JP2005089744A - Ring-opening polymer, hydrogenated product of the ring-opening polymer, method for producing the same, and polymerization catalyst composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a ring-opening polymer of a norbornene-based monomer with three or more rings, having a syndiotactic structure, to provide a hydrogenated product of the same, to provide a method for producing the polymer, to provide a method for producing the hydrogenated product, and to provide a polymerization catalyst composition suitable for the method for producing the polymer. <P>SOLUTION: This ring-opening polymer contains repeating units formed by conducting ring-opening polymerization of the polycyclic norbornene-based monomer with three or more rings in whole repeating units of the polymer, has a weight-average molecular weight of 500-1,000,000, and further has a ratio of racemo diads of not less than 51%. The method for producing the ring-opening polymer comprises polymerizing the polycyclic norbornene-based monomer with three or more rings by using a metal compound as a polymerization catalyst, wherein the metal compound is composed of a metal which belongs to the group 6 in the periodic table and with which an aryloxy group having a hydroxy group or an alkoxy group having the hydroxy group combines. The hydrogenated product of the ring-opening polymer which is obtained by hydrogenating 50% or more of double bonds of the main chain of the ring-opening polymer and the method for producing the hydrogenated product are provided, respectively. The catalyst composition for polymerizing the polycyclic norbornene-based monomer with three or more rings comprises the metal compound composed of the transition metal belonging to the group 6 in the periodic table and an activator. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a norbornene-based ring-opening polymer having a syndiotactic structure and a hydride thereof, a production method thereof, and a polymerization catalyst composition suitable for the production method.

  Norbornene-based ring-opening polymers and their hydrides have been known to be excellent in transparency, heat resistance, low birefringence, moldability, etc., and may be suitable as materials for optical disks and optical lenses. Although proposed, it also has other excellent properties such as low dielectric properties and chemical resistance, so its application field is expanding beyond optical applications. The structure of the norbornene-based ring-opening polymer and its hydride used here is usually an atactic and amorphous polymer. However, when used in various applications other than optical applications, mechanical strength, Since further improvement in solvent resistance, heat resistance and the like is desired, stereoregular polymerization of norbornene monomers has been proposed as a countermeasure.

  For example, Non-Patent Document 1 discloses 2,3-bis (trifluoromethyl) norbornadiene ring-opening polymer obtained by polymerizing a molybdenum complex in which a biphenoxy group and an imide group are coordinated as a polymerization catalyst, and 2,3- There is a description about the tacticity of a bis (dicarbomethoxy) norbornadiene ring-opening polymer. Non-patent document 2 describes the tacticity of a hydride of norbornene ring-opened polymer obtained by polymerization using a tantalum complex as a polymerization catalyst. Further, Non-Patent Document 3 describes the tacticity of a dicyclopentadiene ring-opened polymer hydride polymerized using a tungsten or molybdenum complex in which two biphenoxy groups are coordinated.

  However, all of these are meso-dyad ratios of 50% or more, that is, isotactic polymers, and syndiotactic weights that can be expected to have higher heat resistance, mechanical strength, and faster crystallization speed. It was not a coalescence.

  As the norbornene-based ring-opening polymer having a syndiotactic structure, 2,3-bis (trifluoromethyl) norbornadiene ring-opening polymer polymerized using a molybdenum complex in which two alkoxyl groups are coordinated is used as a polymerization catalyst. It is disclosed (see Non-Patent Document 4). However, the heat resistance of the polymer is not sufficient, and no polycyclic norbornene-based ring-opening polymer having high heat resistance and a hydride thereof having a syndiotactic structure have been obtained so far.

Macromolecules, 1995, 28, p. 5933-5940 Organometallics, 1998, Vol. 17, p. 4183-4195 Proceedings of the Society of Polymer Science, 2002, Vol. 8, p. 1629-1630 Journal of American Chemical Society, 1994, 116, p. 3414-3423

  The present invention has been made in view of the above-described prior art, and a norbornene-based ring-opening polymer having a syndiotactic structure, a hydride thereof, a production method thereof, and a polymerization catalyst suitable for the production method It is an object to provide a composition.

  As a result of intensive studies to solve the above problems, the present inventors have used a periodic table Group 6 transition metal compound in which an aryloxy group having a hydroxyl group or an alkoxyl group having a hydroxyl group is bonded as a polymerization catalyst. When a polycyclic norbornene monomer such as dicyclopentadiene is polymerized as a polycyclic norbornene monomer, the resulting ring-opening polymer has a syndiotactic structure, and hydrogen It was found that the compound has crystallinity. Moreover, it discovered that this ring-opening polymer and its hydride had high heat resistance. The present invention has been completed based on these findings.

  Thus, according to the first aspect of the present invention, a repeating unit formed by ring-opening polymerization of three or more polycyclic norbornene monomers in all the repeating units of the polymer has a weight average molecular weight of 500 to 1, There is provided a ring-opening polymer characterized in that the ratio of racemo dyad is 51% or more.

  The ring-opening polymer of the present invention preferably has a racemo dyad ratio of 70% or more, and preferably a tricyclic or higher polycyclic norbornene monomer is dicyclopentadiene.

  According to the second aspect of the present invention, a polycyclic norbornene system having 3 or more rings is used as a polymerization catalyst using a group 6 transition metal compound of a periodic table to which an aryloxy group having a hydroxyl group or an alkoxyl group having a hydroxyl group is bonded. A method for producing the ring-opening polymer of the present invention, which comprises polymerizing monomers, is provided.

According to the third aspect of the present invention, there is provided a hydrogenated ring-opening polymer obtained by hydrogenating 50% or more of the main chain double bond of the ring-opening polymer of the present invention.
The ring-opening polymer hydride of the present invention contains a repeating unit derived from a polycyclic norbornene-based monomer having three or more rings in the entire repeating unit of the polymer, and has a weight average molecular weight of 500 to 1,000,000. The ratio of racemo dyad is preferably 51% or more, and crystalline is preferable.

  According to the fourth aspect of the present invention, a polycyclic norbornene system having 3 or more rings is used as a polymerization catalyst using a periodic table Group 6 transition metal compound to which an aryloxy group having a hydroxyl group or an alkoxyl group having a hydroxyl group is bonded. Provided is a method for producing a hydride of a ring-opened polymer according to the present invention comprising a step of polymerizing a monomer to obtain a ring-opened polymer, and a step of hydrogenating a carbon-carbon double bond in the ring-opened polymer. Is done.

  According to the fifth aspect of the present invention, a polycyclic norbornene having three or more rings, comprising an aryloxy group having a hydroxyl group or an alkoxyl group having a hydroxyl group and a periodic table Group 6 transition metal compound and an activator. A monomer-based polymerization catalyst composition is provided.

According to the present invention, a novel norbornene ring-opening polymer containing a repeating unit formed by ring-opening polymerization of a polycyclic norbornene monomer having three or more rings and having a syndiotactic structure and a hydride thereof are provided. can get. The resulting ring-opened polymer hydride is a crystalline polymer, has excellent heat resistance, has a syndiotactic structure, and has a high crystallization speed, making it suitable as a molding material and film material for various applications. It is.
According to the production method of the present invention, the ring-opened polymer and the ring-opened polymer hydride of the present invention can be efficiently produced.
The polymerization catalyst composition of the present invention is useful as a polymerization catalyst used in a reaction in which a polycyclic norbornene-based monomer having three or more rings is polymerized to obtain the ring-opened polymer of the present invention.

Preferred embodiments of the present invention will be described in detail below.
[Norbornene-based ring-opening polymer]
The norbornene-based ring-opening polymer of the present invention contains a repeating unit formed by ring-opening polymerization of three or more polycyclic norbornene-based monomers in all repeating units of the polymer. The repeating unit formed by ring-opening polymerization of three or more polycyclic norbornene monomers is a norbornene-based single unit having a norbornene ring and one or more rings condensed with the norbornene ring in the molecule. It is a repeating unit obtained by ring-opening polymerization of a monomer. Specific examples thereof include those represented by the following general formula (1) or (2).

（式中、Ｒ^１及びＲ^２はそれぞれ独立に水素原子；ハロゲン原子；置換基を有していてもよい炭素数１〜２０の炭化水素基；又はケイ素原子、酸素原子もしくは窒素原子を含む置換基；を表し、互いに結合して環を形成していてもよい。Ｒ^３は置換基を有していてもよい炭素数１〜２０の二価の炭化水素基である。）

(Wherein R ¹ and R ² are each independently a hydrogen atom; a halogen atom; an optionally substituted hydrocarbon group having 1 to 20 carbon atoms; or a substitution containing a silicon atom, an oxygen atom or a nitrogen atom) And R ³ is a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

(Wherein R ^{4 to} R ⁷ are each independently a hydrogen atom; a halogen atom; an optionally substituted hydrocarbon group having 1 to 20 carbon atoms; or a substitution containing a silicon atom, an oxygen atom or a nitrogen atom) And R ⁴ and R ⁶ may be bonded to each other to form a ring, and m is 1 or 2.)

  The ratio of the repeating unit obtained by ring-opening polymerization of a polycyclic norbornene-based monomer having 3 or more rings to the total repeating unit of the polymer contained in the ring-opening polymer of the present invention is usually 10 mol% or more, preferably Is at least 50 mol%, more preferably at least 70 mol%, particularly preferably at least 90 mol%. A ring-opening polymer in which the ratio of repeating units obtained by ring-opening polymerization of three or more polycyclic norbornene-based monomers is in this range and its hydride are excellent in heat resistance.

The weight average molecular weight (Mw) measured by gel permeation chromatography of the ring-opening polymer of the present invention is 500 to 1,000,000, preferably 1,000 to 600,000, more preferably 5, in terms of polystyrene. 000 to 400,000. If Mw is too low, the mechanical strength may decrease, and if Mw is too high, molding becomes difficult.
Further, the content of the cis isomer of the ring-opening polymer of the present invention is usually 80 mol% or more, preferably 85 mol% or more.

Since the carbon represented by (i) and (iii) is an asymmetric carbon in the general formula (1) or (2), the ring-opening polymer of the present invention has stereoregularity (tacticity). To do. The ring-opening polymer of the present invention is a syndiotactic polymer in which the ratio of racemo dyad is 51% or more, preferably the ratio of racemo dyad is 60% or more, more preferably 70% or more. The ratio of meso dyad and racemo dyad can be measured by ¹³ C-NMR spectral analysis. Specifically, it is measured by quantifying the spectrum of at least one carbon atom represented by (i) to (v) in the general formula (1) or (2) of the ring-opening polymer of the present invention. it can.

In addition, when the ¹³ C-NMR spectrum of the ring-opened polymer of the present invention cannot be quantified, the ¹³ C-NMR spectrum of a hydride obtained by hydrogenating the main chain double bond of the ring-opened polymer is measured to obtain a meso • The ratio of Dyad and Racemo Dyad can be determined.

Although the method of quantification varies depending on the polymer, for example, in the case of a ring-opened polymer of dicyclopentadiene, the hydrogenated product is subjected to ¹³ C-NMR measurement at 150 ° C. using orthodichlorobenzene-d ₄ as a solvent, The ratio of racemo dyad can be determined from the intensity ratio of 43.35 ppm signal derived from meso dyad and 43.43 ppm signal derived from racemo dyad.

[Method for producing ring-opening polymer]
The method for producing a ring-opening polymer of the present invention is one example of the method for producing the ring-opening polymer of the present invention, and is a cycle in which an aryloxy group having a hydroxyl group or an alkoxyl group having a hydroxyl group is bonded. A polymerization catalyst containing a Table 6 group 6 transition metal compound is used to polymerize a tricyclic or higher polycyclic norbornene-based monomer.

[Monomer]
In the present invention, as a monomer, a polycyclic norbornene monomer having three or more rings (hereinafter sometimes referred to as “polycyclic norbornene monomer (α)”), a polycyclic norbornene. A combination of two or more types of monomer (α) or a combination of a polycyclic norbornene monomer (α) and another monomer copolymerizable therewith can be used.

  The polycyclic norbornene monomer having three or more rings is a norbornene monomer having a norbornene ring and one or more rings condensed with the norbornene ring in the molecule. Specific examples thereof include monomers represented by general formula (3) or general formula (4).

^(Wherein, R 1 to R ³ are the same as in the general formula (1).)

(In the formula, R ^{4 to} R ⁷ and m are the same as those in the general formula (2).)
Specific examples of the monomer represented by the general formula (3) include dicyclopentadiene, methyldicyclopentadiene, and tricyclo [5.2.1.0 ^2,6 ] dec-8-ene. it can. In addition, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene), tetracyclo [10.2.1.0 ^{2 , 11} . Norbornene derivatives having an aromatic ring such as 0 ^4,9 ] pentadeca-4,6,8,13-tetraene (also referred to as 1,4-methano-1,4,4a, 9,9a, 10-hexahydroanthracene) Can also be mentioned.

Examples of the monomer represented by the general formula (4) include tetracyclododecenes in which m is 1 and hexacycloheptadecenes in which m is 2.
Specific examples of tetracyclododecenes include tetracyclododecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, and 8-cyclopentyltetracyclododecene. Tetracyclododecenes having a substituted or alkyl group; 8-methylidenetetracyclododecene, 8-ethylidenetetracyclododecene, 8-vinyltetracyclododecene, 8-propenyltetracyclododecene, 8-cyclohexenyltetra Tetracyclododecenes having a double bond outside the ring such as cyclododecene and 8-cyclopentenyltetracyclododecene; tetracyclododecenes having an aromatic ring such as 8-phenyltetracyclododecene; 8-methoxy Carbonyltetracyclododecene, 8-methyl -8-methoxycarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, 8-carboxytetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid, tetracyclododecene-8,9-dicarboxylic acid Tetracyclododecenes having a substituent containing an oxygen atom such as anhydride; tetracyclododecene having a substituent containing a nitrogen atom such as 8-cyanotetracyclododecene and tetracyclododecene-8,9-dicarboxylic imide Dodecenes; tetracyclododecenes having substituents containing halogen atoms such as 8-chlorotetracyclododecene; tetracyclododecenes having substituents containing silicon atoms such as 8-trimethoxysilyltetracyclododecene And the like.

  Specific examples of hexacycloheptadecenes include hexacycloheptadecene, 12-methylhexacycloheptadecene, 12-ethylhexacycloheptadecene, 12-cyclohexylhexacycloheptadecene, and 12-cyclopentylhexacycloheptadecene. Hexacycloheptadecenes having a substituted or alkyl group; 12-methylidenehexacycloheptadecene, 12-ethylidenehexacycloheptadecene, 12-vinylhexacycloheptadecene, 12-propenylhexacycloheptadecene, 12-cyclohexenylhexa Hexacycloheptadecenes having a double bond outside the ring such as cycloheptadecene and 12-cyclopentenylhexacycloheptadecene; aromatic rings such as 12-phenylhexacycloheptadecene Hexacycloheptadecenes; 12-methoxycarbonylhexacycloheptadecene, 12-methyl-12-methoxycarbonylhexacycloheptadecene, 12-hydroxymethylhexacycloheptadecene, 12-carboxyhexacycloheptadecene, hexacycloheptadecene Hexacycloheptadecenes having a substituent containing an oxygen atom such as 12,13-dicarboxylic acid and hexacycloheptadecene 12,13-dicarboxylic anhydride; 12-cyanohexacycloheptadecene, hexacycloheptadecene 12,13 A hexacycloheptadecene having a substituent containing a nitrogen atom such as dicarboxylic imide; a hexacycloheptadecene having a substituent containing a halogen atom such as 12-chlorohexacycloheptadecene; Such as hexamethylene cycloheptanone decene compound having a substituent containing a silicon atom such as trimethoxy silyl hexamethylene cycloheptanone decene and the like.

In the production method of the present invention, since the stereoregularity at the time of the polymerization reaction depends on the three-dimensional structure of the portion related to the ring-opening reaction of the monomer, the ratio of racemo dyad is not limited to any of the above monomers. 51% or more of the ring-opening polymer can be obtained. Among them, the monomer represented by the general formula (3) or the tetracyclododecenes in which m is 1 in the general formula (4) is preferable in that the obtained ring-opened polymer hydride has high crystallinity. . Among these, dicyclopentadiene, tricyclo [5.2.1.0 ^2,6] dec-8-ene, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8] tetradec -3,5,7,12- tetraene, tetracyclo [10.2.1.0 ^2,11. 0 ^4,9] pentadeca -4,6,8,13- tetraene, tetracyclododecene, 8-methyl tetracyclododecene more preferably, dicyclopentadiene is particularly preferable.

  In the production method of the present invention, the amount of the polycyclic norbornene monomer (α) used is usually 10 mol% or more, preferably 50 mol% or more, more preferably 70 mol% or more, based on the total monomers. Especially preferably, it is 90 mol% or more.

  The polycyclic norbornene-based monomer includes an isomer of an endo isomer and an exo isomer. The monomer used in the present invention may be a mixture of these isomers. However, in order to further improve the crystallinity, the composition ratio of any isomer component in the isomer mixture should be higher. preferable. Specifically, it is preferable that any isomer is 70% or more, particularly 80% or more. By increasing the composition ratio of any of the isomer components, the resulting polymer is highly crystallized, so that the heat resistance can be further improved.

  Examples of the monomer copolymerizable with the polycyclic norbornene monomer (α) include cyclic olefins (β). Examples of the cyclic olefins (β) include norbornene monomers that do not have a ring condensed with a norbornene ring in the molecule, and monocyclic olefins.

  Specific examples of the norbornene-based monomer having no ring condensed with the norbornene ring in the molecule include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-hexylnorbornene, 5-decylnorbornene, Norbornenes having an unsubstituted or alkyl group such as 5-cyclohexylnorbornene and 5-cyclopentylnorbornene; alkenyl such as 5-ethylidenenorbornene, 5-vinylnorbornene, 5-propenylnorbornene, 5-cyclohexenylnorbornene and 5-cyclopentenylnorbornene Norbornenes having a group; norbornenes having an aromatic ring such as 5-phenylnorbornene; 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5 Methoxycarbonylnorbornene, 5-methyl-5-ethoxycarbonylnorbornene, norbornenyl-2-methylpropionate, norbornenyl-2-methyloctanoate, 5-hydroxymethylnorbornene, 5,6-di (hydroxymethyl) norbornene, 5, Norbornenes having polar groups containing oxygen atoms, such as 5-di (hydroxymethyl) norbornene, 5-hydroxy-isopropylnorbornene, 5,6-dicarboxynorbornene, 5-methoxycarbonyl-6-carboxynorbornene; 5-cyano And norbornenes having a polar group containing a nitrogen atom such as norbornene.

  The monocyclic olefins are cyclic olefins or diolefins having 4 to 20 carbon atoms and substituted products thereof, preferably cyclic olefins or diolefins having 4 to 10 carbon atoms and derivatives thereof.

  Specific examples of monocyclic olefins or diolefins include monocyclic olefin monomers such as cyclobutene, cyclopentene, methylcyclopentene, cyclohexene, methylcyclohexene, cycloheptene, and cyclooctene; cyclohexadiene, methylcyclohexadiene And cyclic diolefin monomers such as cyclooctadiene, methylcyclooctadiene, and phenylcyclooctadiene.

[Polymerization catalyst]
In the present invention, a polymerization catalyst for a Group 6 transition metal compound (hereinafter sometimes referred to as “Group 6 transition metal compound”) to which an aryloxy group having a hydroxyl group or an alkoxyl group having a hydroxyl group is bonded is used. Use.

Examples of the Group 6 transition metal of the Group 6 transition metal compound include chromium, molybdenum, tungsten, and the like. Molybdenum and tungsten are preferable, and tungsten is particularly preferable.
The Group 6 transition metal compound is a compound having a structure represented by the following general formula (5).

(In the formula, M represents a Group 6 transition metal, and R ⁸ represents a divalent hydrocarbon group which may have a substituent.)

Specific examples of R ⁸ include a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a divalent aliphatic hydrocarbon group having 6 to 50 carbon atoms. An aromatic hydrocarbon group or a hydrocarbon group in which these are bonded to each other can be used.

  The group 6 transition metal compound is preferably a compound represented by the general formula (6) in which the hydroxyl group is coordinated to the group 6 transition metal compound as a neutral ligand. More preferred is a compound.

(In the formula, M and R ⁸ have the same meaning as described above.)

In formula (7), M and R ⁸ represent the same meaning as described above.
Z represents a group represented by an oxygen atom or NR ^9, NR ⁹ are preferred. R ⁹ represents a hydrocarbon group which may have a substituent. R ⁹ includes a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 24 carbon atoms which may have a substituent, and the like. Can be mentioned.

  X represents a halogen atom, a hydrocarbon group, an alkylsilyl group, an alkoxyl group or an aryloxy group. When there are a plurality of X, Xs may be the same or different from each other, and may be bonded to each other.

Examples of the halogen atom for X include a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, benzyl group, neophyll group, phenyl group, and naphthyl group. . Examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a t-butyldimethylsilyl group. Examples of the alkoxyl group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, and a t-butoxy group. Examples of the aryloxy group include phenoxy group, 2,6-dimethylphenoxy group, 2,6-diisopropylphenoxy group. Examples of a plurality of X bonded to each other include a biphenoxy group and a phenyldioxy group.
p represents 1 or 2, and 1 is preferable.

L is an electron-donating neutral ligand. Examples of the electron-donating neutral ligand include electron-donating compounds containing atoms of Group 14 or Group 15 of the Periodic Table. Specific examples thereof include phosphines such as trimethylphosphine, triisopropylphosphine, tricyclohexylphosphine, and triphenylphosphine; ethers such as diethyl ether, dibutyl ether, 1,2-dimethoxyethane, and tetrahydrofuran; trimethylamine, triethylamine, pyridine, Amines such as lutidine; and the like. Of these, ethers are preferable.
b is an integer of 0-2. When b is 2, L may be the same as or different from each other.

  In the compound represented by formula (7), more preferred compounds include compounds represented by formulas (8) to (10).

In the formulas (8) to (10), M, Z, X, L, b, and p represent the same meaning as described above.
R ^{10 to} R ²⁷ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a substituent containing a halogen atom, a silicon atom, an oxygen atom or a nitrogen atom, and groups bonded to adjacent carbon atoms are mutually They may combine to form a ring.

  Q is a kind selected from an oxygen atom, a sulfur atom, and the following formulas (11) to (14).

In formulas (11) to (14), R ^{28 to} R ³² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.

Specific examples of R ^{10 to} R ²⁷ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, and a phenyl group.

In addition, groups bonded to adjacent carbon atoms of R ^{10 to} R ²⁷ may be bonded to each other to form a ring. Examples of groups in which adjacent carbon atoms are bonded to each other to form a ring include compounds in which R ¹¹ and R ¹² are combined to form a naphthalene ring; R ¹⁴ and R ¹⁵ or R ¹⁸ and R ¹⁹ Are bonded to form an anthracene ring; R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ are bonded to form a phenanthrene ring; R ²² and R ²³ and / or R ²⁴ and R ²⁵ And a compound in which a naphthalene ring is bonded to each other; and the like.
q is 0 or 1.

  Among these, in the present invention, the Group 6 transition metal compound is particularly preferably a Group 6 transition metal compound of the periodic table represented by the following general formula (a).

In formula (a), M, X, L and b represent the same meaning as described above.
R ^a represents a phenyl group which may have a substituent at any of the 3, 4, and 5 positions, or a group represented by —CH ₂ R ^d .

  Examples of the substituent of the phenyl group which may have a substituent at any of the 3, 4 and 5 positions include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, Alkyl groups such as isobutyl group and t-butyl group; cycloalkyl groups such as cyclopropyl group, cyclopentyl group and cyclohexyl group; halogen atoms such as fluorine atom, chlorine atom and bromine atom; methoxy group, ethoxy group, propoxy group, iso And alkoxyl groups such as propoxy group, butoxy group and t-butoxy group.

  Specific examples of the phenyl group which may have a substituent at any of the 3, 4 and 5 positions include phenyl group; 4-methylphenyl group, 4-chlorophenyl group, 3-methoxyphenyl group, 4- Monosubstituted phenyl groups such as cyclohexylphenyl group and 4-methoxyphenyl group: Disubstituted groups such as 3,5-dimethylphenyl group, 3,5-dichlorophenyl group, 3,4-dimethylphenyl group, and 3,5-dimethoxyphenyl group And phenyl group; trisubstituted phenyl groups such as 3,4,5-trimethylphenyl group and 3,4,5-trichlorophenyl group; Moreover, the 2-naphthyl group which may have substituents, such as 2-naphthyl group, 3-methyl-2- naphthyl group, and 4-methyl-2-naphthyl group, may be sufficient.

R ^d of the -CH ₂ R ^d is a hydrogen atom, have an alkyl group or a substituted group which may have a substituent represents an even aryl group, an alkyl which may have a substituent Groups are preferred.

The carbon number of the alkyl group which may have a substituent for R ^d is not particularly limited, but is usually 1 to 20, preferably 1 to 10. These alkyl groups may be linear or branched. Examples of the substituent of the alkyl group which may have a substituent for R ^d include a phenyl group which may have a substituent such as a phenyl group and a 4-methylphenyl group; a methoxy group, an ethoxy group and the like And the like.

The aryl group which may have a substituent for R ^d is preferably an aryl group having 6 to 20 carbon atoms, and specific examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. Etc. Examples of the substituent of the aryl group which may have a substituent of R ^d are examples of the substituent of the phenyl group which may have a substituent at any of the 3, 4, and 5 positions of R ^a. The same thing as what was done is mentioned.

  Y represents the above aryloxy group having a hydroxyl group or an alkoxyl group having a hydroxyl group.

  The Group 6 metal compound comprises a Group 6 transition metal halide, oxyhalide, dioxyhalide, imide halide, diimide halide or imideoxyhalide, diols, and electron-donating neutrality. It can be obtained by mixing with the ligand (L). More specifically, Journal of American Chemical Society, 1993, 115, p. 7916-7917; Polyhedron, 1992, Vol. 11, p. 2039-2044; Polyhedron, 1995, Vol. 14, p. 3255-3271; and the like.

  In the production method of the present invention, the Group 6 transition metal compound is used as a polymerization catalyst, and the polymerization is performed by mixing with the monomer. As for the ratio of the amount of the monomer and the polymerization catalyst used, the molar ratio (Group 6 transition metal compound: monomer) is usually from 1: 100 to 1: 2,000,000, preferably from 1: 500 to 1. 1,000,000, more preferably 1: 1,000 to 1: 500,000. If the amount of catalyst is too large, it is difficult to remove the catalyst, and if it is too small, sufficient polymerization activity cannot be obtained.

  Moreover, in the manufacturing method of this invention, when using a group 6 transition metal compound, it is preferable to use an activator together. That is, the polymerization activity can be further improved by using a polymerization catalyst composition comprising a Group 6 transition metal compound and an activator. This polymerization catalyst composition comprising a Group 6 transition metal compound and an activator is useful as a catalyst composition for polymerization of a tricyclic or higher polycyclic norbornene monomer.

  Examples of the activator include organometallic compounds of Groups 1, 2, 12, 13, and 14 of the periodic table having a hydrocarbon group having 1 to 20 carbon atoms. Among these, organic lithium, organic magnesium, organic zinc, organic aluminum, and organic tin are preferable, and organic aluminum and organic tin are particularly preferable. Examples of the organic lithium include n-butyl lithium, methyl lithium, and phenyl lithium. Examples of the organic magnesium include butylethylmagnesium, butyloctylmagnesium, dihexylmagnesium, ethylmagnesium chloride, n-butylmagnesium chloride, and allylmagnesium bromide. Examples of the organic zinc include dimethyl zinc, diethyl zinc, and diphenyl zinc. Examples of organic aluminum include trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum ethoxide, diisobutylaluminum isobutoxide, ethylaluminum diethoxide, isobutylaluminum diisobutoxide, etc. Can be mentioned. Examples of the organic tin include tetramethyltin, tetra (n-butyl) tin, and tetraphenyltin.

  The amount of the activator used is preferably 0.1 to 100 times, more preferably 0.2 to 50 times, and particularly preferably 0.5 to 20 times in terms of molar ratio with respect to the Group 6 transition metal compound. . If the amount used is too small, the polymerization activity does not improve, and if it is too large, side reactions are likely to occur.

[solvent]
In the present invention, the polymerization reaction can be carried out in the absence of a solvent. However, when a hydrogenation reaction is carried out after the polymerization, the polymerization is preferably carried out in an organic solvent (solution polymerization). The organic solvent used in the present invention is not particularly limited as long as the polymer and the polymer hydride are dissolved or dispersed under predetermined conditions and do not inhibit polymerization and hydrogenation.

  Specific examples of such organic solvents include aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, and bicyclohexane. Alicyclic hydrocarbons such as heptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; Halogen-based aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; Nitrogen-containing hydrocarbon solvents such as nitromethane, nitrobenzene, and acetonitrile; Diethyl ether, tetrahydrofuran, etc. D - it can be used solvents such as ethers. Among these solvents, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons and ethers are preferable.

  When the polymerization is performed in an organic solvent, the concentration of the monomer is preferably 1 to 50% by weight in the solution, more preferably 2 to 45% by weight, and particularly preferably 3 to 40% by weight. If the monomer concentration is too low, the productivity is poor, and if it is too high, the solution viscosity after polymerization is too high, and the subsequent hydrogenation reaction may be difficult.

  In the polymerization reaction, an activity regulator can be added. The activity regulator is used to stabilize the polymerization catalyst, to adjust the polymerization reaction rate, and to adjust the molecular weight distribution of the polymer. The activity regulator is not particularly limited as long as it is an organic compound having a functional group, but is preferably an oxygen-containing, nitrogen-containing, or phosphorus-containing organic compound. Specifically, ethers such as diethyl ether, diisopropyl ether, dibutyl ether, anisole, furan and tetrahydrofuran; ketones such as acetone, benzophenone and cyclohexanone; esters such as ethyl acetate; nitriles such as acetonitrile benzonitrile; triethylamine , Triisopropylamine, quinuclidine, amines such as N, N-diethylaniline; pyridines such as pyridine, 2,4-lutidine, 2,6-lutidine, 2-t-butylpyridine; triphenylphosphine, tricyclohexylphosphine Phosphines such as triphenyl phosphate and trimethyl phosphate; triphenyl phosphine, tricyclohexyl phosphine, triphenyl phosphate, trimethyl phosphate - phosphines such as preparative; phosphine oxides such as triphenylphosphine oxide; and the like, but not limited thereto. These can be used individually by 1 type or in mixture of 2 or more types. The amount of the activity regulator to be added can be arbitrarily selected between 0.01 and 100 mol% with respect to the polymerization catalyst.

  In the polymerization reaction, a molecular weight modifier can be added to adjust the molecular weight of the polymer. Examples of molecular weight modifiers include α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; aromatic vinyl compounds such as styrene and vinyltoluene; ethyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether, acetic acid Oxygen-containing vinyl compounds such as allyl, allyl alcohol, and glycidyl methacrylate; halogen-containing vinyl compounds such as allyl chloride; nitrogen-containing vinyl compounds such as acrylamide; 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1 , 6-heptadiene, 2-methyl-1,4-pentadiene, non-conjugated dienes such as 2,5-dimethyl-1,5-hexadiene; 1,3-butadiene, 2-methyl-1,3-butadiene, 2, 3-dimethyl-1,3-butadiene, 1, - pentadiene, a conjugated diene such as 1,3-hexadiene; can be mentioned. The amount of the molecular weight modifier to be added can be arbitrarily selected from 0.1 to 50 mol% based on the monomer depending on the desired molecular weight.

  The polymerization temperature is not particularly limited, but is generally -78 ° C to 200 ° C, preferably -30 ° C to 180 ° C. The polymerization time is 1 minute to 1000 hours and is not particularly limited.

[Norbornene ring-opening polymer hydride]
The hydride of norbornene-based ring-opening polymer of the present invention contains a repeating unit derived from a tricyclic or more polycyclic norbornene-based monomer. In the hydride of norbornene-based ring-opening polymer of the present invention, the repeating unit derived from three or more polycyclic norbornene-based monomers is a norbornene ring in the molecule and one or more condensed with the norbornene ring. Is a repeating unit obtained by ring-opening polymerization of a norbornene-based monomer having the following ring, and then hydrogenating a main chain double bond in the obtained ring-opening polymer.

  The hydrogenated norbornene-based ring-opening polymer of the present invention can be obtained by hydrogenating 50% or more of the main chain double bond of the ring-opening polymer of the present invention. Since the ring-opening polymer of the present invention can maintain tacticity after hydrogenation, the resulting ring-opening polymer hydride has a racemo dyad ratio of 51% or more, preferably 60% or more, more preferably. Is a syndiotactic polymer of 70% or more. The hydrogenation rate is preferably 70% or more, more preferably 80% or more, and particularly preferably 90% or more. The higher the hydrogenation rate, the better the heat resistance of the ring-opening polymer hydride.

  The ring-opening polymer hydride of the present invention is usually crystalline and has a melting point (Tm). The melting point can be observed by an endothermic peak due to melting of the crystalline component of the polymer when measured with a differential scanning calorimeter. The ring-opening polymer hydride of the present invention has a melting point of usually 150 ° C. or higher, preferably 200 ° C. to 400 ° C.

[Hydrogenation reaction]
The method for producing a hydride of a ring-opened polymer according to the present invention comprises a step of obtaining a ring-opened polymer by the method for producing a ring-opened polymer according to the present invention, Including the step of. The hydrogenation reaction is performed by supplying hydrogen into the reaction system in the presence of a hydrogenation catalyst. Any hydrogenation catalyst can be used as long as it is generally used in the hydrogenation of olefin compounds, and is not particularly limited. Examples thereof include the following.

  As the homogeneous catalyst, a catalyst system comprising a combination of a transition metal compound and an alkali metal compound, such as cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec- Examples include butyl lithium, tetrabutoxy titanate / dimethyl magnesium, and the like. Further examples include noble metal complex catalysts such as dichlorobis (triphenylphosphine) palladium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, and chlorotris (triphenylphosphine) rhodium.

  As the heterogeneous catalyst, nickel, palladium, platinum, rhodium, ruthenium, or a solid catalyst in which these metals are supported on a support such as carbon, silica, diatomaceous earth, alumina, titanium oxide, for example, nickel / silica, nickel / Examples of the catalyst system include diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, and palladium / alumina.

The hydrogenation reaction is usually carried out in an inert organic solvent. Examples of such inert organic solvents include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as pentane and hexane; alicyclic hydrocarbons such as cyclohexane and decahydronaphthalene; tetrahydrofuran, ethylene glycol dimethyl ether, and the like. Ethers; and the like.
The inert organic solvent is usually the same as the solvent used for the polymerization reaction, and the hydrogenation catalyst may be added to the polymerization reaction solution as it is and allowed to react.

  The suitable conditions for the hydrogenation reaction vary depending on the hydrogenation catalyst used, but the reaction temperature is usually -20 ° C to 250 ° C, preferably -10 ° C to 220 ° C, more preferably 0 ° C to 200 ° C. If the hydrogenation temperature is too low, the reaction rate is slow, and if it is too high, side reactions may occur. The hydrogen pressure is usually 0.01 to 20 MPa, preferably 0.05 to 15 MPa, more preferably 0.1 to 10 MPa. If the hydrogen pressure is too low, the hydrogenation rate is slow, and if it is too high, a high pressure reactor is required. Although reaction time will not be specifically limited if it can be set as the desired hydrogenation rate, Usually, it is 0.1 to 10 hours.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, unless otherwise indicated, the part and% in a manufacture example, an Example, and a comparative example are a basis of weight.

(1) The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the ring-opening polymer were obtained as polystyrene conversion values by gel permeation chromatography measurement using chloroform as a solvent.
(2) The isomer ratio (cis / trans ratio) of the ring-opening polymer and the hydrogenation rate of the ring-opening polymer hydride were determined by ¹ H-NMR measurement.
(3) The ratio of racemo dyad in the ring-opened polymer hydride was measured by performing ¹³ C-NMR measurement at 150 ° C. using orthodichlorobenzene-d ₄ as a solvent, and a 43.35 ppm signal derived from meso dyad, It was determined from the intensity ratio of the 43.43 ppm signal from Racemo Dyad.
(4) The glass transition temperature (Tg) and melting point (Tm) and heat of fusion (ΔH) of the ring-opening polymer hydride were measured by raising the temperature at 10 ° C./min using a differential scanning calorimeter.

[Production Example 1]
To a glass reactor equipped with a stirrer, 1.35 parts of tungsten (2,6-dimethylphenylimide) tetrachloride and 21 parts of diethyl ether were added and cooled to -78 ° C. Further, 0.74 part of 3,3 ′, 5,5′-tetramethyl-2,2′-biphenol dissolved in 21 parts of diethyl ether was added. The mixture was gradually warmed to 0 ° C., and maintained at 0 ° C. for 24 hours. After the reaction, diethyl ether was distilled off to obtain a dark red purple solid.
To the obtained solid, 13 parts of hexane and 4.2 parts of diethyl ether were added, and this was cooled to −78 ° C. and allowed to stand for 1 hour to precipitate a microcrystalline insoluble matter. The soluble part was filtered off, and the remaining insoluble matter was further washed with 6.6 parts of hexane, and then the solvent was distilled off to obtain 1.84 parts of compound (a).

The ¹ H-NMR spectrum measured in C ₆ D _{6 of} this compound (a) was as follows.
δppm: 7.79 (s, 1H), 6.98 (d, 1H), 6.88 (d, 1H), 6.77 (s, 2H), 6.75 (s, 2H), 6.26 (T, 1H), 3.27 (q, 4H), 3.07 (s, 6H), 2.41 (s, 3H), 2.37 (s, 3H), 2.23 (s, 3H) , 2.05 (s, 3H), 1.00 (t, 6H)

  The results of elemental analysis of this compound (a) were carbon 46.39%, hydrogen 5.07%, and nitrogen 1.91%. This result was in good agreement with the calculated value of the elemental composition of the compound represented by formula (15), 46.40% carbon, 5.01% hydrogen, and 1.93% nitrogen. From the above results, it was confirmed that the compound (a) had a structure represented by the formula (15).

[Production Example 2]
Compound (b) was prepared in the same manner as in Production Example 1 except that 1.13 g of tungsten (phenylimide) tetrachloride / diethyl ether complex was used instead of 1.35 g of tungsten (2,6-dimethylphenylimide) tetrachloride. ) 1.34 parts were obtained.

The ¹ H-NMR spectrum measured in C ₆ D _{6 of} this compound (b) was as follows.
δppm: 9.13 (s, 1H), 7.29 (s, 1H), 7.14 (s, 1H), 6.80 (d, 2H), 6.36 (t, 1H), 3.33 (Q, 4H), 3.17 (s, 6H), 1.40 (s, 9H), 1.30 (s, 9H), 1.12 (t, 6H).

  The results of elemental analysis of this compound (b) were carbon 44.91%, hydrogen 4.61% and nitrogen 2.05%. This result was in good agreement with the calculated elemental composition of the compound represented by formula (16), 44.82% carbon, 4.63% hydrogen, and 2.01% nitrogen. From this result, it was confirmed that the structure of the compound (b) was a structure represented by the formula (16).

[Example 1]
0.082 parts of the compound (a) obtained in Production Example 1 and 3.5 parts of toluene were added as a polymerization catalyst to a glass reactor equipped with a stirrer, and this was cooled to -78 ° C. Further, a solution obtained by dissolving 0.027 part of diethylaluminum chloride in 0.87 part of toluene was added, and this was returned to 0 ° C. and reacted for 1 hour. To the resulting mixture, 7.5 parts of dicyclopentadiene, 23 parts of toluene, and 0.65 part of 1-octene were added, and a polymerization reaction was performed at 0 ° C. After the polymerization reaction started, the viscosity of the solution gradually increased. After the reaction for 24 hours, a large amount of methanol was poured into the polymerization reaction solution to aggregate the precipitate, washed by filtration, and dried under reduced pressure at 40 ° C. for 24 hours to obtain 7.4 parts of the ring-opened polymer (1). . Mn of the ring-opening polymer (1) was 42,000, and Mw was 210,000. The cis / trans ratio of the carbon-carbon double bond of the ring-opening polymer main chain was 93/7.

[Example 2]
In the same manner as in Example 1 except that 0.079 part of the compound (b) obtained in Production Example 2 was used as a polymerization catalyst instead of 0.082 part of the compound (a), a ring-opening polymer (2) 7.1 parts of was obtained. Mn of the ring-opening polymer (2) was 8,100, and Mw was 25,000. The cis / trans ratio of the carbon-carbon double bond of the ring-opening polymer main chain was 92/8.

[Example 3]
To an autoclave equipped with a stirrer, 3 parts of the ring-opening polymer (1) obtained in Example 1 and 47 parts of cyclohexane were added. Next, a hydrogenation catalyst solution in which 0.0187 part of bis (tricyclohexylphosphine) benzilidineruthenium (IV) dichloride and 0.45 part of ethyl vinyl ether were dissolved in 7.8 parts of cyclohexane was added, and the hydrogen pressure was 0.8 MPa, 160 Hydrogenation reaction was carried out at 0 ° C. for 8 hours. The hydrogenation reaction solution was poured into a large amount of isopropanol to completely precipitate the polymer, washed by filtration and dried under reduced pressure at 40 ° C. for 24 hours to obtain a ring-opened polymer hydride (1). When ¹ H-NMR of this product was measured, no peak derived from a carbon-carbon double bond was observed, and the hydrogenation rate was 99% or more. The ratio of racemo dyad in the ring-opened polymer hydride (1) was 68%. The melting point (Tm) was 270 ° C. and the heat of fusion (ΔH) was 49 J / g.

[Example 4]
A hydrogenated ring-opened polymer (2) was obtained in the same manner as in Example 3 except that 3 parts of the ring-opened polymer (2) obtained in Example 2 was used as the ring-opened polymer. When ¹ H-NMR of this product was measured, no peak derived from a carbon-carbon double bond was observed, and the hydrogenation rate was 99% or more. The ratio of racemo dyad in the ring-opened polymer hydride (2) was 80%. The melting point (Tm) was 271 ° C. and the heat of fusion (ΔH) was 49 J / g.

[Comparative Example 1]
7.4 parts of ring-opened polymer (3) were obtained in the same manner as in Example 1 except that 0.05 part of tungstenoxytetrachloride was used as a polymerization catalyst instead of 0.082 part of compound (a). It was. Mn of the ring-opening polymer (3) was 5,200, and Mw was 26,100. The cis / trans ratio of the carbon-carbon double bond of the ring-opening polymer main chain was 80/20.

[Comparative Example 2]
Using the ring-opening polymer (3) obtained in Comparative Example 1, a hydrogenation reaction was carried out in the same manner as in Example 3 to obtain a ring-opening polymer hydride (3). When ¹ H-NMR of this product was measured, no peak derived from a carbon-carbon double bond was observed, and the hydrogenation rate was 99% or more. The ratio of racemo dyad in the ring-opened polymer hydride (3) was 50%. The melting point (Tm) was not observed, and the glass transition point (Tg) was observed at 98 ° C.
The above results are shown in Table 1.

第１表から明らかなように、実施例１，２では、シス体の含有量（シス／トランス比）が高い開環重合体（１）及び（２）が得られた。また、得られた開環重合体（１）、（２）を水素化することにより、ラセモ・ダイアッドの割合が５１％以上（６８％、８０％）での融点（Ｔｍ）を有する結晶性の重合体（開環重合体水素化物（１）、（２））を得ることができた。得られた開環重合体水素化物（１）及び（２）は、約２７０℃という高い融点と４９Ｊ／ｇという高い融解熱を示し、耐熱性が高いことが分かる（実施例３，４）。
これに対し、比較例１では、シス体の含有量（シス／トランス比）が比較的低い開環重合体（３）が得られた。また、このものを水素化することで得られた開環重合体水素化物（３）は、ラセモ・ダイアッドの割合が５０％であって、融点を示さない非晶性の重合体であり、ガラス転移温度が１０３℃と低く、耐熱性が低いものであった（比較例１，２）。

As is apparent from Table 1, in Examples 1 and 2, ring-opening polymers (1) and (2) having a high cis content (cis / trans ratio) were obtained. Further, by hydrogenating the obtained ring-opening polymers (1) and (2), a crystalline property having a melting point (Tm) at a racemo dyad ratio of 51% or more (68%, 80%) is obtained. A polymer (ring-opening polymer hydride (1), (2)) could be obtained. The obtained ring-opened polymer hydrides (1) and (2) have a high melting point of about 270 ° C. and a high heat of fusion of 49 J / g, and are found to have high heat resistance (Examples 3 and 4).
On the other hand, in Comparative Example 1, a ring-opening polymer (3) having a relatively low cis content (cis / trans ratio) was obtained. Further, the hydrogenated ring-opening polymer (3) obtained by hydrogenating this product is an amorphous polymer having a racemo dyad ratio of 50% and showing no melting point. The transition temperature was as low as 103 ° C. and the heat resistance was low (Comparative Examples 1 and 2).

Claims (9)

  It contains a repeating unit formed by ring-opening polymerization of three or more polycyclic norbornene monomers in all the repeating units of the polymer, and has a weight average molecular weight of 500 to 1,000,000. A ring-opening polymer characterized in that the ratio is 51% or more.   The norbornene-based ring-opening polymer according to claim 1, wherein the ratio of racemo dyad is 70% or more.   The ring-opening polymer according to claim 1 or 2, wherein the tricyclic or higher polycyclic norbornene monomer is dicyclopentadiene.   A polycyclic norbornene monomer having three or more rings is polymerized using a transition metal compound of Group 6 of the periodic table to which an aryloxy group having a hydroxyl group or an alkoxyl group having a hydroxyl group is bonded as a polymerization catalyst. The manufacturing method of the ring-opening polymer in any one of Claims 1-3.   A hydrogenated ring-opened polymer obtained by hydrogenating 50% or more of the main chain double bond of the ring-opened polymer according to any one of claims 1 to 3.   A repeating unit derived from a polycyclic norbornene monomer having 3 or more rings is contained in all the repeating units of the polymer, the weight average molecular weight is 500 to 1,000,000, and the ratio of racemo dyad is 51% or more. A ring-opened polymer hydride.   The ring-opening polymer hydride according to claim 5 or 6, which is crystalline.   Periodic table group 6 transition metal compound to which an aryloxy group having a hydroxyl group or an alkoxyl group having a hydroxyl group is bonded is used as a polymerization catalyst to polymerize a polycyclic norbornene monomer having 3 or more rings to open the ring. The method for producing a hydrogenated ring-opened polymer according to claim 6 or 7, comprising a step of obtaining a polymer and a step of hydrogenating a carbon-carbon double bond in the ring-opened polymer.   Polymerization catalyst composition of tricyclic or higher polycyclic norbornene monomer comprising an aryloxy group having a hydroxyl group or an alkoxyl group having a hydroxyl group bonded to a periodic table Group 6 transition metal compound and an activator .