JP2697195B2 - Hydrogenation of ring-opening polymer - Google Patents

Description

The present invention relates to hydrogenation (hydrogenation) of a ring-opened polymer of a compound having a norbornene ring or a copolymer of the compound and a monomer copolymerized therewith. ) Method.

[Prior Art] In recent years, as a transparent resin having excellent optical properties and heat resistance, various (co) polymers and a method for producing the same have been proposed as a transparent resin having excellent optical properties and heat resistance. I have.

For example, norbornene, dicyclopentadiene, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene and a monomer selected from derivatives thereof, W, Mo, Re, transition metals such as Ti BACKGROUND ART Polymers obtained by ring-opening polymerization using a polymerization catalyst selected from compounds or a catalyst obtained by combining a transition metal thereof and an organometallic compound such as Li, Mg, Al, or Sn are known. It is also well known that the ring-opened polymer is hydrogenated in order to improve the thermal stability and weather resistance of these polymers.

Such hydrogenation methods for (co) polymers include Ti, Co, Ni
And organic salts or acetylacetone salts such as Li, Mg,
A method of performing a hydrogenation reaction in the presence of a so-called Ziegler-type homogeneous catalyst combining organic metal compounds such as Al and Sn, and converting noble metals such as palladium, platinum, ruthenium and rhodium to carbon, alumina, silica alumina, and diatomaceous earth. A method of performing a hydrogenation reaction in the presence of a supported noble metal-based catalyst supported on a carrier, a method of performing a hydrogenation reaction in the presence of a catalyst using a base metal such as nickel,
Methods using a noble metal complex catalyst such as Rh, Re, and Ru are well known.

[Problems to be Improved by the Invention] As described above, various methods are known as hydrogenation catalysts, but none of these methods is decisive from an industrial point of view, At present, various catalyst systems are selected depending on the conditions.

That is, the method uses an expensive noble metal, but the activity is not so high, and it is difficult to reuse the catalyst, so that the catalyst cost is extremely high. Although the catalyst itself is inexpensive, the method has a drawback that the hydrogenation rate is not sufficiently increased in a reaction in which hydrogenation is relatively difficult to proceed, such as hydrogenation of a polymer. Can obtain a high degree of hydrogenation even if a polar substituent is present in the polymer.Also, even if water is present in the hydrogenation reaction system, the activity is not substantially affected, and the used catalyst can be recovered. It is preferable because it has an advantage that it can be easily performed by just passing through. However, this method has a serious industrial problem that when the hydrogenation target is a ring-opened polymer of a norbornene compound, an extremely large amount of catalyst is required, and the catalyst life is short. Since the catalyst is more sensitive to air, water and other polar compounds than the method of heterogeneous reaction and is easily deactivated, the substance causing the deactivation is removed before the reaction, Although it has the drawback that it is difficult to handle, for example, the addition reaction must be carried out with sufficient exclusion of air and water, the reaction proceeds under mild hydrogenation conditions at a low reaction temperature and low hydrogen pressure with a relatively small amount of catalyst. There is. However, even when this catalyst system is used, a large amount of catalyst must be used to increase the hydrogenation rate to nearly 100%, and in this case, there is a disadvantage that gel is generated in the polymer. Was. When a hydrogenated product of a ring-opened polymer of a norbornene ring-containing compound is used for an optical application as its main use, the higher the hydrogenation rate is, the better the heat stability is. The gel must be suppressed as much as possible, since the gel becomes an optical scratch and the product cannot withstand its use.

[Means for Solving the Problems] In the method for hydrogenating a ring-opened (co) polymer of a compound having a norbornene ring, the present inventors have intensively studied so-called Ziegler type catalysts for solving the above problems. As a result, in performing the hydrogenation reaction, the activity was greatly increased by selecting a specific solvent, and more surprisingly, it was found that a high hydrogenation rate could be easily obtained without generating a gel, and the present invention was reached. .

That is, the present invention provides a polymer obtained by ring-opening polymerization of a compound having a norbornene ring or a copolymer obtained by copolymerizing the compound and a monomer copolymerizable with the compound, a nickel compound, a cobalt compound, One or more compounds selected from iron compounds, titanium compounds, vanadium compounds, chromium compounds, and manganese compounds;
a, IIa, IIIb, IVa, IVa At least one compound selected from the group consisting of organometallic compounds and hydrides of hydrides is hydrogenated in the presence of a catalyst. 20 to 90% by weight and 10 to 80 aromatic hydrocarbons
A method for hydrogenating a norbornene-based ring-opening polymer, which comprises hydrogenating the mixture in a mixed solvent of 1% by weight.

[Specific description of the invention] The compound having a norbornene ring referred to in the present invention is a compound represented by the structural formula I.

Structural formula I [Wherein, A and B are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, A and B may be the same or different, and A and B are hydrocarbon groups. X and Y may be a hydrogen atom, having 1 carbon atom
10 hydrocarbon ^{_{group, CH 2 n COOR 1, CH}} 2 n OCOR 2, CH 2 n OR 3, CH 2
_n CN, or composed of X and Y Wherein X and Y may be the same or different, and R ¹ , R ² , R ³ and R ⁴ are a hydrocarbon group having 1 to 20 carbon atoms, and n is an integer of 0 to 10 , M represents 0 to 2. These norbornene compounds need not necessarily be used alone, and may be copolymerized using two or more compounds.

Examples of the compound copolymerizable with the structural formula (I) include cycloolefins such as cyclopentene, cyclohexene, cycloheptene and cyclooctene.

The compound represented by the structural formula (I) has a carbon-carbon double bond in the main chain of polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-propylene-non-conjugated diene copolymer, polynorbornene, or the like. Polymerization can also be carried out in the presence of a contained unsaturated hydrocarbon-based polymer, and in this case, the impact resistance of the resin is generally improved.

Of these unsaturated copolymerized hydrocarbon-based polymers, butadiene-styrene copolymer and isoprene-styrene copolymer can easily produce the highly transparent copolymer of the present invention by changing the ratio of diene to styrene. It is preferable because it can be obtained. In this case, the copolymer of diene and styrene may be a random copolymer or a block copolymer. In the polymerization in the presence of an unsaturated hydrocarbon polymer, the polymer is used in an amount of 1 to 90% by weight, preferably 3 to 70% by weight, more preferably 5 to 40% by weight based on the compound represented by the structural formula (I). Is done.

The ring-opened (co) polymer that is the object of the present invention is obtained by reacting a compound having a norbornene ring represented by the above structural formula (I) or a compound copolymerizable with the compound in the presence of a polymerization solvent. It is manufactured using a metathesis polymerization catalyst.

The metathesis polymerization catalyst used for ring-opening polymerization is performed using a platinum group compound such as ruthenium, rhodium, palladium, iridium, and platinum. (A) W, Mo
And at least one compound selected from the group consisting of compounds of Group Ia, IIa, IIb, IIIb, IVa and IVb of the periodic table Ia, IIa, IIb, IVb or IVa. A catalyst comprising at least one combination selected from those having a bond or the element-hydrogen bond may be used, and in this case, an additive (c) which enhances catalytic activity may be added. Good.

Representative examples of suitable W, Mo or Re compounds as component (a) include WCl ₆ , MoCl ₅ and ReOCl ₃ , and the compounds disclosed in Japanese Patent Application No. 63-65817 can be used.

Specific examples of the component (b) include n-BuLi, (C _{2
H 5) 3 Al, (C} 2 H 5) 2 AlCl, there are such LiH, No. Sho 63
The compound shown in -65817 can also be used.

As typical examples of the component (c), alcohols, aldehydes, ketones, amines and the like can be suitably used, and in addition, the compounds shown in Japanese Patent Application No. 63-65817 can also be used.

The use ratio of component (a) to component (b) is such that (a) :( b) is in the range of 1: 1 to 1:20, preferably 1: 2 to 1:10 in terms of metal atom ratio.

The molar ratio of component (c) to component (a) is (c) :( a) 0.005: 1 to 10: 1, preferably 0.05: 1 to
Used in the range of 2: 1.

The molecular weight of the polymer can be adjusted by the polymerization temperature, the type of catalyst, and the type of solvent, but more preferably, α-olefins such as 1-butene, 1-pentene, 1-hexene, and 1-octene are reacted. It is advisable to coexist in the system and adjust the amount by changing the amount.

The polymer used in the present invention has a molecular weight of _0.3 to η _inh .
A range of 3 can be applied, but as the molecular weight increases, it becomes more difficult to obtain a high degree of hydrogenation.

The catalyst used for hydrogenating the obtained (co) polymer is a nickel compound, a cobalt compound, an iron compound,
At least one compound selected from a titanium compound, a vanadium compound, a chromium compound, and a manganese compound, and a periodic table
A combination of at least one compound selected from the group consisting of organometallic compounds of Group Ia, IIa, IIIb, IVa, and IVb elements and hydrides is used.

Examples of the nickel compound as one component of the hydrogenation catalyst used in the present invention include nickel carboxylate such as nickel naphthenate and nickel octanoate, nickel acetylacetonate, nickel chloride, nickel carbonyl, nickelocene and the like. .

Examples of the cobalt compound include cobalt carboxylate such as cobalt naphthenate and cobalt octanoate, cobalt acetylacetonate, cobalt chloride, cobalt carbonyl, and cobalt cene.

Examples of the iron compound include iron carboxylate such as iron naphthenate and iron octanoate, iron acetylacetonate, iron chloride, iron carbonyl, and ferrocene.

Examples of the titanium compound include titanium carboxylate such as titanium naphthenate and titanium octanoate, titanium acetylacetonate, titanium chloride, titanium carbonyl, titanocene, titanocene dichloride and the like.

As the vanadium compound, vanadium naphthenate,
Examples thereof include vanadium carboxylate such as vanadium octanoate, vanadium acetylacetonate, vanadium chloride, vanadyl chloride, vanadium carbonyl, and vanadinocene.

Examples of the chromium compound include chromium carboxylate such as chromium naphthenate and chromium octanoate, chromium acetylacetonate, chromium chloride, chromium carbonyl, chromocene, and the like.

Examples of the manganese compound include manganese carboxylate such as manganese naphthenate and manganese octanoate, manganese acetylacetonate, manganese chloride, manganese carbonyl, and manganocene.

Among these compounds, when a nickel compound or a cobalt compound is used, the activity is high and the catalytic activity is not significantly affected even when a polar substituent is present, so that it can be used also for a norbornene compound having a polar group, which is particularly preferable. It is.

Preferred examples of Group Ia, IIa, IIIb, IVa and IVb elements as one component of the hydrogenation catalyst used in the present invention include Li, Na, K, Mg, Ca, B , Al, Ti, Zr, Sn and the like, and more preferable is Al.

Examples of the organometallic compounds of these elements include alkyl lithium such as n-butyllithium and sec-butyllithium, triethyllithium borohydride, and tri-se hydride.
c-butylboron lithium, sodium-naphthalene adduct, potassium-naphthalene adduct, ethylmagnesium bromide, alkyltin compounds such as dibutyltin dichloride, tetrabutyltin, tributyltin hydride, lithium hydride, sodium hydride, hydrogenation Potassium, calcium hydride, lithium aluminum hydride, lithium borohydride, sodium borohydride,
In addition to hydrides such as titanium hydride and zirconium hydride, the following organoaluminum compounds may be mentioned.

As the organoaluminum compound used in the present invention, a compound having a hydrocarbon group directly connected to aluminum is used, and usually, a compound represented by the formula AlR _n X _3-n [R is a hydrocarbon group, X is a halogen, 0 <n ≦ 3 ] Is used.

In the above formula, R is usually a hydrocarbon group having 1 to 18, preferably 1 to 12 carbon atoms, and may be an alkenyl group, a cycloalkyl group or an aryl group as well as an alkyl group. When there are a plurality of Rs, they may be the same or different from each other.

These include, for example, trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum; dialkylaluminum halides such as diethylaluminum chloride, diethylaluminum bromide, dipropylaluminum chloride, diisobutylaluminum chloride; ethylaluminum sesquichloride, isobutylaluminum sesquichloride Alkyl aluminum dihalides such as alkyl aluminum sesquihalide, ethyl aluminum dichloride and isobutyl aluminum dichloride; and mixtures thereof. Among them, trimethylaluminum, which is a highly active catalyst,
Trialkylaluminums such as triethylaluminum and triisobutylaluminum are preferable, and triethylaluminum is more preferable.

In some cases, it is possible to further increase the hydrogenation activity by adding a third component to the catalyst system. A third that can be used for this purpose
Components include dienes such as butadiene and isoprene, as well as phenols, BF ₃ , water, and alcohol.

In the present invention, hydrogenation is carried out by dissolving the polymer in a specific solvent described below in the presence of the above-mentioned catalyst, and by using hydrogen. That is, the solvent that can be used in the present invention is a mixture of an alicyclic hydrocarbon and an aromatic hydrocarbon.

As an example of the alicyclic hydrocarbon, an alicyclic hydrocarbon having 5 to 20 carbon atoms is preferable, and an alicyclic hydrocarbon having 5 to 12 carbon atoms is more preferable. It is preferable that these alicyclic hydrocarbons have no substituent other than the hydrocarbon. Specific examples include cyclopentane, cyclohexane, cycloheptane, cyclooctane, decalin, and substituted hydrocarbons thereof.

As the aromatic compound, a compound having 6 to 20 carbon atoms can be preferably used. Specific examples of the compound include benzene, toluene, xylene, ethylbenzene, dimethylbenzene, trimethylbenzene, naphthalene, methylnaphthalene, and tetralin.

Mixing ratio of alicyclic hydrocarbon and aromatic hydrocarbon is 20 ~ 90/8
0 to 10 (% by weight), preferably 30 to 85/70 to 15, more preferably 40 to 80/60 to 20, and particularly preferably 45 to 80/55 to 20
It is. If the ratio is out of the range, not only a high hydrogenation ratio cannot be obtained, but also a gel is generated under the conditions for obtaining a high hydrogenation ratio (for example, hydrogenation ratio> 90%).

Further, in some cases, it is possible to mix up to 20 parts by weight of an aliphatic hydrocarbon with respect to 100 parts by weight of a mixed solvent of an alicyclic hydrocarbon and an aromatic hydrocarbon. These hydrogenated solvents may be the same as those used in the ring-opening polymerization reaction. In this case, the polymerization and the hydrogenation can be carried out with the same solvent, which is industrially particularly preferable.

The concentration of the polymer in the polymerization solution subjected to the hydrogenation reaction is usually 1 to 40% by weight, preferably 3 to 30% by weight, more preferably 5 to 20% by weight. If the polymer concentration is high, the rate of the hydrogenation reaction will be low, and if the polymer concentration is too low, the economic efficiency will be impaired.

The temperature of the hydrogenation reaction is usually 0 ° C to 200 ° C, preferably 2 ° C.
The reaction is carried out at 0 ° C at 150 ° C, more preferably at 30 ° C to 100 ° C. If the temperature is low, the rate of the hydrogenation reaction is not sufficient, and if the temperature is too high, the catalyst is deactivated or the aromatic hydrocarbon used as the solvent is hydrogenated, which is not preferable.

The pressure of the hydrogenation reaction is usually 1 kg / cm ² to 200 kg / cm ² , preferably 2 kg / cm ² to 150 kg / cm ² , more preferably 5 kg / cm ²
From 120 kg / cm ² . If the pressure is low, the hydrogenation reaction rate is not sufficient, and if it is too high, the reaction rate is high, but the apparatus becomes expensive and not economical.

The hydrogenation reaction time is usually 30 minutes to 100 hours, preferably 1 hour to 30 hours.

After the hydrogenation reaction, the hydrogenation catalyst is removed by a known method such as washing with an acid or washing with a surfactant, and then the solvent is removed to obtain a polymer.

An ultraviolet absorber, a lubricant, a colorant, and a pigment can be added to the hydrogenated polymer obtained in the present invention, if necessary.

Methods for adding these antioxidants and the like include a method of adding them to the polymer solution after hydrogenation and a method of adding them during pelletization, and are not particularly limited.

The hydrogenated norbornene-based resin of the present invention can be used in the production of various molded products as window glass, automotive glass, films, sheets, and general molding materials, in addition to optical materials such as lenses, optical disk substrates, and optical fibers.

[Examples] Hereinafter, the present invention will be specifically described with reference to examples.

The hydrogenation rate was measured by 60 MHz NMR and calculated from the decrease in the peak in the range of δ = 4.5 to 6.0 ppm due to the hydrogenation reaction.

The gel amount was calculated as the amount based on the polymer from the weight of the dried polymer solution after passing the polymer solution after the hydrogenation reaction through a 200-mesh wire gauze, washing well with toluene. In Examples,% means% by weight unless otherwise specified.

Reference Example 1 Under a nitrogen atmosphere, in a reaction vessel purged with nitrogen,
Is norbornene ring-containing monomer 8-methyl-8-methoxymethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10]
-3-dodecene 500 g, toluene 1700 ml, molecular weight regulator 1-hexene 83 g, catalyst WCl ₆ concentration 0.05 M
/ Chlorobenzene solution 8.5 ml, paraaldehyde concentration 0.1 M / 1,2-dichloroethane solution 4.3 ml, diethyl aluminum chloride concentration 0.8 M / toluene solution 1
1 ml, and reacted at 60 ° C. for 4 hours. This polymer solution is poured into a large amount of methanol to precipitate a polymer, and the polymer is precipitated, washed, and dried to obtain an intrinsic viscosity (η
_inh ) 0.45dl / g (in chloroform, 30 ℃, concentration 0.5g / d
480 g of the polymer of l) were obtained.

Reference Example 2 In a nitrogen atmosphere, in a reaction vessel purged with nitrogen,
Tetracyclo which is a norbornene ring-containing monomer [4.4.
0.1 ^2,5 .1 ^7,10] -3-dodecene 350 g, using a pentacyclo ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} -4- pentadecene 150 g, and toluene 2,000 ml, molecular weight 7.5 ml of 1-hexene as a regulator, 15 ml of a toluene solution having a concentration of 1.0 M / TiCl _{4 as} a catalyst, 20 ml of a toluene solution of 0.1 M / triethylamine, and a concentration of 1.0 M / triethylaluminum.
Was added thereto and reacted at 25 ° C. for 2.5 hours. The polymer was recovered from this polymer solution in the same manner as in Reference Example 1 to obtain 260 g of a polymer having an intrinsic viscosity (η _inh ) of 0.47 dl / g (in chloroform, at 30 ° C. and a concentration of 0.5 g / dl).

Example 1 A three-necked flask purged with nitrogen was charged with a solution in which 28 g of nickel naphthenate having a nickel content of 5% by weight was dissolved in 112 g of toluene. After cooling to 0 ° C, 47 g of a 1M hexane solution of triethylaluminum was further added with stirring. Was added to form a catalyst solution.

Next, a polymer solution obtained by dissolving 44 g of the polymer obtained in Reference Example 1 in 396 g of a mixed solution of cyclohexane / toluene (weight ratio = 75/25) was charged into a high-pressure autoclave equipped with an electromagnetic induction stirrer, and the catalyst prepared above was prepared. 19 g of the solution were added.
Hydrogen was introduced into the autoclave to adjust the pressure to 110 kg / cm ² , and then the temperature was raised to 60 ° C with stirring. After maintaining at this temperature for 6 hours, the temperature was returned to room temperature, and after releasing hydrogen, the reaction solution was added to a large amount of methanol / hydrochloric acid to deactivate the catalyst and precipitate a polymer. After dissolving the obtained polymer in toluene, it was added again to a methanol solution to purify the polymer. After drying the obtained polymer, the hydrogenation rate was measured by NMR. The peak attributed to the olefin completely disappeared in the hydrogenation reaction, the degree of hydrogenation was 100%, and no gel was formed.

Example 2 A hydrogenation reaction was carried out in the same manner as in Example 1 except that the solvent (cyclohexane / toluene) in which the mixing ratio (weight ratio) was changed to 50/50 was used. The degree of hydrogenation was 98%, and no gel was formed.

Comparative Example 1 A hydrogenation reaction was carried out in the same manner as in Example 1, except that the solvent (cyclohexane / toluene) in which the mixing ratio (weight ratio) was changed to 10/90 was used. The degree of hydrogenation was 92%, and no gel was formed.

Comparative Example 2 A hydrogenation reaction was carried out in the same manner as in Example 1 except that 396 g of toluene was used instead of the mixture of cyclohexane / toluene as the solvent. Hydrogenation rate is 90
% And no gel was formed.

Comparative Example 3 A hydrogenation reaction was carried out in the same manner as in Example 1, except that 396 g of toluene was used instead of the mixture of cyclohexane / toluene as the solvent and the amount of the catalyst was further increased to 57 g. Hydrogenation rate was 99%, but gel was 1.5%
%Occurred.

Example 3 A three-necked flask purged with nitrogen was charged with 23 g of nickel octanoate having a nickel content of 6% by weight dissolved in 115 g of toluene. After cooling to 0 ° C., a 1M hexane solution of triisobutylaluminum was further added with stirring. 47 g was added to make a catalyst solution.

Next, a polymer solution obtained by dissolving 44 g of the polymer obtained in Reference Example 2 in 396 g of a mixed solution of cyclohexane / toluene (weight ratio = 65/35) was charged into a high-pressure autoclave equipped with an electromagnetic induction stirrer, and the catalyst prepared above was prepared. 19 g of the solution were added.
Thereafter, the same hydrogenation reaction as in Example 1 was performed to obtain a hydrogenated polymer. The degree of hydrogenation was 100%, and no gel was formed.

Comparative Example 4 A hydrogenation reaction was carried out in the same manner as in Example 3, except that 396 g of toluene was used instead of the mixture of cyclohexane / toluene as the solvent. The degree of hydrogenation was 93%, and 0.2% of gel was generated.

Comparative Example 5 A hydrogenation reaction was carried out in the same manner as in Example 3, except that 396 g of toluene was used instead of the mixture of cyclohexane / toluene as the solvent, and the amount of the catalyst was further increased to 46 g. Hydrogenation rate was 100%, but gel was 1.0%
%Occurred.

Comparative Example 6 A hydrogenation reaction was carried out in the same manner as in Example 3 except that 396 g of cyclohexane was used instead of the mixture of cyclohexane / toluene as the solvent. Hydrogenation rate is 89
% And no gel was formed.

Example 4 A three-necked flask purged with nitrogen was charged with 8.5 g of cobalt acetylacetonate dissolved in 130 g of toluene.
After cooling to ° C., 47 g of a 1M triethylaluminum hexane solution was further added with stirring to form a catalyst solution.
Hereinafter, using the catalyst, the polymer obtained in Reference Example 1 was hydrogenated under the same conditions as in Example 1. The hydrogenation rate is 100%,
There was no gel formation.

Comparative Example 7 A hydrogenation reaction was carried out in the same manner as in Example 4, except that 396 g of a mixture of cyclohexane / dimethoxyethane (80/20) was used instead of the mixture of cyclohexane / toluene as the solvent. The degree of hydrogenation was 85%, and no gel was generated.

Example 5 In Example 4, except that 13.1 g of manganese naphthenate and 47 g of triethylaluminum were used as catalyst components.
A catalyst solution was prepared in the same manner as in Example 4, and using this catalyst solution, the polymer obtained in Reference Example 2 was hydrogenated under the same conditions as in Example 3. The degree of hydrogenation was 97%, and no gel was generated.

Example 6 A catalyst solution was prepared in the same manner as in Example 4 except that 8.4 g of iron acetylacetonate and 47 g of triethylaluminum were used as the catalyst components, and the catalyst solution was obtained in Reference Example 2 using this catalyst solution. Hydrogenation of the polymer was carried out under the same conditions as in Example 3. The degree of hydrogenation was 96%, and no gel was generated.

Example 7 A catalyst solution was prepared in the same manner as in Example 4 except that 8.3 g of chromium acetylacetonate and 47 g of triethylaluminum were used as the catalyst components. Hydrogenation of the polymer was carried out under the same conditions as in Example 3. The degree of hydrogenation was 96%, and no gel was generated.

Example 8 A catalyst solution was prepared in the same manner as in Example 4 except that 5.9 g of biscyclopentadienyltitanium dichloride and 47 g of triethylaluminum were used as the catalyst components. Was hydrogenated under the same conditions as in Example 3. The degree of hydrogenation was 99%, and no gel was generated.

Example 9 A catalyst solution was prepared in the same manner as in Example 4 except that 6.8 g of tributoxyvanadyl and 47 g of triethylaluminum were used as the catalyst components. The combined hydrogenation was performed under the same conditions as in Example 3. The degree of hydrogenation was 95%, and no gel was generated.

Example 10 The procedure of Example 1 was repeated, except that the hexane solution of triethylaluminum was replaced with a 1M hexane solution of n-butyllithium.
A hydrogenation reaction was carried out in the same manner as in Example 1 except that 47 g was used. The degree of hydrogenation was 100%, and no gel was generated.

Comparative Example 8 A hydrogenation reaction was carried out in the same manner as in Example 10, except that toluene was used as a solvent. The degree of hydrogenation was 88%, and no gel was generated.

Comparative Example 9 A hydrogenation reaction was carried out in the same manner as in Example 10, except that toluene was used as a solvent and the amount of the catalyst was increased to 76 g. The degree of hydrogenation was 99%, but 2.8% of gel was generated.

[Effects of the Invention] According to the present invention, a (co) polymer having a high degree of hydrogenation can be obtained without generating a gel, and therefore, a transparent resin having excellent heat resistance and weather resistance can be produced at low cost.

Claims (1)

(57) [Claims] 1. A nickel compound, a cobalt compound, a polymer obtained by ring-opening polymerization of a compound having a norbornene ring or a copolymer obtained by copolymerizing the compound with a monomer copolymerizable therewith. Iron compounds, titanium compounds,
At least one compound selected from a vanadium compound, a chromium compound, and a manganese compound; and a periodic table Ia, IIa, III
When hydrogenating with hydrogen in the presence of a catalyst comprising at least one compound selected from organometallic compounds of group b, IVa and IVb elements and hydrides, alicyclic hydrocarbons 20 to 90 as a solvent Wt% and aromatic hydrocarbon 10 ~ 80wt%
Hydrogenation in a mixed solvent comprising: hydrogenating a ring-opened polymer.