WO2001032739A1 - Procede de production d'un polymere cyclo-olefinique - Google Patents

Procede de production d'un polymere cyclo-olefinique Download PDF

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Publication number
WO2001032739A1
WO2001032739A1 PCT/JP2000/007620 JP0007620W WO0132739A1 WO 2001032739 A1 WO2001032739 A1 WO 2001032739A1 JP 0007620 W JP0007620 W JP 0007620W WO 0132739 A1 WO0132739 A1 WO 0132739A1
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polymerization
solution
reaction
catalyst
ylidene
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PCT/JP2000/007620
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Japanese (ja)
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Tomoo Sugawara
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Zeon Corporation
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring

Definitions

  • 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.
  • post-curing post-curing
  • ruthenium complexes have been known as catalysts for ring-opening polymerization of cyclic olefins.
  • 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.
  • 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.
  • 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.
  • 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%.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a ruthenium complex represented by the following general formulas [1] to [3] is used.
  • 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.
  • 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.
  • 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 .
  • 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.
  • carbene compound containing a hetero atom examples include 1,3-diisopropyl-14-imidazoline_2-ylidene, 1,3-dicyclohexyl-4-imidazoline-2-ylidene, and 1,3-di (methylphenyl) -4.
  • 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
  • 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.
  • 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.
  • 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.
  • RR 2 , R 3 and R 4 include hydrogen, alkenyl, alkynyl, alkyl, aryl, alkoxyl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, and alkoxycarbonyl groups.
  • ruthenium complexes represented by the formulas [1] to [3] include the following.
  • 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,
  • 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
  • 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.
  • 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].
  • 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.
  • 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.
  • alkoxy group examples 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.
  • halogen-containing alkoxy group examples 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.
  • the alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a sec-butyl group.
  • 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.
  • 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.
  • 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.
  • 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.
  • Lewis bases include triisopropylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, triphenylphosphine, pyridine, propylamine, tri-n-butylphosphine, benzonitrile, triphenylarsine, acetonitrile anhydride, thiophene. , Franc and the like.
  • triisopropylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, triphenylphosphine, and tri-n-butylphosphine are preferred.
  • the monomer subjected to ring-opening polymerization is a cyclic olefin.
  • 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.
  • 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.
  • dicyclopentenes are most preferable in terms of economy.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the reaction stock solution 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.
  • 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.
  • SBR styrene-butadiene copolymer
  • SBS styrene-butane distyrene-styrene block copolymer
  • Isoprene-styrene examples include a styrene copolymer (SIS), an ethylene-propylene-diene
  • 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.
  • 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.
  • 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.
  • a solvent that dissolves the produced polymer and does not inhibit the polymerization is used.
  • 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 te
  • 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.
  • 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.
  • RTM resin transfer molding
  • RIM reaction injection molding
  • 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.
  • 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.
  • 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.
  • the maximum temperature of the contents in the mold is 140 or more.
  • a more preferred maximum temperature is 150 to 250.
  • 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.
  • 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.
  • 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).
  • 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.
  • Example 1 The same operation as in Example 1 was performed except that the Lewis acid was not added. Table 1 shows the measurement results.
  • 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).
  • Example 8 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
  • B is the thermocouple on the back side.
  • the pair C was set.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Tg glass transition temperature
  • 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 :.
  • 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.
  • Catalyst Solution 3 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.
  • catalyst solution 4 6 ml 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.
  • 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.
  • 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.
  • 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
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

L'invention se rapporte à un procédé de production d'un polymère cyclo-oléfinique consistant à mélanger un mélange réactionnel liquide de départ comportant une cyclo-oléfine avec un catalyseur comportant un complexe contenant du ruthénium et, associé à celui-ci en tant que ligand, au moins un élément sélectionné parmi des donneurs d'électrons neutres et des composés carbène contenant des hétéroatomes, et à polymériser la cyclo-oléfine par métathèse avec ouverture de cycle. Ce procédé se caractérise en ce que le mélange réactionnel liquide de départ est préparé dans une atmosphère gazeuse inerte. La polymérisation par métathèse avec ouverture de cycle est effectuée comme une polymérisation en masse ou une polymérisation en solution. Selon le cas, un acide de Lewis est incorporé au mélange réactionnel liquide de départ comportant une cyclo-oléfine, et une base de Lewis est utilisée en association au catalyseur. Selon ce procédé, il est possible d'obtenir, avec un taux de conversion élevé, un polymère qui ne nécessite pas de post-traitement après la polymérisation.
PCT/JP2000/007620 1999-11-01 2000-10-30 Procede de production d'un polymere cyclo-olefinique WO2001032739A1 (fr)

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JP31082599 1999-11-01

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005089744A (ja) * 2003-08-13 2005-04-07 Nippon Zeon Co Ltd 開環重合体、開環重合体水素化物およびそれらの製造方法、並びに重合触媒組成物
WO2005114711A1 (fr) * 2004-05-21 2005-12-01 Jsr Corporation Liquide pour exposition par immersion et procédé d’exposition par immersion
JP2006052333A (ja) * 2004-08-12 2006-02-23 Nippon Zeon Co Ltd ノルボルネン系開環重合体水素化物の製造方法およびノルボルネン系開環重合体水素化物
JP2008173979A (ja) * 2008-02-06 2008-07-31 Nippon Zeon Co Ltd 積層体

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4426502A (en) * 1982-06-14 1984-01-17 The B. F. Goodrich Company Bulk polymerization of cycloolefins
US5312940A (en) * 1992-04-03 1994-05-17 California Institute Of Technology Ruthenium and osmium metal carbene complexes for olefin metathesis polymerization

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4426502A (en) * 1982-06-14 1984-01-17 The B. F. Goodrich Company Bulk polymerization of cycloolefins
US5312940A (en) * 1992-04-03 1994-05-17 California Institute Of Technology Ruthenium and osmium metal carbene complexes for olefin metathesis polymerization

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005089744A (ja) * 2003-08-13 2005-04-07 Nippon Zeon Co Ltd 開環重合体、開環重合体水素化物およびそれらの製造方法、並びに重合触媒組成物
WO2005114711A1 (fr) * 2004-05-21 2005-12-01 Jsr Corporation Liquide pour exposition par immersion et procédé d’exposition par immersion
US7580111B2 (en) 2004-05-21 2009-08-25 Jsr Corporation Liquid for immersion exposure and immersion exposure method
JP2006052333A (ja) * 2004-08-12 2006-02-23 Nippon Zeon Co Ltd ノルボルネン系開環重合体水素化物の製造方法およびノルボルネン系開環重合体水素化物
JP2008173979A (ja) * 2008-02-06 2008-07-31 Nippon Zeon Co Ltd 積層体
JP4548491B2 (ja) * 2008-02-06 2010-09-22 日本ゼオン株式会社 積層体

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