WO2001032739A1

WO2001032739A1 - Process for producing cycloolefin polymer

Info

Publication number: WO2001032739A1
Application number: PCT/JP2000/007620
Authority: WO
Inventors: Tomoo Sugawara
Original assignee: Zeon Corporation
Priority date: 1999-11-01
Filing date: 2000-10-30
Publication date: 2001-05-10

Abstract

A process for producing a cycloolefin polymer which comprises mixing a starting liquid reaction mixture comprising a cycloolefin with a catalyst comprising a complex comprising ruthenium and, coordinated thereto as a ligand, at least one member selected among neutral electron donors and heteroatom-containing carbene compounds and polymerizing the cycloolefin by ring-opening metathesis polymerization, characterized in that the starting liquid reaction mixture is prepared in an inert gas atmosphere. The ring-opening metathesis polymerization is conducted by bulk polymerization or solution polymerization. According to need, a Lewis acid is incorporated in the starting liquid reaction mixture comprising a cycloolefin, and a Lewis base is used in combination with the catalyst. By the process, a polymer which need not be postcured after polymerization can be obtained at a high conversion.

Description

Description Method for producing cyclic olefin polymer

The present invention relates to a method for producing a ring-opened polymer of cyclic olefin using a ruthenium complex as a catalyst. More specifically, an improvement in the method of producing a ring-opened polymer of a cyclic olefin using a ruthenium complex as a catalyst, which produces a polymer that does not require post-curing treatment (post-curing) after polymerization and provides a high reaction rate. About. Background art

Conventionally, various ruthenium complexes have been known as catalysts for ring-opening polymerization of cyclic olefins. For example, Japanese Patent Application Laid-Open No. 10-508991 describes a complex compound in which a tertiary phosphine ligand or the like is bonded to at least one divalent cationic compound of ruthenium or osmium. ing.

In addition, Japanese Patent Publication No. 9-5122828 discloses a carbene complex compound of ruthenium or osmium metal having various ligands, which is used as a catalyst for bulk polymerization of dicyclopentene. Experimental examples are described.

The catalysts described in these publications have an advantage in that the polymerization of cyclic olefins is relatively insensitive to deactivated substances such as water and air. However, when applied to bulk polymerization, there is a drawback in that polymerization is performed using a system with a slow reaction rate in order to increase the reaction rate, and furthermore, it is necessary to use a post-polymer of the resulting polymer. I have.

For example, according to the experimental example of Japanese Patent Application Laid-Open No. 91-12828, the reaction solution containing the catalyst is reacted at about 65 for 1 hour, and further reacted in an oven at 130 ° C. for 3 hours. The reaction yield after the reaction is stated to be 86%.

The need to employ a reaction system with a slow reaction rate in order to increase the reaction rate, and the necessity of a single post-curing process are major problems in the production of molded products on an industrial scale. I have. Disclosure of the invention

In view of the above-mentioned problems of the prior art, an object of the present invention is to provide a polymer in which ring-opening polymerization of cyclic olefins using a ruthenium complex as a polymerization catalyst does not require a bostokine and has a high reaction rate. It is another object of the present invention to provide a method for producing a ring-opened polymer.

The present inventors have conducted intensive studies on the conditions for bulk polymerization of cyclic olefins using a ruthenium complex. As a result, in a special situation where the temperature rise occurs rapidly in a short time due to the heat of polymerization reaction, oxygen (air ) The catalyst deactivates and degrades in the presence of, and the catalyst deactivation at high temperatures is suppressed by reacting in an inert gas atmosphere. At the same time, a high reaction rate is achieved by self-heating due to self-heating. It has been found that post-curing of the produced polymer becomes unnecessary.

Furthermore, in the bulk polymerization in the voids in the mold, even if the voids are not replaced with an inert gas such as nitrogen, a polymer that does not require a post-curing agent can be prepared simply by preparing the reaction stock solution in an inert gas atmosphere. And found that the present invention was completed.

Thus, according to the present invention, a catalyst comprising at least one complex selected from a neutral electron donor and a heteroatom-containing carbene compound coordinated to ruthenium as a ligand can be used as a cyclic olefin. A method for producing a cyclic olefin polymer, comprising mixing the cyclic olefin with a reaction mixture containing the mixture and subjecting the cyclic olefin to ring-opening polymerization, wherein the reaction mixture is prepared under an inert gas atmosphere. .

The ring-opening polymerization may be either bulk polymerization or solution polymerization. However, it is preferable to use bulk polymerization in which the undiluted solution is poured into a mold and cured, and the maximum temperature of the polymer in the bulk polymerization is preferably 140 ° C. or higher. BEST MODE FOR CARRYING OUT THE INVENTION

Ruthenium complex catalyst

The catalyst for ring-opening polymerization of cyclic olefins used in the present invention is a neutral electron donor and At least one selected from terrorist atom-containing carbene compounds is a complex in which ruthenium is coordinated as a ligand. As the ruthenium complex, usually, a ruthenium complex represented by the following general formulas [1] to [3] is used.

((X,) _m (L,) _n R u) _z [1]

(Wherein each independently represents an anionic ligand, and 1 ^ independently represents at least one selected from a neutral electron donor and a heteroatom-containing carbene compound. And two, three or four of the following may combine with each other to form a polydentate chelating ligand: m is an integer from 0 to 2 and n is an integer from 1 to 3 Z is 1 or 2.

(Wherein, and R ₂ may independently include hydrogen or at least one atom selected from a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom. X ₂ and X ₃ each independently represent any anionic ligand L ₂ and L ₃ each independently represent any neutral electron donor and hetero atom-containing ligand At least one selected from carbene compounds: 2, 3, 4, or 5 of R ₂ , X ₂ , X ₃ , L ₂ and L ₃ are bonded to each other to form a polydentate compound. To form a ligand.

(Wherein, R ₃ and R ₄ may each independently include hydrogen or at least one atom selected from a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom and a silicon atom C

. And X ₄ and X ₅ each independently represent an anionic ligand. L ₄ and L ₅ independently represent at least one kind selected from arbitrary neutral donors and heteroatom-containing carbene compounds. Show. Two, three, four or five of R ₃ , R ₄ , X ₄ , X ₅ , L ₄ , and L ₅ may combine with each other to form a multidentate chelating ligand. )

The “carbene compound” is a general term for compounds having a methylene free radical, and refers to a compound having an uncharged divalent carbon atom represented by OC :). The carbene is generally present as an unstable intermediate generated during the reaction, but it can be isolated as a relatively stable carbene compound if it has a heteroatom. These are the atoms of Groups 15 and 16 of the Table, and specifically include nitrogen, oxygen, phosphorus, sulfur, arsenic, and selenium atoms. Among them, a nitrogen atom, an oxygen atom, a phosphorus atom and a sulfur atom are preferable for obtaining a stable carbene compound, and a nitrogen atom and a phosphorus atom are particularly preferable.

Specific examples of the carbene compound containing a hetero atom include 1,3-diisopropyl-14-imidazoline_2-ylidene, 1,3-dicyclohexyl-4-imidazoline-2-ylidene, and 1,3-di (methylphenyl) -4. —Imidazoline- 1- 2-ylidene, 1,3-Di (methylnaphthyl) — 4-—Imidazoline— 2-—Ilidene, 1,

3—Dimesityl-4 _Imidazoline— 2-Ilidene, 1,3-Diadamantyl—

4-imidazoline—2-ylidene, 1,3-diphenyl 4-imidazoline-one-one-ylidene, 1,3,4,5-tetramethyl—4-imidazoline-one-two-ylidene, 1,3,4,5- Tetraphenyl-2-imidazoline-2-ylidene, 1,3-diisopropylimidazolidin-2_ylidene, 1,3-dicyclohexylimidamidazolidine 1-2_ylidene, 1,3-di (methylphenyl) imidazolidine-2-1-ylidene , 1,3-di (methylnaphthyl) imidazolidine—2-ylidene, 1,3-dimesitylimidazolidine-1-ylidene, 1,3-diadamantyl imidazolidine 1-2_ylidene, 1,3 —Diphenylimidazolidin — 2-ylidene, 1,3,4,5-tetramethylimidazolidine—2-ylidene, 1,3-dicyclohexylhexahexahydropyrimidine —2-ylidene, N, N N ', N'-tetraisopropylformamidinylidene, 1,3,4-triphenyl-4,5-dihydro-1H_1,2,4-triazol-5-ylidene, 3_ (2,6 —Diisopropylpropyl) _ 2,3-dihydrothiazole—2-ylidene Can be

Among these, those in which the hetero atom adjacent to the carbene has a bulky substituent are preferable, and specifically, 1,3-diisopropyl-14-imidazoline-2-ylidene, 1,3-dicyclohexyl- 4 —Imidazoline— 2 —Ilidene, 1,3-di (methylphenyl) — 4 —Imidazoline-1- 2 —Ilidene, 1,3-Di (methylnaphthyl) -14 —Imidazoline — 2 —Ylidene, 1,3-dimesityl— 4 1-imidazoline—2—ylidene, 1,3—diadamantyl—4—imidazoline—2—ylidene, 1,3—diphenyl—4_imidazoline 1-2—ylidene, 1,3,4,5-tetramethyl— 4-Imidazoline- 1 2 _ylidene, 1,3,4,5-tetraphenyl- 4 -imidazoline-2 -ylidene, 1,3-diisopropylimidazolidin- 1 -2-ylidene, 1,3-disi Rohexylimidazolidine-1_2-ylidene, 1,3-di (methylphenyl) imidazolidine-2_ylidene, 1,3-di (methylnaphthyl) imidazolidine-2'-ylidene, 1,3-dimesitylimidazolidine-1 ' _Ilidene, 1,3-Diadamantylimidazolidine—2—Ilidene, 1,3-Diphenylimidazolidine—2 _Ylidene, 1,3,4,5—Tetramethylimidazolidine-1-2-Ylidene And the like.

The anionic ligand in the formulas [1] to [3] may be any ligand as long as it has a negative charge when separated from the central metal. The neutral electron-donating compound can be any ligand that has a neutral charge when separated from the central metal, ie, a Lewis base.

Specific examples of XX ₂ , X ₃ , X ₄ and X ₅ include halogen atoms such as F, Br, C 1 and I, hydrogen, acetylacetonato group, diketonate group, substituted cyclopentenyl group, Substituted aryl, alkenyl, alkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, carboxyl, alkylsulfonate, arylsulfonate, alkylthio, alkenylthio, aryl Examples thereof include an alkylthio group, an alkylsulfonyl group, and an alkylsulfinyl group.

Specific examples of neutral electron donors include oxygen, water, heplonyl, amines, pyridines, ethers, nitriles, esters, phosphines, phosphinates, Examples include phosphites, stibines, sulfoxides, thioethers, amides, aromatic compounds, cyclic diolefins, olefins, isocyanides, thiosineates, and the like.

Specific examples of RR ₂ , R ₃ and R ₄ include hydrogen, alkenyl, alkynyl, alkyl, aryl, alkoxyl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, and alkoxycarbonyl groups. , An alkylthio group, an arylthio group, an alkylsulfonyl group, an alkylsulfinyl group, and the like.

Specific examples of the ruthenium complexes represented by the formulas [1] to [3] include the following.

That is, examples of the general formula [1] include (P-cumene) tricyclohexylphosphine ruthenium dichloride, bis (tricyclohexylphosphine) ruthenium dichloride, [1,3-di (methylphenyl) 1-4] Imidazoline—2-ylidene] (p-cymene) ruthenium dichloride;

Specific examples of the general formula [2] include benzylidenebis (tricyclohexylphosphine) ruthenium dichloride, (phenylthiomethylene) bis (triisopropylpropylphosphine) ruthenium dichloride, and (1,3-dicyclohexylimiimi) Dazolidine_2-ylidene) (tricyclohexylphosphine) benzylidene tenidimdichloride, (1,3-dicyclohexyl-4_imidazoline-l-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride,

(1,3-dimesitylimidazolidine-1-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, (1,3-dimesitylimidazolysine_2_ylidene) (triphenylphosphine) benzylidene ruthenium Dichloride, (1,3-dimesityl-4-imidazoline-2-imidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, (1,3-dimesityl-4-imidazoline 1-2-ylidene) (triphenyl) Phosphine) benzylidene ruthenium dichloride, [1,3-di (methylphenyl) imidazolidine—2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3-di (methylnaphthyl) imidazolidine] 2 _Iliden] (G Benzylidene ruthenium dichloride, (1,3,4,5-tetraphenylimidazolidin-1-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, (1,3-dicyclohexyl) Hexahydropyrimidine—2_ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, bis (1,3-diisopropylimidazolidin-2-ylidene) benzylidene ruthenium dichloride, bis (1,3-dicyclic) Mouth-hexylimidazolidine—2-ylidene) benzylidene ruthenium dichloride, bis (1,3-diisopropyl—4-imidazoline-12-ylidene) benzylidene ruthenium dichloride, bis (1,3-dicyclohexyl) -4 One imidazoline one two-ylidene) ben Benzylidene ruthenium dichloride Donado;

Specific examples of the general formula [3] include phenylvinylidenebis (tricyclohexylphosphine) ruthenium dichloride, (1,3-dicyclohexylimidazolidine-2-ylidene) (tricyclohexylphosphine) phenyl N-vinylidene ruthenium dichloride, (1,3-dimesitylimidazolidine-1-ylidene) (tricyclohexylphosphine) t-butylvinylidene ruthenium dichloride, (1,3-dimesityl-14-imidazoline-1) 2-ylidene) (tricyclohexylphosphine) phenylvinylidene ruthenium dichloride, [1,3-di (methylphenyl) imidazolidine-12-ylidene] (tricyclohexylphosphine) t-butylvinylidene ruthenium Dichloride, [1,3-di (methylnaphthyl) imidazolidine—2 [Den] (Trin) phenylene bilidene ruthenium dichloride, (1,3,4,5 tetraphenylimidazolidinin-2-ylidene) (trin) t-butylvinylidene ruthenium dichloride, (1 , 3D-pyrimidine-1-ylidene) (tricyclohexylphosphine) phenylvinylidene ruthenium dichloride, bis (1,3-diisopropylimidazolidin-2_ylidene) phenylvinylidene ruthenium dichloride, bis (1,3-dicyclohexylimidazolidine-1-ylidene) t-butylpyridinyl ruthenium dichloride, bis (1,3-diisopropyl-14-imidazoline-2-ylidene) t-butylpyridene ruthenium dichloride , Bis (1,3-dicyclohexyl—4-imida Zoline-2_ylidene) phenylene bilidene ruthenium dichloride.

Further, the complex compound represented by the above general formula [2] or [3] is converted to di-chlorobis [(p-cymene) chlororuthenium], di-chlorobis [[p-cymene) chloro Osmium], a dinuclear (pentamethylcyclopentenyl) rhodium dimer and other dinuclear metal complexes such as ruthenium-carbene complex compounds obtained by reaction with a dinuclear metal complex may also be used.

The ratio of the ruthenium complex to the cyclic olefin, which is a polymerization raw material, is usually from 1: 100 to 2,000,000, preferably 1: 500, as represented by the molar ratio of (metal ruthenium in the ruthenium complex: cyclic olefin). ~: L ,, 000,000, more preferably 1: 1,000 to 500,000. If the amount of the ruthenium complex is too large, the cost increases, and if it is too small, sufficient activity cannot be obtained.

The ruthenium complex can be used by dissolving it in a monomeric cyclic olefin under the condition that polymerization of the cyclic olefin does not proceed. The product may be suspended or dissolved in a small amount of a solvent as long as the properties of the product are not essentially impaired.

In the present invention, a Lewis acid can be used in combination to increase the polymerization activity of the ruthenium complex catalyst. The Lewis acid used is an electron pair acceptor defined by Lewis and is usually represented by the following formulas [4] to [5].

(M _x ) (X ₆ ) (X ₇ ) (X ₈ ) [4]

(Mi) (X ₉ ) (X ₁₀ ) (X (X ₁₂ ) [5]

(In the formula, represents a Group 3 or Group 13 element of the Periodic Table, for example, aluminum, boron, and scandium. M ₂ is a Group 4 element of the Periodic Table or a period of 3rd period or less (germanium or less) X represents an element of group 14 of the table, for example, titanium, tin, zirconium, and X ₆ , X ₇ , X ₈ , X ₉ , X ₁₀ , and X ₁₂ are each independently a halogen atom or a halogen atom, May contain at least one atom selected from oxygen atom, nitrogen atom, sulfur atom, phosphorus atom and silicon atom

. Represents a hydrocarbon group. )

Specific examples of X ₆ , X ₇ , X ₈ , X ₉ , X ₁₀ , X and X ₁₂ include F, Br, Halogen atom such as C1 and I, acetyl acetonato group, diketonate group, substituted cyclopentenyl group, substituted aryl group, alkenyl group, alkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl Groups, carboxy groups, alkyl or arylsulfonate groups, alkylthio groups, alkenylthio groups, arylthio groups, alkylsulfonyl groups, and alkylsulfinyl groups.

Preferred examples of the above formula [4] include trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, trialkylaluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride, and dialkylaluminum chloride. And trialkoxy scandium.

Preferred examples of the formula [5] include tetraalkoxytitanium, tetraalkoxytin, and tetraalkoxyzirconium.

Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and an n-octoxy group. Use of a halogen-containing alkoxy group in which a halogen is bonded to the 3-position in addition to these alkoxy groups is particularly preferable because not only the reaction rate is improved but also the reaction rate is increased.

Specific examples of such a halogen-containing alkoxy group include a 2-chloroethoxy group, a 2,2-dichloroethoxy group, a 2,2,2-trichloroethoxy group, a 2-chloro-1-propoxy group, , 3-Dichloro_2-propoxy group, 1,1-dichloro-2-propoxy group, 1,1,1-trichloro-2-propoxy group, hexachloro-2-propoxy group, 2-chloro-2 —Propene-1 1-oxy group, 2-chloro-1-butoxy group, 1 —Chloro-3 —methoxy-2 —propoxy group, 1,3-dibromo — 2 —propoxy group, 1,3 —Jodo 2 — Examples include a propoxy group and a 2-chlorocyclohexoxy group. Among these, a 1,3-dichloro-2-propoxy group is particularly preferred.

Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a sec-butyl group. When a Lewis acid is used in combination, the ratio of the Lewis acid to the ruthenium complex is usually 1: 0.05 to: L00, preferably expressed as a molar ratio of (metal ruthenium in the ruthenium complex: Lewis acid). Is from 1: 0.2 to 20, more preferably from 1: 0.5 to: 10. If the amount of Lewis acid is too large or too small, a sufficiently high polymerization activity cannot be obtained. When the Lewis acid is added to the undiluted reaction solution in this way, a Lewis base can be added to the catalyst solution containing the ruthenium complex, and the Lewis acid and the Lewis base can be used in combination. By adding a Lewis base to the catalyst solution, the stability of the catalyst solution and the mixing property between the catalyst solution and the reaction solution are improved. The amount of the Lewis base to be added to the catalyst solution is usually represented by a molar ratio of (metal ruthenium in the ruthenium complex: Lewis base) of 1: 0.01 to: 100, preferably 1: 0.05. ~ 20, more preferably 1: 0.1 ~: L0.

Although the Lewis base to be added is not particularly limited, for example, phosphines, sulfonated phosphines, phosphites, phosphinates, phosphonites, arsines, stibines, ethers, amines, amides, sulfoxides, Examples include carboxyls, nitrosyls, pyridines, thioethers, nitriles, thiophenes, and furans. Specific examples of such Lewis bases include triisopropylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, triphenylphosphine, pyridine, propylamine, tri-n-butylphosphine, benzonitrile, triphenylarsine, acetonitrile anhydride, thiophene. , Franc and the like. Among these, triisopropylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, triphenylphosphine, and tri-n-butylphosphine are preferred.

Cyclic olefins

In the present invention, the monomer subjected to ring-opening polymerization is a cyclic olefin. Examples of the cyclic olefin include (1) polycyclic cyclic olefins having a norpolene ring, such as norbornenes, dicyclopentenes, trimers of cyclopentene (symmetric and asymmetric), and tetracyclododecenes; (2) Monocyclic cyclic olefins and the like can be used. These cyclic olefins may have a substituent such as an alkyl group, an alkenyl group or an alkylidene group, and may have a polar group. You may have. Further, in addition to the double bond of the norbornene ring, it may further have a double bond.

Among these cyclic olefins, it is preferable to use tricyclic to hexacyclic cyclic olefins having a norporene ring, and tricyclic cyclic olefins such as dicyclopentene digenes and trimers of cyclopentadiene (Symmetric and asymmetric types) and tetracyclic cyclic olefins such as tetracyclododecene and methyltetracyclododecene are particularly preferred. In particular, dicyclopentenes are most preferable in terms of economy.

The above-mentioned cyclic olefins may be used alone or in combination of two or more, but the use of two or more is preferred. This is because, when two or more types are used, the range in which the monomer can be handled as a liquid is broadened due to the freezing point drop as compared with the case of single use. In addition, it is preferable to copolymerize dicyclopentenes or tetracyclododecenes with a cyclic olefin which can be copolymerized with these, and in this case, dicyclopentenes or tetracyclododecenes may be used as a whole monomer. Usually, it is sufficient to use 1 to 100% by weight based on the body weight. However, from the viewpoint of the heat resistance of the polymer and the availability of the monomer, it is preferably used.

It is used in an amount of 10 to 100% by weight, more preferably 20 to 100% by weight.

Preparation of reaction stock solution

The production method of the present invention is characterized in that a reaction stock solution is prepared in an inert gas atmosphere. The unreacted solution refers to a liquid substance containing the cyclic olefin (monomer) as a main component and giving a ring-opened polymer of the cyclic olefin by mixing with the ruthenium complex.

The inert gas used in the present invention includes nitrogen, helium, neon, argon, krypton, xenon, radon and the like. Preferred are nitrogen, helium, neon, and argon. From the standpoint of industrial availability, nitrogen and argon are more preferred, and nitrogen is most preferred. The inert gas can be used alone or in combination of two or more.

In the present invention, "preparing a reaction stock solution" means that cyclic olefin or cyclic olefin and various additives are subjected to treatment such as distillation, degassing, dehydration, mixing, heating, stirring, and dissolving as necessary. , The process up to filling the storage container described below, and preparation This refers to the step of storing the resulting reaction stock solution in a container until it is used for polymerization. In the present invention, all of these processing steps may be performed in an inert gas atmosphere. However, if the storage state immediately before molding is an inert gas atmosphere, all the steps need to be performed in an inert gas atmosphere. There is no. For example, various additives are dissolved in cyclic olefins in the air, and in the final treatment step, the solution is replaced by publishing with an inert gas, or the solution is degassed under reduced pressure and then inert gas. May be introduced into the system and replaced with an inert gas, etc. to make the reaction stock solution an inert gas atmosphere.

In the step of storing the undiluted reaction solution in an inert gas atmosphere, the undiluted reaction solution prepared as described above is filled in a storage container without being substantially in contact with air and sealed, or an open container is used. Includes storing, transporting, and transporting the undiluted solution until it is used in the polymerization reaction described below, such as by sealing with an inert gas to block contact with air. . Also, even if the reaction stock solution filled in a storage container is temporarily brought into contact with air when transferring it to another storage container, if it is returned to an inert gas atmosphere again, it is included in the concept of the storage process. You. The gas phase part of the storage container may be substantially an inert gas atmosphere, but the oxygen content in the gas phase part in the container is usually 1% or less, preferably 0.1% or less. The amount of dissolved oxygen in the reaction stock solution is usually 50 ppm or less, preferably 5 ppm or less, and more preferably 1 ppm or less.

The storage period of the undiluted reaction solution and the filling rate in the storage container are not particularly limited. Examples of the storage container include various tanks, containers, drums, pail cans, and kerosene cans. The material of the container is not particularly limited, but a material having air permeability is not preferred. In the present invention, it is preferable to add the above-mentioned Lewis acid to the reaction stock solution, but if necessary, various additives such as an antioxidant, an ultraviolet absorber, an elastomer, a polymer modifier, and a filler , A coloring agent, a flame retardant, a cross-linking agent, a sliding agent, an odorant, a class of filler for reducing the weight, a foaming agent, and a whisker for smoothing the surface.

Examples of the elastomer to be added to the reaction stock solution include natural rubber, polybutene diene, polyisoprene, styrene-butadiene copolymer (SBR), styrene-butane distyrene-styrene block copolymer (SBS), and styrene Isoprene-styrene Examples include a styrene copolymer (SIS), an ethylene-propylene-diene terpolymer (EPDM), an ethylene-vinyl acetate copolymer (EVA), and hydrides thereof. The addition of these elastomers to the reaction solution not only imparts impact resistance to the resulting polymer, but also controls the viscosity of the reaction solution. Antioxidants include various antioxidants for plastics and rubbers, such as hindered phenol-based, phosphorus-based, and amine-based antioxidants. Although these antioxidants may be used alone, it is preferable to use two or more kinds in combination. The mixing ratio is usually 0.5 part by weight or more, preferably 1 to 3 parts by weight, based on the norbornene-based monomer. Further, the antioxidant may be one which can be copolymerized with the monomer, and specific examples thereof include a norbornenylphenol compound such as 5- (3,5-di-tert-butyl-4-hydroxybenzyl-2-norbornene). (See Japanese Patent Application Laid-Open No. 57-83522).

Fillers include inorganic fillers such as glass powder, force pump racks, talc, calcium carbonate, mica, and aluminum hydroxide. It is preferable that such a filler is surface-treated with a silane coupling agent or the like. The use of iodide or peroxide as a crosslinking agent improves heat resistance.

The undiluted reaction solution thus prepared can be stored for a long time, and is usually used immediately before the start of the polymerization by mixing with the above-mentioned catalyst solution containing the ruthenium complex.

Method for producing polymer

In the present invention, the ring-opening polymerization reaction may be a solution polymerization performed in a solvent or a bulk (bulk) polymerization, but the bulk polymerization in which a reaction solution is injected into a mold and cured is used. preferable.

As the solvent used for the solution polymerization, a solvent that dissolves the produced polymer and does not inhibit the polymerization is used. Specific examples thereof include aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclopentane Alicyclics such as hexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, getylcyclohexane, decahydronaphthylene, bicycloheptane, tricyclo mouth decane, hexahydroindenecyclohexane, and cyclooctane Aromatic hydrocarbons such as benzene, toluene and xylene; nitromethane, Nitrogen-containing hydrocarbons such as ditrobenzene and acetonitrile; ethers such as getyl ether and tetrahydrofuran; halogen-containing hydrocarbons such as chloroform, dichloromethane, cyclobenzene, and dichlorobenzene can be used. Among these solvents, aromatic, aliphatic, and alicyclic hydrocarbon-based solvents and ethers, which are widely used in industry, are preferable, and are inert during the polymerization reaction, and have excellent polymer solubility. From the viewpoint of, it is most preferable to use an alicyclic hydrocarbon solvent such as cyclohexane.

When the polymerization is carried out in a solvent, the concentration of the cyclic olefin is preferably 1 to 50% by weight, more preferably 2 to 45% by weight, and particularly preferably 5 to 40% by weight. If the concentration of the cyclic olefins is too low, the productivity is deteriorated. If the concentration is too high, the viscosity after polymerization is too high, and post-treatment becomes difficult.

The polymerization temperature of the solution polymerization is generally from 130 ° C. to 200 ° C., preferably from 0 ° C. to 180 ° C. The polymerization time is generally from 1 minute to 100 hours.

In the present invention, when performing bulk polymerization, it is particularly useful to use a resin transfer molding (RTM) method or a reaction injection molding (RIM) method to polymerize cyclic olefins in a bulk in a mold. These methods need only be substantially bulky, and may contain a small amount of an inert compound in the polymerization system. In these methods, a molding machine conventionally known as an RTM machine or a RIM machine can be used for mixing two or more kinds of reaction stock solutions and catalyst solutions.

An RTM machine generally consists of a reaction stock solution tank, a catalyst formulation solution tank, a metering pump, a mixer, etc., and the reaction stock solution and the catalyst formulation solution described above are metered by a metering pump into a volume of 100: 1 to 10: 1. The mixture is sent to a mixer at a specific ratio, and then injected into a molding die heated to a predetermined temperature, where it is immediately subjected to bulk polymerization to obtain a molded product. A preferred molding method using an RTM machine is a reaction solution in which a cyclic olefin is optionally added with a Lewis acid, a neutral electron donor as a ligand and a carbene compound containing Z or a hetero atom coordinated with ruthenium. Is prepared by dissolving the complex in a solvent, preparing a catalyst compounding solution to which a Lewis base is added as required, and mixing and molding these.

The RIM machine feeds two or more kinds of undiluted reaction solutions into a mixing head, mixes them by means of collision energy, and then injects them into a hot molding die, where they immediately mass-react. It is comprised so that a molded article may be obtained by combining them. A preferred molding method using a RIM machine is to divide the cyclic olefin into two parts (solution A and solution B) and use a solution (solution C) in which a ruthenium complex catalyst is dissolved in a solvent as a third solution. This is a method of mixing and molding the three liquids by collision mixing. A Lewis acid may be added to one or both of the solution A and the solution B as desired, and a Lewis base may be added to the solution C as desired.

As the mold, a mold having a split mold structure, that is, a core mold and a cavity mold is usually used, and the reaction liquid is injected into the cavity (cavity) to perform bulk polymerization. The core mold and the cavity mold are formed so as to form voids that match the shape of the target molded product. There is no particular limitation on the shape, material, and size of the mold. Since it can be molded at a relatively low temperature and low pressure using a low-viscosity reaction solution, not only metal molds but also various materials such as various synthetic resins and low melting point alloys can be used. The temperature of the reaction solution before it is fed into the cavity is preferably 20 to 8 Ot :. The viscosity of the reaction solution at, for example, 30 is usually 2 to 5,000 cps, preferably 5 to 1.00 cps. The filling pressure (injection pressure) when filling the reaction stock solution into the cavity is usually 0.01 to 50 kgf Zcm ² , preferably 0.1 to: L 0 kgf Zcm ² .

The mold temperature is usually room temperature or higher, preferably 40 to 200: particularly preferably 50 to 130. Clamping pressure is usually 0. 1 Ru 1 0 0 range der of kg / cm ^2. The polymerization time may be appropriately selected, but is usually from 10 seconds to 20 minutes, preferably within 5 minutes.

It is preferable to control the maximum temperature of the contents in the mold to be 140 or more. A more preferred maximum temperature is 150 to 250. By controlling the maximum temperature in this way, a polymer having a particularly high glass transition temperature (Tg) can be obtained at a high conversion.

When a reaction solution obtained by mixing the above-mentioned “reaction stock solution” and “ruthenium complex” with an RTM machine or a RIM machine is injected into the cavity of the mold, a bulk polymerization reaction is immediately started and the mixture is cured. The polymerization reaction is exothermic, and after reaching the maximum temperature, the temperature of the molded product in the mold gradually decreases as the curing time (curing one hour) increases. Normally, The mold is released after the temperature of the molded article has reached the glass transition temperature or lower.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. The present invention is not limited to these Examples.

Bulk polymerization of norbornene monomers under nitrogen atmosphere

Example 1

In a 30m1 wide-mouth glass bottle, benzylidenebis (tricyclohexylphosphine) ruthenium dichloride (manufactured by Strem Chemical Co.) 4 mg (0.5 mmol Z liter in polymerization system) stirred finely in a mortar I have a child. A rubber stopper and a polyethylene T-tube that can be sealed at the wide mouth of this glass bottle were prepared, and the T-tube was penetrated near the center of the rubber stopper so as to form a horizontal T-shape, and then attached to the glass bottle. A nitrogen stream was flowed through the lateral mouth of the T-tube, and the operation of pressing and releasing the upper mouth of the T-tube with fingers was repeated about 40 times, and the inside of the glass bottle was purged with nitrogen. After that, the nitrogen stream continued to flow slowly.

After setting a thermocouple for temperature measurement through a T-tube, 1 Om 1 of dicyclopentene (containing about 10% of a cyclopentene trimer) was added with a syringe, and the mixture was vigorously stirred with a magnetic stirrer. 10 seconds after the introduction of the monomer, 0.025 ml of a solution of bis (1,3-dichloro mouth_2-propoxy) aluminum chloride in dicyclopentene (0.2 mol / liter) was added as a Lewis acid using a small syringe (polymerization). Concentration in the system 0.5 mmol / l) was injected. The containers containing the monomer solution and Lewis acid solution, the reaction glass bottles, and the syringes were placed in a thermostat set at 25 ° C, and used immediately.

Stop stirring 30 seconds after the monomer injection, record the temperature rise of the reaction solution with a thermocouple and a temperature recorder, and measure the time from the monomer injection until the solution temperature reaches 100 ° C (Table 1). The T100 of the sample was measured in seconds, and the maximum liquid temperature (peak temperature in Table 1 was measured in ° C). After completion of the polymerization, the glass bottle containing the polymer was cooled to room temperature, the polymer was taken out, and its glass transition temperature (Tg) was measured by a differential scanning calorimeter. Further, in the same manner as in the T g measurement, a reaction rate (%) was obtained from the polymer taken out of the glass bottle by heating from room temperature to 400 ° C. by using a heating stirrer, based on the residual ratio of the weight obtained.

Table 1 shows the measurement results. Example 2

The same operation as in Example 1 was performed except that the Lewis acid was not added. Table 1 shows the measurement results.

Example 3

As the ruthenium complex, (phenylthiomethylene) bis (triisopropylphosphine) ruthenium dichloride 6.1 mg (concentration 1 mmol in the polymerization system) was used, except that no Lewis acid was added. The procedure was as in Example 1. Table 1 shows the measurement results.

Small-scale bulk polymerization of norbornene-based monomers in air

Comparative Example 3

The same as in Examples 1 to 3, except that the rubber stopper and the polyethylene T-tube were not used, the nitrogen replacement step was omitted, the upper part of the glass bottle was opened, and the reaction was performed in air. Operated. Table 1 shows the measurement results. When compared with Examples 1 to 3, it can be seen that Tg and the reaction rate are reduced when the reaction is performed in the air.

table 1

Small-scale bulk polymerization of norbornene-based monomers under nitrogen atmosphere and in air Example 4, Comparative Example 4

As the ruthenium complex, (1,3-dimesitylimidazolidine-1-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride (Org. Lett. 1999, 1, 953, synthesized based on the description) Was charged in the same glass bottle as in Example 1 and charged with 1.Omg (concentration in the polymerization system: 0.125 mmol Z liter), followed by purging with nitrogen. After adding 0.05 ml of dichloromethane to dissolve the catalyst, add 0.95 ml of dicyclopentene (containing about 10% cyclopentene trimer) preheated to 50, and add the magnetics. The mixture was stirred vigorously in the evening stirrer (Example 4). The maximum liquid temperature in the polymerization reaction was 220 ° C. The Tg of the obtained polymer was 152 ° C., and the conversion was 97.5%.

On the other hand, when this reaction was carried out in air, the T g of the obtained polymer was 130 ° (:, the reaction rate was 94.8% (Comparative Example 4)).

Example 5, Comparative Example 5

As a ruthenium complex, (1,3-dimesitylimidazolidine_2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride 0.4 mg (concentration in polymerization system 0.05 mol / l) Other than that used, it operated similarly to Example 4. The maximum liquid temperature in the polymerization reaction was 201 ° C. The T g of the obtained polymer was 145 ° C., and the conversion was 97.2% (Example 5).

On the other hand, when this reaction was performed in air, the Tg of the obtained polymer was 29 ° C., and the conversion was 72.0% (Comparative Example 5).

Example 6, Comparative Example 6

As the ruthenium complex, (1,3-dimesityl_4-imidazoline-2_ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride was used in an amount of 2. lmg (concentration in a polymerization system of 0.25 mmol liter). Otherwise, the procedure was the same as in Example 4. The maximum liquid temperature in the polymerization reaction was 215 ° C. The Tg of the obtained polymer was 152 ° (:, the conversion was 97.0% (Example 6)).

On the other hand, when this reaction was performed in air, the Tg of the obtained polymer was 132 ° C., and the conversion was 94.9% (Comparative Example 6).

Example 7, Comparative Example 7

Example 2 was repeated except that bis (1,3-diisopropyl_4-imidazoline-2-ylidene) benzylidene ruthenium dichloride (2.8 mg (concentration in the polymerization system: 0.5 mmol)) was used as the ruthenium complex. The operation was the same as in 4. The highest liquid temperature in the polymerization reaction was 218. The Tg of the obtained polymer was 119 ° C, and the conversion was 94.2% (Example 7).

On the other hand, when this reaction was carried out in air, the Tg of the obtained polymer was 86 ° C., and the conversion was 90.2% (Comparative Example 7).

Flat plate forming under nitrogen atmosphere

Example 8 (1) Die: Two pieces of iron plate with a thickness of 200 mm and a thickness of 200 mm and a thickness of 500 W were used. In order to create a cavity inside the two iron plates, a U-shaped resin spacer (4 mm thick) that matches the size of the iron plate is sandwiched between the four iron plates, and the four corners are shaky. It was a vise. A thermocouple for temperature control was attached to the upper part of the mold on the product side of the simple mold made in this way, and this was connected to a heater temperature controller so that the temperature of the mold could be adjusted. The back side mold was not energized. A thermocouple for temperature measurement was attached near the center of the upper inside of both molds while being insulated from the iron plate. A is the thermocouple on the product side, and B is the thermocouple on the back side. Also, apply a piece of gum tape about 15 mm thick to the end of the thermocouple to a thickness of about 4 mm, insert it around the center of the inside of the mold, and measure the temperature inside the molded product. The pair C was set.

(2) Reaction stock solution: 90 mg of benzylidenebis (tricyclohexylphosphine) ruthenium dichloride (manufactured by Strem Chemica 1) finely ground in a mortar in a 50 Om1 wide-mouth polyethylene bottle was charged with 90 mg and a stirrer. . A rubber stopper, a polyethylene T-shaped tube, and a glass tube which can be hermetically sealed were prepared at the wide mouth of the polyethylene bottle, and a polyethylene T-shaped tube was attached to the rubber stopper in the same manner as in Example 1 above. In addition, a glass tube used to transfer the undiluted reaction solution to the mold was passed through a rubber stopper, and the rubber stopper was attached to the mouth of a polyethylene bottle. Close the silicone rubber tube for transferring the reaction solution, which is connected to the top of the glass tube, with a clip and close it.A nitrogen stream flows from the lateral mouth of the T-tube, and the upper mouth of the T-tube is pressed with a finger. The separation operation was repeated about 40 times, and the inside of the bottle was replaced with nitrogen. After that, the clip of the silicon rubber tube was removed, and the nitrogen gas flow was kept flowing slowly.

The stirrer was rotated, and the same monomer (2,25 m 1) as in Example 1 was charged with a syringe. After 10 seconds, 0.56 ml of a dicyclopentene solution of 0.2 mol bis (1,3-dichloro-2-propoxy) aluminum chloride separately prepared as a Lewis acid was injected with a syringe. Then, the mixture was vigorously stirred for 20 seconds.

(3) Molding method: In the preparation of the reaction stock solution, 20 seconds after the addition of the Lewis acid, insert the lower end of the glass tube for transferring the reaction stock solution deep below the liquid level of the bottle, and place it on the T-tube. The opening on the side was closed, and the reaction stock solution was pressure-fed to the above-mentioned mold (mold temperature on the product side 95 ° C, mold temperature on the back side 65 ° C) by nitrogen pressure. At this time, the nitrogen inside the mold was not replaced before the injection. When the remaining amount of the undiluted solution in the bottle reached about 40 m1, the pumping was stopped and the transfer rubber tube was closed with a clip.

The internal temperature was measured for 3 minutes after transferring the undiluted reaction solution, and the mold was removed to obtain a molded product. Table 2 shows the maximum temperature in the reaction system inside the mold, the glass transition temperature (Tg) and the reaction rate of the sample cut from the molded product. It can be seen that if the compounding and preparation are performed in a nitrogen atmosphere, high Tg and high conversion can be achieved without replacing the inside of the mold with nitrogen.

Flat plate forming in air

Comparative Example 8

(1) Die: Same as in Example 8.

(2) Unreacted solution: A stirrer of 90 mg of benzylidenebis (tricyclohexylphosphine) ruthenium dichloride (manufactured by Strain Chemica 1 Co.) was finely ground in a mortar into a 50 Om1 wide-mouth polyethylene bottle. The stirrer was rotated, and 225 ml of the same monomer as in Example 1 was charged in the air. 10 seconds later, 0.2 mol of the bis (1,3-dichloro-2--2-propoxy) aluminum chloride in dicyclopentene was prepared separately as a Lewis acid.

56 ml was injected with a syringe. And it stirred vigorously for 20 seconds.

(3) Molding method: 20 seconds after the addition of the Lewis acid in the preparation of the reaction stock solution, the reaction stock solution is poured into the above-mentioned mold (mold temperature 95 ° on the product side (65 ° C on the back side)). After measuring the internal temperature for 3 minutes after pouring the undiluted solution, the mold was removed to obtain a molded product.The maximum temperature in the reaction system inside the mold and the glass transition of the sample cut from the molded product The temperature (Tg) and the reaction rate are shown in Table 2. Comparing with Example 8, it is understood that the Tg and the reaction rate decrease when the mixed solution is prepared in the air.

Table 2

Example 8 Comparative Example 8

Maximum temperature (t :) 184 157

Tg (.c) 147 95

Reaction rate (%) 98.4 93.1 Bulk polymerization of dicyclopentadiene using toluene solution of benzylidenebis (tricyclohexylphosphine) ruthenium dichloride and triphenylphenylphosphine (Lewis base)

Example 9

In a 500 ml eggplant-shaped flask equipped with a magnetic stirrer, 176 g of dicyclopentene (98.5% purity), 9 g of 5-ethylidene-2-norbornene (99% purity) and SIS (Quintac 3530, 15 g (manufactured by Zeon Corporation) was added, and the mixture was stirred at 80 under a nitrogen atmosphere for 2 hours and dissolved. Thereafter, the pressure was reduced while stirring, and only 0.5 g of low boiling components was removed (composition liquid 1).

In a 20 ml eggplant-shaped flask equipped with a magnetic stirrer, benzylidenebis (tris-hexyl hexylphosphine) ruthenium dichloride (manufactured by Strain Chemica 1) 0.2 1 g, tricyclohexylphosphine 0 28 g and toluene (4.5 ml) were added and dissolved by stirring (catalyst solution 1, ruthenium and phosphine concentrations were 0.05 mol liter and 0.2 mol no liter, respectively).

In a 20 Om 1 eggplant-shaped flask equipped with a magnetic stirrer, 48 g of dicyclopentene (including 10% of cyclopentane trimer), 0.63 ml of getyl aluminum chloride, 1,3-dichloro 0.95 ml of 2-propanol was added with stirring to react, and a solution of bis (1,3-dichloro-2--2-propoxy) aluminum chloride having a concentration of 0.1 mol liter was prepared (Lewis acid solution). 1)

A stirrer was placed in a 3 Om 1 wide-mouthed glass bottle, and 9.4 ml of the composition solution 1 and 0.5 ml of the Lewis acid solution 1 were added and stirred.After mixing, 0.1 ml of the catalyst solution 1 was stirred. After a further 10 seconds of stirring, the catalyst was thoroughly mixed and became a homogeneous solution. Thereafter, the stirring was stopped, and the internal temperature was measured with a thermocouple. The internal temperature gradually increased, and reached a maximum temperature of 179 ° C 6 minutes and 10 seconds after the introduction of the catalyst solution 1.

The above operation was performed in a nitrogen atmosphere. The polymerization was performed at room temperature. Room temperature was 23 ° C. The same applies to the operations of Comparative Examples 1 and 2 below.

After the polymer cooled, the glass transition temperature (Tg) was measured. In the test method, Tig was measured in accordance with JISK 7121 and defined as Tg. The same applies to the following Tg measurement. T g was 142 ° C. Comparative Example 9

In a 20 ml eggplant-shaped flask equipped with a magnetic stirrer, 0.21 g of benzylidenebis (tricyclohexylphosphine) ruthenium dichloride (manufactured by Strain Chemica 1) and 4.8 ml of toluene In addition, it was dissolved by stirring (catalyst solution 2, ruthenium concentration: 0.05 mol Z liter).

Put a stirrer into a 3 Om 1 wide-mouthed glass bottle, add 9.4 m1 of the composition solution 1 and 0.5 ml of dicyclobenzene (including 10% of cyclopentene trimer) and stir. After mixing, add 0.1 ml of catalyst solution 2 with stirring, and further stir for 10 seconds, the mixing is insufficient, and a state where some solidified parts and parts that remain liquid are mixed became.

From the above, it can be seen that in the system containing no Lewis base (tricyclohexylphosphine), poor mixing occurs.

Comparative Example 10

A stirrer is placed in a 3 Om 1 wide-mouthed glass bottle, and 9.4 m 1 of the composition liquid 1 and 0.5 ml of dicyclobenzene (including 10% of cyclopentamer) are added and stirred. After mixing, 0.1 ml of the catalyst liquid 1 was added with stirring, and the mixture was further stirred for 10 seconds. As a result, the catalyst was sufficiently mixed and became a homogeneous solution. Then, the stirring was stopped and the internal temperature was measured with a thermocouple. The internal temperature gradually increased, and reached a maximum temperature of 79 18 minutes and 50 seconds after the introduction of the catalyst solution 1. The Tg of the polymer was 42 :.

From the above, even if a Lewis base (tricyclohexylphosphine) is added, mixing failure does not occur in a system in which Lewis acid (bis (1,3-dichloro-2-propoxy) aluminum chloride) is not added. However, it can be seen that the activity of the catalyst decreases, resulting in a low reaction rate and low Tg.

Bulk polymerization of dicyclopentadiene using toluene solution of ruthenium dichloride and tri-n-butylphosphine (Lewis base) with benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) Example 10

In a 1 Om 1 eggplant type flask equipped with a magnetic stirrer, benzylidene (1,3-dimesitylimimidazolidine-2-ylidene) (tricyclohexylphosphine) Tendium dichloride (synthesized based on the description in Org. Lett. 1999, 1, 953) 51 mg, triluene solution of η_butylphosphine in toluene (concentration: 10 mmolΖl) 3.0 ml 1 In addition, it was dissolved by stirring (catalyst solution 3, ruthenium and phosphine concentrations were 20 mmol mol and 10 mol mol, respectively). The above operation was performed at room temperature under a nitrogen atmosphere.

A stirrer was placed in a 30-m1 wide-mouth glass bottle, 9.9 m of dicyclopentene (99.8% purity) was added, and 0.05 m1 of Lewis acid solution 1 was added. After stirring and mixing, the catalyst solution 3 was stirred while stirring. Was added, and the mixture was further stirred for 10 seconds. As a result, the catalyst was sufficiently mixed and became a homogeneous solution. After that, stirring was stopped and the internal temperature was measured with a thermocouple. The internal temperature gradually increased, and reached a maximum temperature of 219 ° C 1 minute and 12 seconds after the introduction of the catalyst solution 3. The above polymerization operation was performed at 40 ° C. under a nitrogen atmosphere. The T g of the polymer was 145.

In addition, in order to examine the storage stability of Catalyst Solution 3, only 0.5 mL of Catalyst Solution 3 was placed in a 6-mL screw-down tube under a nitrogen atmosphere, and placed in a warm and cold bath at 55 for a 6-hour heating acceleration test. However, there was no change in the initial light brown color, and no precipitate was formed.

Comparative Example 1 1

In a 1 Om 1 eggplant-shaped flask equipped with a magnetic stirrer, benzylidene (1,3-dimesitylimimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride (〇rg. Lett. 1999) , 1, 953) 5 1 mg, toluene 3. Om1 were added and dissolved by stirring (catalyst solution 4, ruthenium concentration: 20 mmol Z liter). The above operation was performed at room temperature in a nitrogen atmosphere.

Put a stirrer into a 3 Om 1 wide-mouthed glass bottle, add 9.95 ml of dicyclopentenegen (purity 99.8%), add 0.05 ml of catalyst solution 4 with stirring, and wait another 10 seconds As a result of the stirring, the mixing was insufficient, and a portion of the solidified portion and a portion of the liquid remained mixed. The above polymerization operation was performed at 40 ° C. under a nitrogen atmosphere.

In addition, to examine the storage stability of catalyst solution 4, 6 ml of catalyst solution 4 was placed in a nitrogen atmosphere. A 0.5 ml aliquot was placed in a screw tube and placed in a 55 ° C water bath to conduct a heating promotion test.At the beginning, the color was light brown, but after 1 hour it turned black and after 4 hours As a result, a precipitate was formed which was considered to be a decomposition product of the catalyst.

From the above, it can be seen that in the system not containing the Lewis base (tree n-butylphosphine), the mixing was poor and the stability of the catalyst solution was poor.

Comparative Example 1 2

A stirrer was placed in a 30 ml wide-mouthed glass bottle, and 9.95 ml of dicyclopentene (purity: 99.8%) was added. Then, 0.05 ml of catalyst solution 3 was added with stirring, and then 1 ml. After stirring for 0 seconds, the catalyst was thoroughly mixed and became a homogeneous solution. Then, stirring was stopped and the internal temperature was measured with a thermocouple. The internal temperature gradually increased, and reached a maximum temperature of 203 ° C. 7 minutes and 30 seconds after the introduction of the catalyst solution 3. The above polymerization operation was performed at 40 ° C. under a nitrogen atmosphere. The Tg of the polymer was 138 ° C.

From the above, even if the Lewis base (tri-n_butylphosphine) is added, mixing failure does not occur in a system to which the Lewis acid (bis (1,3-dichloro_2-propoxy) aluminum chloride) is not added. However, it can be seen that the activity of the catalyst is reduced and the reaction rate is reduced. When applied to actual production, the molding cycle becomes longer, which is not desirable.

Solution Polymerization of Norbornene-Based Monomer with Ruthenium Complex Catalyst and Lewis Acid Example 11

In a 100-ml glass pressure-resistant reaction vessel equipped with a magnetic stirrer, dicyclopentene-diene and 8-ethylidenetetracyclododecene having a purity of 99% and a weight ratio of 85: 1 were distilled and purified under a nitrogen gas atmosphere. Dissolve 2 g (14.5 mmol) of the monomer mixed in 5 and 0.4 mg (0.48 // mol) of benzylidenebis (tris-kilohexylphosphine) ruthenium dichloride manufactured by Strain Chemical 0.5 ml of purified cyclohexane solution, 0.5 ml of a cyclohexane solution containing 1-hexene (12.2 mg, 0.145 mmol) as a chain transfer agent, and cyclohexane distilled and purified 2 A solution of (1,3-dichloro-2-propoxy) ethylaluminum chloride in dicyclopentene (containing about 10% cyclopentene trimer) was prepared separately as a Lewis acid. The ruthenium metal of the ruthenium complex It was charged so as to be 5 times the mol of the compound.

The reaction vessel was sealed with a crown and placed in an oil bath at 100 ° C., and the reaction solution was stirred well for 2 hours. After removing the reaction vessel from the oil bath and returning to room temperature, the content was poured into about 100 ml of 2-propanol to coagulate the formed polymer. The coagulated polymer was washed with 2-propanol and dried under reduced pressure in an oven at 120 ° C. for about 3 hours. As a result of measuring the weight of the dried polymer, the yield was 90%. Industrial applicability

In a method of performing ring-opening polymerization by mixing a ruthenium complex catalyst with a reaction solution containing a cyclic olefin, the glass transition temperature (T g) can be increased by preparing the reaction solution under an inert gas atmosphere. A cyclic olefin polymer that does not require post-curing after polymerization can be obtained at a high conversion.

Claims

The scope of the claims

1. A catalyst consisting of a complex in which at least one selected from a neutral electron donor and a hetero atom-containing carbene compound is coordinated to ruthenium as a ligand is mixed with a reaction solution containing a cyclic olefin. A method for producing a cyclic olefin polymer, which comprises subjecting the cyclic olefin to ring-opening polymerization by preparing the reaction solution under an inert gas atmosphere.

2. The method for producing a cyclic olefin polymer according to claim 1, wherein the ring-opening polymerization is a solution polymerization.

3. The method for producing a cyclic olefin polymer according to claim 1, wherein the ring-opening polymerization is a bulk polymerization in which an undiluted reaction solution is injected into a mold and cured.

4. The process for producing a cyclic olefin polymer according to claim 3, wherein the maximum temperature of the polymerization reaction mixture in the mold in the bulk polymerization is 14 O: or more.

5. The method for producing a cyclic olefin polymer according to claim 1, wherein a reaction solution containing a Lewis acid is used.

6. The method for producing a cyclic olefin polymer according to claim 5, wherein the catalyst solution containing the catalyst and the Lewis base is mixed with a reaction solution containing cyclic olefin, and the mixture is subjected to ring-opening polymerization.