JP2007169342A - Method for producing hydrogenated product of ring-opening metathesis polymer of alicyclic olefin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing the hydrogenated product of a ring-opening metathesis polymer of an alicyclic olefin by which the high quality hydrogenated product of the same is efficiently produced without using a metal removing agent, reduced in the metal content to be in a practically sufficient level and without contamination of foreign materials from the metal removing agent. <P>SOLUTION: The method for producing the hydrogenated product of the ring-opening metathesis polymer of an alicyclic olefin comprises a process (I) for preparing a polymer solution containing the ring-opening metathesis polymer of the alicyclic olefin by carrying out a polymerization reaction of the alicyclic olefin using a ring-opening metathesis polymerization catalyst in a solution, a process (II) for carrying out a hydrogenation reaction of the ring-opening metathesis polymer of the alicyclic olefin in the polymer solution I prepared in the process (I) and a process (III) for precipitating the metal component dissolved in the polymer solution II by raising the temperature higher than the reaction temperature during the polymerization reaction and the hydrogenation reaction. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a hydride of an alicyclic olefin ring-opening metathesis polymer.

  Synthetic resins such as acrylic resins, phenol resins, and alicyclic olefin resins are widely used in fields such as electrical insulating films and resists for semiconductor manufacturing; transparent cover films for liquid crystal display elements. In improving the performance of products using such synthetic resins, it has been pointed out that electrical noise and transparency hindrance due to the metal remaining in the resin become problems. In applications of semiconductors and transparent molded products, the metal content in the resin is required to be 1 ppm or less.

  As a metal component (metal or metal-containing material) remaining in the polymer such as the synthetic resin, a metal component derived from a metal-containing catalyst used in a step of preparing a polymer such as a polymerization reaction or a polymer modification reaction; And metal components derived from the environment mixed in from a reactor, a dryer, a transfer pipe, and the like. In particular, the metal component derived from the metal-containing catalyst used in the process of preparing the polymer, such as a polymerization reaction or a hydrogenation reaction to the carbon-carbon double bond of the polymer, occupies a lot, and this can be removed. is important.

Examples of a method for removing the metal component from the polymer after synthesis include, for example, a polymer solution using at least one adsorbent selected from the group consisting of clay intercalation compounds, activated carbon, graphite, silica gel, alumina gel, and alumino-silica gel. A filter cartridge comprising a method for removing a metal component from inside (Patent Document 1), a fiber material in which an ion exchange group and / or a chelate group are introduced into an organic polymer fiber substrate, and a porous membrane material A method of removing metal components from a polymer solution by using a method (Patent Document 2), a method of extracting impurities containing a metal component in a polymer solution with a poor solvent, and removing the extracted impurities by filtration or the like (patent Document 3) has been proposed. In addition, a method for producing a norbornene-based ring-opening polymer in which a catalyst deactivator is added to a polymer solution obtained by ring-opening polymerization of a norbornene-based monomer using a metathesis catalyst to precipitate and remove the catalyst residue (patent) Document 4) has been proposed.
JP-A-7-74073 JP 2003-251120 A JP-A-7-109310 JP-A-4-161421

  However, the conventional metal component removal method uses a metal remover such as an adsorbent to remove the metal component from the polymer solution, and the operation is complicated and time-consuming. There was a problem. Further, when the polymer solution is treated with a metal remover, there is a possibility that foreign matters are mixed into the polymer.

  The object of the present invention is to efficiently remove metal components from a hydride solution of an alicyclic olefin ring-opening metathesis polymer by a simple operation without using a metal remover, and therefore the metal content is practical. A method for producing a hydride of an alicyclic olefin ring-opening metathesis polymer, which is reduced to a sufficient extent and can efficiently obtain the high-quality hydride without contamination by foreign substances from a metal remover. It is to provide.

  As a result of diligent studies to solve the above problems, the present inventors raised the polymer solution in which the metal-containing catalyst used in the ring-opening metathesis polymerization reaction and the subsequent hydrogenation reaction is dissolved to a predetermined temperature. The present inventors have found that a metal component dissolved in can be deposited, and have completed the present invention based on such knowledge.

That is, the present invention
[1] A step (I) of obtaining a polymer solution I containing an alicyclic olefin ring-opening metathesis polymer by performing a polymerization reaction of an alicyclic olefin in a solution using a ring-opening metathesis polymerization catalyst;
A step (II) of performing a hydrogenation reaction of an alicyclic olefin ring-opening metathesis polymer in the polymer solution I obtained in the step (I), and a polymer solution II after the step (II) are polymerized. (III), the temperature is raised to a temperature higher than the reaction temperature at the time of the hydrogenation reaction, and the metal component dissolved in the polymer solution II is precipitated.
A process for producing a hydride of an alicyclic olefin ring-opening metathesis polymer,
[2] The production method of the above-mentioned [1], wherein the ring-opening metathesis polymerization catalyst comprises ruthenium.
[3] The production method of the above-mentioned [2], wherein the ring-opening metathesis polymerization catalyst is a ruthenium-carbene catalyst.
[4] The production method according to [2] or [3], wherein the hydrogenation reaction is performed using a ring-opening metathesis polymerization catalyst.
[5] The production method according to any one of [1] to [4], wherein the solvent of the solution performing the polymerization reaction is a polar solvent having a boiling point of 100 to 250 ° C.
[6] The production method according to any one of [1] to [5], wherein the polymerization reaction is performed in the presence of a non-conjugated polyene compound having two or more terminal vinyl groups.
[7] The production method according to any one of [1] to [6], wherein the alicyclic olefin ring-opening metathesis polymer has a polar group.
[8] The production method according to the above [7], wherein the polar group is a carboxyl group, and [9] the polymerization reaction of the monomer using the polymerization catalyst in the solution, and the polymerization in the resulting polymer solution I From the polymer solution II after further performing the hydrogenation reaction of the coal, the polymer solution II is heated to a temperature higher than the reaction temperature during the polymerization reaction and the hydrogenation reaction, and dissolved in the polymer solution II. Removing the metal component from the polymer solution, by precipitating and removing the metal component that is present,
Is to provide.

  According to the method for producing a hydride of an alicyclic olefin ring-opening metathesis polymer of the present invention, the hydride in which the metal content is reduced to a practically sufficient level can be obtained efficiently. Moreover, since a metal removing agent is not required, it is possible to obtain a high-quality hydride by preventing foreign substances from entering the removing agent.

  The method for producing a hydride of an alicyclic olefin ring-opening metathesis polymer according to the present invention (hereinafter sometimes simply referred to as a hydride) is a method of polymerizing an alicyclic olefin in a solution using a ring-opening metathesis polymerization catalyst. Step (I) to obtain polymer solution I containing alicyclic olefin ring-opening metathesis polymer, hydrogen of alicyclic olefin ring-opening metathesis polymer in polymer solution I obtained in step (I) The step (II) for carrying out the addition reaction and the polymer solution II after the step (II) are heated to a temperature higher than the reaction temperature at the time of the polymerization reaction and the hydrogenation reaction, and dissolved in the polymer solution II. A step (III) of depositing a metal component.

  In step (I) of the present invention, an alicyclic olefin ring-opening metathesis polymer (hereinafter simply referred to as “open”) is obtained by performing a polymerization reaction of the alicyclic olefin in a solution of the alicyclic olefin using a ring-opening metathesis polymerization catalyst. A polymer solution I containing a “ring metathesis polymer” may be obtained.

  The alicyclic olefin may be a compound having at least one ring structure having a carbon-carbon double bond capable of ring-opening metathesis reaction in the molecule, and there is no particular limitation on the structure of the portion other than the ring structure. . Moreover, although there is no restriction | limiting in particular in the number of carbon which comprises an alicyclic olefin, Usually, 4-25, Preferably it is 5-20, More preferably, it is 7-15. The alicyclic olefin may be composed of a single ring or a plurality of rings. When there are a plurality of rings, there is no limitation on the ring bonding mode.

The alicyclic olefin used in the present invention may be one having no polar group or one having a polar group.
Specific examples of the alicyclic olefin having no polar group include bicyclo [2.2.1] hept-2-ene (common name: norbornene), 5-ethyl-bicyclo [2.2.1] hept-2. -Ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-methylidene-bicyclo [2.2.1] ] Hept-2-ene, 5-vinyl-bicyclo [2.2.1] hept-2-ene, tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (common name: diene) cyclopentadiene), tetracyclo ^{[8.4.0.1 11,14.} 0 ^3,7 ] pentadeca-3,5,7,12,11-pentaene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dec-3-ene (common name: tetracyclododecene), 8-methyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-vinyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-3,10-diene, cyclopentene, cyclopentadiene, 1,4-methano -1,4,4a, 5,10,10a hexa hydro anthracene, 8-phenyl - tetracyclo [4.4. 0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene), pentacyclo [7.4.0.1 ^{3 , 6} . 110, 13.0 ^2,7 ] pentadeca-4,11-diene, and pentacyclo [9.2.1.1 ^4,7 . 0 ^2,10 . 0 ^3,8 ] pentadeca-5,12-diene and the like.

  The polar group of the alicyclic olefin having a polar group can be divided into a protic polar group and another polar group. Therefore, the alicyclic olefin having a polar group is divided into an alicyclic olefin having a protic polar group and an alicyclic olefin having a polar group other than the protic polar group (aprotic polar group). be able to.

  A protic polar group is an atom belonging to a hetero atom, preferably an atom belonging to Groups 15 and 16 of the periodic table, more preferably an atom belonging to Groups 15 and 16 of the periodic table. More preferably, it means an atomic group in which a hydrogen atom is directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom, particularly preferably an oxygen atom. Here, the hetero atom refers to an atom other than a carbon atom.

  Specific examples of the protic polar group include a polar group having an oxygen atom such as a carboxyl group (hydroxycarbonyl group), a sulfonic acid group, a phosphoric acid group, and a hydroxyl group; a primary amino group, a secondary amino group, A polar group having a nitrogen atom such as a primary amide group and a secondary amide group (imide group); a polar group having a sulfur atom such as a thiol group; and the like. Among these, what has an oxygen atom is preferable, More preferably, they are a carboxyl group and a hydroxyl group, More preferably, it is a carboxyl group. The carboxyl group can be generated by hydrolysis of a nitrile group, ester group, amide group, acid anhydride group (—C (═O) —O—C (═O) —), etc. It may occur after hydrolysis by hydrolysis.

Specific examples of the alicyclic olefin having a protic polar group include 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-hydroxycarbonylbicyclo [2.2.1]. Hept-2-ene, 5-carboxymethyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-exo-6-endo-dihydroxycarbonylbicyclo [2.2.1] hept-2 -Ene, 8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, and 8-exo-9-endo-dihydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1, ¹⁰ ] alicyclic olefin having a carboxyl group such as dodec-3-ene; 5- (4-hydroxyphenyl) bicyclo [2.2.1] hept-2-ene, 5-methyl-5- ( 4-hydroxyphenyl) bicyclo [2.2.1] hept-2-ene, 8- (4-hydroxyphenyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, and 8-methyl-8- (4-hydroxyphenyl) tetracyclo [4.4.0.1 ^2,5 . And cycloaliphatic olefins having a hydroxyl group, such as ^{17, 10} ] dodec-3-ene, and the like. Among these, alicyclic olefins having a carboxyl group are preferred.

  Specific examples of aprotic polar groups include ester groups (collectively referring to alkoxycarbonyl groups and aryloxycarbonyl groups), N-substituted imide groups, epoxy groups, halogen atoms, cyano groups, carbonyloxycarbonyl groups (dicarboxylic acid). Acid anhydride residues), alkoxy groups, carbonyl groups, tertiary amino groups, sulfone groups, acryloyl groups, and the like. Of these, ester groups, N-substituted imide groups, cyano groups, halogen atoms and alkoxy groups are preferred, and ester groups and N-substituted imide groups are more preferred. In particular, an N-substituted imide group is preferable.

  Specific examples of the alicyclic olefin having an aprotic polar group include the following.

Examples of the alicyclic olefin having an ester group include 5-acetoxybicyclo [2.2.1] hept-2-ene, 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5- Ethoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-n-propoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-isopropoxycarbonylbicyclo [2.2.1] hept -2-ene, 5-n-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5- (2-methylbutoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5- (2-Ethylbutoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5-n-pentoxycarbonylbicyclo [2.2.1] hept-2-ene, 5- (2-methylpentoxy) Carbonyl) Bishi B [2.2.1] hept-2-ene, 5- (2-ethylpentoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5-n-hexylcarbonylbicyclo [2.2. 1] Hept-2-ene, 5- (2-methylhexylcarbonyl) bicyclo [2.2.1] hept-2-ene, 5- (2-ethylhexylcarbonyl) bicyclo [2.2.1] hept-2 -Ene, 5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-ethoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl -5-n-propoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-isopropoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5- n-butoxycarbonylbicyclo [2.2.1] hept- -Ene, 5-methyl-5- (2-methylbutoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5-methyl-5- (2-ethylbutoxycarbonyl) bicyclo [2.2.1] ] Hept-2-ene, 5-methyl-5-n-pentoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5- (2-methylpentoxycarbonyl) bicyclo [2. 2.1] Hept-2-ene, 5-methyl-5- (2-ethylpentoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5-methyl-5-n-hexylcarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-methyl-5- (2-methylhexylcarbonyl) bicyclo [2.2.1] hept-2-ene, 5-methyl-5- (2-ethylhexylcarbonyl) ) Bicyclo [2.2.1] hept-2-ene, 8-acetoxy Tetracyclo [4.4.0.1 ^2,5. 1 ^7,10 ] dodec-3-ene, 8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (2-methylbutoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (2-ethylbutoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-pentoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (2-methylpentoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (2-ethylpentoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-hexylcarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (2-methylhexylcarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (2-ethylhexylcarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (2-methylbutoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (2-ethylbutoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-n-pentoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (2-methylpentoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (2-ethylpentoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-n-hexylcarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (2-methylhexylcarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (2-ethylhexylcarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 5,6-dimethoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-diethoxycarbonylbicyclo [2.2.1] hept-2- Ene, 5,6-di-n-propoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-diisopropoxycarbonylbicyclo [2.2.1] hept-2-ene, 5, 6-di-n-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (2-methylbutoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5, 6-di (2-ethylbutoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di-n-pentoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-Di (2-methylpentoxycarbonyl) bicyclo [2.2.1] hept- 2-ene, 5-6-di (2-ethylpentoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5-6-di-n-hexylcarbonylbicyclo [2.2.1] hept -2-ene, 5,6-di (2-methylhexylcarbonyl) bicyclo [2.2
. 1] Hept-2-ene, 5,6-di (2-ethylhexylcarbonyl) bicyclo [2.2.1] hept-2-ene, 8,9-dimethoxycarbonyltetracyclo [4.4.0.1 ^{2 , 5} . 1 ^7,10 ] dodec-3-ene, 8,9-diethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-diisopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di (2-methylbutoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di (2-ethylbutoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di-n-pentoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di (2-methylpentoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di (2-ethylpentoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di-n-hexylcarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di (2-methylhexylcarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, and 8,9-di (2-ethylhexylcarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like.

  Examples of the alicyclic olefin having an N-substituted imide group include N- (4-phenyl)-(5-norbornene-2,3-dicarboximide).

Examples of the alicyclic olefin having a cyano group include 8-cyanotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-cyanotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 5-cyanobicyclo [2.2.1] hept-2-ene, and the like.

Examples of the alicyclic olefin having a halogen atom include 8-chlorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, and 8-methyl-8-chlorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like.

Examples of the alicyclic olefin having an alkoxy group include 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, and 5-n. -Propoxybicyclo [2.2.1] hept-2-ene, 5-isopropoxybicyclo [2.2.1] hept-2-ene, 5-n-butoxybicyclo [2.2.1] hept-2 -Ene, 5-n-pentoxybicyclo [2.2.1] hept-2-ene, 1,4-dihydro-5-methoxy-1,4-methanonaphthalene, 1,4-dihydro-6-methoxy- 1,4-methanonaphthalene, 1,4-dihydro-5-ethoxy-1,4-methanonaphthalene, 1,4-dihydro-5,8-dimethoxy-1,4-methanonaphthalene, 1,4-dihydro-5 , 8-Diethoxy-1,4-methanonaphthalene, 8-methoxytetra Black [4.4.0.1 ^2,5. 1 ^7,10 ] dodec-3-ene, 8-ethoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-propoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-isopropoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-butoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-pentoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5,6-di-n-propoxybicyclo [2.2.1] hept-2-ene, 5,6-diisopropoxybicyclo [2.2.1] hept-2-ene, 5,6-di- n-butoxybicyclo [2.2.1] hept-2-ene, 5,6-di-n-pentoxybicyclo [2.2.1] hept-2-ene, 8,9-dimethoxytetracyclo [4 .4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-diethoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di-n-propoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di-isopropoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di-n-butoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, and 8,9-di-n-pentoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like.

  These alicyclic olefins may be used alone or in admixture of two or more. Among the above alicyclic olefins, those having a norbornene skeleton are preferable from the viewpoint of obtaining a hydride having high heat resistance, low water permeability, and high transparency.

  In obtaining the hydride of the present invention, one or more non-alicyclic olefins may be used in combination. Specific examples thereof include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl- 1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1- Examples thereof include ethylene or α-olefin having 2 to 20 carbon atoms such as octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicocene. In addition, any monomer copolymerizable with an alicyclic olefin may be used in combination.

  The ring-opening metathesis polymerization catalyst used in the present invention comprises a complex formed by bonding a plurality of ions, atoms, polyatomic ions or compounds with a transition metal atom as a central atom. The bond such as the ion may be an ionic bond, a covalent bond, or a coordinate bond. Examples of the transition metal atom include atoms of Group 5, Group 6, and Group 8 of the periodic table. Of these, Group 8 ruthenium and osmium are preferable, and ruthenium is more preferable.

  Of the ring-opening metathesis polymerization catalysts in which the transition metal atom is ruthenium, a ruthenium-carbene catalyst is preferred. The ruthenium-carbene catalyst is stable against oxygen and moisture, hardly deactivates, and has excellent catalytic activity.

  The ruthenium-carbene catalyst is composed of a metal complex represented by the following formula (1) or (2).

In the formulas (1) and (2), R ¹ and R ² may each independently contain a hydrogen atom or a halogen atom; or a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. Represents a hydrocarbon group having 1 to 20 carbon atoms; X ¹ and X ² each independently represents an arbitrary anionic ligand. L ¹ and L ² each independently represents any neutral electron donating compound. R ¹ , R ² , X ¹ , X ² , L ¹ and L ² may be bonded together in any combination to form a multidentate chelating ligand.

  The anionic ligand is a ligand having a negative charge when separated from a central metal atom (ruthenium). Specific examples thereof include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, diketonate group, substituted cyclopentadienyl group, alkoxy group, aryloxy group, carboxyl group, acyloxy group, alkylsulfonyloxy group. And an arylsulfonyloxy group. Among these, as the anionic ligand, a halogen atom is preferable, and a chlorine atom is more preferable.

The neutral electron donating compound may be any ligand as long as it has a neutral charge when separated from the central metal atom. Specific examples thereof include carbene compounds, carbonyls, amines, ethers, nitriles, esters, phosphines, thioethers, aromatic compounds, olefins, isocyanides, and thiocyanates. Among these, carbene compounds, phosphines and pyridines are preferable as neutral electron donating compounds, carbene compounds and trialkylphosphines are more preferable, carbene compounds are further preferable, and heteroatom-containing carbene compounds are particularly preferable. It should be noted that at least one of L ¹ and L ² may be a carbene compound.

  The hetero atom in the hetero atom-containing carbene compound means, in particular, the atoms of Group 15 and Group 16 of the periodic table, and specifically includes nitrogen atom, oxygen atom, phosphorus atom, sulfur atom, arsenic atom, and selenium. An atom etc. are mentioned. Among these, from the viewpoint of obtaining a stable carbene compound, a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom are preferable, and a nitrogen atom is more preferable.

  As the heteroatom-containing carbene compound, a compound in which heteroatoms are adjacently bonded to both sides of the carbene carbon atom in the molecule is preferable, and a heterocycle including the carbene carbon atom and the heteroatoms on both sides thereof is formed. It is more preferable. The hetero atom adjacent to the carbene carbon atom is preferably a bulky atom, such as N, S, O, and P.

  Examples of the heteroatom-containing carbene compound include compounds represented by the following formula (3) or formula (4).

In formula (3) and (4), R < ³ > -R < ⁶ > represents a hydrogen atom, a halogen atom, or a C1-C20 hydrocarbon group each independently. The hydrocarbon group may have a carbon atom substituted with an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom, or may have a halogen atom or other substituent. R ^{3 to} R ⁶ may be bonded to each other in any combination to form a ring.

  Specific examples of the compounds represented by the above formulas (3) and (4) include 1,3-dimesitylimidazoline-2-ylidene, 1,3-dimesitylimidazolidine-2-ylidene, 1,3 -Di (1-adamantyl) imidazolidin-2-ylidene, 1-cyclohexyl-3-mesitylimidazolidin-2-ylidene, 4,5-dichloro-1,3-dimesitylimidazolidin-2-ylidene, 4 , 5-Dibromo-1,3-dimesitylimidazolidine-2-ylidene, 1,3-diisopropylimidazoline-2-ylidene, 1,3-di (1-phenylethyl) imidazoline-2-ylidene, 4,5 -Dichloro-1,3-dimesitylimidazoline-2-ylidene, 4,5-dibromo-1,3-dimesitylimidazoline-2-ylidene, 1,3-dimesityloctahydrobenzimidazole-2-ylidene And 1,3-dimesityl -2,3-dihydrobenzimidazole-2-ylidene and the like.

  As the heteroatom-containing carbene compound, in addition to the compounds represented by the formulas (3) and (4), 1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1, 2,4-triazole-5-ylidene, 1,3-dicyclohexylhexahydropyrimidine-2-ylidene, N, N, N ′, N′-tetraisopropylformamidinylidene, 1,3,4-triphenyl-4 , 5-dihydro-1H-1,2,4-triazole-5-ylidene, 3- (2,6-diisopropylphenyl) -2,3-dihydrothiazol-2-ylidene, and the like.

  Examples of the metal complex represented by the formula (1) include (4,5-dibromo-1,3-dimesitylimidazoline-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, (4,5- Dichloro-1,3-dimesitylimidazoline-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, (1,3-dimesitylimidazoline-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, (1, 3-Dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, (1,3-Dimesitylimidazolidine-2-ylidene) (3-Methyl-2-butene-1-ylidene) ( Tricyclopentylphosphine) ruthenium dichloride, benzylidene 1,3-Dimesityl-octahydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, [1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) benzylidene Ruthenium dichloride, (1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, (tricyclohexylphosphine) (1,3,4-triphenyl-2,3, 4,5-tetrahydro-1H-1,2,4-triazole-5-ylidene) benzylidene ruthenium dichloride, (1,3-diisopropylhexahydropyrimidine-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, And And ruthenium complexes in which a heteroatom-containing carbene compound and other neutral electron donating compound such as (1,3-dimesitylimidazolidine-2-ylidene) pyridinebenzylidene ruthenium dichloride are bonded; bis (1,3- Ruthenium complexes in which two heteroatom-containing carbene compounds such as dicyclohexylimidazolidine-2-ylidene) benzylidene ruthenium dichloride and bis (1,3-diisopropyl-4-imidazoline-2-ylidene) benzylidene ruthenium dichloride are bonded; Can be mentioned.

  Examples of the metal complex represented by the formula (2) include (1,3-dimesitylimidazolidine-2-ylidene) (phenylvinylidene) (tricyclohexylphosphine) ruthenium dichloride, (t-butylvinylidene) ( 1,3-diisopropyl-4-imidazoline-2-ylidene) (tricyclopentylphosphine) ruthenium dichloride, bis (1,3-dicyclohexyl-4-imidazoline-2-ylidene) phenylvinylidene ruthenium dichloride, and the like.

  The ruthenium-carbene catalyst as described above is described in, for example, Org. Lett. 1999, Vol. 1, p. 953, Tetrahedron. Lett. 1999, Vol. 40, page 2247, and the like.

  The amount of the ring-opening metathesis polymerization catalyst used in the present invention is not particularly limited and may be appropriately adjusted. For example, when the catalyst is a ruthenium-containing catalyst, a ruthenium atom in the catalyst: an alicyclic olefin The molar ratio is usually in the range of 1: 1,000 to 1: 1,000,000, preferably 1: 2,000 to 1: 500,000, more preferably 1: 3,000 to 1: 300,000. It is.

  The polymerization reaction of the alicyclic olefin is preferably performed in the presence of a non-conjugated polyene compound having two or more terminal vinyl groups from the viewpoint of reducing the low molecular weight product.

  Specific examples of the non-conjugated polyene compound having two or more terminal vinyl groups include compounds represented by the following general formula (5).

In Formula (5), R ⁷ and R ⁸ are each a vinyl group which may have a substituent; R ^{9 to} R ¹² are each a hydrogen atom or an alkyl group; X is a divalent organic group M and n are each 0 or a positive integer; However, when X is a group represented by C = Q (Q is an atom capable of forming a double bond with a carbon atom), m and n are positive integers.

  Specific examples of X in the general formula (5) include an alkylene group, a cycloalkylene group, an ether group [—O—], a vinylidene group (wherein Q is a carbon atom), a carbonyl group (wherein Q is an oxygen atom), thiocarbonyl Groups (Q is a sulfur atom), imino groups (where Q is a nitrogen atom), oxycarbonyl groups [—C (═O) —O—], and carbonate groups [—O—C (═O) —O— ] Etc. are mentioned. These groups may have a substituent.

  As the non-conjugated polyene compound having two or more terminal vinyl groups, those having a boiling point of 175 ° C. or less at normal pressure are preferable in consideration of purification and removal after polymerization.

  Specific examples of the non-conjugated polyene compound having two or more terminal vinyl groups include 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, and 1 Non-conjugated diene compounds such as 1,9-decadiene; alicyclic diallyl compounds such as 1,3-diallylcyclohexane and 1,3-diallylcyclopentane; allyl ketone compounds such as diallyl ketone;

  Among these, non-conjugated diene compounds are preferable, and aliphatic non-conjugated diene compounds are more preferable. As the aliphatic non-conjugated diene compound, 1,5-hexadiene is more preferable.

  The amount of the non-conjugated polyene compound having two or more terminal vinyl groups is usually 0.1 to 20 mol, preferably 0.5 to 15 mol, based on 100 mol of the alicyclic olefin used in the polymerization reaction. Preferably it is 1-10 mol.

  The ring-opening metathesis polymerization of the alicyclic olefin is performed in a solution obtained by dissolving the above-described components in a solvent in addition to the alicyclic olefin. The solvent is not particularly limited as long as such a solution can be prepared. The hydride of the present invention can be used, for example, for the preparation of a radiation sensitive resin composition as will be described later. However, a radiation sensitive compound (ultraviolet ray or electron beam) is added to the polymer solution without separating the hydride from the polymer solution. If a radiation-sensitive resin composition can be prepared by directly adding a compound capable of absorbing radiation and causing a chemical reaction, etc., environmental pollution caused by solvent removal from the polymer solution can be suppressed. Since the steps of isolation, drying and re-dissolution in a solvent can be omitted, the productivity of the radiation sensitive resin composition can be improved. From this point of view, it is preferable to use the same solvent as the solvent for the polymerization reaction that is used for the radiation-sensitive resin composition.

  Specific examples of such solvents include monoalkylene glycol solvents; polyalkylene glycol solvents; monoalkylene glycol alkyl ester solvents; polyalkylene glycol alkyl ester solvents; monoalkylene glycol diester solvents; and polyalkylene glycol diester solvents. Is mentioned. A solvent can be used individually or in mixture of 2 or more types, respectively.

  Examples of monoalkylene glycol solvents include ethylene glycol and monoalkylene glycols such as propylene glycol; monoalkylene glycol monoethers such as ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether Monoalkylene glycol dialkyl ethers such as ethylene glycol diethyl ether and propylene glycol dimethyl ether;

  Examples of polyalkylene glycol solvents include polyalkylene glycols such as diethylene glycol, triethylene glycol, and tetraethylene glycol; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol Polyalkylene glycol monoalkyl ethers such as monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, dipropylene group Polyalkylene glycol dialkyl ethers such as coal dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, and tripropylene glycol ethyl methyl ether; Is mentioned.

  Specific examples of monoalkylene glycol alkyl ester solvents include propylene glycol monoethyl ether acetate, propylene glycol mono n-propyl ether acetate, propylene glycol mono n-butyl ether acetate, propylene glycol mono sec-butyl ether acetate, and propylene glycol mono t- Examples include butyl ether acetate.

  Specific examples of the polyalkylene glycol alkyl ester solvent include diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and dipropylene glycol monomethyl ether acetate.

  Specific examples of the monoalkylene glycol diester solvent include ethylene glycol diacetate and propylene glycol diacetate.

  Specific examples of the polyalkylene glycol diester solvent include diethylene glycol diacetate, dipropylene glycol diacetate, and triethylene glycol diacetate.

  In addition to these, high-boiling ketone solvents such as 2-heptanone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone; high-boiling alcohol solvents such as 3-methoxy-3-methylbutanol and 3-methoxybutanol; Such as ethyl lactate, n-propyl lactate, isopropyl lactate, 3-methoxybutyl acetate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, ethyl 3-ethoxypropionate, and γ-butyllactone Examples include high-boiling ester solvents; amide solvents such as N-methylformamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-methylacetamide, and N, N-dimethylacetamide; dimethyl sulfoxide;

  The solvent is preferably a polar solvent having a boiling point of 100 ° C. or higher, more preferably a polar solvent having a boiling point of 100 to 250 ° C., and a boiling point of 150 to 250 ° C. from the viewpoint of preventing bumping during the polymerization reaction. Polar solvents are more preferred. Preferable specific examples of such a solvent include polyalkylene glycol solvents, monoalkylene glycol alkyl ester solvents, and polyalkylene glycol alkyl ester solvents having the above boiling points.

  In the present invention, the polymerization conditions are not particularly limited for ring-opening metathesis polymerization of alicyclic olefins. The polymerization temperature is usually −50 to + 150 ° C., preferably 0 to 100 ° C. The polymerization time may be appropriately determined according to the polymerization temperature, the amount of catalyst used, etc., but is usually 1 minute to 24 hours. The polymerization reaction may be completed depending on a given purpose, but the polymerization reaction is usually completed when the polymerization conversion rate is preferably 90% by weight or more, more preferably 99% by weight or more. The polymerization conversion can be determined by measuring the residual monomer by gas chromatography. The polymerization atmosphere is not particularly limited, and when the ring-opening metathesis polymerization catalyst is stable, the polymerization reaction may be performed in air or the like, but it is performed under an inert gas atmosphere such as nitrogen gas, carbon dioxide gas, or rare gas. Is preferred.

  By the above operation, a polymer solution I containing a ring-opening metathesis polymer is obtained. The concentration (solid content concentration) of the ring-opening metathesis polymer in the polymer solution I is usually preferably about 5 to 40% by weight in consideration of the ease of subsequent operations.

  The weight average molecular weight (Mw) of the ring-opening metathesis polymer is usually in the range of 1,000 to 1,000,000, preferably 1,500 to 100,000, more preferably 2,000 to 50,000. . Further, the molecular weight distribution of the ring-opening metathesis polymer is usually 4 or less, preferably 3 or less, more preferably 2.5 or less, as a weight average molecular weight / number average molecular weight (Mw / Mn) ratio. Further, for example, from the viewpoint of ensuring good patternability and developability when used in a radiation sensitive resin composition, the weight average molecular weight is 2,000 to 10,000, and the number average molecular weight is 1,000. The content of the following oligomer component (hereinafter simply referred to as oligomer component) is preferably 2% by weight or less. In addition, the Mw, Mw / Mn ratio of the hydride of the ring-opening metathesis polymer contained in the polymer solution II after the step (II), and the content of the oligomer component are also as described above for the ring-opening metathesis polymer. It is preferable to be in the same range.

  The weight average molecular weight and the number average molecular weight can be measured by gel permeation chromatography using polystyrene as a standard sample and tetrahydrofuran as an eluent. The content of the oligomer component can be calculated from a peak area ratio measured by gel permeation chromatography-low angle laser light scattering light intensity (GPC-LALLS) method.

  In addition, the ring-opening metathesis polymer has a polar group from the viewpoint of improving the adhesion to the substrate when used in a radiation-sensitive resin composition and from the viewpoint of increasing the compatibility with other substances. Is preferred. The abundance ratio of the polar group in the polymer is not particularly limited and may be appropriately selected depending on the purpose. The polar group is usually in the total number of moles of the constituent monomer units of the polymer. , 30 to 100 mol%, preferably 50 to 100 mol%, more preferably 70 to 100 mol%. There is no particular limitation on the type or number of polar groups present in each constituent monomer unit. Examples of the polar group include the protic polar group and the aprotic polar group, and the preferred embodiments thereof are also the same.

  The ring-opening metathesis polymer may contain monomer units other than the alicyclic olefin, but in that case, the proportion of the structural unit derived from the alicyclic olefin is high heat resistance, low water permeability, and high transparency. From the viewpoint of obtaining a functional hydride, it is usually 30 to 100% by weight, preferably 50 to 100% by weight, more preferably 70 to 100% by weight.

  When the ring-opening metathesis polymer is an addition polymer of an alicyclic olefin and another monomer, the polar group may be bonded to the alicyclic olefin unit and / or other monomer unit, It is preferably bonded to an alicyclic olefin unit.

  In step (II), a hydrogenation reaction of the ring-opening metathesis polymer is performed in the polymer solution I obtained in step (I). Although a hydrogenation catalyst is used in the hydrogenation reaction, such a catalyst is a solution that performs a polymerization reaction together with a ring-opening metathesis polymerization catalyst at the start of the polymerization reaction even when added to the polymer solution I after the completion of the polymerization reaction. May be added to the catalyst, and may be appropriately selected according to the properties of the hydrogenation catalyst to be used. In the present invention, as will be described later, the hydrogenation reaction can be carried out using the ring-opening metathesis polymerization catalyst used in the polymerization reaction.

  As the hydrogenation catalyst, for example, those generally used for hydrogenation of olefin compounds can be used. Specifically, a Ziegler type homogeneous catalyst, a noble metal complex catalyst, a supported noble metal-containing catalyst, and the like can be used. Among these hydrogenation catalysts, side reactions such as modification of functional groups such as protic polar groups do not occur, and carbon-carbon unsaturated bonds in the polymer can be selectively hydrogenated, so rhodium, ruthenium, etc. And a ruthenium catalyst coordinated with a nitrogen-containing heterocyclic carbene compound or phosphine having a high electron donating property is more preferable.

  On the other hand, for example, when a ruthenium-containing catalyst is used as a ring-opening metathesis polymerization catalyst, the ruthenium-containing catalyst is used as it is by setting the reaction conditions to conditions suitable for the hydrogenation reaction when the polymerization reaction is completed. The hydrogenation reaction can be performed without adding a hydrogenation catalyst to the polymer solution I. In addition, when implementing a hydrogenation reaction by this aspect, it is arbitrary to add the catalyst similar to the ruthenium containing catalyst used as a ring-opening metathesis polymerization catalyst, and other well-known hydrogenation catalysts.

  The conditions for carrying out the hydrogenation reaction may be any known conditions and are not particularly limited. The conditions for the hydrogenation reaction are usually a temperature in the range of −20 to + 250 ° C., preferably 0 to 200 ° C., and a hydrogen pressure in the range of usually 0.1 to 30 MPa, preferably 1 to 25 MPa. As hydrogen, molecular hydrogen is usually used.

The hydrogenation reaction may be completed depending on a given purpose, but may be performed until the hydrogenation rate of the ring-opening metathesis polymer is preferably 95% or more, more preferably 99% or more. The hydrogenation rate can be measured by a ¹ H-NMR method according to a conventional method.

  In step (III), the polymer solution II after step (II) is heated to a temperature higher than the reaction temperature during the polymerization reaction and during the hydrogenation reaction, and the metal component dissolved in the polymer solution II To precipitate.

  Here, “heating the polymer solution II after step (II) to a temperature higher than the reaction temperature during the polymerization reaction and the hydrogenation reaction” means that the temperature of the polymer solution II is changed during the polymerization reaction. It means that the temperature is increased to a temperature exceeding the average temperature and the average temperature during the hydrogenation reaction.

  The conditions for carrying out the step (III) are not particularly limited, and the properties of the metal-containing catalyst used in the polymerization reaction and the hydrogenation reaction, which occupies most of the metal components dissolved in the polymer solution II. However, when a generally available ring-opening metathesis catalyst and hydrogenation catalyst are used, for example, a polymerization reaction is performed at 60 to 100 ° C., followed by a hydrogenation reaction at 120 to 150 ° C. It is preferable that the temperature of the polymer solution II is raised to 170 ° C. or higher so that it usually exceeds 150 ° C. The temperature raising condition is not particularly limited, and the temperature may be raised linearly or stepwise, but usually the temperature should be raised linearly. Note that the upper limit of the temperature to be raised is about 300 ° C. in view of the quality of the hydride of the present invention.

  Although the time for depositing the metal component is not particularly limited, it is usually 30 minutes or more, preferably 60 minutes or more after the start of temperature increase. The temperature during the deposition of the metal component does not need to be constant.

  Although the influence of the pressure when depositing the metal component is unknown, it is usually about 0.1 to 30 MPa, preferably about 1 to 25 MPa.

  For example, the precipitation of the metal component from the polymer solution II in the step (III) is performed by putting the polymer solution II in an autoclave, dissolving hydrogen at a pressure of 1 to 25 MPa, raising the temperature to a predetermined temperature, It is preferable to carry out by heating and pressurizing the polymer solution II over the period of time. At that time, it is also preferable to stir the polymer solution II.

  Since the metal component is precipitated from the polymer solution II in the step (III), the hydride of the ring-opening metathesis polymer can be obtained in the form of a solution by removing the precipitate by any method. The method for removing the precipitate is not particularly limited, but it is usually selected from the group consisting of filtration, static separation and centrifugation because it is easy to operate and can minimize contamination. It is preferred to remove the precipitate by at least one method.

  When performing filtration, various known filter media such as filter paper, nonwoven fabric, metal mesh, sintered metal, perforated plate, porous ceramic, and filter can be used. The mesh of the filter medium is not particularly limited as long as the metal component precipitates can be removed. Usually, a mesh of about 0.02 to 0.5 μm is preferably used. Filtration of the polymer solution II containing the precipitate may be usually performed at room temperature under normal pressure or reduced pressure. By filtration, the precipitate is separated from the liquid portion in which the hydride is dissolved, and the precipitate is removed.

  When removing the precipitate by centrifugation, for example, the polymer solution II containing the precipitate is subjected to centrifugation at 1000 × g for about 10 to 120 minutes at room temperature, and the precipitate and ring-opening metathesis are removed. The precipitate may be removed separately from the liquid portion in which the polymer is dissolved. In the case where the separation is performed by standing separation, the polymer solution II containing the precipitate is allowed to stand at room temperature for about 24 hours, and then, by decantation, the precipitate and the liquid portion in which the ring-opening metathesis polymer is dissolved. The precipitate may be removed separately. These conditions are examples, and the conditions for removing the precipitates may be appropriately set according to the composition of the polymer solution II.

  In the case where mixing of the effluent from the metal remover into the hydride is not particularly problematic, for example, when depositing the metal component, a known metal remover is present in the polymer solution II, or the metal component is removed. The polymer solution II after precipitation and / or after removal of the metal component deposits may be further purified by contacting with a metal remover.

  By the above operation, a desired hydride is obtained. Such a hydride can be suitably used as a resin component of a so-called radiation-sensitive resin composition. The radiation-sensitive resin composition typically contains a resin component, an acid generator, a crosslinking agent, and a solvent, and is described in, for example, JP-A-2004-212450. Such a composition includes an element such as a display display element and an integrated circuit element, a protective film such as a color filter for a liquid crystal display, a planarizing film for planarizing the element surface and wiring, and an insulating film for maintaining electrical insulation. It is suitable as a material for various resin pattern films for electronic parts such as thin-film transistor liquid crystal display elements and interlayer insulating films that are electric insulating films of integrated circuit elements, solder resist films, and the like.

  As described above, in the method for producing a hydride of the present invention, a polymer solution I is obtained, then a hydrogenation reaction is performed, and the resulting polymer solution II is heated to a predetermined temperature to precipitate a metal component. The desired hydride can be obtained by removing it. Therefore, as one aspect of the present invention, the monomer polymerization reaction was further performed in the monomer solution using the polymerization catalyst, and the polymer hydrogenation reaction was further performed in the resulting polymer solution I. From the later polymer solution II, the polymer solution II is heated to a temperature higher than the reaction temperature during the polymerization reaction and the hydrogenation reaction, and the metal components dissolved in the polymer solution II are precipitated and removed. A method for removing a metal component from a polymer solution can be provided. Such a method for removing a metal component can be carried out according to the method for producing a ring-opening metathesis polymer of the present invention, but is not limited to the above-described embodiment described for the production method.

  Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. Parts and% are based on weight unless otherwise specified. Moreover, the test and evaluation were based on the following methods.

(1) Polymerization conversion rate The polymerization conversion rate was determined by measuring unreacted monomers after the polymerization reaction using a Shimadzu gas chromatography device “GC-17A” with tetrahydrofuran as the diluent solvent and n-decane as the standard solution. The weight was calculated.

(2) Weight average molecular weight, number average molecular weight and hydrogenation rate The weight average molecular weight and number average molecular weight of a polymer or a hydride of a polymer are determined using a high-speed gel permeation chromatography apparatus “HLC-8220GPC” manufactured by Tosoh Corporation. Tetrahydrofuran was used as an eluent and measured in terms of polystyrene. The hydrogenation rate of the polymer hydride was measured by ¹ H-NMR using a nuclear magnetic resonance spectrometer “JNM-ECA500” manufactured by JEOL Ltd.

(3) Content of oligomer component The content of the oligomer component in the polymer or the hydride of the polymer is a high speed manufactured by Tosoh Corporation according to gel permeation chromatography-low angle laser light scattering light intensity (GPC-LALLS) method. Using a liquid chromatograph “LS-8000”, calculation was performed from the peak area ratio of the polymer or polymer hydride measured using tetrahydrofuran as an eluent.

(4) Metal content The metal content in the polymer hydride is measured by decomposing the hydride using sulfuric acid and nitric acid, mixing with ultrapure water, dissolving the metal in the water, and extracting. A sample was prepared, and the sample was measured by a calibration curve method using an ICP emission spectroscopic analyzer (manufactured by PerkinElmer, trade name “Optima 2000 DV”).

(5) Detection of eluate derived from metal remover in hydride The polymer solution after removal of metal was filtered with a fluororesin filter having a pore size of 0.2 μm, and 300 nm with a UV-visible spectrophotometer manufactured by JASCO Corporation. The absorbance at the wavelength was measured.

[Example 1]
8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene 60 parts, N- (4-phenyl)-(5-norbornene-2,3-dicarboximide) 40 parts, 1,5-hexadiene 2.8 parts, (1, 3-dimesitylimidazolidin-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride 0.05 part and diethylene glycol ethyl methyl ether (boiling point: 176 ° C.) 400 parts were charged into a nitrogen-substituted pressure-resistant glass reactor and stirred. A polymer solution (solid content concentration 20%) containing a ring-opening metathesis polymer A1 was obtained by performing a polymerization reaction at 80 ° C. for 2 hours. The polymerization conversion rate was 99.9% or more. This polymer A1 has a weight average molecular weight (Mw) of 3,200, a number average molecular weight (Mn) of 1,900, a molecular weight distribution (Mw / Mn) of 1.68, and an oligomer component content of 1.35%. there were.

  Next, the polymer solution containing the ring-opening metathesis polymer A1 is put in an autoclave, hydrogen is dissolved at 150 ° C. at a pressure of 4 MPa for 5 hours to advance the hydrogenation reaction, and hydrogen of the ring-opening metathesis polymer A1 is obtained. Compound A2 was obtained. Obtained hydride A2 had Mw of 4,430, Mn of 2,570, Mw / Mn of 1.72, and an oligomer component content of 0.91%. The hydrogenation rate was 99.9%.

  Furthermore, the polymer solution containing this hydride A2 is put in an autoclave, heated to 190 ° C., and hydrogen is dissolved at a pressure of 3.5 MPa for 3 hours with stirring to dissolve the metal component in the polymer solution. Was precipitated. Subsequently, the polymer solution was taken out and filtered through a fluororesin filter having a pore diameter of 0.2 μm, and the metal component thus deposited was removed to obtain a metal-removed hydride A3. The yield of hydride A3 was 98.3 parts. There was no change in the content of Mw, Mn, Mw / Mn, and oligomer component of the hydride A3.

  In Table 1, “Metal content in hydride” is the metal content in hydride A3, and “Eluate from metal remover” is the presence or absence of effluent from metal remover in hydride A3. The evaluation results are shown below (the same applies hereinafter).

[Example 2]
A polymer solution containing the ring-opening metathesis polymer B1 was obtained in the same manner as in Example 1 except that 4.8 parts of 1,9-decadiene was used instead of 1,5-hexadiene. The polymerization conversion rate was 99.9% or more. Mw of this polymer B1 was 3,450, Mn was 2,000, Mw / Mn was 1.73, and the content of the oligomer component was 1.15%.

  This polymer B1 was hydrogenated in the same manner as in Example 1 to obtain a hydride B2 of the polymer B1. Mw of the obtained hydride B2 was 4,760, Mn was 2,700, Mw / Mn was 1.76, and the content of the oligomer component was 0.78%. The hydrogenation rate was 99.9%.

  Further, for the polymer solution containing the hydride B2, the metal component was deposited in the same manner as in Example 1 to obtain a hydride B3 from which the metal was removed. The yield of hydride B3 was 93.4 parts. There was no change in the contents of Mw, Mn, Mw / Mn, and oligomer component of hydride B3. Table 1 shows the results.

[Example 3]
A polymer solution containing the ring-opening metathesis polymer C1 was obtained in the same manner as in Example 1 except that 2.6 parts of 1-hexene was used instead of 1,5-hexadiene. The polymerization conversion rate was 99.9% or more. Mw of this polymer C1 was 3,920, Mn was 2,120, Mw / Mn was 1.85, and the content of the oligomer component was 1.38%.

  This polymer C1 was hydrogenated in the same manner as in Example 1 to obtain a hydride C2 of the ring-opening metathesis polymer C1. Mw of the obtained hydride C2 was 5,460, Mn was 2,700, Mw / Mn was 2.02, and the content of the oligomer component was 1.08%. The hydrogenation rate was 99.9%.

  Further, the polymer solution containing the hydride C2 was subjected to precipitation of metal components in the same manner as in Example 1 to obtain a metal-removed hydride C3. The yield of hydride C3 was 95.7 parts. There was no change in the contents of Mw, Mn, Mw / Mn, and oligomer component of hydride C3. Table 1 shows the results.

[Example 4]
Instead of N- (4-phenyl)-(5-norbornene-2,3-dicarboximide), 8-methyl-tetracyclo [4.4.0.1 ^2,5 . A polymer solution containing the ring-opening metathesis polymer D1 was obtained in the same manner as in Example 1 ^{except that} 1 ^7,10 ] dodec-3-ene was used. The polymerization conversion rate was 99.9% or more. Mw of this polymer D1 was 3,000, Mn was 1,700, Mw / Mn was 1.70, and the content of the oligomer component was 1.55%.

  The polymer D1 was hydrogenated in the same manner as in Example 1 to obtain a hydride D2 of the ring-opening metathesis polymer D1. Mw of the obtained hydride D2 was 4,360, Mn was 2,500, Mw / Mn was 1.75, and the content of the oligomer component was 0.95%. The hydrogenation rate was 99.9%.

  Further, the polymer solution containing hydride D2 was subjected to precipitation of metal components in the same manner as in Example 1 to obtain hydride D3 from which metal was removed. The yield of hydride D3 was 98.6 parts. There was no change in the content of Mw, Mn, Mw / Mn, and oligomer component of the hydride D3. Table 1 shows the results.

[Comparative Example 1]
Hydride A2 was obtained in the same manner as in Example 1. In addition, precipitation of a metal component was not performed about the polymer solution containing hydride A2. On the other hand, using this polymer solution, the detection operation of the eluate derived from the metal remover in the hydride A2 was performed. Table 1 shows the results.

[Comparative Example 2]
Hydride A2 was obtained in the same manner as in Example 1. 5 parts of activated carbon as a metal remover is added to the polymer solution of hydride A2 and maintained at room temperature with stirring for 3 hours. The polymer solution is then filtered through a fluororesin filter having a pore size of 0.2 μm, and activated carbon At the same time, the metal component was removed to obtain hydride A2 ′ from which metal was removed. The yield of hydride A2 ′ was 98.1 parts. The contents of Mw, Mn, Mw / Mn, and oligomer components of the hydride A2 ′ were the same as those of the hydride A2. Table 1 shows the results.

[Comparative Example 3]
Hydride A2 was obtained in the same manner as in Example 1. Next, the polymer solution containing hydride A2 is circulated at SV = 1 for 6 hours through a column having an inner diameter of 20 mm and packed with 70 g of an ion exchange resin as a metal remover to remove the metal from the polymer solution. And metal-removed hydride A2 ″ was obtained. The yield of hydride A2 '' was 95.3 parts. The contents of Mw, Mn, Mw / Mn, and oligomer components of the hydride A2 ″ were the same as those of the hydride A2. Table 1 shows the results.

From Table 1, according to Examples 1 to 4, the metal component is precipitated and efficiently removed from the polymer solution without using a metal remover, and the metal content is reduced to a sufficient level. It turns out that the hydride of a polymer without the mixing of the effluent from a metal removal agent is obtained. On the other hand, in Comparative Example 1 where metal removal was not performed, the metal content in the hydride was high, and in Comparative Examples 2 and 3 where metal removal was performed using a metal remover, the metal content in the hydride was low. It can be seen that contamination of the eluate from the metal remover occurs.

Claims (9)

A step (I) of obtaining a polymer solution I containing an alicyclic olefin ring-opening metathesis polymer by polymerizing an alicyclic olefin using a ring-opening metathesis polymerization catalyst in the solution;
A step (II) of performing a hydrogenation reaction of an alicyclic olefin ring-opening metathesis polymer in the polymer solution I obtained in the step (I), and a polymer solution II after the step (II) are polymerized. (III), the temperature is raised to a temperature higher than the reaction temperature at the time of the hydrogenation reaction, and the metal component dissolved in the polymer solution II is precipitated.
A process for producing a hydride of an alicyclic olefin ring-opening metathesis polymer.   The process according to claim 1, wherein the ring-opening metathesis polymerization catalyst contains ruthenium.   The process according to claim 2, wherein the ring-opening metathesis polymerization catalyst is a ruthenium-carbene catalyst.   The production method according to claim 2 or 3, wherein the hydrogenation reaction is carried out using a ring-opening metathesis polymerization catalyst.   The manufacturing method according to any one of claims 1 to 4, wherein the solvent of the solution for performing the polymerization reaction is a polar solvent having a boiling point of 100 to 250 ° C.   The production method according to any one of claims 1 to 5, wherein the polymerization reaction is performed in the presence of a non-conjugated polyene compound having two or more terminal vinyl groups.   The production method according to claim 1, wherein the alicyclic olefin ring-opening metathesis polymer has a polar group.   The production method according to claim 7, wherein the polar group is a carboxyl group. Polymerization reaction of the monomer is performed in the solution using a polymerization catalyst, and the polymer solution II is polymerized from the polymer solution II after further performing the hydrogenation reaction of the polymer in the obtained polymer solution I. A method for removing a metal component from a polymer solution, wherein the temperature is raised to a temperature higher than the reaction temperature during the reaction and the hydrogenation reaction, and the metal component dissolved in the polymer solution II is precipitated and removed.