CN101180303A - Metal hydride complex, hydrogenation method of cyclic olefin-based ring-opening polymer, and method for preparing hydrogenated product of cyclic olefin-based ring-opening polymer - Google Patents

Abstract

The metal hydride complexes of the present invention are hydride complexes of metals selected from ruthenium, rhodium, osmium, and iridium, having one or more aromatic carboxylic acid residues. According to the present invention, novel metal hydride complexes with high catalytic activity for hydrogenating carbon-carbon double bonds can be provided, exhibiting high solubility in low-polarity organic solvents such as hydrocarbon solvents. The metal hydride complexes of the present invention are particularly suitable as catalysts for the hydrogenation reactions of cyclic olefin ring-opening polymers.

Description

Metal hydride complex, hydrogenation method of cyclic olefin-based ring-opening polymer, and method for preparing hydrogenated product of cyclic olefin-based ring-opening polymer

technical field

The invention relates to a novel metal hydride complex, a hydrogenation method of a cyclic olefin ring-opening polymer and a preparation method of a hydrogenated cyclic olefin ring-opening polymer. More specifically, it relates to a novel metal hydride complex useful as a hydrogenation catalyst for hydrogenating carbon-carbon unsaturated bonds in alkenes or alkynes, and an olefin isomerization catalyst, and a cyclic olefin using the metal hydride complex A hydrogenation method for a ring-opening polymer, and a method for preparing a hydrogenated cyclic olefin-based ring-opening polymer using the metal hydride complex.

Background technique

Metal complexes of ruthenium, rhodium, and the like are known to be compounds useful as catalysts for hydrogenation of carbon-carbon unsaturated bonds in alkenes or alkynes, hydrosilylation catalysts, hydroboration catalysts, or olefin isomerization catalysts. It is known that especially metal hydride complexes having metal-hydrogen bonds have high catalytic activity. For example, RuHCl(CO)(PPh ₃ ) ₃ (Ph represents phenyl) is reported to be an excellent catalyst for hydrogenating carbon-carbon double bonds in polymers (see Patent Document 1).

However, the solubility of conventionally known metal hydride complexes in organic solvents is low, and in particular, the solubility in hydrocarbon solvents such as toluene is as low as about 0.03% by weight. Therefore, when the catalyst solution is supplied to the reaction vessel, it has to be made into a dilute solution, which leads to problems such as a decrease in production efficiency and an increase in the amount of solvent used. In addition, when a high concentration is supplied to the reaction vessel, a suspension-like slurry will be formed, so that the amount of feed will inevitably become inaccurate.

If only the solubility of these metal hydride complex catalysts is improved, the method of adding a small amount of polar solvents such as tetrahydrofuran or ethyl acetate is effective, but has the following disadvantages: since these polar solvents are coordination compounds, leading to a decrease in catalytic activity.

In addition, 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. As shown in the following reaction formula, it is known that such a metal hydride complex can be synthesized by reacting a metal dihydride complex with a carboxylic acid (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 .)

In previous reports, only the carboxylic acid residues are CH ₃ CO ₂ - or CF ₃ CO ₂ - complexes. Although these complexes have high catalytic activity for the hydrogenation of carbon-carbon unsaturated bonds of olefins, acetylenes, etc., their solubility in hydrocarbon solvents such as toluene is extremely small, and the solubility at 20 ° C is only less than 0.1% by weight. It lacks practicality when used as a catalyst in industry.

Therefore, in order to design an industrial-scale reaction, in order to maintain the activity of the catalyst as it is, to reduce the amount of solvent used and to control the correct supply amount, etc., it is necessary to improve the solubility in hydrocarbon solvents such as toluene solvents that have a low coordination force for metals. sex.

When supplying the metal hydride complex as a catalyst to the reaction system, in order to adjust the overall amount of the reaction solvent to an appropriate range, the concentration of the catalyst supply line is designed to be 0.2% by weight or more, more preferably 1.0% by weight. Above, it is desired to reduce the excess solvent amount. In addition, in order to increase the catalytic reaction rate and achieve an increase in the reaction yield, the appearance of a catalyst that is uniformly dissolved at a high concentration is also strongly desired.

In addition, cyclic olefin-based resins have a high glass transition temperature due to the rigidity of the main chain structure, are amorphous and have high light transmittance due to the presence of bulky groups in the main chain structure, and have high light transmittance due to the refractive index. Since it exhibits advantages such as low anisotropy and low birefringence, 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 resin obtained by further hydrogenating a polymer containing dicyclopentadiene (hereinafter abbreviated as "DCP") which is industrially easily available and inexpensive can be cited. ) or derivatives thereof through ring-opening polymerization; for example, it is proposed to apply to optical materials such as optical discs, optical lenses, optical fibers, packaging materials for packaging optical semiconductors, optical films and sheets, or pharmaceuticals, etc. container etc. (refer to Patent Documents 2 and 3).

Generally speaking, the ring-opening polymer of DCP or its derivatives (hereinafter including DCP are referred to as "DCP-based monomers") can be obtained by putting DCP-based monomers in a suitable solvent in a ring-opening polymerization catalyst such as a metathesis catalyst system. obtained by ring-opening polymerization in the presence of . Furthermore, its hydrogenated product can be obtained by reacting with hydrogen after adding a suitable hydrogenation catalyst to the solution of the above-mentioned ring-opened polymer (see Patent Documents 4 to 7).

However, since the DCP-based monomer has a plurality of olefinic unsaturated bonds in its molecule, there is a problem that an unnecessary cross-linking reaction occurs in a ring-opening polymerization reaction or a hydrogenation reaction, and an insoluble gel is formed in an organic solvent. . In addition, DCP-based monomers have many olefinic unsaturated bonds, so the calorific value in the hydrogenation reaction is large, and the maximum temperature rises. Therefore, the amount of feed cannot be increased from the point of view of the design temperature of the reactor, and there is a problem of poor productivity. . If the above-mentioned gel is included in the product, there will be serious problems such as the following: becoming a foreign matter of the optical film as a starting point of light scattering, or breaking the film with the foreign matter as a starting point when stress is applied, so it is required to reduce the generation of this gel as much as possible. .

Conventionally, various methods have been proposed as a method for producing a substantially gel-free ring-opened polymer and its hydrogenated product using a DCP-based monomer. For example, Patent Document 2 discloses that when DCP-based monomers are ring-opened and polymerized in the presence of a tungsten-based ring-opening polymerization catalyst, compounds such as nitriles, ketones, ethers, and esters as reaction regulators coexist to obtain basically A gel-free ring-opened polymer, and by hydrogenating the ring-opened polymer using a diatomaceous earth-supported nickel catalyst or the like, a hydrogenated ring-opened polymer substantially free of gel can be obtained.

However, the conventionally proposed method requires a step of removing the reaction regulator and the like, and thus the productivity is low. Furthermore, even though the generation of large gels that can be confirmed visually or the like can be suppressed, the generation of so-called microgels having a submicron size or less cannot be sufficiently suppressed. Therefore, in the resin preparation process, if filtering is performed to remove foreign substances, there are problems that the filter is clogged in a short time and the production line is stopped, or the filter must be replaced frequently, or the filter is damaged and cannot be removed. foreign body.

The applicant of the present invention has already proposed a production method that basically does not contain a gel component, requires little load in the filtration process, and utilizes a simple process (see Patent Document 8). However, this preparation method starts hydrogenation at a high temperature above 130°C to start the hydrogenation reaction, so the maximum reaching temperature becomes high. In order to increase the amount of feed, it is necessary to increase the equipment investment such as the design temperature of the reactor, or in order to suppress the maximum reaching temperature, It is necessary to employ conditions such as reducing the amount of feed, increasing the amount of solvent, and slowing down the hydrogen supply rate to expect an increase in productivity.

Therefore, there is a need for the emergence of a high-productivity production method that does not substantially contain a gel component, has a small load in the filtration step, and can perform hydrogenation reaction at low temperature.

Patent Document 1: Japanese Unexamined Patent Publication No. 4-202404

Patent Document 2: Japanese Unexamined Patent Publication No. 11-124429

Patent Document 3: Japanese Unexamined Patent Publication No. 11-130846

Patent Document 4: JP-A-63-264626

Patent Document 5: Japanese Unexamined Patent Publication No. 1-158029

Patent Document 6: Japanese Unexamined Patent Publication No. 1-168724

Patent Document 7: Japanese Unexamined Patent Publication No. 1-168725

Patent Document 8: JP-A-2005-213370

Non-Patent Document 1: A, Dobson, et al., Inorg. Synth., 17, 126-127 (1977)

Contents of the invention

The object of the present invention is to provide a metal hydride complex having high solubility in an organic solvent, especially a hydrocarbon solvent such as toluene, and a high activity as a hydrogenation catalyst, and a cyclic olefin-based ring-opened compound using the metal hydride complex ( Process for the hydrogenation of co)polymers.

In addition, the object of the present invention is to provide a method for producing a hydrogenated cyclic olefin-based ring-opening polymer: when hydrogenating a (co)polymer of a cyclic olefin-based compound having a plurality of olefinic unsaturated bonds in the molecule, Gel generation is suppressed, the load in the filtration step is small, and a hydrogenated cyclic olefin-based ring-opening polymer substantially free of gel components including microgels can be produced with good productivity.

The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, found that a metal hydride complex incorporating an aromatic carboxylic acid residue has greatly improved solubility in toluene, etc., and exhibited high activity for the hydrogenation reaction of unsaturated hydrocarbons .

Furthermore, the present inventors have found that when hydrogenating a (co)polymer of a cyclic olefin compound having a plurality of olefinic unsaturated bonds in the molecule, the cyclic olefin compound is hydrogenated in the presence of a specific metal hydride complex. The compound (co)polymer solution is pre-adjusted to a low temperature and contacted with hydrogen, which can inhibit the generation of gel components, and by reducing the maximum temperature of the hydrogenation reaction, the amount of feed can be increased without changing the design temperature of the reactor, which can significantly Improve productivity. It was found that especially when a carboxylic acid-modified ruthenium complex is used as a hydrogenation catalyst, the formation of gel components including microgels can be effectively suppressed.

The metal hydride complex of the present invention is characterized by being represented by the following general formula (1).

MQ _n H _k T _p Z _q (1)

In formula (1), M represents a metal selected from ruthenium, rhodium, osmium, iron, cobalt and iridium, Q independently represents a group shown in the following formula (i), T independently represents CO or NO, and Z independently represents PR ⁶ R ⁷ R ⁸ (R ⁶ , R ⁷ and R ⁸ each independently represent an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group), k represents 1 or 2, n represents 1 or 2, and p represents 0-4 is an integer, q represents an integer of 0 to 4, and the total of k, n, p, and q is 4, 5, or 6.

In formula (i), R ¹ to R ⁵ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an alkoxy group, an amino group, a nitro group, a cyano group, a carboxyl group or a hydroxyl group.

In such a metal hydride complex of the present invention, it is preferable that M in the above formula (1) is ruthenium, and it is also preferable that R ¹ to R ⁵ in the above formula (i) are each independently a hydrogen atom and have 1 to 18 carbon atoms. Alkyl, cycloalkyl or aryl.

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

The method for hydrogenating a cyclic olefin-based ring-opened polymer of the present invention is characterized in that the hydrogenation reaction of the cyclic olefin-based ring-opened polymer is carried out in the presence of the above-mentioned metal hydride complex of the present invention. As the above-mentioned cyclic olefin-based ring-opening polymer, ring-opening (co)polymerization of monomers containing one or more compounds selected from compounds represented by the following general formulas (I), (II) and (III) is preferred. thing.

In formulas (I), (II) and (III), R ⁹ to R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group with 1 to 30 carbon atoms or other monovalent organic groups; R ⁹ and R ¹⁰ , or R ¹¹ and R ¹² can be integrated to form a divalent hydrocarbon group; R ⁹ or R ¹⁰ and, R ¹¹ or R ¹² can be combined to form a monocyclic or polycyclic structure; h, i and j are independently 0 or a positive integer.

The preparation method of the cyclic olefin-based ring-opening polymer hydrogenated product of the present invention is characterized in that the monomer containing the cyclic olefin-based compound represented by the above general formula (II) is ring-opened and polymerized, and the obtained ring-opened polymer is After the solution has reached a temperature of 40° C. or higher and lower than 120° C., the solution is brought into contact with hydrogen in the presence of the above-mentioned metal hydride complex of the present invention to start a hydrogenation reaction.

In the preparation method of the cyclic olefin-based ring-opened polymer hydrogenated product of the present invention, it is preferable to use a ring-opened polymer obtained by copolymerizing a monomer containing the compound represented by the above general formula (II) and the compound represented by the above general formula (I). The copolymer is characterized by hydrogenation.

In the preparation method of the cyclic olefin-based ring-opening polymer hydrogenated product of the present invention, the obtained cyclic olefin-based ring-opened polymer hydrogenated product is processed by three filters connected in series in order of filter aperture from large to small When a polymer solution with a solid content concentration of 20% by weight is continuously filtered at 50°C under a nitrogen pressure of 3.0kgf/cm ² , the ratio of the filtration rate after 1 hour from the start of filtration to the filtration rate after 1000 hours is preferably 0.85 to 1.00; the three filters are filters with an average pore size of 2.0 μm and a filtration area of 2000 cm ² , an average pore size of 1.0 μm and a filtration area of 2000 cm ² , and an average pore size of 0.2 μm and a filter area of 1800 cm ² .

According to the present invention, it is possible to provide a novel metal hydride complex that is dissolved in a low-polarity organic solvent such as a hydrocarbon solvent at a high concentration and has high catalytic activity for hydrogenating a carbon-carbon double bond. Therefore, when using the metal hydride complex of the present invention as a hydrogenation catalyst, the metal hydride complex dissolved in a solvent at a high concentration can be supplied to the reaction system, thereby reducing the amount of solvent, which is economical and can control the amount of supply The operation is easy, and the industrial production efficiency can be improved.

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

In addition, according to the present invention, hydrogenation of polymers or copolymers of cyclic olefinic compounds having a plurality of olefinic unsaturated bonds in the molecule can be carried out by suppressing the generation of gel components through a simple process, and microgels can be prepared. Hydrogenated cyclic olefin-based polymers containing significantly less or substantially no gel component.

The cyclic olefin-based polymer hydrogenated product obtained by the present invention has a very small gel component content, so there is no need for removal of the gel component by high-grade filtration, etc., and it can be molded into an appropriate desired shape for use, and can be used in various Applications for optical parts or molded products of electrical and electronic materials, etc.

Description of drawings

FIG. 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.

FIG. 3 shows the ¹ H-NMR spectrum of the ruthenium hydride complex obtained in Example 3. FIG.

FIG. 4 shows the ³¹ P-NMR spectrum of the ruthenium hydride complex obtained in Example 1. FIG.

FIG. 5 shows the ³¹ P-NMR spectrum of the ruthenium hydride complex obtained in Example 2. FIG.

FIG. 6 shows the ³¹ P-NMR spectrum of the ruthenium hydride complex obtained in Example 3. FIG.

FIG. 7 shows the IR spectrum of the ruthenium hydride complex obtained in Example 1. FIG.

FIG. 8 shows the IR spectrum of the ruthenium hydride complex obtained in Example 2. FIG.

FIG. 9 shows the IR spectrum of the ruthenium hydride complex obtained in Example 3. FIG.

10 is a ¹ H-NMR chart of the copolymer obtained in Example 9 (before hydrogenation). A signal of an unsaturated bond (double bond) can be observed around 5.1 to 5.8 ppm, and a signal of a methoxy group can be observed at 3.7 ppm.

11 is a ¹ H-NMR chart of the hydrogenated copolymer (hydrogenated product) obtained in Example 9. FIG. The methoxyl group signal was observed at 3.7 ppm, but the unsaturated bond (double bond) signal was not observed around 5.1 to 5.8 ppm.

12 is a ¹ H-NMR chart of the copolymer obtained in Example 10 (before hydrogenation). A signal of an unsaturated bond (double bond) can be observed around 5.1 to 5.8 ppm, and a signal of a methoxy group can be observed at 3.7 ppm.

13 is a ¹ H-NMR chart of the hydrogenated copolymer (hydrogenated product) obtained in Example 10. FIG. The methoxyl group signal was observed at 3.7 ppm, but the unsaturated bond (double bond) signal was not observed around 5.1 to 5.8 ppm.

Detailed ways

The present invention will be described in detail below.

It should be noted that, in the present invention, the cyclic olefinic polymer includes not only homopolymers or copolymers of monomers composed of at least one cyclic olefinic compound, but also a mixture of cyclic olefinic compounds and A copolymer formed by copolymerizing monomers composed of other compounds that are copolymerized. In the present invention, ring-opening polymerization means both ring-opening polymerization and ring-opening copolymerization, and ring-opening polymer means both ring-opening polymer and ring-opening copolymer. In addition, hydrogenation (hydrogenation) in the present invention refers to the olefinic unsaturated bond in the main chain of the cyclic olefin-based polymer produced by metathesis ring-opening polymerization, or the 5-membered ring side of DCP, unless otherwise specified. Hydrogenation of aliphatic olefinic unsaturated bonds that have not undergone ring-opening polymerization such as unsaturated bonds, rather than hydrogenation of other unsaturated bonds such as aromatic unsaturated bonds.

<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 ruthenium, rhodium, osmium, iron, cobalt and iridium. Among such metals M, ruthenium, which is the cheapest and has high catalytic activity, is preferable.

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

In the above formula (i), each of R ¹ to R ⁵ may be the same or different, and each is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an alkoxy group, an amino group, a nitro group, a cyano group, a carboxyl group or hydroxyl. Among them, a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group and an aryl group are preferable.

Examples of the alkyl group having 1 to 18 carbon atoms include methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, etc.

Examples of the cycloalkyl group include cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4-dimethyl Cyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl and the like.

Examples of the aryl group include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylbenzene base, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 1-naphthyl, 2-naphthalene Base etc.

T in the above 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 each of R ⁶ , R ⁷ and R ⁸ may be the same or different, and represent an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group.

Examples of the alkyl group in R ⁶ to R ⁸ include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl and the like.

Examples of the cycloalkyl group in R ⁶ to R ⁸ include cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, etc. .

Examples of the aryl group in R ⁶ to R ⁸ include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,3-dimethylphenyl, 2 , 4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 1 -naphthyl, 2-naphthyl, etc.

In the above formula (1), k is 1 or 2, n is 1 or 2, p is an integer of 0 to 4, q is an integer of 0 to 4, and the total of k, n, p, and q is 4, 5, or 6 .

In addition, when there are a plurality of Q, T, and Z in the above formula (1), each may be the same or different.

As specific examples of the metal hydride complexes 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 and so on.

The metal hydride complexes according to the invention are obtainable, for example, by reaction of the corresponding metal polyhydride complexes with carboxylic acids. Furthermore, the above-mentioned metal polyhydride complexes can be obtained by reacting the corresponding metal halide hydride complexes 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, under nitrogen or argon atmosphere, the alcohol solution of the metal halide hydride complex is put into the reaction container, and then the alcohol solution of KOH is added dropwise, and reacted for a certain period of time, thereby obtaining the metal dihydride complex. Next, a specific carboxylic acid is added to the obtained metal dihydride complex and reacted for a certain period of time, whereby the target complex is formed as a precipitate. After the supernatant is filtered or separated by decantation, if necessary, the precipitate is washed with a low-solubility solvent such as methanol, and the residual solvent is dried to obtain the target product.

The temperature of the reaction system is not particularly limited, and it is operated at a temperature ranging from -20°C to 200°C depending on the acidity of the carboxylic acid. In addition, there is no particular limitation on the amount of carboxylic acid used. In order to make the conversion rate of the metal polyhydride complex reach 90% or more, it is more desirable to add 1 part or more, Preferably 3 or more parts, more preferably 5 or more parts of carboxylic acid.

Alcohols are used as solvents in the reaction from metal halide hydride complexes to metal dihydride complexes. Examples of the alcohol include methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, 2-methoxyethanol, diethylene glycol and the like. These alcohols may be used alone or in combination of two or more.

In the reaction to obtain the final target compound-metal hydride complex from the metal hydride complex, an appropriate solvent can be used as necessary. 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 can be used; Chloromethane, dichloromethane, 1,2-dichloroethane, 1,1-dichloroethane, tetrachloroethane, chloroform, carbon tetrachloride, chlorocyclopentane, chlorocyclohexane, Halogenated hydrocarbon solvents such as chlorobenzene and dichlorobenzene; alcohol solvents such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, 2-methoxyethanol, diethylene glycol, etc.

The above solvents may be used alone or in combination of two or more. Among them, it is preferable to use an alcoholic solvent or a mixed solvent containing an alcoholic solvent from the viewpoint of the solubility of the raw material, the insolubility of the product, and versatility. In addition, depending on the case, the reaction can also be performed without a solvent.

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

The metal hydride complexes of the present invention can also be prepared from MCl ₃ ·(H ₂ O) _m in a one pot reaction 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 an integer of 0 to 3) is reacted with formaldehyde in the presence of a compound capable of forming a phosphorus ligand, Formation of metal halide hydride complexes. Next, the metal halide hydride complex is reacted with an alkali metal hydroxide in an alcohol solvent to produce a metal dihydride complex. Furthermore, the metal dihydride complex is reacted with the carboxylic acid R ¹ COOH without isolating the metal dihydride complex from the reaction system. Through such a reaction scheme, metal hydride complexes can be prepared 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 is used as a hydrogenation reaction for carbon-carbon unsaturated bonds such as alkenes and alkynes, a hydrosilylation reaction, a hydroboration reaction, a hydrostannyl reaction, and an olefin isomerization reaction. catalysts with high activity. Especially for the hydrogenation reaction of norbornene-based ring-opening metathesis polymers, a high hydrogenation rate of 99.8% or more can be achieved. Therefore, the metal hydride complexes of the present invention can be widely used in these catalytic reactions on laboratory scale or industrial scale.

Such metal hydride complexes of the present invention are uniformly dissolved at high concentrations in hydrocarbon solvents such as benzene, toluene, xylene, cyclohexane, and methylcyclohexane, although their solubility varies depending on the type. The solubility of the metal hydride complex of the present invention in toluene at 20° C. is preferably 0.2% by weight or more, more preferably 0.2% by weight to 10% by weight, and still more preferably 1.0% by weight to 10% by weight. If it is less than 0.2% by weight, the solubility will be low and the addition amount of the catalyst must be increased, and if it exceeds 10% by weight, it will tend to be difficult to remove the catalyst.

<Hydrogenation method of cyclic olefin-based ring-opening polymer>

The method for hydrogenating a cyclic olefin-based ring-opening polymer of the present invention is carried out by hydrogenating a cyclic olefin-based ring-opening polymer using the metal hydride complex of the present invention as a catalyst. As the method and conditions of the hydrogenation reaction, other than the use of the metal hydride complex of the present invention, general methods and conditions of the hydrogenation reaction can be used. In addition, since the metal hydride complex of the present invention has high solubility in hydrocarbon solvents such as toluene, it can be supplied to the reaction system at a high concentration. Therefore, the reaction efficiency and the like can be improved, and the amount of solvent supplied to the catalyst can be reduced. In addition, since the catalyst can be used as a uniform solvent system, it is easy to control the addition amount of the catalyst and the like.

Cyclic olefin-based ring-opening polymer

As the cyclic olefin-based ring-opening polymer used in the hydrogenation method of the cyclic olefin-based ring-opened polymer of the present invention, ring-opening metathesis of a monomer containing a cyclic olefin-based compound having a norbornene skeleton can be used arbitrarily. (co)polymer. That is, the cyclic olefin-based ring-opening polymer as a raw material may be a ring-opening (co)polymer of one or more cyclic olefin-based compounds, or may be one or more cyclic olefin-based compounds and other copolymerizable compounds. ring-opening copolymers.

·monomer

In the hydrogenation method of the present invention, the cyclic olefin-based ring-opened polymer is preferably a ring-opened monomer containing one or more compounds selected from the following general formulas (I), (II) and (III) (co)polymer.

In formulas (I), (II) and (III), R ⁹ to R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group with 1 to 30 carbon atoms or other monovalent organic groups; R ⁹ and R ¹⁰ , or R ¹¹ and R ¹² can be integrated to form a divalent hydrocarbon group; R ⁹ or R ¹⁰ and, R ¹¹ or R ¹² can be combined to form a single ring structure or a polycyclic structure; h, i and j are independent, is 0 or a positive integer. As the hydrocarbon group having 1 to 30 carbon atoms in R ⁹ to R ¹⁴ above, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group having 1 to 10 carbon atoms are preferable. In addition, examples of the above-mentioned other monovalent organic groups include polar groups such as alkoxy groups, hydroxyl groups, ester groups, cyano groups, nitro groups, amido groups, amino groups, and thiol groups, as well as halogen atoms and/or thiol groups. The group substituted by the polar group, etc.

Specific examples of such cyclic olefin-based compounds are shown below, but the present invention is not limited to these specific examples.

As the cyclic olefin-based compound represented by general formula (I) (hereinafter also referred to as "compound (I)"), a compound in which j=0 in the above formula (I) is preferably used. Moreover, in said formula (I), it is preferable that i is 0 or the integer of 1-3, and it is more preferable that i=1. Examples of such compound (I) include the following compounds.

Bicyclo[2.2.1]hept-2-ene (norbornene),

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-propoxycarbonyl tetracyclo[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-heptafluoroisopropyl-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-heptafluoroisopropyl-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

5-cyclohexylbicyclo[2.2.1]hept-2-ene,

5-(4-biphenyl)bicyclo[2.2.1]hept-2-ene,

5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene,

5-phenoxyethylcarbonylbicyclo[2.2.1]hept-2-ene,

5-Phenylcarbonyloxybicyclo[2.2.1]hept-2-ene,

5-methyl-5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene,

5-methyl-5-phenoxyethylcarbonylbicyclo[2.2.1]hept-2-ene,

5-vinylbicyclo[2.2.1]hept-2-ene,

5,5-Dimethylbicyclo[2.2.1]hept-2-ene,

5,6-Dimethylbicyclo[2.2.1]hept-2-ene,

5-Chlorobicyclo[2.2.1]hept-2-ene,

5-Bromobicyclo[2.2.1]hept-2-ene,

5,6-dichlorobicyclo[2.2.1]hept-2-ene,

5,6-Dibromobicyclo[2.2.1]hept-2-ene,

5-Hydroxybicyclo[2.2.1]hept-2-ene,

5-Hydroxyethylbicyclo[2.2.1]hept-2-ene,

5-Aminobicyclo[2.2.1]hept-2-ene,

Tricyclo[4.3.0.1 ^2,5 ]dec-3-ene,

7-Methyltricyclo[4.3.0.1 ^2,5 ]dec-3-ene,

7-Ethyltricyclo[4.3.0.1 ^2,5 ]dec-3-ene,

7-cyclohexyltricyclo[4.3.0.1 ^2,5 ]dec-3-ene,

7-phenyltricyclo[4.3.0.1 ^2,5 ]dec-3-ene,

7-(4-biphenyl)tricyclo[4.3.0.1 ^2,5 ]dec-3-ene,

7,8-Dimethyltricyclo[4.3.0.1 ^2,5 ]dec-3-ene,

7,8,9-trimethyltricyclo[4.3.0.1 ^2,5 ]dec-3-ene,

8-methyltricyclo[4.4.0.1 ^2,5 ]undec-3-ene,

8-phenyltricyclo[4.4.0.1 ^2,5 ]undec-3-ene,

7-Fluorotricyclo[4.3.0.1 ^2,5 ]dec-3-ene,

7-chlorotricyclo[4.3.0.1 ^2,5 ]dec-3-ene,

7-Bromotricyclo[4.3.0.1 ^2,5 ]dec-3-ene,

7,8-dichlorotricyclo[4.3.0.1 ^2,5 ]dec-3-ene,

7,8,9-trichlorotricyclo[4.3.0.1 ^2,5 ]dec-3-ene,

7-chloromethyltricyclo[4.3.0.1 ^2,5 ]dec-3-ene,

7-dichloromethyltricyclo[4.3.0.1 ^2,5 ]dec-3-ene,

7-trichloromethyltricyclo[4.3.0.1 ^2,5 ]dec-3-ene,

7-Hydroxytricyclo[4.3.0.1 ^2,5 ]dec-3-ene,

7-cyanotricyclo[4.3.0.1 ^2,5 ]dec-3-ene,

7-aminotricyclo[4.3.0.1 ^2,5 ]dec-3-ene,

pentacyclo[7.4.0.1 ^2,5 .1 ^8,11 .0 ^7,12 ]pentadeca-3-ene,

Hexacyclo[8.4.0.1 ^2,5 .1 ^7,14 .1 ^9,12 .0 ^8,13 ]heptadec-3-ene,

8-Methyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dode-3-ene,

8-Ethyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dode-3-ene,

8-cyclohexyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dode-3-ene,

8-(4-biphenyl)tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dode-3-ene,

8-phenoxycarbonyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dode-3-ene,

8-phenoxyethylcarbonyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dode-3-ene,

8-Phenylcarbonyloxytetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dode-3-ene,

8-methyl-8-phenoxycarbonyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dode-3-ene,

8-methyl-8-phenoxyethylcarbonyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dode-3-ene,

8-vinyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dode-3-ene,

8,8-Dimethyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dode-3-ene,

8,9-Dimethyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dode-3-ene,

8-Chlorotetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dode-3-ene,

8-Bromotetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dode-3-ene,

8,8-dichlorotetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dode-3-ene,

8,9-dichlorotetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dode-3-ene,

8,8,9,9-tetrachlorotetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dode-3-ene,

8-Hydroxytetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dode-3-ene,

8-Hydroxyethyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dode-3-ene,

8-Methyl-8-hydroxyethyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dode-3-ene,

8-cyanotetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dode-3-ene,

8-aminotetracyclo[ ^{4.4.0.12,5.17,10} ]dode-3 ^- ene.

In addition, examples of the cyclic olefin-based compound (hereinafter also referred to as "compound (II)") represented by the general formula (II) include the following compounds.

Bicyclo[2.2.1]hepta-2,5-diene,

5-Methylbicyclo[2.2.1]hepta-2,5-diene,

5-Ethylbicyclo[2.2.1]hepta-2,5-diene,

5-methoxycarbonylbicyclo[2.2.1]hepta-2,5-diene,

Tricyclo[4.3.0.1 ^2,5 ]dec-3,8-diene (DCP),

Pentacyclo[8.3.0.1 ^2,9 .1 ^4,7 .0 ^3,8 ]pentadeca-5,12-diene,

Heptacyclo[12.3.0.1 ^{2, 13} .1 4 ^{, 11} .1 ^{6, 9} .0 3 ^{, 12} .0 5, ¹⁰ ] eicos-7, 16-diene,

8-methyltricyclo[4.3.0.1 ^2,5 ]dec-3,8-diene,

8-Ethyltricyclo[4.3.0.1 ^2,5 ]dec-3,8-diene,

8-cyclohexyltricyclo[4.3.0.1 ^2,5 ]dec-3,8-diene,

8-Phenyltricyclo[4.3.0.1 ^2,5 ]dec-3,8-diene,

8-(4-biphenyl)tricyclo[4.3.0.1 ^2,5 ]dec-3,8-diene,

8-methoxycarbonyltricyclo[4.3.0.1 ^2,5 ]dec-3,8-diene,

8-phenoxycarbonyltricyclo[4.3.0.1 ^2,5 ]dec-3,8-diene,

8-Methoxycarbonylethyltricyclo[4.3.0.1 ^2,5 ]dec-3,8-diene,

8-Methoxycarbonylethyloxytricyclo[4.3.0.1 ^2,5 ]dec-3,8-diene,

8-methyl-9-methoxycarbonyltricyclo[4.3.0.1 ^2,5 ]dec-3,8-diene,

8,9-Dimethyltricyclo[4.3.0.1 ^2,5 ]dec-3,8-diene,

8-fluorotricyclo[4.3.0.1 ^2,5 ]dec-3,8-diene,

8-Chlorotricyclo[4.3.0.1 ^2,5 ]dec-3,8-diene,

8-bromotricyclo[4.3.0.1 ^2,5 ]dec-3,8-diene,

8,9-Dichlorotricyclo[4.3.0.1 ^2,5 ]dec-3,8-diene.

In addition, examples of the cyclic olefin-based compound represented by the general formula (III) (hereinafter also referred to as "compound (III)") include the following compounds.

(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 ]dec-3-ene],

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

(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-methoxyfluorene-9,11'-pentacyclo[6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ][4]pentadecene],

(20) Spiro[2-ethoxyfluorene-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[ ^{6.5.1.13.6.0 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-diphenoxyfluorene-9,11'-pentacyclo[6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ][4]pentadecene],

(25) Spiro[3,6-dimethoxyfluorene-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-difluorofluorene-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-methoxyfluorene-9,13'-hexacyclo[7.7.0.1 ^3.6 .1 ^10.16 .0 ^2.7 .0 ^11.15 ][4]octadecene],

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

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

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

(35) spiro[2,7-diethoxyfluorene-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-dimethoxyfluorene-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, as a monomer for obtaining a ring-opened olefin-based ring-opened polymer, any one of the above-mentioned cyclic olefin-based compounds (I) to (III) may be used alone, or two or more of them may be combined use. In addition, as a monomer composition for obtaining a cyclic olefin-based ring-opened polymer, one or more kinds selected from the above-mentioned cyclic olefin-based compounds (I) to (III) and a compound having a norbornene skeleton can be mixed as needed. Other cyclic olefin-based compounds and copolymerizable copolymerizable monomers are used in combination.

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

In the present invention, the type and compounding ratio of the monomers for ring-opening polymerization are appropriately selected according to the properties required for the obtained resin, and cannot be determined uniformly. Printability or dispersibility of other raw materials such as pigments is improved, so it is preferable to select a monomer containing a cyclic olefin compound having a structure containing at least one member selected from an oxygen atom, a nitrogen atom, and a sulfur atom in its molecule. A structure of at least one of atoms or silicon atoms (hereinafter referred to as "polar structure"). Of course, monomers having the polar structure may be used alone, 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, wherein, if at least one of R ⁹ to R ¹² in the above general formula (I) is used, the following general formula (IV) is used: Compounds of the groups shown above are more preferable since the resulting hydrogenated cyclic olefin-based ring-opening polymer tends to balance heat resistance and water absorption (moisture) property.

-(CH ₂ ) _z COOR (IV)

In formula (IV), 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.

In the above-mentioned general formula (IV), the smaller the value of z, the higher the glass transition temperature of the resulting hydride, which is preferable in terms of heat resistance. Furthermore, the synthesis of monomers in which z is 0 is easy. One point is preferred. In addition, as the number of carbon atoms in R increases, the water absorption (moisture) property of the resulting hydrogenated cyclic olefin-based ring-opened polymer tends to decrease, but the glass transition temperature also tends to decrease, so the number of carbon atoms is preferably 1. -6 alkyl, particularly preferably methyl.

In addition, in the general formula (I), a monomer having only one group represented by the general formula (IV) is preferably used because it is easy to synthesize and industrially available. Moreover, in the above general formula (I), if an alkyl group with 1 to 5 carbon atoms, especially a methyl group, is bonded to the carbon atom of the group represented by the above general formula (IV), the heat resistance and The balance of water absorption (wetness) is preferable. Furthermore, in the general formula (I) above, a monomer in which i is 1 and j is 0 can be used preferably because a hydrogenated product of a cyclic olefin-based ring-opening polymer having high heat resistance can be obtained and is industrially easy to obtain.

The ring-opened olefin-based ring-opened polymer used in the present invention is obtained by ring-opening (co)polymerizing the above monomers containing a cyclic olefin-based compound.

· Polymerization temperature

In the present invention, ring-opening polymerization or ring-opening copolymerization of monomers containing at least one cyclic olefin compound represented by the above-mentioned formulas (I) to (III) is carried out in the presence of a polymerization catalyst. During the polymerization, adding The timing of the polymerization catalyst becomes an important technical point. That is, it is desirable to add the polymerization catalyst when the temperature of the monomer solution containing the monomer and the solvent reaches 90 to 140°C, preferably 90 to 120°C. It is preferable to carry out the polymerization reaction in this temperature range because the reactivity ratio of the monomers becomes close and a copolymer with good randomness can be obtained. It is considered that by adding a polymerization catalyst in this temperature range, the generation of a multibranched polymer or microgel, which is a source of gel, can be suppressed. Such an effect is particularly remarkable when using a cyclic olefin-based monomer having two or more olefinic unsaturated bonds in the molecule, for example, a DCP-based monomer.

· Polymerization catalyst

As the catalyst for ring-opening (co)polymerization, known metathesis catalysts can be used, for example, the catalyst described in Olefin Metathesis and Metathesis Polymerization (K.J.IVIN, J.C.MOL, Academic Press 1997) is preferably used.

As such a catalyst, for example, a metathesis polymerization catalyst in which (a) and (b) are combined, the (a) is selected from at least one compound selected from W, Mo, Re, V, and Ti; the (b) At least one compound selected from Li, Na, K, Mg, Ca, Zn, Cd, Hg, B, Al, Si, Sn, Pb, Ti, Zr, etc., and the compound has at least one Selected element-carbon bond or selected element-hydrogen bond. In order to improve the activity of the catalyst, an additive (c) described later may be added to the catalyst. In addition, examples of other catalysts include (d) metathesis catalysts composed of transition metal-carbene complexes of Groups 4 to 8 of the Periodic Table, metalacyclobutene complexes, and the like that do not use a co-catalyst.

Representative examples of W, Mo, Re, V, and Ti compounds suitable as the above-mentioned component (a) include WCl ₆ , MoCl ₅ , ReOCl ₃ , VOCl ₃ , TiCl ₄ and the like described in JP-A-1-240517. compound.

Examples of the above component (b) include nC ₄ H ₉ Li, (C ₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) ₂ AlCl, (C ₂ H ₅ ) _1.5 AlCl _1.5 , (C ₂ H ₅ ) AlCl _2. Compounds described in JP-A-1-240517 such as methylaluminoxane and LiH.

As typical examples of the component (c) of the additive, alcohols, aldehydes, ketones, amines and the like can be preferably used, and compounds disclosed in JP-A-1-240517 can also be used.

Representative examples of the aforementioned catalyst (d) include W(=N-2,6-C ₆ H ₃ iPr ₂ )(=CHtBu)(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 preferably "component (a): monomer" in terms of the molar ratio of the above-mentioned component (a) to the monomer (total amount of monomers for ring-opening (co)polymerization). Usually, it is in the range of 1:500 to 1:500000, preferably in the range of 1:1000 to 1:100000. The ratio of the component (a) to the component (b), in terms of metal atomic ratio, is preferably "(a):(b)" in the range of 1:1 to 1:50, preferably 1:2 to 1:30 . In addition, the ratio of the component (a) to the component (c) is a molar ratio, and "(c):(a)" is preferably in the range of 0.005:1 to 15:1, preferably 0.05:1 to 7:1. . In addition, the amount of the catalyst (d) used is based on the molar ratio of the (d) component to the monomer, and it is ideal that "(d) component:monomer" is usually in the range of 1:50 to 1:50000, preferably 1: The range of 100～1:10000.

・Molecular weight of cyclic olefin-based ring-opening polymer

The molecular weight of the cyclic olefin-based ring-opening polymer is preferably adjusted to a desired molecular weight according to the use of the hydrogenated cyclic olefin-based ring-opened polymer to be produced. Therefore, there is no uniform regulation, usually the intrinsic viscosity (η _inh ) is 0.2-5.0, preferably 0.4-1.5. In addition, the weight-average molecular weight (Mw) is usually 1.0×10 ³ to 1.0×10 ⁶ , preferably 5.0×10 ³ to 5.0×10 as a molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC). ^5. The molecular weight distribution (Mw/Mn) is usually 1-10, preferably 1-5, more preferably 1-4. If the molecular weight of the ring-opened polymer is too high, the efficiency of the hydrogenation reaction may decrease, and there may be problems such as that the hydrogenation rate of the hydrogenated product of the obtained cyclic olefin-based ring-opened polymer does not reach a desired value or the reaction time becomes longer.

The molecular weight adjustment of the cyclic olefin-based ring-opened polymer can also be performed depending on the polymerization temperature, the type of catalyst, and the type of solvent, but in the present invention, it is preferably adjusted by allowing a molecular weight modifier to coexist in the reaction system. Examples of suitable molecular weight regulators include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, etc. - Olefins and styrene, among which 1-butene and 1-hexene are particularly preferable. These molecular weight modifiers can be used individually or in mixture of 2 or more types. The molecular weight modifier is used in an amount of 0.001 to 0.6 mol, preferably 0.02 to 0.5 mol, based on 1 mol of the monomer for the ring-opening (co)polymerization reaction.

·Polymerization solvent

As the solvent used in the ring-opening (co)polymerization reaction, that is, as a solvent for dissolving the norbornene-based monomer, metathesis catalyst, and molecular weight modifier, the following solvent I, solvent II, or a mixture thereof is preferably used.

Solvent I is formed of a mixed solvent of solvent component (1) and solvent component (2).

As the solvent component (1), an alicyclic saturated hydrocarbon and/or an aliphatic saturated hydrocarbon having 10 or less carbon atoms, preferably 5 to 8 carbon atoms, is used. Specific examples of the aforementioned alicyclic saturated hydrocarbons include cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, cycloheptane, decalin etc. In addition, specific examples of the aforementioned saturated aliphatic hydrocarbons include n-pentane, isopentane, n-hexane, n-heptane, n-octane and the like.

As the solvent component (2), dialkyl glycol ether is used. Specific examples thereof include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, Triethylene glycol dimethyl ether, etc.

The mixing ratio of the solvent component (1) and the solvent component (2) in the solvent I is usually 95:5 to 30:70, preferably 90:10 to 40:60 by weight ratio. When the ratio of the solvent component (1) is too large, the solubility of the solvent I to the polymer to be produced is insufficient. On the other hand, if the ratio is too small, the reactivity of the polymerization reaction may be lowered and a polymer with a high degree of polymerization may not be obtained.

In addition, as the solvent II, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene having 6 to 10 carbon atoms; alkanes such as pentane, hexane, heptane, nonane, and decane; cyclohexane Cycloalkanes such as alkane, cycloheptane, cyclooctane, decalin, norbornane; chlorobutane, bromohexane, dichloromethane, dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform , tetrachloroethylene and other halogenated alkanes or halogenated aryl compounds; ethyl acetate, methyl propionate and other saturated carboxylic acid esters, etc. These solvents can be used not only individually but in combination of 2 or more types.

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

The thus obtained cyclic olefin-based ring-opened polymer has a carbon-carbon double bond in the main chain.

hydrogenation reaction

In the hydrogenation method of the cyclic olefin-based ring-opening polymer of the present invention, the hydrogenation reaction of the cyclic olefin-based ring-opened polymer is carried out in the presence of the metal hydride complex of the present invention described above.

In the hydrogenation reaction, the olefinic unsaturated group represented by the formula: -CH=CH- present in the main chain of the cyclic olefin-based ring-opening polymer is hydrogenated and converted into a formula: -CH ₂ CH ₂ - group. When the cyclic olefin-based ring-opened polymer has unsaturated bonds other than the main chain in the ring structure, the unsaturated bonds other than the main chain may not be hydrogenated.

In addition, the hydrogenation rate of the cyclic olefin-based ring-opened polymer (the ratio of carbon-carbon double bonds present in the main chain of the cyclic olefin-based ring-opened polymer to be hydrogenated) in the hydrogenation method of the present invention is usually 40 mol% or more , preferably 60 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more. The higher the hydrogenation rate, the more likely it is possible to suppress the occurrence of coloring and deterioration of the obtained hydrogenated product under high-temperature conditions, and it can also impart toughness to the molded product obtained therefrom, so it is preferable.

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

In the present invention, the metal hydride complex is preferably used in a ratio such that the weight ratio of the ring-opening polymer:metal hydride complex is usually 1:1×10 ^-6 to 1:1×10 ^-2 .

To the hydrogenated product of the cyclic olefin-based ring-opened polymer obtained by the production method of the present invention, various additives such as antioxidants, ultraviolet absorbers, and lubricants may be added as needed.

Such additives include, for example, 2,6-di-tert-butyl-4-methylphenol, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,5- Di-tert-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, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)octadecyl propionate, 3, 3', 3", 5, 5', 5"-hexa-tert-butyl-a, a', a"-(Mesitylene-2,4,6-triyl) tri-p-cresol and other phenolic series , Hydroquinone-based antioxidants; tris(4-methoxy-3,5-diphenyl)phosphite, tris(nonylphenyl)phosphite, tris(2,4-di-tert-butyl Phosphorus-based antioxidants such as phenyl) phosphite. By adding one or more of these antioxidants, the oxidation degradation resistance of the ring-opened (co)polymer can be improved.

In addition, by adding, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-methylenebis[4-(1,1,3 , 3-tetramethylbutyl)-6-[(2H-benzotriazol-2-yl)phenol]] and other UV absorbers to improve light resistance.

Furthermore, in addition to lubricants for improving processability, known additives such as flame retardants, antibacterial agents, petroleum resins, plasticizers, colorants, mold release agents, and foaming agents can be added as needed, and these additives can be used alone. Or use it in combination of 2 or more types.

The hydrogenated product of the cyclic olefin-based ring-opening polymer obtained in the present invention can be suitably molded and used particularly in the fields of optical parts, electrical and electronic materials, and the like. Specific examples of such uses include optical discs, magneto-optical discs, optical lenses (Fθ lenses, imaging lenses, laser printer lenses, camera lenses, etc.), spectacle lenses, optical films (films for displays, retardation films, polarizing film, transparent conductive film, wavelength plate, anti-reflection film, optical pickup film (opital pickup film, etc.), optical sheet, optical fiber, light guide plate, light diffusion plate, optical card, optical mirror, IC LSI LED packaging materials wait.

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

<Method for producing hydrogenated cyclic olefin-based ring-opening polymer>

The method for preparing a hydrogenated cyclic olefin-based ring-opening polymer of the present invention is a particularly preferred mode of the hydrogenation method of the above-mentioned cyclic olefin-based ring-opened polymer. In the presence of the metal hydride complex of the present invention described above, the The cyclic olefin-based ring-opening polymer is hydrogenated after being adjusted to a relatively low temperature. Thereby, the maximum attained temperature of the hydrogenation reaction is lowered, the productivity is remarkably improved, and the generation of gel components including microgels can be remarkably suppressed.

Cyclic olefin-based ring-opening polymer

The cyclic olefin-based polymer used in the production method of the present invention can be obtained by ring-opening polymerization of a monomer containing the above compound (II). Among the above compounds (II), it is particularly preferable to use tricyclo[4.3.0.1 ^2,5 ]deca-3,8-diene (DCP), which is industrially available and inexpensive. Moreover, these compounds may be used individually by 1 type, and may use 2 or more types together. In addition, polymers obtained by ring-opening copolymerization of monomers containing the above compound (II) and the above compounds (I) and/or (III) are also preferred. Furthermore, in addition to these, the above-mentioned monomers containing other copolymerizable compounds can also be used.

The method and conditions of the ring-opening polymerization, the catalyst, the solvent, and the like used in the ring-opening polymerization are as described above. The olefinic unsaturated bonds of the obtained cyclic olefin-based ring-opened polymer are hydrogenated in the presence of a hydrogenation catalyst.

hydrogenation catalyst

The hydrogenation catalyst used in the production method of the present invention is the above-mentioned metal hydride complex of the present invention. The added amount of the metal hydride complex is as follows: metal amount/monomer added amount is 5-200 ppm, preferably 10-100 ppm. When the amount added is less than 5 ppm, a sufficient hydrogenation reaction may not proceed, and when it exceeds 200 ppm, it tends to be difficult to remove the catalyst. In addition, the timing of adding the hydrogenation catalyst may be added in advance to the ring-opening polymer solution before temperature adjustment, or may be added during temperature adjustment.

Solvent for hydrogenation reaction

The solvent used in the hydrogenation reaction is not particularly limited as long as it is a good solvent for the cyclic olefin-based ring-opened polymer to be hydrogenated and is not itself hydrogenated. Specifically, there may be mentioned the same solvents as the above-mentioned polymerization reaction solvents. Therefore, it is also preferable to supply the cyclic olefin-based ring-opening polymer solution obtained by monomer polymerization to the hydrogenation reaction as it is. The weight ratio of the cyclic olefin-based ring-opening polymer to the solvent in the solution for the hydrogenation reaction is usually 5:1 to 1:20, preferably 2:1 to 1:15, more preferably 1:1 to 1:10.

hydrogenation reaction

In the production method of the present invention, it is very important to carry out the hydrogenation reaction by contacting the solution temperature of the cyclic olefin-based ring-opening polymer to 40° C. or higher and lower than 120° C. to carry out the hydrogenation reaction. Generally, in the hydrogenation of a cyclic olefin-based ring-opened polymer, a hydrogenation catalyst and hydrogen are added to a solution obtained by dissolving the ring-opened polymer in a suitable solvent to carry out a hydrogenation reaction. However, in the production method of the present invention, The timing of contacting the ring-opened polymer with hydrogen becomes an important technical point.

In the preparation method of the present invention, the temperature is adjusted by heating the solution of the cyclic olefin-based ring-opening polymer as required. Preferably, when the temperature of the solution containing the ring-opening polymer reaches 40°C or more and less than 120°C, It is preferable to add hydrogen at a timing of 70° C. or higher and lower than 120° C., more preferably 80 to 110° C., to start contact with hydrogen. If hydrogen is added in a state where the temperature of the solution containing the ring-opened polymer is lower than 40° C., the hydrogenation reaction rate will decrease, the hydrogenation reaction will take a long time, and the generation of microgels may not be suppressed. In addition, if the temperature of the polymer solution during the hydrogenation reaction is too high, the hydrogenation catalyst may be deactivated or may be reduced in molecular weight due to thermal decomposition reaction.

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 takes a long time, which may cause a problem in productivity. On the other hand, increasing the pressure can obtain a high reaction rate, but it is uneconomical because an expensive pressure-resistant device is required as an apparatus.

In addition, the hydrogenation reaction referred to in the present invention is the hydrogenation of the olefinic unsaturated bonds in the cyclic olefin-based ring-opened polymer molecule, and the other unsaturated bonds may not be hydrogenated. For example, when the polymer has an aromatic group, the aromatic group does not necessarily have to be hydrogenated. The presence of an aromatic group in the molecule may also be beneficial to the optical properties such as heat resistance and refractive index of the resulting hydrogenated cyclic olefin-based ring-opened polymer. Conditions where the above is not hydrogenated are preferred. In addition, when an aromatic solvent such as toluene is used as a solvent, it is a matter of course that the solvent is preferably not hydrogenated.

Antioxidants

In the production method of the present invention, the hydrogenation of the cyclic olefin-based ring-opened polymer may be carried out in the presence of a known antioxidant in order to further suppress gel generation during the hydrogenation reaction. In the present invention, examples of antioxidants that can be preferably used include antioxidants selected from phenolic compounds, thiol-based compounds, thioether-based compounds, disulfide-based compounds, and phosphorus-based compounds. These antioxidants can be used individually by 1 type or in appropriate combination of 2 or more types. Specific examples of these compounds that can be used as an antioxidant in the present invention include the compounds shown below.

·Phenolic compounds

Examples of the phenolic compound include triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[ 3(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylaniline base)-3,5-triazine, pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2-thiodiethylenebis[3 -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N, N-hexamethylenebis[3,5-di-tert-butyl-4-hydroxy-hydrogenated cinnamamide], 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert Butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 3,9-bis[2-[3-(3-tert-butyl base-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, etc. Preferable examples include 3-(3,5-di-tert-butyl-4-hydroxyphenyl)octadecyl propionate, 1,3,5-trimethyl-2,4,6-tri(3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, pentaerythritol-tetrakis [3-(3,5-di-tert-butyl-hydroxyphenyl) propionate], particularly preferably 3-(3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, etc.

·Thiol compounds

Examples of thiol-based compounds include alkyl mercaptans such as t-dodecylmercaptan and hexanethiol, 2-mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1-methyl-2 -(methylthio)benzimidazole, 2-mercapto-1-methylbenzimidazole, 2-mercapto-4-methylbenzimidazole, 2-mercapto-5-methylbenzimidazole, 2-mercapto- 5,6-Dimethylbenzimidazole, 2-(methylthio)benzimidazole, 1-methyl-2-(methylthio)benzimidazole, 2-mercapto-1,3-dimethylbenzene And imidazole, thioglycolic acid, etc.

·Sulfur ether compounds

Examples of thioether compounds include 2,2-thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,4-bis(n-octylthiomethyl)-6-methylphenol, 3,3'-didodecylthiodipropionate , 3,3'-ditetradecyl thiodipropionate, 3,3'-dioctadecyl thiodipropionate, pentaerythritol tetrakis(3-dodecyl thiopropionate) , 3,3'-ditridecyl thiodipropionate, etc.

· Disulfide compounds

Examples of disulfide compounds include bis(4-chlorophenyl) disulfide, bis(2-chlorophenyl) disulfide, bis(2,5-dichlorophenyl) disulfide, bis( 2,4,6-Trichlorophenyl) disulfide, bis(2-nitrophenyl) disulfide, ethyl 2,2'-dithiodibenzoate, bis(4-acetylphenyl ) disulfide, bis(4-carbamoylphenyl) disulfide, 1,1'-binaphthyl disulfide, 2,2'-binaphthyl disulfide, 1,2'-binaphthyl disulfide 2,2'-bis(1-chloronaphthyl)disulfide, 1,1'-bis(2-chloronaphthyl)disulfide, 2,2'-bis(1-cyano 1-naphthyl) disulfide, 2,2'-bis(1-acetylnaphthyl) disulfide, 3,3'-didodecyl thiodipropionate, etc.

·Phosphorus compounds

Examples of phosphorus compounds include tris(4-methoxy-3,5-diphenyl)phosphite, tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl) ) phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, etc.

In the production method of the present invention, the hydrogenation reaction of the cyclic olefin-based ring-opening polymer is preferably carried out in the presence of 0.01 to 10 parts by weight of such an antioxidant relative to 100 parts by weight of the ring-opening polymer. That is, at least one compound selected from the above-mentioned compounds can be added to a solution of a cyclic olefin-based ring-opening polymer to perform a hydrogenation reaction, and the added amount is 0.01 to 10 parts by weight relative to 100 parts by weight of the ring-opening polymer. parts by weight. It is particularly preferable to use a phenolic compound so that gelation can be suppressed without reducing the hydrogenation rate by adding a small amount.

Compared with the hydrogenated product of the cyclic olefin ring-opening polymer produced by the conventionally known method, according to the production method of the hydrogenated product of the cyclic olefin ring-opened polymer of the present invention, the generation of the gel component can be significantly suppressed, and the It is suitable for producing a hydrogenated cyclic olefin-based ring-opening polymer that generates little gel component and substantially does not contain gel component.

The hydrogenated cyclic olefin-based ring-opened polymer obtained in this way can be used after being concentrated and desolventized by a known method if necessary. In addition, the hydrogenated product of the obtained cyclic olefin-based ring-opening polymer may be used after appropriately adding known additives.

The cyclic olefin-based ring-opened polymer hydrogenated product obtained by the production method of the present invention basically does not contain gel components, and also basically does not contain microgels that are difficult to remove by filtration or the like, so the uniformity of the resin is excellent, and the preparation It is also not easy to deform when molding.

In the method for producing a hydrogenated cyclic olefin-based ring-opening polymer of the present invention, the generation of so-called microgels below the submicron size can be suppressed, and the filtration step of filtering the obtained hydrogenated cyclic olefin-based ring-opened polymer Productivity is good.

In the present invention, three filters with an average pore size of 2.0 μm and a filtration area of 2000 cm ² , an average pore size of 1.0 μm and a filtration area of 2000 cm ² , and an average pore size of 0.2 μm and a filtration area of 1800 cm ² are arranged in order of filter pore size from large to small These filters are connected in series, and the resulting purified polymer solution having a solid content concentration of 20% by weight of the hydrogenated cyclic olefin-based ring-opening polymer before the filtration step is placed at 50° C. under a nitrogen pressure of 3.0 kgf/cm ² In the case of continuous filtration, the ratio of the filtration rate after 1 hour from the start of filtration to 1000 hours after the start of filtration preferably satisfies 0.85 to 1.00. Such a hydrogenated cyclic olefin-based ring-opened polymer substantially does not contain a gel component, and has good productivity in the filtration step. If the ratio is less than 0.85, there may be problems in that the filter is clogged in a short time and the production line stops, the filter must be replaced frequently, or the filter is damaged and foreign matter cannot be removed.

The cyclic olefin-based ring-opened polymer hydrogenated product obtained by the production method of the present invention can be used after being molded into a suitable desired shape by a known method. Excellent, less uneven strength. Therefore, the cyclic olefin-based polymer hydrogenated product of the present invention can be suitably used in applications of various molded articles such as films and sheets represented by optical parts, electric and electronic materials, etc. as described above.

Example

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

It should be noted that, in the following examples, RuHCl(CO)(PPh ₃ ) 3 as a raw material is 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 by bubbling these reagents manufactured by Wako Pure Chemical Industries, Ltd. with nitrogen to reduce dissolved oxygen, water, and the like. In addition, the identification of the generated complexes was carried out using the analytical equipment described below.

(1) ¹ H-NMR, ³¹ P-NMR:

Using deuterated chloroform as a solvent, it measured with "AVANCE500" manufactured by BRUKER.

(2)IR:

Measurement was performed with "FT/IR-480 Plus" manufactured by JASCO Corporation.

In addition, various physical properties were measured or evaluated as follows.

<Glass transition temperature (Tg)>

Using DSC6200 manufactured by Seiko Instruments, the measurement was carried out at a heating rate of 20° C./min and nitrogen flow.

<Hydrogenation rate>

As a nuclear magnetic resonance spectrometer (NMR), AVANCE500 manufactured by Bruker was used, and ¹ H-NMR was measured using deuterated chloroform as a measurement solvent. The monomer composition was calculated from the integrated values of 5.1 to 5.8 ppm of vinylidene groups, 3.7 ppm of methoxy groups, and 0.6 to 2.8 ppm of aliphatic protons, and then the hydrogenation rate was calculated.

<Intrinsic viscosity (η _inh )>

A chlorobenzene solution with a concentration of 0.5 g/100 ml was prepared and measured at 30°C.

<Molecular Weight>

The polystyrene-equivalent weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) were measured in a tetrahydrofuran (THF) solvent using HLC-8020 gel permeation chromatography (GPC) manufactured by Tosoh Corporation. Mn represents a number average molecular weight.

<Measurement of Filtration Speed>

Membrane filter elements (Compact Cartridge Filter) manufactured by ADVANTEC: MCP-HX-E10S (average pore diameter 2.0 μm, filtration area 2000 cm ² ), MCP-JX-E10S (average pore diameter 1.0 μm, filtration area 2000 cm ² ), MCS- 020-E10SR (average pore size: 0.2μm, filtration area: 1800cm ² ) are connected in series in this order, and after the hydrogenated polymer solution is purified, it is continuously filtered at room temperature under a nitrogen pressure of 3.0kgf/cm ² and the filtration is measured. Time-dependent changes in speed. In addition, as these filters, a filter for filter cartridges (Compact Cartridge Housing): MTA-2000T was used.

[Example 1]

<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 RuHCl(CO)(PPh ₃ ) ₃ 18.0 g (18.9 mmol), and heated to reflux at 125° C. for 1 hour. The RuHCl(CO)(PPh ₃ ) ₃ used here has a solubility in toluene at 20° C. of 0.03% by weight.

Next, 73 mL of n-butanol solution of benzoic acid (23.1 g, 189.0 mmol) was added, followed by heating to reflux for 1 hour, whereby a yellow-white powdery product precipitated. After cooling the reaction liquid to room temperature, the solid powder was washed with 100 mL of cold methanol (0° C.), and the resulting solid was separated by filtration from the supernatant. Furthermore, this was washed with 50 mL of water and 200 mL of cold methanol (0° C.), and dried under reduced pressure to obtain the target product (13.9 g, 18.0 mmol, yield 95%).

The resulting product was analyzed by ¹ H-NMR. As a result, the integral ratio of 7.0 to 7.1 ppm of unsaturated hydrocarbons bound to the aromatics of carboxylic acids to 7.2 to 7.6 ppm of unsaturated hydrocarbons of triphenylphosphine was 5: 30, it can be seen that it is in good agreement with the theoretical value. Furthermore, as a result of analysis by ³¹ P-NMR, a single peak of triphenylphosphine was detected at 45.3 ppm. Furthermore, by IR measurement, absorption was observed at 2011cm ^-1 (Ru-H), 1938cm ^-1 (CO), 1520cm ^-1 (metal-coordinated carboxylic acid residue), and it was confirmed that the target compound RuH(OCOPh)( CO)(PPh ₃ ) ₂ . The ¹ H-NMR spectrum of the obtained ruthenium hydride complex is shown in FIG. 1 , ^{the 31} P-NMR spectrum is shown in FIG. 4 , and the IR spectrum is shown in FIG. 7 . In addition, the solubility of the obtained ruthenium hydride complex in toluene at 20° C. was 0.5% by weight.

[Example 2]

<Synthesis of RuH(OCOPh-C ₅ H ₁₁ )(CO)(PPh ₃ ) ₂ >

Except that n-pentylbenzoic acid was used instead of benzoic acid, the same reaction operation as in Example 1 was carried out to obtain the corresponding product (13.8 g, 16.3 mmol, yield 86%). The resulting product was analyzed by ¹ H-NMR. As a result, the integral ratio of the saturated hydrocarbon range of 0.8 to 2.5 ppm to the unsaturated hydrocarbon range of 6.7 to 7.6 ppm was 11:34, which was found to be in good agreement with the theoretical value. Furthermore, as a result of analysis by ³¹ p-NMR, a single peak of triphenylphosphine was detected at 45.2 ppm. Furthermore, by IR measurement, absorption was observed at 2012cm ^-1 (Ru-H), 1913cm ^-1 (CO), 1541cm ^-1 (metal-coordinated carboxylic acid residue), and it was confirmed that the target compound RuH(OCOPh-C ₅ H ₁₁ )(CO)(PPh ₃ ) ₂ . The ¹ H-NMR spectrum of the obtained ruthenium hydride complex is shown in FIG. 2 , ^{the 31} P-NMR spectrum is shown in FIG. 5 , and the IR spectrum is shown in FIG. 8 . In addition, the solubility of the obtained ruthenium hydride complex in toluene at 20° C. was 1.0% by weight.

[Example 3]

<Synthesis of RuH(OCOPh-C ₈ H ₁₇ )(CO)(PPh ₃ ) ₂ >

Except that n-octylbenzoic acid was used instead of benzoic acid, the same reaction operation as in Example 1 was carried out to obtain the corresponding product (13.6 g, 15.3 mmol, yield 81%). The resulting product was analyzed by ¹ H-NMR. As a result, the integral ratio of the saturated hydrocarbon range of 0.8 to 2.5 ppm to the unsaturated hydrocarbon range of 6.7 to 7.6 ppm was 17:34, which was found to be in good agreement with the theoretical value. Furthermore, as a result of analysis by ³¹ P-NMR, a single peak of triphenylphosphine was detected at 45.2 ppm. Furthermore, by IR measurement, absorption was observed at 2014cm ^-1 (Ru-H), 1934cm ^-1 (CO), 1546cm ^-1 (metal-coordinated carboxylic acid residue), and it was confirmed that the target compound RuH(OCOPh-C ₈ H ₁₇ )(CO)(PPh ₃ ) ₂ . The ¹ H-NMR spectrum of the obtained ruthenium hydride complex is shown in FIG. 3 , ^{the 31} P-NMR spectrum is shown in FIG. 6 , and the IR spectrum is shown in FIG. 9 . In addition, the solubility of the obtained ruthenium hydride complex in toluene at 20° C. was 5.0% by weight.

[Example 4]

<Preparation of Cyclic Olefin Ring-Opening Polymer>

250 parts of 8-methyl-8-methoxycarbonyl tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene, 18 parts of 1-hexene (molecular weight regulator) and 750 parts of toluene Portions were charged to a reaction vessel purged with nitrogen, and the solution was heated to 80°C. Then, in the solution in the reaction vessel, add 0.62 parts of toluene solution of triethylaluminum (1.5mol/L) as a polymerization catalyst and tungsten hexachloride modified with tert-butanol and methyl alcohol (tert-butanol: methanol: tungsten = 0.35mol: 0.3mol: 1mol) of toluene solution (concentration 0.05mol/L) 3.7 parts, the system was heated and stirred at 80°C for 3 hours, thereby performing ring-opening copolymerization reaction to obtain 8-methyl-8-methoxy Ring-opening metathesis polymer solutions ^of ylcarbonyltetracyclo[ ^{4.4.0.12,5.17,10} ]-3-dodecene. The polymerization conversion rate of this polymerization reaction was 97%.

<hydrogenation>

1000 parts of the ring-opened polymer solution obtained above are packed into an autoclave, and the ruthenium hydride complex obtained in Example 1 as a hydrogenation catalyst is added as a toluene solution of 0.5% by weight in this ring-opened polymer solution, The amount of the toluene solution added was such that the amount of the complex added was 0.06 parts (12 parts), and hydrogenation reaction was carried out by heating and stirring at a hydrogen pressure of 100 kg/cm ² and a reaction temperature of 165° C. for 3 hours. After cooling the obtained reaction solution (hydrogenated polymer solution), hydrogen gas was released and the pressure was reduced. After pouring this reaction solution into a large amount of methanol, the coagulated matter was separated and recovered, and dried to obtain a hydrogenated polymer. The polymer was measured by ¹ H-NMR, and the hydrogenation rate was determined from the ratio of the integral value of 0.6 to 2.5 ppm of saturated hydrocarbons to the integral value of 5.0 to 5.6 ppm of unsaturated hydrocarbons. The hydrogenation rate was 99.99%.

[Example 5]

The ruthenium hydride complex obtained in Example 2 is a 1.0% by weight toluene solution, and the amount of the toluene solution is such that the addition of the complex reaches 0.06 parts (6 parts), instead of the ruthenium hydride complex used in Example 4 as The hydrogenation catalyst used in the hydrogenation reaction was 8-methyl-8-methoxy Hydrogenation of ring-opening metathesis polymers of carbonyltetracyclo[ ^{4.4.0.12,5.17,10 ]} -3-dodecene to give hydrogenated polymers. The hydrogenation rate of the obtained hydrogenated polymer was determined in the same manner as in Example 4, and was 99.95%.

[Example 6]

The ruthenium hydride complex obtained in Example 3 is a 5.0% by weight toluene solution, and the amount of the toluene solution is such that the addition of the complex reaches 0.06 parts (1.2 parts), instead of the ruthenium hydride complex used in Example 4. The hydrogenation catalyst used in the hydrogenation reaction was 8-methyl-8-methoxy Hydrogenation of ring-opening metathesis polymers of carbonyltetracyclo[ ^{4.4.0.12,5.17,10 ]} -3-dodecene to give hydrogenated polymers. The hydrogenation rate of the obtained hydrogenated polymer was determined in the same manner as in Example 4, and was 99.90%.

[Comparative example 1]

Use a 0.03% by weight toluene solution of the ruthenium complex RuHCl(CO)(PPh ₃ ) ₃ without carboxylic acid modification, and the amount of the toluene solution is such that the amount of the complex added reaches 0.06 parts (200 parts) , instead of the hydrogenation catalyst used in the hydrogenation reaction in Example 4, the ruthenium hydride polymer obtained in Example 1 was a toluene solution of 0.5% by weight, except that 8- Hydrogenation of ring-opening metathesis polymers of ^methyl -8-methoxycarbonyltetracyclo[ ^{4.4.0.12,5.17,10} ]-3-dodecene to give hydrogenated polymers. The hydrogenation rate of the obtained hydrogenated polymer was determined in the same manner as in Example 4, and was 99.75%.

[Example 7]

Using 187.5 parts of 8-methyl-8-methoxycarbonyltetracyclo[ ^{4.4.0.12,5.17,10} ]-3- ^dodecene and tricyclo[ ^4.3.0.12,5 ]dec-3, 62.5 parts of 8-diene to replace 250 parts of 8-methyl-8-methoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene, in addition, carry out with The same operation as in Example 4 was performed to obtain a ring-opened copolymer solution. The polymerization conversion rate of this polymerization reaction was 98%.

1000 parts of the ring-opened copolymer solution obtained in this way were charged into an autoclave, and the ruthenium hydride complex obtained in Example 2 was added to the toluene solution of 1.0% by weight in the ring-opened copolymer solution, and the toluene solution The addition amount of the complex is such that the addition amount of the complex reaches 0.06 parts (6 parts), and the hydrogenation reaction is carried out by heating and stirring for 3 hours under the conditions of a hydrogen pressure of 100 kg/cm ² and a reaction temperature of 165°C. After cooling the obtained reaction solution (hydrogenated polymer solution), hydrogen gas was released and the pressure was reduced. After pouring this reaction solution into a large amount of methanol, the coagulated matter was separated and recovered, and dried to obtain a hydrogenated polymer. The polymer was measured by ¹ H-NMR, and the hydrogenation rate was determined from the ratio of the integrated value of saturated hydrocarbons of 0.6 to 2.5 ppm to the integrated value of unsaturated hydrocarbons of 5.0 to 5.6 ppm. The results showed that a high hydrogenation rate was obtained as follows: the hydrogenation rate of the unsaturated double bond derived from the side chain of tricyclo[4.3.0.1 ^2,5 ]dec-3,8-diene reached 99.99% or more, and the copolymer main chain The hydrogenation rate reaches 99.97%.

[Example 8]

Use 190 parts of 8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene and spiro[fluorene-9,8'-tricyclo[4.3. 0.1 ^2.5 ] dec-3-ene] 60 parts to replace 250 parts of 8-methyl-8-methoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene, in addition Except that, the same operation as in Example 4 was carried out to obtain a ring-opened copolymer solution. The polymerization conversion rate of this polymerization reaction was 96%.

1000 parts of the ring-opening copolymer solution obtained in this way are packed into an autoclave, and the ruthenium hydride complex obtained in Example 2 is added to the toluene solution of 1.0% by weight in the ring-opening copolymer solution. The amount added was such that the added amount of the complex reached 0.06 parts (6 parts), and the hydrogenation reaction was carried out by heating and stirring for 3 hours under the conditions of a hydrogen pressure of 100 kg/cm ² and a reaction temperature of 165°C. After cooling the obtained reaction solution (hydrogenated polymer solution), hydrogen gas was released and the pressure was reduced. After pouring this reaction solution into a large amount of methanol, the coagulated matter was separated and recovered, and dried to obtain a hydrogenated polymer. The polymer was measured by ¹ H-NMR, and the hydrogenation rate was determined from the ratio of the integrated value of saturated hydrocarbons of 0.6 to 2.5 ppm to the integrated value of unsaturated hydrocarbons of 5.0 to 5.6 ppm. As a result, the hydrogenation rate of the main chain of the copolymer was 99.93%. When the same operation was carried out using RuHCl(CO)(PPh ₃ ) ₃ as a catalyst, the hydrogenation rate was 99.30%, showing that a high hydrogenation rate can be obtained by using this catalyst.

[Example 9]

Add 8-methoxycarbonyl-8-methyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene (DNM) 75 wt. 25 parts by weight of dicyclopentadiene (DCP), 6 parts by weight of 1-butene and 170 parts by weight of toluene were added as a molecular weight regulator, and heated to 100°C. 0.005 parts by weight of triethylaluminum and 0.005 parts by weight of methanol-modified WCl ₆ (anhydrous methanol: PhPOCl ₂ : WCl ₆ =103:630:427 (weight ratio)) were added thereto, and reacted at 100° C. for 1 hour, thereby to obtain a polymer. The response rate was 100%.

Then, using a design temperature of 185 ° C, 1.25 m ³ autoclave, add the solution of the polymer obtained above, the solution is 350 kg in terms of solid content; as a hydrogenation catalyst, add the saturated solubility in toluene at 25 ° C of 5 wt% of RuH(CO)[P(C ₆ H ₅ )] ₂ (OCO-p-Ph-nC ₅ H ₁₃ ), the amount of the catalyst added is 0.0335 parts by weight, after heating to 100°C, introduce hydrogen gas into the reactor to make the pressure reach 10MPa. The highest attained temperature in the hydrogenation reaction was 179°C. The theoretical calorific value was calculated from DNM=129.3kcal/kg and DCP=452.3kcal/kg. Thereafter, the pressure was kept at 10 MPa, and reaction was performed at 165° C. for 3 hours to obtain a hydride. The obtained hydride had intrinsic viscosity (η _inh )=0.53, weight average molecular weight (Mw)=6.03×10 ⁴ , molecular weight distribution (Mw/Mn)=2.7, glass transition temperature (Tg)=146.6°C. In addition, the hydrogenation rate of the hydride was determined by ¹ H-NMR measurement, and 99.9% or more of the olefinic unsaturated bonds in the main chain were hydrogenated. The ¹ H-NMR measurement results before and after hydrogenation are shown in Fig. 10 and Fig. 11 .

After completion of the reaction, it was diluted to 500 parts by weight of toluene, 3 parts by weight of distilled water, 0.72 parts by weight of lactic acid, and 0.00214 parts by weight of hydrogen peroxide were added, and heated at 60° C. for 30 minutes. Then, 200 parts by weight of methanol was added, followed by heating at 60° C. for 30 minutes. Then, it cooled to 25 degreeC and separated into two layers. After removing 500 parts by weight of the supernatant, 350 parts by weight of toluene and 3 parts by weight of water were added, followed by heating at 60° C. for 30 minutes. Next, 240 parts by weight of methanol was added, followed by heating at 60° C. for 30 minutes. Then, it cooled to 25 degreeC and separated into two layers. 500 parts by weight of the supernatant were removed again, 350 parts by weight of toluene and 3 parts by weight of water were added, and the mixture was heated at 60° C. for 30 minutes. Next, 240 parts by weight of methanol was added, followed by heating at 60° C. for 30 minutes. Thereafter, it was cooled to 25° C. and separated into two layers. Finally, 500 parts by weight of the supernatant was removed, the polymer solution in the lower layer was heated to 50° C., and the solid content concentration was diluted to 20%, followed by three-stage filtration of 2.0 μm, 1.0 μm, and 0.2 μm. The polymer solid content was concentrated to 55%, and the solvent was removed at 250° C., 4 torr, and a residence time of 1 hour, and passed through a 10 μm polymer filter to obtain a hydrogenated copolymer (1).

In addition, the purified liquid before desolventization was kept heated at 50° C. and filtered continuously, and the time-dependent change of the filtration rate was followed. After 1000hr, the filter is still not clogged, and the filtration rate has not decreased, 1000hr filtration rate/1 hr filtration rate=1.00. It can be confirmed that the solution does not contain gel.

[Example 10]

In Example 9, 65 parts by weight of 8-methoxycarbonyl-8-methyltetracyclo[4.4.0.12,5.17,10]-3-dodecene (DNM) and dicyclopentadiene were added as monomers. (DCP) 25 parts by weight and norbornene (NB) 10 parts by weight, toluene is 190 parts by weight, synthetic polymer, polymer conversion in the hydrogenation reaction is that the charging amount of solid content is 330kg, in addition and embodiment 1 In the same manner, the hydride was obtained. The obtained hydride had intrinsic viscosity (η _inh )=0.52, weight average molecular weight (Mw)=6.28×10 ⁴ , molecular weight distribution (Mw/Mn)=3.2, glass transition temperature (Tg)=120.0°C. The highest attained temperature in the hydrogenation reaction was 179°C. The theoretical calorific value was calculated from DNM=129.3kcal/kg, DCP=452.3kcal/kg, and NB=319.3kcal/kg. The hydrogenation rate of this hydride was determined by ¹ H-NMR measurement, and 99.9% or more of the olefinic unsaturated bonds in the main chain were hydrogenated. The ¹ H-NMR measurement results before and after hydrogenation are shown in Figs. 12 and 13, respectively.

In addition, the purified liquid before desolventization was kept heated at 50° C. and filtered continuously, and the time-dependent change of the filtration rate was followed. After 1000hr, the filter is still not clogged, and the filtration rate has not decreased, 1000hr filtration rate/1 hr filtration rate=1.00.

[Comparative example 2]

In the hydrogenation reaction of embodiment 9, use 3-(3,5-di-tert-butyl-4-hydroxyphenyl) stearyl propionate 1 weight part, toluene 600 weight parts ( 100 parts by weight relative to the polymer solid content) and RuH(CO)[P(C 6 H 5 )] 0.0565 parts by weight of RuH(CO)[P(C ₆ H ₅ )] ₃ Cl 0.0565 parts by weight (ruthenium metal/unit Bulk charge = 60ppm), the hydrogen introduction temperature was 150°C, and the feed amount of the polymer converted into solid content was 120kg, except that it was performed in the same manner as in Example 1 to obtain a hydrogenated product. Intrinsic viscosity (η _inh )=0.53, weight average molecular weight (Mw)=6.03×10 ⁴ , molecular weight distribution (Mw/Mn)=2.7, and glass transition temperature (Tg)=146.6°C of the obtained hydride. The hydrogenation rate of this hydride was determined by ¹ H-NMR measurement, and 99.9% or more of the olefinic unsaturated bonds in the main chain were hydrogenated. The highest temperature achieved in the hydrogenation reaction is 179°C, but the hydrogenation reaction starts at a high temperature, so when the autoclave is operated below the design temperature, the amount of monomer feed is small and the amount of solvent is large, so the productivity is poor.

In addition, the purified liquid before desolventization was kept heated at 50° C. and filtered continuously, and the time-dependent change of the filtration rate was followed. After 1000 hr, the filter is still not clogged, and the filtration rate does not decrease, 1000 hr filtration rate/1 hr filtration rate=1.00.

[Comparative example 3]

In the hydrogenation reaction of Example 10, 1 weight part of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate and 700 parts by weight of toluene ( 0.0565 parts by weight of RuH(CO)[P(C ₆ H ₅ )] ₃ Cl as a hydrogenation catalyst having a saturation solubility in toluene of 0.05 wt% at 25°C relative to 100 parts by weight of the polymer solid content ( Ruthenium metal/monomer feeding amount = 60ppm), hydrogen introduction temperature is 150°C, and the feeding amount of the polymer converted into solid content is 110 kg, except that it is operated in the same manner as in Example 3 to obtain a hydride. The obtained hydride had intrinsic viscosity (η _inh )=0.52, weight average molecular weight (Mw)=6.28×10 ⁴ , molecular weight distribution (Mw/Mn)=3.2, glass transition temperature (Tg)=120.0°C. The hydrogenation rate of this hydride was determined by ¹ H-NMR measurement, and 99.9% or more of the olefinic unsaturated bonds in the main chain were hydrogenated. The highest temperature achieved in the hydrogenation reaction is 179°C, but the hydrogenation reaction starts at a high temperature, so when the autoclave is operated below the design temperature, the amount of monomer feed is small and the amount of solvent is large, so the productivity is poor. In addition, the purified liquid before desolventization was kept heated at 50° C. and filtered continuously, and the time-dependent change of the filtration rate was followed. After 1000 hr, the filter is still not clogged, and the filtration rate does not decrease, 1000 hr filtration rate/1 hr filtration rate=1.00.

[Comparative example 4]

In the hydrogenation reaction in Example 9, 1 part by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was used as a gelation inhibitor and the temperature was 25° C. The saturated solubility in toluene is 0.05wt% RuH(CO)[P(C ₆ H ₅ )] ₃ Cl 0.0565 parts by weight (ruthenium metal/monomer feed = 60ppm), the hydrogen introduction temperature is 100°C, except Otherwise, it carried out similarly to Example 1, and obtained the hydride. Intrinsic viscosity (η _inh )=0.53, weight average molecular weight (Mw)=6.03×10 ⁴ , molecular weight distribution (Mw/Mn)=2.7, and glass transition temperature (Tg)=146.6°C of the obtained hydride. The hydrogenation rate of this hydride was determined by ¹ H-NMR measurement, and 99.9% or more of the olefinic unsaturated bonds in the main chain were hydrogenated. The highest attained temperature in the hydrogenation reaction was 179°C. In addition, the purified liquid before desolventization was kept heated at 50° C. and filtered continuously, and the time-dependent change of the filtration rate was followed. After 1000hr, the filter was clogged and could not be filtered. 1000 hr filtration rate/1 hr filtration rate=0.

[Comparative Example 5]

In the hydrogenation reaction in Example 10, 1 part by weight of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was used as a gelation inhibitor and the temperature was 25° C. 0.0565 parts by weight of RuH(CO)[P(C ₆ H ₅ )] ₃ Cl with a saturated solubility in toluene of 0.05wt% (ruthenium metal/monomer feed = 60ppm), hydrogen introduction temperature is 100°C, except Except for the same operation as in Example 3, a hydride was obtained. The obtained hydride had intrinsic viscosity (η _inh )=0.52, weight average molecular weight (Mw)=6.28×10 ⁴ , molecular weight distribution (Mw/Mn)=3.2, glass transition temperature (Tg)=120.0°C. The hydrogenation rate of this hydride was determined by ¹ H-NMR measurement, and 99.9% or more of the olefinic unsaturated bonds in the main chain were hydrogenated. In addition, the purified liquid before desolventization was kept heated at 50° C. and filtered continuously, and the time-dependent change of the filtration rate was followed. After 1000hr, the filter was clogged and could not be filtered. 1000 hr filtration rate/1 hr filtration rate=0.

Claims (10)

1. A metal hydride complex, characterized in that it is represented by the following general formula (1); MQ _n H _k T _p Z _q (1) In formula (1), M represents a metal selected from ruthenium, rhodium, osmium, iron, cobalt and iridium; Q independently represents a group shown in the following formula (i); T independently represents CO or NO; Z independently represents PR ⁶ R ⁷ R ⁸ , wherein, R ⁶ , R ⁷ and R ⁸ each independently represent 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 0～ An integer of 4, q represents an integer of 0 to 4 and the total of k, n, p, and q is 4, 5 or 6;

In formula (i), R ¹ to R ⁵ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an alkoxy group, an amino group, a nitro group, a cyano group, a carboxyl group or a hydroxyl group. 2. The metal hydride complex according to claim 1, characterized in that, M in the formula (1) is ruthenium. 3. The metal hydride complex according to claim 1 or 2, characterized in that R ¹ to R ⁵ in the formula (i) are each independently a hydrogen atom or an alkyl group with 1 to 18 carbon atoms , cycloalkyl or aryl. 4 . The metal hydride complex according to claim 1 , wherein the solubility in toluene at 20° C. is 0.2% by weight or more. 5 . The metal hydride complex according to claim 1 , wherein the solubility in toluene at 20° C. is 1.0% by weight or more. 6. The hydrogenation method of cyclic olefin-based ring-opening polymer, characterized in that the hydrogenation of cyclic olefin-based ring-opening polymer is carried out in the presence of the metal hydride complex described in any one of claims 1 to 5 reaction. 7. the hydrogenation method of cyclic olefin ring-opening polymer according to claim 6, is characterized in that, cyclic olefin ring-opening polymer is to contain and be selected from following general formula (I), (II) and ( III) A ring-opening (co)polymer of monomers of more than one compound among the compounds shown;

In formulas (I), (II) and (III), R ⁹ to R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group with 1 to 30 carbon atoms or other monovalent organic groups; R ⁹ and R ¹⁰ , or R ¹¹ and R ¹² can be integrated to form a divalent hydrocarbon group; R ⁹ or R ¹⁰ and, R ¹¹ or R ¹² can be combined to form a monocyclic or polycyclic structure; h, i and j are independently 0 or a positive integer. 8. The preparation method of cyclic olefin-based ring-opening polymer hydrogenated product is characterized in that, the ring-opening polymerization of monomers containing cyclic olefin-based compounds shown in the general formula (II) according to claim 7 makes the resulting open After the solution of the cyclic polymer has previously reached a temperature of 40°C to less than 120°C, it is brought into contact with hydrogen in the presence of the metal hydride complex according to any one of claims 1 to 5 to start a hydrogenation reaction. 9. the preparation method of cyclic olefin ring-opening polymer hydrogenated product according to claim 8, is characterized in that, will contain the compound shown in the general formula (II) described in claim 7 and the compound described in claim 7 A ring-opened copolymer obtained by copolymerizing monomers of compounds represented by the general formula (I) is hydrogenated. 10. according to the preparation method of the cyclic olefin ring-opening polymer hydrogenated product described in claim 8 or 9, it is characterized in that, with three filters connected in series by filter aperture from large to small order, the gained ring When a polymer solution having a solid content concentration of 20% by weight of a hydrogenated olefin-based ring-opening polymer is continuously filtered at 50°C under a nitrogen pressure of 3.0kgf/cm ² , the filtration rate after 1 hour from the start of filtration and 1000 hours The ratio of the final filtration speed is 0.85 to 1.00; the three filters are filters with an average pore size of 2.0 μm and a filtration area of 2000 cm ² , an average pore size of 1.0 μm and a filtration area of 2000 cm ² , and an average pore size of 0.2 μm and a filter area of 1800 cm ² .

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