JP2003301032A - Norbornene-based ring-opening polymer, hydrogenated norbornene-based ring-opening polymer and process for production thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a norbornene-based ring-opening polymer (ring-opening polymer) obtained by subjecting a norbornene-based monomer (2) (wherein R<SP>1</SP>and R<SP>2</SP>are each H or the like; X is O, NH or the like; Y is a methylene group or the like; and m is 0 or 1) having a substituent comprising a functional spiran ring and having high polymerization reactivity to ring-opening metathesis polymerization, its production process, a hydrogenated norbornene-based ring- opening polymer (hydrogenated derivative) obtained by hydrogenating the ring- opening polymer, and its production process. <P>SOLUTION: The ring-opening polymer has repeating units (1) (wherein R<SP>1</SP>and R<SP>2</SP>are each H or the like; X is O, NH or the like; Y is methylene group or the like; and m is 0 or 1) derived from a norbornene-based monomer in the molecule and a weight-average molecular weight determined by the gel permeation chromatography of 1,000 to 1,000,000. Its production process is provided. The hydrogenated derivative is obtained by hydrogenating at least 50% of the double bonds of the ring-opening polymer. Its production process is provided. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a norbornene ring-opening polymer having a spirane ring containing a carboxylic acid anhydride group or a carboxylic acid imide group as a substituent, a hydride of the polymer, and a method for producing the same. Regarding

[0002]

2. Description of the Related Art In recent years, ring-opening polymers of norbornene-based monomers having a functional group as a substituent (hereinafter also referred to as "functional group-containing norbornene-based monomers") and hydrides thereof are It has been attracting attention as a functional group-containing polymer having excellent electrical properties and low water absorption. Further, the polymer is
Excellent adhesion to inorganic materials such as metals and glass, and excellent compatibility with organic materials such as antioxidants, plasticizers, UV absorbers, colorants, curing agents, flame retardants, etc. Is expected to be used.

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 efficiently producing a functional group-containing polymer, a norbornene-based monomer having a functional group at the 5-position or 6-position, or at both the 5-position and 6-position, and cyclopentadiene are used in Diels A method of ring-opening polymerization of tetracyclododecenes having a functional group as a substituent at both the 8-position or 9-position or the 8,9-position subjected to alder addition reaction in the presence of a metathesis polymerization catalyst is known ( JP-A-1-132626, WO01 / 4233
No. 2, 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 in order 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]

As a result of intensive studies to solve the above problems, the present inventors have found that a specific norbornene-based monomer having a carboxylic acid anhydride group or a carboxylic acid imide group as a substituent is used. The ring-opening polymer is efficiently subjected to metathesis ring-opening polymerization in the presence of a metathesis reaction catalyst, and a norbornene-based ring-opening polymer containing a functional group can be efficiently obtained. It was found that a hydride of a ring polymer can be efficiently obtained,
The present invention has been completed.

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 and R ² 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. X is an oxygen atom, a sulfur atom or NR ³ (R
³ represents a hydrogen atom, a hydroxyl group, a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms or an alkoxycarbonyl group having 1 to 10 carbon atoms. ), Y represents an alkylene group which may have a substituent, and m is 0 or 1. ] A norbornene-based ring-opening polymer having a repeating unit represented by the following formula, wherein the weight average molecular weight determined by gel permeation chromatography is 1,000 to 1,
Provided is a norbornene-based ring-opening polymer characterized by having a number of, 000,000.

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

[0012]

[Chemical 4]

A norbornene-based monomer represented by the formula (wherein R ¹ , R ² , X, Y and m have the same meanings as described above) is subjected to ring-opening metathesis polymerization in the presence of a metathesis reaction catalyst. A method for producing a norbornene-based ring-opening polymer is provided. In the production method of the present invention, 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 the 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.

[0016]

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 and R ² 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. .

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

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, for example, methyl group, ethyl group, n-propyl group, isopropyl group and n- Butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group 1 to 10 carbon atoms having no substituents such as groups
An alkyl group of

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-methylthio Ethyl group, 3
-C1-10 substituted with a sulfur atom-containing functional group such as a methylthiopropyl group and a 4-methylthiobutyl group.
An alkyl group of

Alkyl groups having 1 to 10 carbon atoms substituted with a functional group containing a nitrogen atom such as dimethylaminomethyl group, diethylaminomethyl group and 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, perfluoro And an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom such as a pentyl group;

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.

Further, the functional group containing a hetero atom or the phenyl group which may be substituted with a halogen atom includes a phenyl group, a 4-methylphenyl group, a 4-chlorophenyl group, a 2-chlorophenyl group and a 3-chlorophenyl group. Examples thereof include a methoxyphenyl group and a 2,4-dimethylphenyl group.
Among these, R ^1, R ² are each independently preferably an alkyl group having 1 to 10 carbon atoms having no hydrogen atom or a substituent, the R ¹ and R ² are both hydrogen atoms Is particularly preferable.

X represents an oxygen atom, a sulfur atom or a group represented by NR ³ . Here, R ³ is a hydrogen atom, a hydroxyl group, a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent,
It represents an alkoxy group having 1 to 10 carbon atoms or an alkoxycarbonyl group having 1 to 10 carbon atoms.

Examples of the hydrocarbon group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n. An alkyl group such as a pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group; a cyclopropyl group,
Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; phenyl group, 4-methylphenyl group, 2,4,6
-Aromatic hydrocarbon groups such as trimethylphenyl group and naphthyl group; and the like.

1 to 1 carbon atoms which may have the above-mentioned substituent
Examples of the substituent of the alkyl group of 10 include an alkoxycarbonyl group, an alkoxy group, an optionally substituted phenyl group, a halogen atom, an alkylthio group, a hydroxyl group, a mercapto group, an amino group, a carboxyl group, and a cyano group. , A nitro group, a group represented by C (═O) NH ₂ , and the like. The alkyl group having 1 to 10 carbon atoms may have these substituents at arbitrary positions, and may be substituted with a plurality of the same or different substituents.

Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group and tert-butoxy group. Examples of the alkoxycarbonyl group having 1 to 10 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group and tert-butoxycarbonyl group.

Of these, R ³ is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, or the formula: CH
A group represented by (r ¹ ) CO ₂ r ² is preferable. here,
r ¹ is a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s
ec-butyl group, phenyl group, benzyl group, 4-hydroxybenzyl group, hydroxymethyl group, 1-hydroxyethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 2-amidoethyl group, 3-amidopropyl group, A 2-mercaptoethyl group, a 3-methylthiopropyl group, a 5-aminopentyl group and the like can be mentioned. Also, r ²
Represents a hydrogen atom; or an alkyl group such as a methyl group and an ethyl group.

Y is a carbon atom 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 ³ r ⁴ ) _n . In the formula, r ³ and r ⁴ 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. r ³ and r ⁴
Examples of the hydrogen atom include a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms substituted with an alkoxy group, and an alkylthio group. A substituted alkyl group having 1 to 6 carbon atoms, an amino group, or a substituted amino group having 1 carbon atom
Examples include an alkyl group having 6 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, and a phenyl group which may have a substituent.

Of these, r ³ and r ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, because they are easily available and have high polymerization reactivity. Are preferred, with both being hydrogen atoms being particularly preferred. 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 formula:
The groups represented by Cr ³ r ⁴ 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 is efficiently obtained. From the viewpoint of the above, it is preferable that m is 0.

Specific examples of the norbornene-based monomer in which m is 0 include cyclopentadiene-itaconic anhydride adduct, cyclopentadiene-itaconimide adduct, cyclopentadiene-N-methylitaconimide adduct,
Cyclopentadiene-N-ethylitaconimide adduct, cyclopentadiene-N-phenylitaconimide adduct, cyclopentadiene-N-hydroxyitaconimide adduct, cyclopentadiene-2-itaconimide acetic acid adduct, cyclopentadiene-3-itaconimide Examples thereof include a propionic acid adduct, a cyclopentadiene-N-methoxycarbonylmethylitaconimide adduct, a cyclopentadiene-N-ethoxycarbonylmethylitaconimide adduct, a cyclopentadiene-N- (1-ethoxycarbonyl) ethylimide adduct, 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.

[0036]

[Chemical 5]

(In the formula, R ¹ , R ² , X 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. Monomer (2-1)
Can be obtained by a Diels-Alder addition reaction of cyclopentadiene (3) with an olefin compound (4).

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).

[0039]

[Chemical 6]

(In the formula, R ¹ , R ² , X and Y have the same meanings as described above.) In any reaction, the reaction solution is known by distillation, column chromatography, recrystallization or the like. The target compound of 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
1,000,000, preferably 3,000 to 500,
000, more preferably 5,000 to 50,000. The weight average molecular weight (Mw) of the ring-opening polymer is a value calculated as a polystyrene conversion value by gel permeation chromatography (GPC).

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 the above (iii) are, for example, 2-norbornene, 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;
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, 1
0] -3-dodecene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ]
Monomers having functional groups such as -3-dodecene; 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 a transition metal compound of Groups 4 to 8 of the periodic table, and is any catalyst 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
An Diego, 1997) can be used.

As the metathesis reaction catalyst, for example,
(i) a ring-opening metathesis polymerization catalyst obtained by combining a transition metal compound with an alkylating agent or a Lewis acid that functions as a cocatalyst, (ii) a transition metal-carbene complex catalyst of Group 4 to Group 8 of the periodic table, and (iii) metallacyclobutane A complex catalyst etc. are mentioned. These metathesis reaction catalysts may be used alone or
A mixture of more than one type can be used. Among these, it is preferable to use a transition metal-carbene complex catalyst of Group 4 to 8 of the periodic table of (ii) because it does not require a cocatalyst and has high activity. Use of a ruthenium carbene complex catalyst Is particularly preferable.

Specific examples of the transition metal halogen compound (i)
As an example, MoBr_Two, MoBr _Three, MoBr_Four, M
oCl_Four, MoCl₅, MoF_Four, MoOCl_Four, Mo
OF _Four, Etc. Molybdenum halides; WBr_Two, WC
l_Two, WBr_Four, WCl_Four, WCl₅, WCl₆, WF
_Four, WI_Two, WOBr_Four, WOCl_Four, WOF_Four, WC
l_Four(OC₆H_FourCl_Two)_TwoTungsten halogen etc.
Compound; VOCl_Three, VOBr_ThreeVanadium halogen etc.
Compound; TiCl_Four, TiBr_FourTitanium halogenation of etc.
Thing; and the like.

Specific examples of the organometallic compound functioning as a cocatalyst include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, triphenyl aluminum, tribenzyl aluminum,
Organic aluminum compounds such as diethyl aluminum monochloride, di-n-butyl 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, dibutyltin 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.

Examples of the transition metal-carbene complex catalysts of Groups 4 to 8 of the periodic table (ii) include a tungsten alkylidene complex catalyst, a molybdenum alkylidene complex catalyst, 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-
The 1,1′-biphenyl-2,2′-dioxy group is replaced with BI
NO represents a 1,1'-dinaphthyl-2,2'-dioxy group, and THF represents tetrahydrofuran.

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

[0058]

[Chemical 7]

In the above formulas (A) and (B), = CR ⁴ R ⁵
And = C = CR ⁴ R ⁵ are carbene compounds containing a carbene carbon as a reaction center. R ⁴ and R ⁵ 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, The carbene compound may or may not contain a heteroatom. 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, the hetero atom-containing carbene compound means a compound containing a carbene carbon and a hetero atom. Both L ¹ and L ² or L ¹ is a hetero atom-containing carbene compound, and a ruthenium metal atom is directly bonded to the carbene carbon contained therein, and a group containing a hetero atom is bonded.

L^ThreeAnd L^FourAre each independently any
An anionic ligand is shown. Also, R ^Four, R⁵, L¹, L
^Two, L^ThreeAnd L^Four2, 3, 4, 5 or 6 of
Are bound to each other to form a polydentate chelating ligand
Good. Further, specific examples of the hetero atom include N, O,
P, S, As, Se atoms and the like can be mentioned. this
Among these, from the viewpoint of obtaining a stable carbene compound
, N, O, P, S atoms and the like are preferable, and N atom is particularly preferable.
Good

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 carbene complex catalyst represented by the general formula (B) include (1,3-dimesitylimidazolidin-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. Further, specific examples of the metallacyclobutane complex catalyst (iii) 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 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 tetrahydrofuran, dioxane; ketones such as acetone, ethyl methyl ketone, cyclopentanone, cyclohexanone; esters such as methyl acetate, ethyl acetate, ethyl propionate, methyl benzoate; chloroform, dichloromethane, 1,2 -Halogenated hydrocarbons such as 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, 1-butene, 1-
Α-olefins such as 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; allyl acetate; Oxygen-containing vinyl compounds such as allyl alcohol and glycidyl methacrylate; nitrogen-containing vinyl compounds such as acrylonitrile and acrylamide can be used. Formula (2)
A polymer having a desired molecular weight can be obtained by using the molecular weight modifier in an amount of 0.1 to 100 mol% with respect to the norbornene-based monomer represented by.

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 Method 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 hydrogenated norbornene ring-opening polymer of the present invention, the hydrogenated ratio of carbon-carbon double bonds (hydrogenation ratio) is usually 50% or more, and from the viewpoint of heat resistance, 70% or more. Is preferred, 80%
The above 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 using hydrogen gas in the presence of a hydrogenation catalyst,
It can be carried out by converting the carbon-carbon double bond in the main chain of the norbornene ring-opening polymer into a saturated single 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 catalysts comprising a combination of a transition metal compound and an alkali metal compound; ruthenium carbene complex catalysts, dichlorotris (triphenylphosphine) rhodium described in the section of the ring-opening metathesis reaction catalyst, JP-A-7-2929, and JP-A-7-2929. 7-149823, JP-A-11-109460, JP-A-11-158256, JP-A-11-193323,
Noble metal complex catalysts composed of ruthenium compounds described in JP-A No. 11-109460 and the like;

Examples of the heterogeneous catalysts include hydrogenation 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.

Of these, the carbon-carbon double bond in the polymer can be selectively hydrogenated without causing side reactions 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 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 metathesis reaction catalyst from the reaction solution without changing the solvent to carry out the reaction.

The conditions for the hydrogenation reaction 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 electrical 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.

[0087]

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 the ring-opening polymer or hydride.
It was measured by C) and converted into polystyrene. (2) Monomer composition ratio and hydrogenation rate The composition ratio of the ring-opening copolymer, and the hydrogenation rate (%) of the hydride of the ring-opening polymer and the hydride of the ring-opening copolymer are ¹ H-
It was determined by NMR spectrum measurement. (3) Polymerization conversion rate The polymerization conversion rate (%) was determined by measurement by gas chromatography. (4) Glass transition temperature The glass transition temperature is 10 per minute with a differential scanning calorimeter.
The temperature was raised at a rate of ° C and the measurement was performed.

Production Example 1: Cyclopentadiene / itacon
Preparation of acid anhydride adduct A solution prepared by dissolving 50 parts of itaconic anhydride in 90 parts of tetrahydrofuran was charged into a glass reactor equipped with a stirrer, and 35 parts of cyclopentadiene was added little by little at 0 ° C for 3 hours.
Stir for hours. The solvent was removed under reduced pressure, and toluene 90 was added to the residue.
Parts were added and stirred well. The precipitated solid component was removed by filtration, 70 parts of n-hexane was added to the filtrate, and -30
Left overnight at ° C. The precipitate was washed with n-hexane and dried to give white crystals. ^{According to 1} H-NMR measurement, this crystal has a cyclopentadiene / itaconic anhydride adduct (formula (2), wherein R ¹ and R ² are hydrogen atoms, X is an oxygen atom, Y is a methylene group, and m is 0). It corresponds to the compound).

Production Example 2: Cyclopentadiene / itacon
Production of acid imide adduct , except that itaconic anhydride was changed to itaconic acid imide,
Crystals were obtained in the same manner as in Production Example 1. ^{According to 1} H-NMR measurement, this crystal was confirmed to be a cyclopentadiene / itaconic acid imide adduct (in formula (2), R ¹ and R ² are hydrogen atoms, X is NH, Y is a methylene group, and m is 0) Equivalent).

Production Example 3: Cyclopentadiene / malein
Production of acid anhydride adduct Crystals were obtained in the same manner as in Production Example 1 except that 50 parts of itaconic anhydride was changed to 45 parts of maleic anhydride. ¹ H-
By NMR measurement, this crystal was found to be a cyclopentadiene / maleic anhydride adduct (bicyclo [2.2.1] hept-
5-ene-2,3-dicarboxylic acid anhydride).

Example 1 Cyclopentadiene / itacon
Production of Ring-Opening Polymer of Acid Anhydride Adduct Tetrahydrofuran (T
HF) 300 parts, cyclopentadiene obtained in Production Example 1 /
After adding 30 parts of itaconic anhydride adduct (CPDIA) and 0.7 part of 1-hexene as a chain transfer agent, 80
Heated to ° C. In addition, the polymerization catalyst benzylidene (1,3-dimesityl imidazolidine-2-ylidene)
4.5 parts of a THF solution (0.162 wt% solution) of (tricyclohexylphosphine) ruthenium dichloride was added, and the mixture was heated and stirred 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. In addition, ¹ H-NMR
By 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 cyclopenta
Preparation of ring-opening copolymer with diene / itaconic anhydride adduct
As concrete monomers, tetracyclo [4.4.0.1 ^{2, 5.}
1 ^7,10 ] dodec-3-ene (TCD) 10.9 parts and cyclopentadiene (CPD) / itaconic anhydride adduct (CPDIA) 21.4 parts (monomer composition: TC
Polymerization was carried out in the same manner as in Example 1 except that a mixture of D / CPDIA = 40/60 (mol / mol)) was used. The polymerization conversion rate was 96%, and the monomer composition ratio in the obtained ring-opening copolymer was TCD / CPDIA = 41/59.
(Mol / mol), weight average molecular weight (Mw) is 10,000
Met.

Example 3 Cyclopentadiene / itacon
Production of ring-opening polymer hydride of acid anhydride adduct All the polymer solution obtained in Example 1 was added to an autoclave equipped with a stirrer, the inside of the autoclave was replaced with nitrogen, and then bis (tricyclohexylphosphine) benzylidene was added. A hydrogenation catalyst solution prepared by dissolving 1.38 parts of ruthenium (IV) dichloride and 1.3 parts of ethyl vinyl ether in 13 parts of toluene was added, and the hydrogen pressure was 4.5 MPa, 16
Hydrogenation was carried out at 0 ° C. for 4 hours. The hydrogenation reaction liquid was poured into a large amount of methanol to completely precipitate solids. The solid content was collected by filtration, washed, and then dried under reduced pressure at 70 ° C. for 12 hours to obtain a hydrogenated ring-opening polymer. Weight average molecular weight (M
w) was 20,000, and it was confirmed from ¹ H-NMR that the carboxylic acid anhydride group was completely preserved and the hydrogenation rate was 91%. The glass transition temperature of this polymer hydride was 153 ° C.

Example 4 Tetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] dodec-3-ene and cyclopenta
Preparation of ring-opening copolymer with diene / itaconic acid imide adduct
As concrete monomers, tetracyclo [4.4.0.1 ^{2, 5.}
1 ^7,10 ] dodec-3-ene (TCD) 10.9 parts and cyclopentadiene (CPD) / itaconic acid imide adduct (CPDII) 21.2 parts (monomer composition: TCD / CPDII) obtained in Production Example 2 = 40/60 (mol / mol)), and polymerization was performed in the same manner as in Example 1. The polymerization conversion rate was 92%, and the monomer composition ratio in the obtained ring-opening copolymer was TCD / CPDII.
= 40/60 (mol / mol) and the weight average molecular weight (Mw) was 12,100.

Comparative Example 1 Bicyclo [2.2.1] hept-
Of the ring-opening polymer of 5-ene-2,3-dicarboxylic anhydride
Polymerization was carried out in the same manner as in Example 1 except that 30 parts of cyclopentadiene / maleic anhydride adduct was used instead of 30 parts of cyclopentadiene / itaconic anhydride adduct in Production Example 1. . Polymerization conversion rate is 10%,
The weight average molecular weight (Mw) was 9,800.

[0097]

INDUSTRIAL APPLICABILITY According to the present invention, ring-opening polymerization is industrially carried out by using a specific norbornene-based monomer having a carboxylic acid anhydride group or a carboxylic acid imide group in the presence of a metathesis reaction catalyst. A norbornene-based ring-opening polymer and a norbornene-based ring-opening polymer hydride can be advantageously produced.

The norbornene-based monomer used in the present invention is
Since the polymerization reactivity is high, the amount of the metathesis reaction catalyst used is small, and a norbornene-based monomer having no functional group and a copolymer having a desired composition ratio and 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 Kazunori Taguchi             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 (5)

[Claims] 1. A compound represented by the formula (1): [In the formula, R ¹ and R ² 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. X is an oxygen atom, a sulfur atom or NR ³ (R ³ is a hydrogen atom, a hydroxyl group, or a carbon atom which may have a substituent, and is 1 to 1).
It represents a hydrocarbon group having 0, an alkoxy group having 1 to 10 carbon atoms, or an alkoxycarbonyl group having 1 to 10 carbon atoms. ) Is represented, Y represents the C1-C5 alkylene group which may have a substituent, 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.
A norbornene-based ring-opening polymer, which is 1,000,000. 2. Formula (2): (Wherein R ¹ , R ² , X, 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. And a method for producing a norbornene ring-opening polymer. 3. The method for producing a norbornene ring-opening polymer according to claim 2, wherein a ruthenium carbene complex catalyst is used as the metathesis reaction catalyst. 4. 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, which comprises 50 parts of the double bond.
% Or more hydrogenated norbornene ring-opening polymer hydride. 5. A method for producing a hydride of a norbornene-based ring-opening polymer, which comprises hydrogenating the carbon-carbon double bond of the norbornene-based ring-opening polymer in the presence of a hydrogenation catalyst. .