in Production Example 2 (monomer composition: TCD / CMCMN). = 50/50 (mol / mol)), and polymerization was carried out in the same manner as in Example 2. The polymerization conversion rate was 99% or more, and the monomer composition ratio in the obtained ring-opening copolymer was TCD.
/ CMCMN = 50/50 (mol / mol) and the weight average molecular weight (Mw) was 36,100.

Comparative Example 1 5-Carboxy-2-norbol
Production of Ring-Opening Polymer of Nene In Example 1, instead of 30 parts of 5-carboxy-5-carboxymethyl-2-norbornene, bicyclo [2.2.1] hept-5-ene-2-carboxylic acid 30 was used.
The polymerization reaction was performed in the same manner as in Example 1 except that parts were used. The polymerization conversion rate was 22%, and the weight average molecular weight (Mw) of the obtained ring-opened polymer was 6,800.

[0101]

According to the present invention, the presence of a metathesis reaction catalyst using a specific norbornene-based monomer having an alkoxycarbonyl group (carboxyl group) and an alkoxycarbonylalkyl group (carboxyalkyl group) as substituents. By ring-opening polymerization below, a norbornene-based ring-opening polymer and a hydrogenated norbornene-based ring-opening polymer can be industrially advantageously produced.

Since the norbornene-based monomer used in the present invention has high polymerization reactivity, the amount of the metathesis reaction catalyst used is small, and the desired composition is obtained by copolymerizing with the norbornene-based monomer having no functional group. A copolymer having a ratio and a molecular weight can be easily produced. Further, the norbornene-based ring-opening polymer and the hydride of the norbornene-based ring-opening polymer of the present invention are excellent in heat resistance, electrical characteristics, and the like, and thus are useful as heat-resistant optical component materials, electronic component materials, and the like.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Seiji Okada             1-2-1, Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa               Zeon Corporation, General Development Center F-term (reference) 4J032 CA34 CA36 CA62 CA68 CB12                       CD02 CF01 CG07

Claims (7)

[Claims] 1. A compound represented by the formula (1): (In the formula, R ^{1 to} R ⁴ each independently represent a hydrogen atom or a functional group containing a hetero atom, or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, and Y represents A norbornene ring-opening polymer having a repeating unit represented by an alkylene group having 1 to 5 carbon atoms, which may have a substituent, and m is 0 or 1. The weight average molecular weight determined by cation chromatography is 1,000 to 1,000.
A norbornene-based ring-opening polymer, characterized in that it is 20,000. 2. The ratio of the repeating unit in which the group represented by C (═O) OR ⁴ in the formula (1) in the exo position among the repeating units represented by the formula (1) is 70. The norbornene-based ring-opening polymer according to claim 1, which is at least mol%. 3. Formula (2): (Wherein R ^{1 to} R ⁴ , Y and m have the same meanings as described above), and a norbornene-based monomer is subjected to ring-opening metathesis polymerization in the presence of a metathesis reaction catalyst. Method for producing norbornene ring-opening polymer. 4. A monomer in which the group represented by the formula: C (═O) OR ⁴ in the formula (2) in the exo position is used as the norbornene-based monomer represented by the formula (2). The method for producing a norbornene-based ring-opening polymer according to claim 3, wherein the content thereof is 70 mol% or more. 5. The method for producing a norbornene ring-opening polymer according to claim 3, wherein a ruthenium carbene complex catalyst is used as the metathesis reaction catalyst. 6. A hydride of a norbornene ring-opening polymer obtained by hydrogenating a carbon-carbon double bond of the norbornene ring-opening polymer according to claim 1 or 2, wherein 50 % Or more hydrogenated norbornene ring-opening polymer hydride. 7. A hydrogenated norbornene ring-opening polymer, characterized in that the carbon-carbon double bond of the norbornene ring-opening polymer according to claim 1 or 2 is hydrogenated in the presence of a hydrogenation catalyst. Production method.