JP5145632B2 - Metal hydride complex and method for hydrogenating cyclic olefin ring-opening polymer using the same - Google Patents

Description

  The present invention relates to a novel metal hydride complex. More specifically, a hydrogenation catalyst for hydrogenating carbon-carbon unsaturated bonds in alkenes and alkynes, a novel metal hydride complex useful as an olefin isomerization catalyst, and cyclic olefin ring-opening using the metal hydride complex The present invention relates to a method for hydrogenating polymers.

Metal complexes such as ruthenium and rhodium are known as useful compounds that serve as hydrogenation catalysts, hydrosilylation catalysts, hydroboration catalysts, or olefin isomerization catalysts for carbon-carbon unsaturated bonds in alkenes and alkynes. In particular, it is known that a metal hydride complex having a metal-hydrogen bond has high catalytic activity. For example, RuHCl (CO) (PP
h ₃ ) ₃ has been reported to be an excellent catalyst for hydrogenating carbon-carbon double bonds in polymers (see Patent Document 1).

  However, conventionally known metal hydride complexes have low solubility in organic solvents, and in particular, solubility in hydrocarbon solvents such as toluene is as low as about 0.03% by weight. For this reason, when this catalyst solution is supplied to the reaction vessel, it must be a dilute solution, which causes problems such as a decrease in production efficiency and an increase in the amount of solvent used. In addition, if an attempt is made to supply the reaction vessel at a high concentration, the slurry becomes a suspended slurry, and the charge amount has to be inaccurate.

  If only the solubility of these metal hydride complex catalysts is improved, a method of adding a small amount of a polar solvent such as tetrahydrofuran or ethyl acetate is effective, but these polar solvents are coordinating compounds. It was difficult to reduce the catalytic activity.

Moreover, as a metal hydride complex into which a carboxylic acid residue is introduced, for example, a ruthenium hydride complex into which a CH ₃ CO ₂ group or a CF ₃ CO ₂ group is introduced has been reported. It is known that such a metal hydride complex can be synthesized by a reaction between a metal dihydride complex and a carboxylic acid as shown in the following reaction formula (see Non-Patent Document 1).

RuH ₂ L (PPh ₃ ) ₃ + RCO ₂ H → RuH (OCOR) L (PPh ₃ ) ₂
(In the above reaction formula, L represents CO or NO, and R represents CH ₃ or CF _3. )
This conventional report was limited to two types of complexes in which the carboxylic acid residue is CH ₃ CO ₂ — or CF ₃ CO ₂ —. These complexes had high catalytic activity for hydrogenation reactions of carbon-carbon unsaturated bonds such as olefins and acetylenes, but their solubility in hydrocarbon solvents such as toluene was extremely small. The solubility at 20 ° C. was less than 0.1% by weight, and it was poor in practicality for industrial use as a catalyst.

  For this reason, in designing reactions on an industrial scale, in order to reduce the amount of solvent used and to accurately control the supply amount while maintaining the catalyst activity, the coordination power to metals must be reduced. There was a need to improve solubility in hydrocarbon solvents such as small toluene solvents.

When supplying the metal hydride complex as a catalyst to the reaction system, in order to adjust the total amount of the reaction solvent within an appropriate range, the concentration of the catalyst supply line is 0.2% by weight or more, more preferably for process design. It is desirable to reduce the excess amount of solvent to 1.0% by weight or more. In addition, in order to improve the reaction rate of the catalyst and increase the reaction yield, the appearance of a catalyst that dissolves uniformly at a high concentration has been strongly desired.

Under such circumstances, the present inventor has found that the metal hydride complex introduced with an aromatic carboxylic acid residue has greatly improved solubility in toluene and the like, and has a high activity for the hydrogenation reaction of unsaturated hydrocarbons. The present invention was completed by finding what is shown.
JP-A-4-202404 A, Dobson, et al., Inorg. Synth., 17, 126-127 (1977)

  An object of the present invention is to provide a metal hydride complex having high solubility in an organic solvent, particularly a hydrocarbon solvent such as toluene, and having high activity as a hydrogenation catalyst. Another object of the present invention is to provide a method for hydrogenating a cyclic olefin-based ring-opening (co) polymer using the metal hydride complex.

The metal hydride complex of the present invention is represented by the following general formula (1).
MQ _n H _k T _p Z _q (1)
(In the formula (1), M represents a metal selected from the group consisting of ruthenium, rhodium, osmium and iridium;
Q independently represents a group represented by the following formula (i),
T independently represents CO or NO;
Z independently represents PR ⁶ R ⁷ R ⁸ (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.)
In such a metal hydride complex of the present invention, M in the above formula (1) is preferably ruthenium, and R ^{1 to} R ⁵ in the above formula (i) are each independently a hydrogen atom or a carbon number of 1 It is also preferable that it is a -18 alkyl group, a cycloalkyl group or an aryl group.

  The metal hydride complex of the present invention preferably has a toluene solubility at 20 ° C. of 0.2% by weight or more, and more preferably has a toluene solubility at 20 ° C. of 1.0% by weight or more.

The method for hydrogenating a cyclic olefin ring-opening polymer of the present invention is characterized in that a hydrogenation reaction of a cyclic olefin ring-opening polymer is carried out in the presence of the metal hydride complex of the present invention.
In the method for hydrogenating a cyclic olefin ring-opening polymer of the present invention, the cyclic olefin ring-opening polymer is at least one selected from compounds represented by the following general formula (I), (II) or (III): It is preferably a monomer ring-opening (co) polymer containing

(In formula (I), (II) or (III), R ^{1 to} R ⁶ are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, an ester group, a nitrile group, a nitro group, etc. R ¹ and R ² or R ³ and R ⁴ may be the same or different from each other.
They may be integrated to form a divalent hydrocarbon group, and R ¹ or R ² and R ³ or R ⁴ may be bonded to each other to form a monocyclic or polycyclic structure. m, p, and q are each independently 0 or a positive integer. )

  ADVANTAGE OF THE INVENTION According to this invention, the novel metal hydride complex which melt | dissolves with high concentration in organic solvents with low polarity, such as a hydrocarbon solvent, and has high catalytic activity which hydrogenates a carbon-carbon double bond can be provided. For this reason, when the metal hydride complex of the present invention is used as a hydrogenation catalyst, a metal hydride complex dissolved in a solvent at a high concentration can be supplied to the reaction system, so that the amount of solvent can be reduced and it is economical. Moreover, handling such as control of the supply amount is easy, and industrial production efficiency can be improved.

  The metal hydride complex according to the present invention is particularly suitable as a catalyst in a hydrogenation reaction of a cyclic olefin ring-opening polymer. According to the present invention, an excellent method for hydrogenating a cyclic olefin ring-opening polymer is provided. be able to.

Hereinafter, the present invention will be specifically described.
<Metal hydride complex>
The metal hydride complex of the present invention is represented by the following general formula (1).

MQ _n H _k T _p Z _q (1)
In the above formula (1), M represents a metal selected from the group consisting of ruthenium, rhodium, osmium and iridium. Of such metals M, ruthenium is preferable because it is the cheapest and has high catalytic activity.

  Q in the above formula (1) is an aromatic carboxylic acid residue represented by the following formula (i).

In the above formula (i), R ^{1 to} R ⁵ may be the same or different and are each a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an alkoxy group, an amino group, a nitro group, or a cyano group. , A carboxyl group or a hydroxyl group. In these, a hydrogen atom, a C1-C18 alkyl group, a cycloalkyl group, and an aryl group are preferable.

  Examples of the alkyl group having 1 to 18 carbon atoms include methyl group, trifluoromethyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n- A pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group and the like can be mentioned.

  Examples of the cycloalkyl group include cyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2,3-dimethylcyclohexyl group, 2,4-dimethylcyclohexyl group, 2,5- Examples thereof include a dimethylcyclohexyl group, a 2,6-dimethylcyclohexyl group, a 3,4-dimethylcyclohexyl group, and a 3,5-dimethylcyclohexyl group.

  Examples of the aryl group include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, Examples include 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 1-naphthyl group, and 2-naphthyl group.

T in the formula (1) is at least one group selected from CO and NO.
Z in the above formula (1) is PR ⁶ R ⁷ R ⁸ , and R ⁶ , R ⁷ and R ⁸ may be the same or different and each represents an alkyl group, an alkenyl group, a cycloalkyl group or an aryl. Indicates a group.

Examples of the alkyl group in R ^{6 to} R ⁸ include, for example, 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 ^{6 to} R ⁸ include cyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2,3-dimethylcyclohexyl group, and 2,4-dimethylcyclohexyl. 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 ^{6 to} R ⁸ 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 said formula (1), k is 1 or 2, n is 1 or 2, p is an integer of 0-4, q is an integer of 0-4, k, n, p, q The sum of is 4, 5 or 6.
In addition, when there are a plurality of Q, T and Z in the above formula (1), they may be the same or different.

As a specific example of the metal hydride complex of 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.)
The metal hydride complex of the present invention can be obtained, for example, by a reaction between a corresponding metal polyhydride complex and a carboxylic acid. The metal polyhydride complex can be obtained by reacting a corresponding metal halide hydride complex with a basic reagent such as KOH in an alcohol solvent. The reaction scheme is shown below.

-OCOR 'in the above reaction scheme corresponds to Q in the above formula (1).
The reaction method is as follows. First, after putting an alcohol solution of a metal halide hydride complex into a reaction vessel in a nitrogen or argon atmosphere, a metal dihydride complex is obtained by dropping an alcohol solution of KOH and reacting for a predetermined time. Next, by adding a specific carboxylic acid to the obtained metal dihydride complex and allowing it to react for a certain period of time, the target complex is produced as a precipitate. After separation of the supernatant by filtration or decantation, the precipitate is washed with a solvent having low solubility such as methanol, if necessary, and the residual solvent is dried to obtain the desired product.

  Although the temperature of a reaction system is not specifically limited, It operates at the temperature of the range of -20 degreeC-200 degreeC according to the acidity of carboxylic acid. Further, although the amount of carboxylic acid used is not particularly limited, in order to make the conversion rate of the metal polyhydride complex 90% or more, at least 1 part or more, preferably 3 parts or more, more than 1 part of the metal polyhydride complex. Preferably, 5 parts or more of carboxylic acid is added.

  In the reaction for obtaining a metal dihydride complex from a metal halide hydride complex, an alcohol is used as a solvent. Examples of the alcohol include methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, 2-methoxyethanol, diethylene glycol and the like. These alcohol solvents may be used alone or in combination of two or more.

  In the reaction for obtaining the metal hydride complex as the final target compound from the metal dihydride complex, a solvent can be appropriately selected and used as necessary. For example, alicyclic hydrocarbon solvents such as cyclohexane, cyclopentane, and methylcyclopentane; aliphatic hydrocarbon solvents such as hexane, heptane, and octane; aromatic hydrocarbon solvents such as toluene, benzene, xylene, and mesitylene; chloromethane, Halogenated hydrocarbon solvents such as dichloromethane, 1,2-dichloroethane, 1,1-dichloroethane, tetrachloroethane, chloroform, carbon tetrachloride, chlorocyclopentane, chlorocyclohexane, chlorobenzene, dichlorobenzene; methanol, ethanol, propanol, butanol, Alcohol solvents such as pentanol, hexanol, octanol, 2-methoxyethanol, and diethylene glycol can be used. These may be used alone or in combination of two or more. Among these, from the viewpoint of solubility of raw materials, insolubility of products and versatility, an alcohol solvent or a mixed solvent containing an alcohol solvent is desirably used. In some cases, it is possible to carry out the reaction without solvent.

  The method for drying the complex is not particularly limited, and a method of removing the residual solvent under reduced pressure, a method of exposing to a nitrogen or argon stream under normal pressure, and scattering of the residual solvent can be employed.

The metal hydride complex of the present invention can also be produced in one pot from MCl _3. (H ₂ O) _{m according} to the reaction scheme shown below.
First, MCl _n · (H ₂ O) _m (wherein M is Ru, Rh, Os or Ir, and m is 0 to 0)
It is an integer of 3. ) And formaldehyde are reacted in the presence of a compound capable of forming a phosphorus ligand to form a metal halide hydride complex. Subsequently, this metal halide hydride complex and an alkali metal hydroxide are reacted in an alcohol solvent to obtain a metal dihydride complex. Further, the metal dihydride complex is reacted with the carboxylic acid R ¹ COOH without isolating the metal dihydride complex from the reaction system. With such a reaction scheme, a metal hydride complex can be produced in one pot. As an example, a reaction scheme using RuCl ₃ .3H ₂ O is shown below.

  The metal hydride complex of the present invention has high activity as a catalyst for hydrogenation reaction, hydrosilylation reaction, hydroboration reaction, hydrostannylation reaction, olefin isomerization reaction to carbon-carbon unsaturated bonds such as alkenes and alkynes. Have In particular, for a hydrogenation reaction of a norbornene-based ring-opening metathesis polymer, a high hydrogenation rate of 99.8% or more can be achieved. For this reason, the metal hydride complex of this invention can be widely used for these catalytic reactions on a laboratory scale or an industrial scale.

Such a metal hydride complex of the present invention is uniformly dissolved at a high concentration in a hydrocarbon solvent such as benzene, toluene, xylene, cyclohexane, methylcyclohexane, etc., depending on the type. The metal hydride complex of the present invention preferably has a toluene solubility at 20 ° C. of preferably 0.2% by weight or more, more preferably 1.0% by weight or more.
<Hydrogenation of cyclic olefin ring-opening polymer>
The method for hydrogenating the cyclic olefin ring-opening polymer of the present invention is carried out by hydrogenating the cyclic olefin ring-opening polymer using the metal hydride complex of the present invention as a catalyst. As the hydrogenation reaction method and conditions, general hydrogenation reaction methods and conditions can be adopted except that the metal hydride complex of the present invention is used. In addition, since the metal hydride complex of this invention has high solubility to hydrocarbon solvents, such as toluene, it can be supplied to a reaction system by high concentration. Therefore, reaction efficiency etc. can be improved and the amount of solvent of a supply catalyst can be decreased. Further, since the catalyst can be used as a uniform solvent system, it is easy to control the addition amount of the catalyst.
Cyclic olefin ring-opening polymer The cyclic olefin ring-opening polymer to be hydrogenated by the hydrogenation method of the cyclic olefin ring-opening polymer of the present invention includes a monomer containing a cyclic olefin compound having a norbornene skeleton. Any ring-opening metathesis (co) polymer can be used. That is, the cyclic olefin ring-opening polymer used as a raw material may be a ring-opening (co) polymer of one or more cyclic olefin compounds, and can be copolymerized with one or more cyclic olefin compounds. It may be a ring-opening copolymer with other compounds.

In the hydrogenation method of the present invention, the cyclic olefin-based ring-opening polymer has the following general formulas (I) and (II):
Or it is preferable that it is a ring-opening (co) polymer of the monomer containing 1 or more types chosen from the compound represented by (III).

(In formula (I), (II) or (III), R ^{1 to} R ⁶ are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, an ester group, a nitrile group, a nitro group, etc. R ¹ and R ² or R ³ and R ⁴ may be the same or different from each other.
They may be integrated to form a divalent hydrocarbon group, and R ¹ or R ² and R ³ or R ⁴ may be bonded to each other to form a monocyclic or polycyclic structure. m, p, and q are each independently 0 or a positive integer. )
Specific examples of such cyclic olefin compounds are shown below, but the present invention is not limited to these specific examples.

Examples of the cyclic olefin compound represented by the general formula (I) include the following compounds.
Bicyclo [2.2.1] hept-2-ene,
Tricyclo [5.2.1.0 ^2,6 ] -8-decene,
Tricyclo [4.4.0.1 ^2,5 ] -3-undecene,
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
Pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene,
5-methylbicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-cyanobicyclo [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,
5-ethylidenebicyclo [2.2.1] hept-2-ene,
8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
5-phenylbicyclo [2.2.1] hept-2-ene,
8-phenyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
5-fluorobicyclo [2.2.1] hept-2-ene,
5-fluoromethylbicyclo [2.2.1] hept-2-ene,
5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-pentafluoroethylbicyclo [2.2.1] hept-2-ene,
5,5-difluorobicyclo [2.2.1] hept-2-ene,
5,6-difluorobicyclo [2.2.1] hept-2-ene,
5,5-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5-methyl-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5,5,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,5,6-tris (fluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrafluorobicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrakis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5-difluoro-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-fluoro-5-pentafluoroethyl-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5-heptafluoro-iso-propyl-6-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-chloro-5,6,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-trifluoromethoxybicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-heptafluoropropoxybicyclo [2.2.1] hept-2-ene,
8-fluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-fluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-difluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-pentafluoroethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8-difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-trifluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-tris (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9,9-tetrafluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9,9-tetrakis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8-difluoro-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-trifluoro-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-trifluoro-9-trifluoromethoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-trifluoro-9-pentafluoropropoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-difluoro-8-heptafluoroiso-propyl-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-chloro-8,9,9-trifluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-dichloro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8- (2,2,2-trifluoroethoxycarbonyl) 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.

Moreover, as a cyclic olefin type compound represented by general formula (II), the following compounds are mentioned, for example.
Bicyclo [2.2.1] hept-2,5-diene,
5-methylbicyclo [2.2.1] hept-2,5-diene,
5-ethylbicyclo [2.2.1] hept-2,5-diene,
5-methoxycarbonylbicyclo [2.2.1] hept-2,5-diene,
Tricyclo [5.2.1.0 ^2,6 ] deca-3,8-diene.

Moreover, as a cyclic olefin type compound represented by general formula (III), the following compounds are mentioned, for example.

(1) Spiro [fluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] dec-3-ene],

(2) Spiro [2,7-difluorofluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] dec-3-ene],

(3) Spiro [2,7-dichlorofluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] dec-3-ene],

(4) Spiro [2,7-dibromofluorene-9,8′-tricyclo [4.3.0.1 ^2.5 ] dec-3-ene],

(5) Spiro [2-methoxyfluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] dec-3-ene]
,

(6) Spiro [2-ethoxyfluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] dec-3-ene]
,

(7) Spiro [2-phenoxyfluorene-9,8′-tricyclo [4.3.0.1 ^2.5 ] dec-3-ene],

(8) Spiro [2,7-dimethoxyfluorene-9,8′-tricyclo [4.3.0.1 ^2.5 ] dec-3-ene],

(9) Spiro [2,7-diethoxyfluorene-9,8′-tricyclo [4.3.0.1 ^2.5 ] dec-3-ene],

(10) Spiro [2,7-diphenoxyfluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] deca-3
-En],

(11) Spiro [3,6-dimethoxyfluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] dec-3-
En],

(12) Spiro [9,10-dihydroanthracene-9,8′-tricyclo [4.3.0.1 ^2.5 ] dec-3-ene],

(13) Spiro [fluorene-9,8 '-[2] methyltricyclo [4.3.0.1 ^2.5 ] dec-3-ene],

(14) Spiro [fluorene-9,8 '-[10] methyltricyclo [4.3.0.1 ^2.5 ] dec-3-ene]
,

(15) spiro [fluorene -9,11'- pentacyclo ^{[6.5.1.1 3.6 .0 2.7 .0 9.13]} [4] pentadecene,

(16) Spiro [2,7-difluorofluorene-9,11′-pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ] [4] pentadecene],

(17) Spiro [2,7-dichlorofluorene-9,11'-pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ] [4] pentadecene],

(18) Spiro [2,7-dibromofluorene-9,11′-pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ] [4] pentadecene],

(19) spiro [2-methoxy fluorene -9,11'- pentacyclo ^{[6.5.1.1 3.6 .0 2.7 .0 9.13]} [4] pentadecene,

(20) spiro [2-ethoxy-fluoren -9,11'- pentacyclo ^{[6.5.1.1 3.6 .0 2.7 .0 9.13]} [4] pentadecene,

(21) Spiro [2-phenoxyfluorene-9,11′-pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ] [4] pentadecene],

(22) Spiro [2,7-dimethoxyfluorene-9,11′-pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ] [4] pentadecene],

(23) Spiro [2,7-diethoxyfluorene-9,11′-pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ] [4] pentadecene],

(24) spiro [2,7-phenoxy fluorene -9,11'- pentacyclo ^{[6.5.1.1 3.6 .0 2.7 .0 9.13]} [4] pentadecene,

(25) spiro [3,6-dimethoxy-fluoren -9,11'- pentacyclo ^{[6.5.1.1 3.6 .0 2.7 .0 9.13]} [4] pentadecene,

(26) Spiro [9,10-dihydroanthracene-9,11′-pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ] [4] pentadecene],

(27) Spiro [fluorene-9,13'-hexacyclo [7.7.0.1 ^3.6 .1 ^10.16 .0 ^2.7 .0 ^11.15 ] [4] octadecene],

(28) spiro [2,7-difluoro-fluorene -9,13'- hexacyclo ^{[7.7.0.1 3.6 .1 10.16 .0 2.7 .0} 11.15] [4] octadecene,

(29) Spiro [2,7-dichlorofluorene-9,13'-hexacyclo [7.7.0.1 ^3.6 .1 ^10.16 .0 ^2.7 .0 ^11.15 ] [4] octadecene],

(30) spiro [2,7-dibromofluorene -9,13'- hexacyclo ^{[7.7.0.1 3.6 .1 10.16 .0 2.7 .0} 11.15] [4] octadecene,

(31) spiro [2-methoxy fluorene -9,13'- hexacyclo ^{[7.7.0.1 3.6 .1 10.16 .0 2.7 .0} 11.15] [4] octadecene,

(32) spiro [2-ethoxy-fluoren -9,13'- hexacyclo ^{[7.7.0.1 3.6 .1 10.16 .0 2.7 .0} 11.15] [4] octadecene,

(33) spiro [2-phenoxyethyl fluorene -9,13'- hexacyclo ^{[7.7.0.1 3.6 .1 10.16 .0 2.7 .0} 11.15] [4] octadecene,

(34) spiro [2,7-dimethoxy-fluoren -9,13'- hexacyclo ^{[7.7.0.1 3.6 .1 10.16 .0 2.7 .0} 11.15] [4] octadecene,

(35) spiro [2,7-diethoxy-fluoren -9,13'- hexacyclo ^{[7.7.0.1 3.6 .1 10.16 .0 2.7 .0} 11.15] [4] octadecene,

(36) Spiro [2,7-diphenoxyfluorene-9,13'-hexacyclo [7.7.0.1 ^3.6 .1 ^10.16 .0 ^2.7 .0 ^11.15 ] [4] octadecene],

(37) spiro [3,6-dimethoxy-fluoren -9,13'- hexacyclo ^{[7.7.0.1 3.6 .1 10.16 .0 2.7 .0} 11.15] [4] octadecene,

(38) Spiro [9,10-dihydroanthracene-9,13'-hexacyclo [7.7.0.1 ^3.6 .1 ^10.16 .0 ^2.7 .0 ^11.15 ] [4] octadecene],

(39) Spiro [fluorene-9,10'-tetracyclo [7.4.0.0 ^8.12 .1 ^2.5 ] [3] tetradecene]
.
In the present invention, these cyclic olefin compounds represented by the general formula (I), (II) or (III) are used alone as a monomer for obtaining a ring-opening olefin ring-opening polymer. It may be used in combination of two or more. Further, as a monomer composition for obtaining a ring-opening olefin-based ring-opening polymer, one or more cyclic olefin-based compounds represented by the above (I), (II) or (III) and a norbornene skeleton You may use the other cyclic olefin type compound which has, and the copolymerizable monomer which can be copolymerized as needed.

  Examples of the copolymerizable monomer include cyclic olefins such as cyclobutene, cyclopentene, cyclooctene, and cyclododecene; and non-conjugated cyclic polyenes such as 1,4-cyclooctadiene and cyclododecatriene. The copolymerizable monomers can be used singly or in combination of two or more.

The ring-opening olefin-based ring-opening polymer used in the present invention is obtained by ring-opening (co) polymerizing the above-described monomer containing a cyclic olefin-based compound.
As a catalyst used for ring-opening (co) polymerization, a known metathesis catalyst can be used. For example, a catalyst described in Olefin Metathesis and Metathesis Polymerization (KJIVIN, JCMOL, Academic Press 1997) is preferably used.

Examples of such a catalyst include (a) at least one selected from compounds of W, Mo, Re, V, and Ti, and (b) Li, Na, K, Mg, Ca, Zn, Cd, and Hg. A metathesis polymerization catalyst comprising a combination of at least one selected from the group consisting of at least one element-carbon bond or the element-hydrogen bond, such as B, Al, Si, Sn, Pb, etc. Can be mentioned. This catalyst may be added with an additive (c) described later in order to increase the activity of the catalyst. Other catalysts include (d) a metathesis catalyst composed of a group 4 to group 8 transition metal-carbene complex, a metallacyclobutene complex, or the like that does not use a promoter.

As typical examples of W, Mo, Re and V, Ti compounds suitable as the component (a),
The compounds described in JP-A-1-240517 such as WCl ₆ , MoCl ₅ , ReOCl ₃ , VOCl ₃ , TiCl ₄ can be mentioned.

As the component (b), n-C ₄ H ₉ Li, (C ₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) ₂ AlCl,
Examples thereof include (C ₂ H ₅ ) _1.5 AlCl _1.5 , (C ₂ H ₅ ) AlCl ₂ , methylalumoxane, LiH and the like described in JP-A-1-240517.

  As typical examples of the component (c) which is an additive, alcohols, aldehydes, ketones, amines and the like can be suitably used, but further compounds described in JP-A-1-240517 are used. be able to.

As typical examples of the catalyst (d), W (= N-2,6-C ₆ H ₃ iPr ₂ ) (= CH tBu) (O tBu) ₂ , Mo (= N-2,6-C ₆ H ₃ iPr ₂ ) (= CH tBu) (O tBu) ₂ , Ru (= CHCH = CPh ₂ ) (PPh ₃ ) ₂ Cl ₂ , Ru (= CHPh) (PC ₆
H ₁₁ ) ₂ Cl _{2 and the} like.

  The amount of the metathesis catalyst used is “(a) component: monomer” in terms of the molar ratio of the above component (a) and the monomer (total amount of monomers to be subjected to ring-opening (co) polymerization). Usually, it is in a range of 1: 500 to 1: 500,000, preferably in a range of 1: 1000 to 1: 100000. The ratio of the component (a) to the component (b) is such that the metal atomic ratio of “(a) :( b)” is in the range of 1: 1 to 1:50, preferably 1: 2 to 1:30. Is desirable. The ratio of the component (a) to the component (c) is 0.005: 1 to 15: 1, preferably 0.05: 1 to 7: 1, as a molar ratio, “(c) :( a)”. It is desirable to be in the range. Further, the amount of the catalyst (d) used is such that “(d) component: monomer” is usually 1:50 to 1: 50000 in terms of the molar ratio of the component (d) to the monomer, preferably A range of 1: 100 to 1: 10000 is desirable.

  The molecular weight of the cyclic olefin ring-opening polymer is desirably adjusted to a desired molecular weight according to the use of the hydride of the cyclic olefin ring-opening polymer to be produced. Although the molecular weight of the cyclic olefin-based ring-opening polymer can be adjusted depending on the polymerization temperature, the type of catalyst, and the type of solvent, in the present invention, the molecular weight regulator can be adjusted to coexist in the reaction system. Is preferred. Examples of suitable molecular weight regulators include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene. And styrene, among which 1-butene and 1-hexene are particularly preferable. These molecular weight regulators can be used alone or in admixture of two or more. The amount of the molecular weight regulator used is 0.001 to 0.6 mol, preferably 0.02 to 0.5 mol, per 1 mol of the monomer subjected to the ring-opening (co) polymerization reaction. Is desirable.

  Examples of the solvent used in the ring-opening (co) polymerization reaction, that is, the solvent for dissolving the norbornene monomer, the metathesis catalyst, and the molecular weight regulator include alkanes such as pentane, hexane, heptane, octane, nonane, and decane. ; Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene Halogenated alkanes such as chloroform, tetrachloroethylene; compounds such as aryl; saturated carboxylic acids such as ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate, dimethoxyethane, etc. Esters; dibutyl ether, tetrahydrofuran, there may be mentioned ethers such as dimethoxyethane, it can be used singly or in combination. Of these, aromatic hydrocarbons are preferred in the present invention.

The amount of the solvent used is desirably an amount such that the solvent: monomer (weight ratio) is usually 1: 1 to 10: 1, preferably 1: 1 to 5: 1.
The cyclic olefin ring-opening polymer thus obtained has a carbon-carbon double bond in the main chain.
Hydrogenation Reaction In the method for hydrogenating a cyclic olefin ring-opening polymer of the present invention, a hydrogenation reaction of the cyclic olefin ring-opening polymer is carried out in the presence of the metal hydride complex of the present invention described above.

In the hydrogenation reaction, an olefinically unsaturated group represented by the formula: —CH═CH— in the main chain of the cyclic olefin ring-opening polymer is hydrogenated, and the formula: —CH ₂ CH ₂ — To the group represented by When the cyclic olefin-based ring-opening polymer has an unsaturated bond other than the main chain such as in a ring structure, the unsaturated bond other than the main chain may not be hydrogenated.

  The hydrogenation rate of the cyclic olefin-based ring-opening polymer in the hydrogenation method of the present invention (ratio of carbon-carbon double bonds present in the main chain of the cyclic olefin-based ring-opening polymer) is Usually, it is 40 mol% or more, preferably 60 mol% or more, more preferably 90 mol% or more, and further preferably 95 mol% or more. A higher hydrogenation rate is preferable because coloring and deterioration of the hydride obtained can be suppressed under high temperature conditions, and toughness can be imparted to a molded product obtained therefrom.

In the hydrogenation reaction, for example, a metal hydride complex according to the present invention is added to a solution of a cyclic olefin-based ring-opening polymer as a catalyst, and hydrogen gas at normal pressure to 30 MPa, preferably 3 to 20 MPa is usually added thereto. In addition, the reaction can usually be carried out by reacting at 0 to 220 ° C, preferably 20 to 200 ° C. The metal hydride complex may be added in any form such as powder, solution, or slurry, but it is preferably added as a metal hydride complex solution. As the metal hydride complex solution, a solution in which a metal hydride complex is dissolved in an organic solvent such as benzene, toluene, xylene, cyclohexane, methylcyclohexane, etc. to a concentration of 0.2% by weight or more, preferably 1.0% by weight or more. Is preferably used. When the hydrogenation reaction is performed subsequent to the polymerization of the cyclic olefin ring-opening polymer, it is preferable to use the solvent used at the time of polymerization or a solvent compatible therewith as the solvent for the metal hydride complex solution.

In the present invention, it is preferable to use the metal hydride complex in such a ratio that the weight ratio of the ring-opening polymer: metal hydride complex is usually 1: 1 × 10 ⁻⁶ to 1: 1 × 10 ⁻² .
The hydride of the cyclic olefin-based ring-opening polymer obtained by the production method of the present invention may be used by adding various additives such as the above-mentioned antioxidant, ultraviolet absorber and lubricant as necessary. Examples of such additives include 2,6-di-t-butyl-4-methylphenol, 2,2′-methylenebis (4-ethyl-6-t-butylphenol), 2,5-di-t. −
Butylhydroquinone, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4,4′-thiobis- (6-tert-butyl-3-methylphenol), 1 , 1-bis (4-hydroxyphenyl) cyclohexane, octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,3 ′, 3 ″, 5,5 ′, 5 ′ '-Hexa-t-butyl-a, a', a ''-(mesitylene-2
, 4,6-triyl) tri-p-cresol and other phenolic and hydroquinone antioxidants; tris (4-methoxy-3,5-diphenyl) phosphite, tris (nonylphenyl) phosphite, tris (2, And phosphorus-based antioxidants such as 4-di-t-butylphenyl) phosphite. Addition of one or more of these antioxidants can improve the oxidation resistance of the ring-opening (co) polymer. Also, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2 ′
Light resistance is improved by adding an ultraviolet absorber such as methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-[(2H-benzotriazol-2-yl) phenol]]. You can also In addition to lubricants that improve processability, known additives such as flame retardants, antibacterial agents, petroleum resins, plasticizers, colorants, mold release agents, foaming agents and the like can be added as necessary. These additives can be used singly or in combination of two or more.

The hydride of the cyclic olefin-based ring-opening polymer obtained in the present invention can be suitably shaped and used particularly suitably for applications in the fields of optical parts and electrical / electronic materials. Specific examples of such applications include optical disks, magneto-optical disks, optical lenses (Fθ lenses, pickup lenses, laser printer lenses, camera lenses, etc.) spectacle lenses, optical films (display films, retardation films). , Polarizing film, transparent conductive film, wavelength plate, antireflection film, optical pickup film, etc.), optical sheet, optical fiber, light guide plate, light diffusion plate, optical card, optical mirror, IC / LSI / LED sealing material, etc. It is done.

  According to the present invention, by appropriately adjusting the composition, a cyclic olefin polymer that exhibits excellent transparency, heat resistance, low water absorption, and has freely controlled birefringence and wavelength dispersion is produced. It is possible to provide a novel cyclic olefin-based ring-opening (co) polymerization-hydrogenated product useful as a precursor monomer.

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

In the following examples, the raw material RuHCl (CO) (PPh ₃ ) ₃ was synthesized according to the literature (N., Ahmad, et al., Inorg. Synth., 15, 45 (1974)). In addition, potassium hydroxide, n-butanol, methanol, benzoic acid and the like were used after nitrogen bubbling manufactured by Wako Pure Chemical Industries, Ltd. to reduce dissolved oxygen and moisture. The product complex was identified by the following analytical instrument.
(1) ¹ H-NMR, ³¹ P-NMR:
Measurement was performed with “AVANCE500” manufactured by BRUKER using deuterated chloroform as a solvent.
(2) IR:
Measured with “FT / IR-480 Plus” manufactured by JASCO Corporation.

<Synthesis of RuH (OCOPh) (CO) (PPh ₃ ) ₂ >
Under a nitrogen atmosphere, 210 mL of an n-butanol solution of potassium hydroxide (7.42 g, 132.3 mmol) was added to 18.0 g (18.9 mmol) of RuHCl (CO) (PPh ₃ ) ₃ and the mixture was stirred at 125 ° C. for 1 hour. Heated to reflux. Of the RuHCl (CO) (PPh ₃ ) ₃ used here, 2
The solubility in toluene at 0 ° C. was 0.03% by weight.

  Subsequently, 73 mL of an n-butanol solution of benzoic acid (23.1 g, 189.0 mmol) was added, and then the mixture was heated to reflux for 1 hour to precipitate a yellowish white powdery product. After cooling the reaction solution to room temperature, the solid powder was washed with 100 mL of cold methanol (0 ° C.), and the resulting solid was filtered off from the supernatant. This was further washed with 50 mL of water and 200 mL of cold methanol (0 ° C.) and then dried under reduced pressure to obtain the desired product (13.9 g, 18.0 mmol, yield 95%).

The resulting product was analyzed by ¹ H-NMR and found to have a region of aromatic unsaturated hydrocarbon bound to 7.0 to 7.1 ppm carboxylic acid and 7.2 to 7.6 ppm trioxy. The integration ratio of unsaturated hydrocarbon of phenylphosphine was 5:30, which was in good agreement with the theoretical value. As a result of ³¹ P-NMR analysis, a triphenylphosphine peak was detected at 45.3 ppm by a singlet. Furthermore, by measurement of IR, 2011 cm ⁻¹ (Ru—H), 1
Absorption was observed at 938 cm ⁻¹ (CO), 1520 cm ⁻¹ (metal coordinated carboxylic acid residue), and it was confirmed that the target compound RuH (OCOPh) (CO) (PPh ₃ ) ₂ was formed. did it. ¹ H-NMR spectrum of the resulting ruthenium hydride complex in Figure 1, ³¹ P-NMR
The spectrum is shown in FIG. 4 and the IR spectrum is shown in FIG. Further, the solubility of the obtained ruthenium hydride complex in toluene at 20 ° C. was 0.5% by weight.

_{<RuH (OCOPh-C 5 H} 11) (CO) Synthesis of (PPh _{3) 2>}
Except that n-pentylbenzoic acid was used in place of benzoic acid, the same reaction operation was carried out as in Example 1, and the corresponding product was obtained (13.8 g, 16.3 mmol, yield 86%). . As a result of analyzing the product by ¹ H-NMR, the integration ratio of the region of 0.8 to 2.5 ppm saturated hydrocarbon and the region of 6.7 to 7.6 ppm unsaturated hydrocarbon was 11:34. It was in good agreement with the theoretical value. As a result of ³¹ P-NMR analysis, a triphenylphosphine peak was detected at 45.2 ppm with a singlet. Furthermore, by IR measurement, absorption was observed at 2012 cm ⁻¹ (Ru—H), 1913 cm ⁻¹ (CO), and 1541 cm ⁻¹ (metal coordinated carboxylic acid residue), and the target compound, RuH (OCOPh— It was confirmed that C ₅ H ₁₁ ) (CO) (PPh ₃ ) ₂ was formed. FIG. 2 shows a ¹ H-NMR spectrum of the obtained ruthenium hydride complex, FIG. 5 shows a ³¹ P-NMR spectrum, and FIG. 8 shows an IR spectrum. Moreover, the solubility in 20 degreeC of toluene of the obtained ruthenium hydride complex was 1.0 weight%.

_{<RuH (OCOPh-C 8 H} 17) (CO) Synthesis of (PPh _{3) 2>}
Except that n-octylbenzoic acid was used in place of benzoic acid, the same reaction operation was carried out as in Example 1, and the corresponding product was obtained (13.6 g, 15.3 mmol, 81% yield). . As a result of analyzing the product by ¹ H-NMR, the integration ratio of the region of 0.8 to 2.5 ppm saturated hydrocarbon and the region of 6.7 to 7.6 ppm unsaturated hydrocarbon was 17:34. It was in good agreement with the theoretical value. As a result of ³¹ P-NMR analysis, a triphenylphosphine peak was detected at 45.2 ppm with a singlet. Further, by IR measurement, absorption was observed at 2014 cm ⁻¹ (Ru—H), 1934 cm ⁻¹ (CO), 1546 cm ⁻¹ (metal coordinated carboxylic acid residue), and the target compound, RuH (OCOPh— It was confirmed that C ₈ H ₁₇ ) (CO) (PPh ₃ ) ₂ was formed. FIG. 3 shows the ¹ H-NMR spectrum of the obtained ruthenium hydride complex, FIG. 6 shows the ³¹ P-NMR spectrum, and FIG. 9 shows the IR spectrum. Further, the solubility of the obtained ruthenium hydride complex in toluene at 20 ° C. was 5.0% by weight.

<Preparation of cyclic olefin ring-opening polymer>
And 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 250 parts of 1-hexene (molecular weight modifier) 18 parts of 750 parts of toluene Were charged into a reaction vessel purged with nitrogen, and the solution was heated to 80 ° C. Next, 0.62 parts of a toluene solution of triethylaluminum (1.5 mol / L) as a polymerization catalyst and tungsten hexachloride modified with t-butanol and methanol (t-butanol: methanol: tungsten) were added to the solution in the reaction vessel. A toluene solution (concentration of 0.05 mol / L) of 0.35 mol: 0.3 mol: 1 mol) was added to 3.7 parts, and this system was heated and stirred at 80 ° C. for 3 hours to cause a ring-opening copolymerization reaction. to give 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- ring-opening metathesis polymer solution dodecene. The polymerization conversion rate in this polymerization reaction was 97%.
<Hydrogenation>
The autoclave was charged with 1000 parts of the ring-opening polymer solution obtained above, and a 0.5 wt% toluene solution of the ruthenium hydride complex obtained in Example 1 was added to the ring-opening polymer solution as a hydrogenation catalyst. Add an amount (12 parts) that makes the amount 0.06 part, hydrogen gas pressure 100 kg /
The hydrogenation reaction was performed by heating and stirring for 3 hours under the conditions of cm ² and a reaction temperature of 165 ° C. After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover a coagulated product, which was dried to obtain a hydrogenated polymer. This polymer was measured by ¹ H-NMR, and the hydrogenation rate was calculated from the ratio of the integrated value of 0.6 to 2.5 ppm saturated hydrocarbon and the integrated value of 5.0 to 5.6 ppm unsaturated hydrocarbon. As a result, the hydrogenation rate was 99.99%.

In Example 4, instead of the 0.5 wt% toluene solution of the ruthenium hydride complex obtained in Example 1 as a hydrogenation catalyst used in the hydrogenation reaction, 1.0 weight of the ruthenium hydride complex obtained in Example 2 was used. 8-methyl-8-methoxycarbonyltetracyclo [4.4.4] in the same manner as in Example 4 except that the amount of the toluene solution used was 0.06 part (6 parts). The ring-opening metathesis polymer of 0.1 ^{2,5.1 7,10} ] -3-dodecene was hydrogenated to obtain a hydrogenated polymer. When the hydrogenation rate of the obtained hydrogenated polymer was determined in the same manner as in Example 4, it was 99.95%.

In Example 4, instead of the 0.5 wt% toluene solution of the ruthenium hydride complex obtained in Example 1 as a hydrogenation catalyst used in the hydrogenation reaction, 5.0 weight of the ruthenium hydride complex obtained in Example 3 was used. 8-methyl-8-methoxycarbonyltetracyclo [4. 4] in the same manner as in Example 4 except that the amount of complex solution added was 0.06 part (1.2 parts). 4.0.1 ^{2,5.1 7,10} ] -3-Dodecene ring-opening metathesis polymer was hydrogenated to obtain a hydrogenated polymer. When the hydrogenation rate of the obtained hydrogenated polymer was determined in the same manner as in Example 4, it was 99.90%.

Comparative Example 1
In Example 4, as a hydrogenation catalyst used in the hydrogenation reaction, instead of the 0.5 wt% toluene solution of the ruthenium hydride complex obtained in Example 1, RuHCl (CO), which is a ruthenium complex not modified with carboxylic acid, is used. 8-Methyl-8 was prepared in the same manner as in Example 4 except that a 0.03% by weight toluene solution of (PPh ₃ ) ₃ was used (200 parts) so that the amount of complex addition was 0.06 parts. - perform hydrogenation of methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene ring-opening metathesis polymer to obtain a hydrogenated polymer. When the hydrogenation rate of the obtained hydrogenated polymer was determined in the same manner as in Example 4, it was 99.75%.

8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene instead of 250 parts of 8-methyl-8-methoxycarbonyltetracyclo [4. 4.0.1, ^2,5 .
1 ^7,10 ] -3-dodecene 187.5 parts and tricyclo [5.2.1.0 ^2,6 ] deca-3,8
-Except having used 62.5 parts of dienes, the polymerization operation similar to Example 4 was performed and the ring-opening copolymer solution was obtained. The polymerization conversion rate in this polymerization reaction was 98%.

1000 parts of the ring-opening copolymer solution thus obtained was charged into an autoclave, and a 1.0 wt% toluene solution of the ruthenium hydride complex obtained in Example 2 was added to this ring-opening copolymer solution. An amount (6 parts) of 0.06 part was added, and the hydrogenation reaction was performed by heating and stirring for 3 hours under the conditions of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C. After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover a coagulated product, which was dried to obtain a hydrogenated polymer. This polymer was measured by ¹ H-NMR, and the hydrogenation rate was calculated from the ratio of the integrated value of 0.6 to 2.5 ppm saturated hydrocarbon and the integrated value of 5.0 to 5.6 ppm unsaturated hydrocarbon. Asked. As a result, the hydrogenation rate of the unsaturated double bond derived from the side chain of tricyclo [5.2.1.0 ^2,6 ] deca-3,8-diene was 99.99% or more, It was found that the chain hydrogenation rate was 99.97%, and a high hydrogenation rate was achieved.

8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene instead of 250 parts of 8-methyl-8-methoxycarbonyltetracyclo [4. 4.0.1, ^2,5 .
1 ^7,10] -3-dodecene 190 parts of spiro [fluorene -9,8'- tricyclo [4.3.0.1 ^2.5] dec-3-ene] Except for using 60 parts of the same polymerization as in Example 4 Operation was performed to obtain a ring-opening copolymer solution. The polymerization conversion rate in this polymerization reaction was 96%.

1000 parts of the ring-opening copolymer solution thus obtained was charged into an autoclave, and a 1.0 wt% toluene solution of the ruthenium hydride complex obtained in Example 2 was added to this ring-opening copolymer solution. An amount (6 parts) of 0.06 part was added, and the hydrogenation reaction was performed by heating and stirring for 3 hours under the conditions of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C. After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover a coagulated product, which was dried to obtain a hydrogenated polymer. This polymer was measured by ¹ H-NMR, and the hydrogenation rate was calculated from the ratio of the integrated value of 0.6 to 2.5 ppm saturated hydrocarbon and the integrated value of 5.0 to 5.6 ppm unsaturated hydrocarbon. Asked. As a result, the hydrogenation rate of the main chain of the copolymer was 99.93%. When the same operation was performed using RuHCl (CO) (PPh ₃ ) ₃ as a catalyst, the hydrogenation rate was 99.30%. Therefore, by using this catalyst, a high hydrogenation rate was obtained. Turned out to be achieved.

1 shows the ¹ H-NMR spectrum of the ruthenium hydride complex obtained in Example 1. FIG. FIG. 2 shows the ¹ H-NMR spectrum of the ruthenium hydride complex obtained in Example 2. FIG. 3 shows the ¹ H-NMR spectrum of the ruthenium hydride complex obtained in Example 3. FIG. 4 shows the ³¹ P-NMR spectrum of the ruthenium hydride complex obtained in Example 1. FIG. 5 shows the ³¹ P-NMR spectrum of the ruthenium hydride complex obtained in Example 2. FIG. 6 shows the ³¹ P-NMR spectrum of the ruthenium hydride complex obtained in Example 3. FIG. 7 shows the IR spectrum of the ruthenium hydride complex obtained in Example 1. FIG. 8 shows the IR spectrum of the ruthenium hydride complex obtained in Example 2. FIG. 9 shows the IR spectrum of the ruthenium hydride complex obtained in Example 3.

Claims (6)

A metal hydride complex represented by the following general formula (1) and having a toluene solubility at 20 ° C. of 1.0% by weight or more.
MQ _n H _k T _p Z _q (1)
(In the formula (1), M represents a ruthenium-time,
Q represents a group represented by the following following formula (i),
T represents CO ,
Z is PR ⁶ R ⁷ R ⁸ independently (R ^6, R ⁷ and R ⁸ each independently represent an A reel group.) Indicates,
k represents an 1, n represents a 1, p represents a 1, q is shows the 2. )

(In the formula (i), R ¹ to R ⁵ is a hydrogen atom or an alkyl group having a carbon number of 5 to 18 independently.) A method for hydrogenating a cyclic olefin ring-opening polymer, wherein a hydrogenation reaction of the cyclic olefin ring-opening polymer is carried out in the presence of a metal hydride complex represented by the following general formula (1 ').
MQ _n H _k T _p Z _q (1 ′)
(In the formula (1 ′), M represents a metal selected from the group consisting of ruthenium, rhodium, osmium and iridium;
Q independently represents a group represented by the following formula (i),
T independently represents CO or NO;
Z independently represents PR ⁶ R ⁷ R ⁸ (R ⁶ , R ⁷ and R ⁸ each independently represents an alkyl group, an alkenyl group or an aryl group);
k represents 1 or 2, n represents 1 or 2, p represents 1, q represents an integer of 0 to 3, and the sum of k, n, p and q is 4, 5 or 6 is there. )

(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 cyclic olefin ring-opening polymer is a monomer ring-opening (co) polymer containing one or more compounds selected from compounds represented by the following general formula (I), (II) or (III) The method for hydrogenating a cyclic olefin-based ring-opening polymer according to claim 2 .

(In formula (I), (II) or (III), R ^{1 to} R ⁶ are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, an ester group, a nitrile group, a nitro group, etc. R ¹ and R ² or R ³ and R ⁴ may be combined to form a divalent hydrocarbon group, and R ¹ or R ² may be the same or different from each other. R ² and R ³ or R ⁴ may combine with each other to form a monocyclic or polycyclic structure, and m, p, and q are each independently 0 or a positive integer.) The method for hydrogenating a cyclic olefin ring-opening polymer according to claim 2 or 3 , wherein the solubility of toluene at 20 ° C of the metal hydride complex is 0.2% by weight or more. R ¹ to R ⁵ in the formula (i) are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, any one of claims 2 to 4, wherein the cycloalkyl group or an aryl group The method for hydrogenating a cyclic olefin-based ring-opening polymer as described in 1. R ¹ to R ⁵ in the formula (i) is a cyclic olefin-based open according to any one of claims 2 to 5, characterized in that each independently a hydrogen atom or an alkyl group having a carbon number of 5 to 18 A method for hydrogenating a ring polymer.

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