JP2010159404A - Method for producing hydrogenated product of cyclic olefin-based ring-opened (co)polymer and the resultant hydrogenated product of cyclic olefin-based ring-opened (co)polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To produce in high productivity a cyclic olefin-based ring-opened (co)polymer nearly transparent in hue and suitable for uses including optical applications by hydrogenating a (co)polymer of the corresponding cyclic olefin-based compound having a plurality of olefinic unsaturated bonds in the molecule. <P>SOLUTION: A method for producing the cyclic olefin-based ring-opened (co)polymer is provided, comprising: the step of starting to bring a solution containing (A) a cyclic olefin-based ring-opened (co)polymer having structural units each derived from a cyclic olefin-based compound represented by general formula(1) and (B) a metal compound into contact with hydrogen under control at 10 to 40°C; and the step of conducting a hydrogenation reaction by raising the temperature of the solution to 100-200°C. In the general formula (1), A<SP>1</SP>and A<SP>2</SP>are each independently H; halogen atom; 1-10C aliphatic hydrocarbon group; alicyclic hydrocarbon group; aromatic hydrocarbon group; or a polar group selected from alkoxy; OH; ester group; cyano; amido; amino and thiol; or an atom or group selected from the category consisting of halogen atom and/or group substituted with the above polar group(s); wherein A<SP>1</SP>and A<SP>2</SP>may be the same as or differing from each other; m is an integer of 0 or 1-3; and n is 0 or a positive integer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a cyclic olefin-based ring-opening (co) polymer hydride. Specifically, the present invention relates to a cyclic olefin-based polymer having excellent transparency by hydrogenating a cyclic olefin-based ring-opening (co) polymer in the presence of a specific metal hydride complex and then adjusting the temperature to a relatively low temperature. The present invention relates to a method for producing a ring-opening (co) polymer hydride. Moreover, it is related with the hydride obtained by this manufacturing method.

  Cyclic olefin resins have a high glass transition temperature due to the rigidity of the main chain structure, and are amorphous and have a high light transmittance due to the presence of bulky groups in the main chain structure. Since it has such features as low birefringence due to its low isotropic property, it has attracted attention as a thermoplastic transparent resin excellent in heat resistance, transparency and optical properties.

  As one of such cyclic olefin-based resins, a ring-opening polymerization of a monomer composition containing dicyclopentadiene (hereinafter abbreviated as “DCP”) or a derivative thereof that is industrially easily available and inexpensive. Examples include a resin obtained by further hydrogenating the polymer obtained in this manner, such as an optical material such as an optical disk, an optical lens, and an optical fiber, a sealing material such as an optical semiconductor sealing, an optical film / sheet, or a container for pharmaceuticals. Application to such as has been proposed. (See Patent Documents 1 and 2)

  In general, a ring-opening polymer of a norbornene-based monomer containing DCP or a derivative thereof (hereinafter also referred to as “norbornene-based monomer”) is obtained by converting a norbornene-based monomer composition into a metathesis catalyst in an appropriate solvent. It can be obtained by ring-opening polymerization in the presence of a ring-opening polymerization catalyst such as a system. Further, the hydrogenated product can be obtained by adding an appropriate hydrogenation catalyst to the ring-opening polymer solution and reacting with hydrogen. (See Patent Documents 3 to 6)

  However, since the ring-opening polymer of the norbornene monomer has an olefinically unsaturated bond in the molecule, an undesired crosslinking reaction proceeds during the hydrogenation reaction, and a gel insoluble in the organic solvent is generated. There's a problem. In addition, the ring-opening polymer of norbornene monomer has a large amount of olefinically unsaturated bonds, so the calorific value of the hydrogenation reaction is large, and the maximum temperature reached is high. There was a problem that productivity could not be improved because it could not be raised. In addition, if a metal compound derived from a catalyst or the like is included in the product, for example, a serious problem such as a problem of coloring of the optical film occurs, so the remaining amount of the metal compound is required to be reduced as much as possible. It has been.

  As a method for producing a ring-opening polymer using a norbornene-based monomer and a hydrogenated product thereof, various methods have been conventionally proposed. For example, Patent Document 1 discloses that when a DCP-based monomer is subjected to ring-opening polymerization in the presence of a tungsten-based ring-opening polymerization catalyst, compounds such as nitrile, ketone, ether, and ester are allowed to coexist as reaction modifiers. Thus, a ring-opening polymer substantially free of gel is obtained, and the ring-opening polymer substantially free of gel is obtained by hydrogenating the ring-opening polymer using a diatomaceous earth supported nickel catalyst or the like. It is disclosed that a combined hydrogenation product is obtained.

  However, in the conventionally proposed method, since the metal catalyst, the double bond in the polymer chain and the trace oxygen are heated together, there is a possibility that the double bond may be oxidized, which causes a decrease in hue. It was one of. Moreover, it was difficult to sufficiently remove the residual amount of the metal compound derived from the catalyst.

  The present applicant has already proposed a production method by a simple process that does not substantially contain a gel content and has a small load in the filtration process (see Patent Document 7). However, since the hydrogenation reaction is started by starting the hydrogenation at a high temperature of 130 ° C. or higher in the production method, the maximum temperature reaches a high level, and the design temperature of the reactor is increased to increase the charged amount. It is necessary to adopt conditions such as reducing the amount of preparation, increasing the amount of solvent, and slowing the hydrogen supply speed in order to suppress the maximum temperature, etc. Furthermore, reduction of the catalyst-derived metal compound residual amount has been desired.

  In view of this, the present applicant has proposed a production method in which the temperature at the start of the hydrogenation reaction is set to a relatively low temperature to suppress the generation of gel content (see Patent Document 8). However, it was desired to obtain a transparent hydride that is less colored.

Japanese Patent Laid-Open No. 11-124429 JP-A-11-130846 JP-A 63-264626 Japanese Patent Laid-Open No. 1-158029 JP-A-1-168724 JP-A-1-168725 JP 2005-213370 A JP 2007-106932 A

  In the hydrogenation of a (co) polymer of a cyclic olefinic compound having a plurality of olefinically unsaturated bonds in the molecule, the present invention provides a cyclic olefinic ring opening suitable for use in optical applications, etc., with a hue that is very transparent. It is an object of the present invention to provide a method for producing a cyclic olefin-based ring-opening (co) polymer hydride for producing a (co) polymer hydride with high productivity.

  As a result of intensive research in this situation, the present inventors have found that a specific metal hydride complex exists in hydrogenating a ring-opened (co) polymer of a cyclic olefin compound having a plurality of olefinically unsaturated bonds in the molecule. Below, when the cyclic olefin ring-opening (co) polymer solution is adjusted to a low temperature in advance and then brought into contact with hydrogen, coloring of the hydride of the cyclic olefin ring-opening (co) polymer can be suppressed, By lowering the maximum temperature of the hydrogenation reaction, the amount charged can be increased without changing the design temperature of the reaction kettle and productivity can be remarkably improved. It has been found that the residual amount is reduced and the transparency of the hydride is improved, and the present invention has been completed.

The method for producing the cyclic olefin-based ring-opening (co) polymer hydride of the present invention includes:
A method for producing a hydride of a cyclic olefin-based ring-opening (co) polymer (A) having a structural unit derived from a cyclic olefin-based compound represented by the following general formula (1):
A step of controlling the solution containing the cyclic olefin-based ring-opening (co) polymer (A) and the metal compound (B) at 10 to 40 ° C. to start contact with hydrogen;
After the start of contact with the hydrogen, a step of performing a hydrogenation reaction by setting the temperature of the solution to 100 to 200 ° C.,
It is characterized by having.

（式（１）中、Ａ¹およびＡ²は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜１０の脂肪族炭化水素基、脂環族炭化水素基、芳香族炭化水素基、もしくはアルコキシ基、水酸基、エステル基、シアノ基、アミド基、アミノ基およびチオール基の群から選ばれた極性基、またはハロゲン原子および／または上記の極性基により置換された基よりなる群より選ばれた原子もしくは基を示し、それぞれ同一でもよく、また異なっていても良い。ｍは０または１〜３の整数、ｎは０または正の整数である。）。

(In Formula (1), A ¹ and A ² are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or A polar group selected from the group consisting of an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amide group, an amino group and a thiol group, or a group consisting of a halogen atom and / or a group substituted by the above polar group An atom or a group, which may be the same or different, m is an integer of 0 or 1-3, and n is 0 or a positive integer.

In the method for producing a cyclic olefin-based ring-opening (co) polymer hydride of the present invention, the metal compound (B) is preferably a compound represented by the following general formula (2).
MQ _n H _k T _p Z _q (2)
(In formula (2), M represents a metal selected from the group consisting of ruthenium, rhodium, osmium, iron, cobalt and iridium;
Q independently represents a group represented by the following formula (i),
H represents a hydrogen atom,
T independently represents CO or NO;
Z independently represents PR ⁶ R ⁷ R ⁸ (P represents a phosphorus atom, and R ⁶ , R ⁷ and R ⁸ each independently represents an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group). ,
k represents 1 or 2, n represents 1 or 2, p represents an integer of 0 to 4, q represents an integer of 0 to 4, and the sum of k, n, p and q is 4, 5 or 6. )

（式（ｉ）中、Ｒ¹〜Ｒ⁵は、それぞれ独立に水素原子、アルキル基、シクロアルキル基、アルケニル基、アリール基、アルコキシ基、アミノ基、ニトロ基、シアノ基、カルボキシル基またはヒドロキシル基を示す。）。

(In the formula (i), R ^{1 to} R ⁵ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, aryl group, alkoxy group, amino group, nitro group, cyano group, carboxyl group or hydroxyl group. Is shown.)

In the method for producing a cyclic olefin-based ring-opening (co) polymer hydride of the present invention, the metal compound (B) is also preferably a compound represented by the following general formula (5).
MX _n H _k T _p Z _q (5)
(In the formula (5), M represents a metal selected from the group consisting of ruthenium, rhodium, osmium, iron, cobalt and iridium;
X represents a halogen atom,
H represents a hydrogen atom,
T independently represents CO or NO;
Z independently represents PR ⁶ R ⁷ R ⁸ (P represents a phosphorus atom, and R ⁶ , R ⁷ and R ⁸ each independently represents an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group). ,
k represents 1 or 2, n represents 1 or 2, p represents an integer of 0 to 4, q represents an integer of 0 to 4, and the sum of k, n, p and q is 4, 5 or 6. )
In the method for producing a cyclic olefin-based ring-opening (co) polymer hydride of the present invention, it is more preferable that M in the formula (2) or the formula (5) is ruthenium.

  In the method for producing a cyclic olefin-based ring-opening (co) polymer hydride of the present invention, the cyclic olefin-based ring-opening (co) polymer (A) is further represented by the following general formula (3): It is preferable to have a structural unit derived from a compound.

（式（３）中、ｍは０または１〜３の整数であり、ｎは０または正の整数である。
Ａ³〜Ａ⁶は、それぞれ独立に下記（a）〜（e）で表されるものを表すか、（f）または（g）を表す。
（a）水素原子、
（b）ハロゲン原子、
（c）酸素原子、硫黄原子、窒素原子もしくはケイ素原子を含む連結基を含む置換または非置換の炭素原子数１〜３０の炭化水素基、
（d）置換または非置換の炭素原子数１〜３０の炭化水素基、
（e）アルコキシ基、水産基、エステル基、シアノ基、アミド基、アミノ基およびチオール基から選ばれる基、
（f）Ａ³とＡ⁴、またはＡ⁵とＡ⁶が、相互に結合して形成されたアルキリデン基を表し、前記結合に関与しないＡ³〜Ａ⁶は相互に独立に前記（a）〜（e）より選ばれるものを表す、
（g）Ａ³とＡ⁴、Ａ⁵とＡ⁶、またはＡ⁴とＡ⁵が、相互に結合して形成された芳香環もしくは非芳香環の単環もしくは多環の炭化水素環または複素環を表し、前記結合に関与しないＡ³〜Ａ⁶は相互に独立に前記（a）〜（e）より選ばれるものを表す。）。

(In Formula (3), m is an integer of 0 or 1-3, and n is 0 or a positive integer.
A ^{3 to} A ⁶ each independently represents one represented by the following (a) to (e), or represents (f) or (g).
(A) a hydrogen atom,
(B) a halogen atom,
(C) a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms including a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom,
(D) a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms,
(E) a group selected from an alkoxy group, a fishery group, an ester group, a cyano group, an amide group, an amino group, and a thiol group,
(F) A ³ and A ⁴ , or A ⁵ and A ⁶ represent an alkylidene group formed by bonding to each other, and A ^{3 to} A ⁶ not participating in the bonding are independent of each other from (a) to (a) to (E) represents one selected from
(G) A ³ and A ⁴ , A ⁵ and A ⁶ , or A ⁴ and A ⁵ bonded together to form an aromatic or non-aromatic monocyclic or polycyclic hydrocarbon ring or heterocyclic ring And A ^{3 to} A ⁶ not involved in the bond are independently selected from the above (a) to (e). ).

  The method for producing a cyclic olefin-based ring-opening (co) polymer hydride of the present invention further includes a step of purifying the solution that has undergone the hydrogenation reaction step using a decatching aid (C) and methanol. It is preferable to have.

The hydride of the cyclic olefin-based ring-opening (co) polymer of the present invention is obtained by the above production method.
The hydride of the cyclic olefin ring-opening (co) polymer of the present invention preferably has a yellow index of 0.20 to 0.37.

  According to the present invention, the hydrogenation of a polymer or copolymer of a cyclic olefin compound having a plurality of olefinically unsaturated bonds in the molecule is carried out in a simple process to produce a cyclic olefin polymer hydride that is not colored. can do. Furthermore, the transparency of the cyclic olefin polymer hydride can be improved by reducing the residual amount of the catalyst-derived metal compound in the obtained cyclic olefin polymer hydride by a simple purification step. The cyclic olefin polymer hydride obtained by the present invention can be used by appropriately forming it into a desired shape, and is excellent in transparency. Therefore, it can be used for various optical parts and electrical and electronic materials. It can be used suitably.

Hereinafter, the present invention will be specifically described.
In the present invention, the cyclic olefin polymer comprises not only a homopolymer or copolymer of a monomer comprising at least one cyclic olefin compound, but also other compounds copolymerizable with the cyclic olefin compound. A copolymer obtained by copolymerizing monomers is also included. In the present invention, ring-opening (co) polymerization represents both ring-opening polymerization and ring-opening copolymerization, and ring-opening (co) polymer represents both a ring-opening polymer and a ring-opening copolymer. In addition, unless otherwise specified, hydrogenation (hydrogenation) in the present invention is an olefinic unsaturated bond in the cyclic olefin polymer main chain produced by metathesis ring-opening polymerization, or DCP on the 5-membered ring side. Like unsaturated bonds, it is for aliphatic olefinically unsaturated bonds that are not ring-opened (co) polymerized and not for other unsaturated bonds such as aromatic unsaturated bonds.
In the method for producing a cyclic olefin-based ring-opening (co) polymer hydride of the present invention, a cyclic olefin-based ring-opening (co) polymer is hydrogenated.

<Cyclic olefin ring-opening (co) polymer>
The cyclic olefin ring-opening (co) polymer used in the present invention has a structural unit derived from a cyclic olefin compound represented by the following general formula (1). Although a manufacturing method is not specifically limited, For example, it can obtain by ring-opening-polymerizing the monomer containing the cyclic olefin type compound represented by following General formula (1).

（式（１）中、Ａ¹およびＡ²は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜１０の脂肪族炭化水素基、脂環族炭化水素基、芳香族炭化水素基、もしくはアルコキシ基、水酸基、エステル基、シアノ基、アミド基、アミノ基およびチオール基の群から選ばれた極性基、またはハロゲン原子および／または上記の極性基により置換された基よりなる群より選ばれた原子もしくは基を示し、それぞれ同一でもよく、また異なっていても良い。ｍは０または１〜３の整数であり、ｎは０または正の整数である。）。

(In Formula (1), A ¹ and A ² are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or A polar group selected from the group consisting of an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amide group, an amino group and a thiol group, or a group consisting of a halogen atom and / or a group substituted by the above polar group An atom or a group, which may be the same or different, m is an integer of 0 or 1-3, and n is 0 or a positive integer.

In the present invention, in the above formula (1), a compound in which m is m = 1 and n is n = 0 is preferably used.
Examples of such cyclic olefin compounds include, for example:
Tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (DCP),
8-methyl-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene,
8-ethyl-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene,
8-cyclohexyl-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene,
8-phenyl-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene,
8- (4-biphenyl) -tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene,
8-methoxycarbonyl-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene,
8-phenoxycarbonyl-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene,
8-methoxycarbonylethyl-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene,
8-methoxycarbonylethyloxy-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene,
7-methyl-8-methoxycarbonyl-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene;
7,8-dimethyl-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene,
8-fluoro-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene,
8-chloro-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene,
8-bromo-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene,
7,8-dichloro-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene and the like.

Among these, industrially easily available and inexpensive tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (DCP) is particularly preferably used. In addition, these may be used individually by 1 type and may use 2 or more types together.

  The cyclic olefin ring-opening (co) polymer used in the present invention further has a structural unit derived from the cyclic olefin compound represented by the above formula (1), and is represented by the following general formula (3). It is preferable to have a structural unit derived from a cyclic olefin compound. As a manufacturing method, the manufacturing method which ring-opening-copolymerizes the compound represented by the said Formula (1) and the monomer represented by following General formula (3) is mentioned, for example.

  The copolymerization ratio is usually the compound represented by the general formula (1): the compound represented by the general formula (3) by the weight ratio of the monomers used = 5-50: 50-95, preferably 10-40: 60. -90, more preferably 20-35: 65-80.

（式（３）中、ｍは０または１〜３の整数、ｎは０または正の整数である。
Ａ³〜Ａ⁶は、それぞれ独立に下記（a）〜（e）で表されるものを表すか、（f）または（g）を表す。
（a）水素原子、
（b）ハロゲン原子、
（c）酸素原子、硫黄原子、窒素原子もしくはケイ素原子を含む連結基を含む置換または非置換の炭素原子数１〜３０の炭化水素基、
（d）置換または非置換の炭素原子数１〜３０の炭化水素基、
（e）アルコキシ基、水酸基、エステル基、シアノ基、アミド基、アミノ基およびチオール基から選ばれる基、
（f）Ａ³とＡ⁴、またはＡ⁵とＡ⁶が、相互に結合して形成されたアルキリデン基を表し、前記結合に関与しないＡ³〜Ａ⁶は相互に独立に前記（a）〜（e）より選ばれるものを表す、
（g）Ａ³とＡ⁴、Ａ⁵とＡ⁶、またはＡ⁴とＡ⁵が、相互に結合して形成された芳香環もしくは非芳香環の単環もしくは多環の炭化水素環または複素環を表し、前記結合に関与しないＡ³〜Ａ⁶は相互に独立に前記（a）〜（e）より選ばれるものを表す。）。

(In Formula (3), m is 0 or an integer of 1-3, n is 0 or a positive integer.
A ^{3 to} A ⁶ each independently represents one represented by the following (a) to (e), or represents (f) or (g).
(A) a hydrogen atom,
(B) a halogen atom,
(C) a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms including a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom,
(D) a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms,
(E) a group selected from an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amide group, an amino group and a thiol group,
(F) A ³ and A ⁴ , or A ⁵ and A ⁶ represent an alkylidene group formed by bonding to each other, and A ^{3 to} A ⁶ not participating in the bonding are independent of each other from (a) to (a) to (E) represents one selected from
(G) A ³ and A ⁴ , A ⁵ and A ⁶ , or A ⁴ and A ⁵ bonded together to form an aromatic or non-aromatic monocyclic or polycyclic hydrocarbon ring or heterocyclic ring And A ^{3 to} A ⁶ not involved in the bond are independently selected from the above (a) to (e). ).

Examples of the cyclic olefin compound represented by the general formula (3) include the following compounds, but are not limited to these examples.
Bicyclo [2.2.1] hept-2-ene (2-norbornene),
5-methyl-bicyclo [2.2.1] hept-2-ene,
5-ethyl-bicyclo [2.2.1] hept-2-ene,
5-cyclohexyl-bicyclo [2.2.1] hept-2-ene,
5-phenyl-bicyclo [2.2.1] hept-2-ene,
5- (4-biphenyl) -bicyclo [2.2.1] hept-2-ene,
5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-phenoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-phenoxyethylcarbonyl-bicyclo [2.2.1] hept-2-ene,
5-phenylcarbonyloxy-bicyclo [2.2.1] hept-2-ene,
5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-methyl-5-phenoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-methyl-5-phenoxyethylcarbonyl-bicyclo [2.2.1] hept-2-ene,
5-vinyl-bicyclo [2.2.1] hept-2-ene,
5-ethylidene-bicyclo [2.2.1] hept-2-ene,
5,5-dimethyl-bicyclo [2.2.1] hept-2-ene,
5,6-dimethyl-bicyclo [2.2.1] hept-2-ene,
5-fluoro-bicyclo [2.2.1] hept-2-ene,
5-chloro-bicyclo [2.2.1] hept-2-ene,
5-bromo-bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-bicyclo [2.2.1] hept-2-ene,
5,6-dichloro-bicyclo [2.2.1] hept-2-ene,
5,6-dibromo-bicyclo [2.2.1] hept-2-ene,
5-hydroxy-bicyclo [2.2.1] hept-2-ene,
5-hydroxyethyl-bicyclo [2.2.1] hept-2-ene,
5-cyano-bicyclo [2.2.1] hept-2-ene,
5-amino-bicyclo [2.2.1] hept-2-ene,
Tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
Tricyclo [4.4.0.1 ^2,5 ] undec-3-ene,
7-methyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7-ethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7-cyclohexyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7-phenyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7- (4-biphenyl) -tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7,8-dimethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
8-methyl-tricyclo [4.4.0.1 ^2,5 ] undec-3-ene,
8-phenyl-tricyclo [4.4.0.1 ^2,5 ] undec-3-ene,
7-fluoro - tricyclo [4.3.0.1 ^{2, 5]} dec-3-ene,
7-chloro-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7-bromo-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7,8-dichloro-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7-chloromethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7-dichloromethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7-trichloromethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7-hydroxy-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7-cyano-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7-amino - tricyclo [4.3.0.1 ^{2, 5]} dec-3-ene,
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
Pentacyclo [7.4.0.1 ^3,7 . 1 ^10,13 . 0 ^2,7 ] pentadec-4-ene,
Hexacyclo [8.4.0.1 ^2,9 . 1 ^4,7 . 1 ^11,14 . 0 ^3,8 ] heptadeca-3-ene,

8-methyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-cyclohexyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-phenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8- (4-biphenyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8 phenoxycarbonyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene,
8-phenoxyethylcarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-phenylcarbonyloxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-phenoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-phenoxyethylcarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-vinyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,8-Dimethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,9-dimethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-fluoro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-chloro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-Bromo-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,8-Dichloro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,9-Dichloro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,8,9,9- tetrachloro - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene,
8-hydroxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-hydroxyethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-hydroxyethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-cyano-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-amino-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene.

Of the above, 8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodec-3-ene is preferred from the viewpoint of the heat resistance of the polymer obtained.

  In the present invention, the cyclic olefin compounds represented by the general formula (1) can be used alone or in combination of two or more as a monomer. Further, in the present invention, one or more cyclic olefin compounds represented by the general formula (1) and one or more cyclic olefin compounds represented by the general formula (3) are used in combination. It can be used as a monomer. Furthermore, in this invention, in addition to these, the monomer containing copolymerizable compounds other than the said General formula (1) or (3) can also be used.

In the present invention, the type and blending ratio of the monomers used for the ring-opening polymerization are appropriately selected according to the characteristics required for the obtained resin, and are not uniquely determined. Because it improves the adhesion and adhesion of molded products using the resulting resin, printability, and dispersibility of other materials such as pigments, it was selected from oxygen, nitrogen, sulfur or silicon atoms in the molecule. It is preferable to select a monomer containing a cyclic olefin compound having a structure containing at least one atom (hereinafter referred to as “polar structure”). Of course, only a monomer having such a polar structure may be used, or a monomer having no polar structure may be used in combination.

In the present invention, it is preferable to use a monomer containing a cyclic olefin compound having a polar structure. Among these, in general formula (3), at least one of A ^{3 to} A ⁶ is represented by the following general formula (4). ) Is more preferable because it is easy to balance the heat resistance and water absorption (wet) property of the resulting cyclic olefin-based ring-opening (co) polymer hydride.
_{- (CH 2) z COOR ...} (4)
(In formula (4), R represents a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms, and z represents 0 or an integer of 1 to 10).

As the cyclic olefin compound (3) having a polar group represented by the above formula (4), specifically,
5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8- (2,2,2-trifluoroethoxy-carbonyl) tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] -3-dodecene,
8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene. In addition, it is not limited to these compounds.

  In the above general formula (4), the smaller the value of z, the higher the glass transition temperature of the hydride obtained, which is preferable in terms of heat resistance, and the monomer having z of 0 is easy to synthesize. This is preferable. In addition, R tends to decrease the water absorption (wet) property of the obtained cyclic olefin-based ring-opening (co) polymer hydride as the number of carbon atoms increases, but also tends to decrease the glass transition temperature. A C1-C6 alkyl group is preferable, and a methyl group is particularly preferable.

  In the general formula (3), a monomer having only one group represented by the general formula (4) is preferably used because it is easily synthesized and easily industrially available. Moreover, in the said General formula (3), when a C1-C5 alkyl group, especially a methyl group have couple | bonded with the carbon atom which the group represented by the said General formula (4) couple | bonded, heat resistance and water absorption. It is preferable in terms of (wet) balance. Further, in the above general formula (3), a monomer in which m is 0 and n is 1 is a cyclic olefin-based ring-opening (co) polymer hydride having high heat resistance, and industrially. Since it is easily available, it is preferably used.

Ring-opening (co) polymerization / polymerization temperature In the present invention, a monomer containing at least one cyclic olefin compound represented by the above formula (1) is subjected to ring-opening polymerization or ring-opening copolymerization in the presence of a polymerization catalyst. However, in such polymerization, the timing of adding the polymerization catalyst is an important technical requirement. That is, it is desirable to add the polymerization catalyst when the temperature of the monomer solution containing the monomer and the solvent reaches 50 to 120 ° C., preferably 80 to 110 ° C. By adding a polymerization catalyst in such a temperature range, it is thought that generation | occurrence | production of the hyperbranched polymer and microgel used as the origin of a gel can be suppressed. Such an effect is particularly remarkable when a cyclic olefin monomer having two or more olefinic unsaturated bonds in the molecule, for example, a DCP monomer is used.

  The polymerization reaction temperature after the addition of the polymerization catalyst is usually 70 to 170 ° C., and the monomer conversion after 1 hour from the start of polymerization is adjusted to 85% or more, preferably 90% or more. Is preferred. When this conversion rate is less than 85%, the polymerization time becomes long and the productivity is lowered, which is not industrially preferable.

-Polymerization catalyst In this invention, when carrying out ring-opening (co) polymerization of the monomer containing a cyclic olefin type compound, a polymerization catalyst is used. In the present invention, a known catalyst can be used as the catalyst used for the ring-opening (co) polymerization, and for example, platinum group compounds such as ruthenium, rhodium, palladium, iridium, and platinum can be used. (A) at least one selected from W, Mo and Re compounds; and (b) Deming periodic table IA group element, IIA group element, IIB group element, IIIA group element, IVA group element or IVB. A catalyst comprising a combination of at least one selected from the group element compounds having at least one of the element-carbon bond or the element-hydrogen bond is also preferably used. Such a catalyst comprising the component (a) and the component (b) may be further added with an additive (c) described later in order to enhance the activity of the catalyst.

Representative examples of W, Mo or Re compounds suitable as the component (a) include compounds described in Japanese Patent Application No. 1-240517 such as WCl ₆ , MoCl ₅ and ReOCl ₃ . Specific examples of the component (b) include n-C ₄ H ₉ Li, (C ₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) ₂ AlCl, LiH, and the like in Japanese Patent Application No. 1-240517. Mention may be made of the compounds described.

  Alcohols, aldehydes, ketones, amines and the like can be suitably used as representative examples of the component (c) which is an additive, but the compounds disclosed in JP-A-1-240517 are also used. can do.

  The amount of the metal polymerization catalyst according to the present invention is 1,000 to 100,000, preferably 5,000 to 50,000, in terms of molar ratio. If the monomer / metal charge exceeds 100,000, the polymerization reaction may not proceed sufficiently. If it is less than 1000, it is difficult to remove the catalyst.

-Polymerization reaction solvent Examples of the solvent used in the ring-opening (co) polymerization reaction (that is, a solvent for dissolving a monomer, a ring-opening polymerization catalyst, a molecular weight regulator, etc.) include pentane, hexane, heptane, octane, and nonane. , Alkanes such as decane; cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutane, bromohexane, methylene chloride, dichloroethane, Compounds such as halogenated alkanes and aryl halides such as hexamethylene dibromide, chlorobenzene, chloroform, and tetrachloroethylene; saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, iso-butyl acetate, and methyl propionate; dibutyl ether Ethers such as sulfur, tetrahydrofuran and dimethoxyethane, among which aromatic hydrocarbons are preferred. These can be used singly or in combination of two or more.

  In the polymerization reaction carried out using the above-mentioned solvent, the ratio of all monomers to the solvent is a weight ratio, usually monomer: solvent = 5: 1 to 1:15, preferably 2: 1 to 1. : 8, more preferably in the range of 1: 1 to 1: 6.

-Molecular weight of cyclic olefin-based ring-opening (co) polymer The molecular weight of the cyclic olefin-based ring-opening (co) polymer in the present invention is determined by desired characteristics and is not uniquely defined. Usually, the intrinsic viscosity (η _inh ) is 0.2 to 5.0, preferably 0.4 to 1.5. Moreover, as a molecular weight of standard polystyrene conversion measured by gel permeation chromatography (GPC), the weight average molecular weight (Mw) is usually 1.0 × 10 ^{3 to} 1.0 × 10 ⁶ , preferably 5.0 ×. It is 10 < ³ > -5.0 * 10 < ⁵ >, and molecular weight distribution (Mw / Mn) is 1-10 normally, Preferably it is 1-5, More preferably, it is 1-4. In the present invention, the conditions for obtaining a cyclic olefin-based ring-opening (co) polymer having such a molecular weight are selected, and the ring-opening (co) polymerization reaction of the monomer containing the cyclic olefin-based monomer is performed. Preferably it is done.

  If the molecular weight of the cyclic olefin-based ring-opening (co) polymer becomes too high, the efficiency of the hydrogenation reaction may be reduced, and the hydrogenation rate of the resulting cyclic olefin-based ring-opening (co) polymer hydride is desired. Problems such as not reaching the value or extending the reaction time may occur.

The molecular weight can be adjusted by the polymerization temperature in the ring-opening (co) polymerization reaction, the type of catalyst, and the type of solvent, but generally, 1-butene, 1-pentene, 1-hexene, 1- A method of adding a quantity regulator such as α-olefins such as octene to the reaction system is easy and can be suitably used because the desired molecular weight can be obtained simply by adjusting the addition quantity.
The cyclic olefin ring-opening (co) polymer thus obtained has an olefinically unsaturated bond generated in the main chain accompanying the ring-opening (co) polymerization.

<Hydrogenation of ring-opening (co) polymer>
In this invention, the hydrogenation reaction which hydrogenates the olefinic unsaturated bond of the cyclic olefin type ring-opening (co) polymer obtained as mentioned above is performed.

Hydrogenation catalyst In the hydrogenation reaction of the ring-opening (co) polymer in the present invention, a metal compound (B) is used as a hydrogenation catalyst.

  As a preferable metal compound (B), a known compound used when hydrogenating a normal olefinically unsaturated bond can be used. For example, so-called Ziegler type homogeneous catalysts combining organic acid salts such as titanium, cobalt and nickel or acetylacetone salts and organic metal compounds such as lithium, magnesium, aluminum and tin, noble metals such as palladium, platinum, ruthenium and rhodium And a noble metal-based catalyst such as rhodium, rhenium, ruthenium, and the like, and a noble metal-based catalyst supported on a carrier such as carbon, alumina, silica alumina, silica magnesia, and diatomaceous earth. Among these, it is preferable to use a metal hydride complex compound represented by the following formula (2) or formula (5), and in particular, in the following formula (2) or formula (5), it is preferable to use a ruthenium compound in which M is ruthenium. preferable.

MQ _n H _k T _p Z _q (2)
(In formula (2), M represents a metal selected from the group consisting of ruthenium, rhodium, osmium, iron, cobalt and iridium;
Q independently represents a group represented by the following formula (i),
H represents a hydrogen atom,
T independently represents CO or NO;
Z independently represents PR ⁶ R ⁷ R ⁸ (P represents a phosphorus atom, and R ⁶ , R ⁷ and R ⁸ each independently represents an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group). ,
k represents 1 or 2, n represents 1 or 2, p represents an integer of 0 to 4, q represents an integer of 0 to 4, and the sum of k, n, p and q is 4, 5 or 6. )

（式（ｉ）中、Ｒ¹〜Ｒ⁵は、それぞれ独立に水素原子、アルキル基、シクロアルキル基、アルケニル基、アリール基、アルコキシ基、アミノ基、ニトロ基、シアノ基、カルボキシル基またはヒドロキシル基を示す。）

(In the formula (i), R ^{1 to} R ⁵ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, aryl group, alkoxy group, amino group, nitro group, cyano group, carboxyl group or hydroxyl group. Is shown.)

Examples of the alkyl group in R ^{1 to} R ⁵ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n- A hexyl group etc. are mentioned.

Examples of the cycloalkyl group in R ^{1 to} R ⁵ include a cyclohexyl group, a 2-methylcyclohexyl group, a 3-methylcyclohexyl group, a 4-methylcyclohexyl group, a 2,3-dimethylcyclohexyl group, and a 2,4-dimethylcyclohexyl group. Group, 2,5-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 3,4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group and the like.

Examples of the aryl group in R ^{1 to} R ⁵ include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2,3-dimethylphenyl group, and a 2,4-dimethylphenyl group. 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 1-naphthyl group, 2-naphthyl group and the like.
In addition, when there are a plurality of Q, T and Z in the above formula (2), they may be the same or different.

As a specific example of such a metal hydride complex according to the present invention, for example,
RuH (OCOPh) (CO) (PPh ₃ ) ₂ ,
_{RuH (OCOPh-CH 3) (} CO) (PPh 3) 2,
_{RuH (OCOPh-C 2 H 5} ) (CO) (PPh 3) 2,
_{RuH (OCOPh-C 5 H 11} ) (CO) (PPh 3) 2,
_{RuH (OCOPh-C 8 H 17} ) (CO) (PPh 3) 2,
RuH (OCOPh-OCH ₃ ) (CO) (PPh ₃ ) ₂ ,
_{RuH (OCOPh-OC 2 H 5} ) (CO) (PPh 3) 2,
RuH (OCOPh) (CO) (P (cyclohexyl) ₃ ) ₂ ,
RuH (OCOPh-NH ₂ ) (CO) (PPh ₃ ) ₂
Etc. (In the formula, Ph represents a phenyl group or a phenylene group.)

Among these compounds, particularly preferably used are
_{RuH (OCOPh-C 5 H 11} ) (CO) (PPh 3) 2
It is a compound represented by these.

The metal hydride complex compound represented by Formula (5) is as follows.
MX _n H _k T _p Z _q (5)
(In the formula (5), M represents a metal selected from the group consisting of ruthenium, rhodium, osmium, iron, cobalt and iridium;
X represents a halogen atom,
H represents a hydrogen atom,
T independently represents CO or NO;
Z independently represents PR ⁶ R ⁷ R ⁸ (P represents a phosphorus atom, and R ⁶ , R ⁷ and R ⁸ each independently represents an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group). ,
k represents 1 or 2, n represents 1 or 2, p represents an integer of 0 to 4, q represents an integer of 0 to 4, and the sum of k, n, p and q is 4, 5 or 6. )
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In addition, when there are a plurality of X, T and Z in the above formula (5), they may be the same or different.
As a specific example of such a metal hydride complex according to the present invention, for example,
RuHF (CO) (PPh ₃ ) ₃ ,
RuHCl (CO) (PPh ₃ ) ₃ ,
RuHBr (CO) (PPh ₃ ) ₃ ,
RuHI (CO) (PPh ₃ ) ₃ ,
Etc. (In the formula, Ph represents a phenyl group.)

Among these compounds, a compound represented by RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ is particularly preferably used.
As for the addition amount of the metal hydride complex according to the present invention, the metal amount / monomer charge amount is usually 5 to 200 ppm, preferably 10 to 100 ppm. If the metal amount / monomer charge amount is less than 5 ppm, sufficient hydrogenation reaction may not proceed. If it exceeds 200 ppm, catalyst removal becomes difficult.

The toluene solubility of the hydrogenation catalyst used in the present invention at 20 ° C. is usually from 0.2% by weight to 10% by weight, and preferably from 1.0% by weight to 10% by weight. If it is less than 0.2% by weight, the solubility is low, and it is necessary to increase the amount of the catalyst added. On the other hand, if it exceeds 10% by weight, it is difficult to remove the catalyst.
In addition, about the timing which adds a hydrogenation catalyst, you may add beforehand to the ring-opening (co) polymer solution before temperature adjustment, and may add during temperature adjustment.

Solvent for the hydrogenation reaction The solvent used for the hydrogenation reaction is not particularly limited as long as it is a good solvent for the hydrogenated cyclic olefin ring-opening (co) polymer and is not hydrogenated itself. . Specifically, the same thing as the said polymerization reaction solvent can be mentioned. For this reason, it is also preferable that the cyclic olefin ring-opening (co) polymer solution obtained by the polymerization of the monomer is directly subjected to a hydrogenation reaction. The weight ratio of the cyclic olefin-based ring-opening (co) polymer and the solvent in the solution subjected to the hydrogenation reaction is usually 5: 1 to 1:20, preferably 2: 1 to 1:15, more preferably. Is preferably 1: 1 to 1:10. When the amount of the solvent is larger than this range, the cost for collecting the solvent becomes high. When the amount of the solvent is less than this range, the viscosity of the solution becomes high and it takes a long time to transfer the solution, resulting in poor production efficiency.

In the present invention, the temperature of the solution containing the cyclic olefin-based ring-opening (co) polymer in the hydrogenation reaction is controlled according to the reaction process in the hydrogen contact initiation stage and the subsequent reaction stage. In general, in hydrogenation of a cyclic olefin-based ring-opening (co) polymer, a hydrogenation catalyst and hydrogen are added to a solution obtained by dissolving the ring-opening (co) polymer in an appropriate solvent, and a hydrogenation reaction is performed. In the present invention, the polymer solution temperature at the start of contact between the ring-opening (co) polymer and hydrogen is an important technical requirement.

  At the start of contact between the solution containing the cyclic olefin ring-opening (co) polymer and hydrogen, the temperature of the solution containing the cyclic olefin ring-opening (co) polymer is 10 ° C. to 40 ° C., preferably 15 ° C. to It is controlled to 40 ° C, more preferably 15 ° C to 35 ° C. When the temperature of the solution containing the cyclic olefin-based ring-opening (co) polymer at the start of hydrogen contact is within this range, the color of the hydride of the cyclic olefin-based ring-opening (co) polymer becomes more transparent. The reason for this is that by not increasing the temperature of the solution containing the cyclic olefin ring-opening (co) polymer before the start of contact between the cyclic olefin ring-opening (co) polymer and hydrogen, the cyclic olefin ring-opening ( This is thought to be because oxidation of the double bond in the (co) polymer via the metal catalyst is suppressed.

  After the start of hydrogen contact, the cyclic olefin ring-opening (co) polymer solution is heated to adjust the temperature as necessary, and the temperature of the solution containing the ring-opening (co) polymer is 100 ° C. to 200 ° C., preferably The temperature is raised to 120 to 200 ° C., more preferably 140 to 180 ° C., and the hydrogenation reaction is carried out while keeping the solution at that temperature. When the temperature of the solution containing the cyclic olefin ring-opening (co) polymer after the start of hydrogen contact is in this range, a high olefin hydrogenation rate can be obtained.

  Here, the time when hydrogen contact starts refers to the time when hydrogen introduction is started into the reactor containing a solution containing a cyclic olefin-based ring-opening (co) polymer, and after hydrogen contact starts To the end of hydrogen supply.

Hydrogen is supplied at 0.0001 MPa / s to 0.01 MPa / s, preferably 0.001 MPa / s to 0.005 MPa / s. If it supplies in this range, the rate of temperature increase in the system due to reaction heat can be suppressed. The pressure of the reaction system in the hydrogenation reaction is usually 50 to 220 kg / cm ² , preferably 70 to 150 kg / cm ² , more preferably 90 to 120 kg / cm ² . If the pressure is too low, the hydrogenation reaction may take a long time, which may cause problems with productivity. On the other hand, if the pressure is increased, a high reaction rate can be obtained. Not right. The system temperature is maintained at the target reaction temperature, and the time from when the hydrogen pressure reaches the target pressure until the reaction is completed is usually 1 to 9 hours, preferably 2 to 5 hours. If it is time of the said range, while being able to perform sufficient hydrogenation, the side reaction which arises when time is too long can also be suppressed.

  The hydrogenation rate of the hydride of the cyclic olefin-based ring-opening (co) polymer thus obtained is usually 99.5 to 100%, preferably 99.7 to 100%. When the hydrogenation rate is within the above range, the resin is hardly deteriorated by oxygen.

  The hydrogenation reaction referred to in the present invention is hydrogenation with respect to the olefinic unsaturated bond in the cyclic olefin-based ring-opening (co) polymer molecule, and other unsaturated bonds may not be hydrogenated. Good.

  For example, if the polymer has an aromatic group, the aromatic group need not necessarily be hydrogenated. The presence of an aromatic group in the molecule may be advantageous for the optical properties such as heat resistance and refractive index of the resulting cyclic olefin-based ring-opening (co) polymer hydride, so depending on the desired properties It may be preferred to select conditions under which the aromatic group is not substantially hydrogenated. Moreover, when using aromatic solvents, such as toluene, as a solvent, it cannot be overemphasized that the conditions in which the solvent concerned is not hydrogenated are preferable.

Antioxidant In the present invention, the cyclic olefin ring-opening (co) polymer may be hydrogenated in the presence of a known antioxidant in order to further suppress the generation of gel during the hydrogenation reaction. it can.

  Examples of the antioxidant that can be preferably used in the present invention include an antioxidant selected from the group consisting of a phenol compound, a thiol compound, a sulfide compound, a disulfide compound, and a phosphorus compound. One type of inhibitor can be used alone, or two or more types can be used in appropriate combination.

  In the present invention, hydrogenation of a cyclic olefin-based ring-opening (co) polymer in the presence of 0.01 to 10 parts by weight of the above-mentioned antioxidant with respect to 100 parts by weight of the cyclic olefin-based ring-opening (co) polymer. It is preferable to carry out the reaction.

  According to such a method for producing a cyclic olefin-based ring-opening (co) polymer hydride of the present invention, compared with the case of producing a hydride of a cyclic olefin-based ring-opening (co) polymer by a conventionally known method. Thus, a substantially transparent cyclic olefin-based ring-opening (co) polymer hydride can be preferably produced.

  The thus obtained cyclic olefin-based ring-opening (co) polymer hydride can be used after being concentrated and desolvated by a known method, if necessary. The obtained cyclic olefin-based ring-opening (co) polymer hydride can be used by appropriately adding known additives.

<Purification process>
The method for producing a cyclic olefin-based ring-opening (co) polymer of the present invention further includes a step of purifying the solution that has undergone the hydrogenation reaction step using a decatching aid (C) and methanol. Also good. The purpose of this purification step is to remove the hydrogenation catalyst. When the polymerization process of the cyclic olefin compound is included before hydrogenation, the polymerization catalyst is also removed.

  Examples of the detouching aid (C) include carboxylic acids such as formic acid, acetic acid, propionic acid, tangle acid and valeric acid, dicarboxylic acids such as oxalic acid, malonic acid and succinic acid, and hydroxy acids such as lactic acid, malic acid and tartaric acid. Is mentioned.

  The detouching aid (C) is preferably 0.1 to 5.0 parts by weight, more preferably 0.1 to 2.0 parts by weight, based on 100 parts by weight of the cyclic olefin-based ring-opening (co) polymer. The methanol is preferably used in an amount of 50 to 500 parts by weight, more preferably 100 to 400 parts by weight, based on 100 parts by weight of the cyclic olefin ring-opening (co) polymer.

  As a purification method, the dehydrogenation aid (C) and methanol are mixed with the solution that has undergone the hydrogenation reaction step and heated and stirred. The mixed solution is separated into two layers, and the catalyst metal is removed by removing the methanol layer.

  By the above purification step, the content of the metal compound resulting from the catalyst in the cyclic olefin ring-opening (co) polymer hydride can be reduced, and the transparency of the cyclic olefin ring-opening (co) polymer hydride is reduced. Can be further improved.

<Cyclic olefin ring-opening (co) polymer hydride>
The cyclic olefin-based ring-opening (co) polymer hydride obtained by the production method of the present invention is also substantially free of gel and further contains a microgel that is difficult to remove by filtration or the like. Absent.

  The cyclic olefin ring-opening (co) polymer hydride obtained by the production method of the present invention has a yellow index (YI) of 0.20 to 0.37, preferably 0.20 to 0.35, more preferably. Is 0.20 to 0.30. The physical properties of such a cyclic olefin ring-opening (co) polymer hydride can be obtained by controlling the temperature at the start of hydrogen contact to a low temperature in the above production method. It is considered that this is obtained by being able to suppress oxidation before the start of hydrogen contact of the double bond and by reducing the residual amount of the metal compound derived from the catalyst in the above purification step.

  The cyclic olefin-based ring-opening (co) polymer hydride obtained by the production method of the present invention can be used by appropriately forming it into a desired shape by a known method, and the obtained molded product has a yellow index. Since it is in the above range, it is very transparent, and as a result, it has excellent optical characteristics and is less uneven in strength. For this reason, the cyclic olefin polymer hydride according to the present invention can be suitably used for various molded products such as optical parts, electrical / electronic materials, and films or sheets.

  Next, the method of the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. The copolymers and molded products obtained in Examples and Comparative Examples were evaluated by the following methods.

<Solution Yellow Index>
Using a touch panel SM color computer (model SM-T45, manufactured by Suga Test Instruments Co., Ltd.), a polymer solution adjusted to 10% by weight with toluene was placed in a 20 g sample cell, and the solution yellow index (YI) was measured.

<Weight average molecular weight and molecular weight distribution>
Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) in terms of polystyrene using gel permeation chromatography (GPC, manufactured by Tosoh Corporation, trade name: HLC-8020), using tetrahydrofuran (THF) as a solvent. Was measured.

<Example 1>
8-Methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] 75.5 parts by weight of dodec-3-ene, 23.5 parts by weight of dicyclopentadiene (DCP), 1 part by weight of 2-norbornene, 11.7 parts by weight of 1-hexene as a molecular weight regulator, and As a solvent, 150 parts by weight of toluene was added to a reaction vessel purged with nitrogen, and heated to 107 ° C. To this, 0.22 parts by weight of a toluene solution of triethylaluminum (0.6 mol / l) and 0.89 parts by weight of a toluene solution of methanol-modified WCl ₆ (0.025 mol / l) are added and reacted at 107 ° C. for 1 hour. As a result, a ring-opening (co) polymer was obtained.

The obtained ring-opening (co) polymer solution is transferred to a hydrogenation reaction vessel, 110 parts by weight of toluene is added and stirred to obtain a homogeneous solution, and the solution temperature is lowered to 30 ° C., which is a hydrogenation reaction catalyst. 0.04 parts by weight of Ru [4-CH ₃ (CH ₂ ) ₄ C ₆ H ₄ CO ₂ ] H (CO) [P (C ₆ H ₅ ) ₃ ] ₂ was added, and hydrogen was introduced up to 7 MPa. After introducing hydrogen to 7 MPa, the solution temperature was raised to 160 to 165 ° C., maintained at that temperature, and finally allowed to react for 3 hours from the time when the introduced hydrogen gas pressure was 9 to 10 MPa. After completion of the reaction, 100 parts by weight of toluene was added to dilute, and 0.12 parts by weight of lactic acid and 144 parts by weight of methanol were added as a decontacting aid to carry out a decatalytic operation to obtain a polymer from which the catalyst had been removed as a solution. Toluene was added to adjust the solution to a polymer concentration of 10% by weight, and the solution yellow index was measured to be 0.34.

  The resulting product was precipitated in a large amount of methanol to obtain a further purified hydride. This hydride was vacuum dried to obtain a cyclic olefin polymer (1). When GPC was measured, it was weight average molecular weight (Mw) = 48300 and molecular weight distribution (Mw / Mn) = 3.6. The hydrogenation rate was 99.9%.

<Example 2>
8-Methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] 75.5 parts by weight of dodec-3-ene, 23.5 parts by weight of dicyclopentadiene (DCP), 1 part by weight of 2-norbornene, 17.7 parts by weight of 1-hexene as a molecular weight regulator, and As a solvent, 150 parts by weight of toluene was added to a reaction vessel purged with nitrogen, and heated to 80 ° C. To this, 0.22 parts by weight of a toluene solution of triethylaluminum (0.6 mol / l) and 0.89 parts by weight of a toluene solution of methanol-modified WCl ₆ (0.025 mol / l) are added and reacted at 80 ° C. for 1 hour. As a result, a ring-opening (co) polymer was obtained.

The obtained ring-opening (co) polymer solution was transferred to a hydrogenation reaction vessel, 110 parts by weight of toluene was added and stirred to obtain a homogeneous solution, the solution temperature was lowered to 30 ° C., and Ru as a hydrogenation reaction catalyst. 0.04 part by weight of [4-CH ₃ (CH ₂ ) ₄ C ₆ H ₄ CO ₂ ] H (CO) [P (C ₆ H ₅ ) ₃ ] ₂ was added, and hydrogen was introduced up to 7 MPa. After introducing hydrogen to 7 MPa, the solution temperature was raised to 160 to 165 ° C., maintained at that temperature, and finally allowed to react for 3 hours from the time when the introduced hydrogen gas pressure was 9 to 10 MPa. After completion of the reaction, 100 parts by weight of toluene was added to dilute, 0.12 parts by weight of lactic acid and 144 parts by weight of methanol were added as detackifying aids, and the catalyst was removed to obtain a polymer from which the catalyst had been removed. Toluene was added to adjust the solution to a polymer concentration of 10% by weight, and the solution yellow index was measured and found to be 0.31.

  The resulting product was precipitated in a large amount of methanol to obtain a further purified hydride. This hydride was vacuum-dried to obtain a cyclic olefin polymer (2). When GPC was measured, it was weight average molecular weight (Mw) = 44100 and molecular weight distribution (Mw / Mn) = 3.5. The hydrogenation rate was 99.8%.

<Example 3>
8-Methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] 75.5 parts by weight of dodec-3-ene, 23.5 parts by weight of dicyclopentadiene (DCP), 1 part by weight of 2-norbornene, 21.6 parts by weight of 1-hexene as a molecular weight regulator, and As a solvent, 150 parts by weight of toluene was added to a reaction vessel purged with nitrogen, and heated to 50 ° C. To this, 0.22 parts by weight of a toluene solution of triethylaluminum (0.6 mol / l) and 0.89 parts by weight of a toluene solution of methanol-modified WCl ₆ (0.025 mol / l) are added and reacted at 50 ° C. for 1 hour. As a result, a ring-opening (co) polymer was obtained.

The obtained ring-opening (co) polymer solution was transferred to a hydrogenation reaction vessel, 110 parts by weight of toluene was added and stirred to obtain a homogeneous solution, the solution temperature was lowered to 30 ° C., and Ru as a hydrogenation reaction catalyst. 0.04 part by weight of [4-CH ₃ (CH ₂ ) ₄ C ₆ H ₄ CO ₂ ] H (CO) [P (C ₆ H ₅ ) ₃ ] ₂ was added, and hydrogen was introduced up to 7 MPa. After introducing hydrogen to 7 MPa, the solution temperature was raised to 160 to 165 ° C., maintained at that temperature, and finally allowed to react for 3 hours from the time when the introduced hydrogen gas pressure was 9 to 10 MPa. After completion of the reaction, 100 parts by weight of toluene was added to dilute, and 0.12 parts by weight of lactic acid and 144 parts by weight of methanol were added as a decontacting aid to carry out a decatalytic operation to obtain a polymer from which the catalyst had been removed as a solution. Toluene was added to adjust the solution to a polymer concentration of 10% by weight, and the solution yellow index was measured and found to be 0.32.

  The resulting product was precipitated in a large amount of methanol to obtain a further purified hydride. This hydride was vacuum-dried to obtain a cyclic olefin polymer (3). When GPC was measured, it was weight average molecular weight (Mw) = 54000 and molecular weight distribution (Mw / Mn) = 4.1. The hydrogenation rate was 99.8%.

<Example 4>
A polymer from which the catalyst was removed was obtained as a solution in the same manner as in Example 2, except that the hydrogenation reaction catalyst was changed to RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ . Toluene was added to adjust the solution to a polymer concentration of 10% by weight, and the solution yellow index was measured and found to be 0.26.

  A hydride was obtained by precipitating the obtained product in a large amount of methanol. This hydride was vacuum-dried to obtain a cyclic olefin polymer (4). When GPC was measured, it was weight average molecular weight (Mw) = 47500 and molecular weight distribution (Mw / Mn) = 3.2. The hydrogenation rate was 99.8%.

<Example 5>
The polymer from which the catalyst was removed was obtained as a solution in the same manner as in Example 2 except that the introduction of hydrogen was started after the solution temperature of the obtained ring-opening (co) polymer was lowered to 20 ° C. . Toluene was added to adjust the solution to a polymer concentration of 10% by weight, and the solution yellow index was measured and found to be 0.31.

  A hydride was obtained by precipitating the obtained product in a large amount of methanol. This hydride was vacuum-dried to obtain a cyclic olefin polymer (5). When GPC was measured, it was weight average molecular weight (Mw) = 49000 and molecular weight distribution (Mw / Mn) = 3.4. The hydrogenation rate was 99.9%.

<Comparative Example 1>
8-Methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] 75.5 parts by weight of dodec-3-ene, 23.5 parts by weight of dicyclopentadiene (DCP), 1 part by weight of 2-norbornene, 14.3 parts by weight of 1-hexene as a molecular weight regulator, and As a solvent, 150 parts by weight of toluene was added to a reaction vessel purged with nitrogen, and heated to 107 ° C. To this, 0.22 parts by weight of a toluene solution of triethylaluminum (0.6 mol / l) and 0.89 parts by weight of a toluene solution of methanol-modified WCl ₆ (0.025 mol / l) are added and reacted at 107 ° C. for 1 hour. As a result, a ring-opening (co) polymer was obtained.

The obtained ring-opening (co) polymer solution was transferred to a hydrogenation reaction vessel, 110 parts by weight of toluene was added and stirred to obtain a homogeneous solution, and Ru [4-CH ₃ (CH ₂₎ as a hydrogenation reaction catalyst. ) ₄ C ₆ H ₄ CO ₂ ] H (CO) [P (C ₆ H ₅ ) ₃ ] ₂ was added in an amount of 0.04 parts by weight. After raising the solution temperature to 90 ° C., hydrogen was introduced up to 7 MPa. Finally, the solution temperature was raised to 160 to 165 ° C., kept at that temperature, and the introduced hydrogen gas pressure was set to 9 to 10 MPa and reacted for 3 hours. After completion of the reaction, 100 parts by weight of toluene was added to dilute, and 0.12 parts by weight of lactic acid and 144 parts by weight of methanol were added as a decontacting aid to carry out a decatalytic operation to obtain a polymer from which the catalyst had been removed as a solution. Toluene was added to adjust the solution to a polymer concentration of 10% by weight, and the solution yellow index was measured and found to be 0.56.

  The resulting product was precipitated in a large amount of methanol to obtain a further purified hydride. This hydride was vacuum-dried to obtain a cyclic olefin polymer (6). When GPC was measured, it was weight average molecular weight (Mw) = 42200 and molecular weight distribution (Mw / Mn) = 3.0. The hydrogenation rate was 99.8%.

<Comparative example 2>
8-Methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] 75.5 parts by weight of dodec-3-ene, 23.5 parts by weight of dicyclopentadiene (DCP), 1 part by weight of 2-norbornene, 13.4 parts by weight of 1-hexene as a molecular weight regulator, and As a solvent, 150 parts by weight of toluene was added to a reaction vessel purged with nitrogen, and heated to 80 ° C. To this, 0.22 parts by weight of a toluene solution of triethylaluminum (0.6 mol / l) and 0.89 parts by weight of a toluene solution of methanol-modified WCl ₆ (0.025 mol / l) are added and reacted at 107 ° C. for 1 hour. As a result, a ring-opening (co) polymer was obtained.

The obtained ring-opening (co) polymer solution was transferred to a hydrogenation reaction vessel, 110 parts by weight of toluene was added and stirred to obtain a homogeneous solution, and Ru [4-CH ₃ (CH ₂₎ as a hydrogenation reaction catalyst. ) ₄ C ₆ H ₄ CO ₂ ] H (CO) [P (C ₆ H ₅ ) ₃ ] ₂ was added in an amount of 0.04 parts by weight. After raising the solution temperature to 90 ° C., hydrogen was introduced up to 7 MPa. Finally, the solution temperature was raised to 160 to 165 ° C., kept at that temperature, and the introduced hydrogen gas pressure was set to 9 to 10 MPa and reacted for 3 hours. After completion of the reaction, 100 parts by weight of toluene was added to dilute, and 0.12 parts by weight of lactic acid and 144 parts by weight of methanol were added as a decontacting aid to carry out a decatalytic operation to obtain a polymer from which the catalyst had been removed as a solution. Toluene was added to adjust the solution to a polymer concentration of 10% by weight, and the solution yellow index was measured to be 0.49.

  The resulting product was precipitated in a large amount of methanol to obtain a further purified hydride. This hydride was vacuum dried to obtain a cyclic olefin polymer (7). When GPC was measured, it was weight average molecular weight (Mw) = 53700 and molecular weight distribution (Mw / Mn) = 3.2. The hydrogenation rate was 99.9%.

<Comparative Example 3>
A polymer from which the catalyst was removed was obtained as a solution in the same manner as in Comparative Example 1, except that the hydrogenation reaction catalyst was changed to RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ . Toluene was added to adjust the solution to a polymer concentration of 10% by weight, and the solution yellow index was measured and found to be 0.38.

  The resulting product was precipitated in a large amount of methanol to obtain a further purified hydride. This hydride was vacuum-dried to obtain a cyclic olefin polymer (8). When GPC was measured, it was weight average molecular weight (Mw) = 44200 and molecular weight distribution (Mw / Mn) = 3.2. The hydrogenation rate was 99.8%.

水素添加触媒Ａ：Ｒｕ［４−ＣＨ₃（ＣＨ₂）₄Ｃ₆Ｈ₄ＣＯ₂］Ｈ（ＣＯ）［Ｐ（Ｃ₆Ｈ₅）₃］₂
水素添加触媒Ｂ：ＲｕＨＣｌ（ＣＯ）［Ｐ（Ｃ₆Ｈ₅）₃］₃

Hydrogenation catalyst A: Ru [4-CH ₃ (CH ₂ ) ₄ C ₆ H ₄ CO ₂ ] H (CO) [P (C ₆ H ₅ ) ₃ ] ₂
Hydrogenation catalyst B: RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃

Claims (8)

A method for producing a hydride of a cyclic olefin-based ring-opening (co) polymer (A) having a structural unit derived from a cyclic olefin-based compound represented by the following general formula (1):
A step of controlling the solution containing the cyclic olefin-based ring-opening (co) polymer (A) and the metal compound (B) at 10 to 40 ° C. to start contact with hydrogen;
After the start of contact with the hydrogen, a step of performing a hydrogenation reaction by setting the temperature of the solution to 100 to 200 ° C.,
A method for producing a hydride of a cyclic olefin-based ring-opening (co) polymer.

(In Formula (1), A ¹ and A ² are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or A polar group selected from the group consisting of an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amide group, an amino group and a thiol group, or a group consisting of a halogen atom and / or a group substituted by the above polar group An atom or a group, which may be the same or different, m is an integer of 0 or 1-3, and n is 0 or a positive integer. The method for producing a hydride of a cyclic olefin-based ring-opening (co) polymer according to claim 1, wherein the metal compound (B) is represented by the following general formula (2):
MQ _n H _k T _p Z _q (2)
(In formula (2), M represents a metal selected from the group consisting of ruthenium, rhodium, osmium, iron, cobalt and iridium;
Q independently represents a group represented by the following formula (i),
H represents a hydrogen atom,
T independently represents CO or NO;
Z independently represents PR ⁶ R ⁷ R ⁸ (P represents a phosphorus atom, and R ⁶ , R ⁷ and R ⁸ each independently represents an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group). ,
k represents 1 or 2, n represents 1 or 2, p represents an integer of 0 to 4, q represents an integer of 0 to 4, and the sum of k, n, p and q is 4, 5 or 6. )

(In the formula (i), R ^{1 to} R ⁵ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, aryl group, alkoxy group, amino group, nitro group, cyano group, carboxyl group or hydroxyl group. Is shown.) The method for producing a hydride of a cyclic olefin-based ring-opening (co) polymer according to claim 1, wherein the metal compound (B) is represented by the following general formula (5):
MX _n H _k T _p Z _q (5)
(In the formula (5), M represents a metal selected from the group consisting of ruthenium, rhodium, osmium, iron, cobalt and iridium;
X represents a halogen atom,
H represents a hydrogen atom,
T independently represents CO or NO;
Z independently represents PR ⁶ R ⁷ R ⁸ (P represents a phosphorus atom, and R ⁶ , R ⁷ and R ⁸ each independently represents an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group). ,
k represents 1 or 2, n represents 1 or 2, p represents an integer of 0 to 4, q represents an integer of 0 to 4, and the sum of k, n, p and q is 4, 5 or 6. )   The method for producing a hydride of a cyclic olefin-based ring-opening (co) polymer according to claim 2 or 3, wherein M in the formula (2) or the formula (5) is ruthenium. The cyclic olefin-based ring-opening (co) polymer (A) further has a structural unit derived from a cyclic olefin-based compound represented by the following general formula (3). A process for producing a hydride of the cyclic olefin ring-opening (co) polymer according to claim 1;

(In Formula (3), m is an integer of 0 or 1-3, and n is 0 or a positive integer.
A ^{3 to} A ⁶ each independently represents one represented by the following (a) to (e), or represents (f) or (g).
(A) a hydrogen atom,
(B) a halogen atom,
(C) a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms including a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom,
(D) a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms,
(E) a group selected from an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amide group, an amino group and a thiol group,
(F) A ³ and A ⁴ , or A ⁵ and A ⁶ represent an alkylidene group formed by bonding to each other, and A ^{3 to} A ⁶ not participating in the bonding are independent of each other from (a) to (a) to (E) represents one selected from
(G) A ³ and A ⁴ , A ⁵ and A ⁶ , or A ⁴ and A ⁵ bonded together to form an aromatic or non-aromatic monocyclic or polycyclic hydrocarbon ring or heterocyclic ring And A ^{3 to} A ⁶ not involved in the bond are independently selected from the above (a) to (e). ) Furthermore, the step of purifying the solution that has undergone the hydrogenation reaction step using a decatching aid (C) and methanol,
The method for producing a hydride of a cyclic olefin-based ring-opening (co) polymer according to any one of claims 1 to 5.   The hydride of the cyclic olefin type ring-opening (co) polymer obtained by the manufacturing method in any one of Claims 1-6.   The hydride of a cyclic olefin-based ring-opening (co) polymer according to claim 7, wherein the solution yellow index is 0.20 to 0.37.