WO2009123209A1 - Composition polymérisable, article moulé en résine et article moulé en résine réticulée - Google Patents

Composition polymérisable, article moulé en résine et article moulé en résine réticulée Download PDF

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Publication number
WO2009123209A1
WO2009123209A1 PCT/JP2009/056707 JP2009056707W WO2009123209A1 WO 2009123209 A1 WO2009123209 A1 WO 2009123209A1 JP 2009056707 W JP2009056707 W JP 2009056707W WO 2009123209 A1 WO2009123209 A1 WO 2009123209A1
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resin molded
polymerizable composition
atom
carbene complex
complex catalyst
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PCT/JP2009/056707
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English (en)
Japanese (ja)
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有信 堅田
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日本ゼオン株式会社
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Priority to JP2010505947A priority Critical patent/JP5365625B2/ja
Publication of WO2009123209A1 publication Critical patent/WO2009123209A1/fr

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O

Definitions

  • the present invention relates to a polymerizable composition, a resin molded body, and a crosslinked resin molded body. More specifically, a cross-linked resin molded article or a cross-linked resin composite suitable as an electric material used for an electric circuit board can be obtained, and the polymerizability that achieves both a rise in viscosity over time and a high polymerization conversion rate. Composition, resin molded body obtained using the polymerizable composition, and electrical insulation, adhesion, mechanical strength, heat resistance, and dielectric properties obtained using the polymerizable composition or the resin molded body The present invention relates to a crosslinked resin molded article excellent in
  • a polymer exhibiting excellent mechanical or electrical properties can be obtained by bulk polymerization of a cycloolefin monomer using a metathesis polymerization catalyst such as a ruthenium carbene complex.
  • Patent Document 1 discloses that a polymerizable composition containing a norbornene-based monomer, a ruthenium carbene complex catalyst, a chain transfer agent, and a crosslinking agent is subjected to metathesis bulk polymerization to obtain a crosslinkable thermoplastic resin, and this crosslinkable thermoplastic resin. Is laminated on a substrate or the like and crosslinked to obtain a composite material.
  • metathesis polymerization using a ruthenium carbene complex catalyst has high activity and extremely high polymerization rate compared to polymerization of an epoxy resin or the like usually used as an insulating material for an electric circuit board. Therefore, when forming into a film shape by impregnating the polymerizable composition into a fiber reinforcement, the molecular weight and viscosity of the polymerizable composition are increased before molding. There is a problem that it becomes difficult to impregnate the product with a fiber reinforcing material, and the properties of the resulting cross-linkable thermoplastic resin become unstable.
  • Patent Document 2 and Patent Document 3 disclose a ruthenium carbene complex having a chelating carbene ligand, and the progress of the reaction is delayed by using the complex having the structure as a metathesis polymerization catalyst. It has been suggested that In particular, in Patent Document 3, by using two types of isomers of a ruthenium carbene complex having a chelating carbene ligand, polymerization latency is exploited by utilizing the difference in polymerization activity between the two types of isomers. It is disclosed that the period can be controlled.
  • Special Table 2002-506455 Special table 2007-530706 gazette
  • Patent Document 4 discloses a method for producing a ruthenium carbene complex catalyst using alkylacetylene, which suggests that the productivity of catalyst synthesis is increased.
  • Patent Document 4 there is no description about the characteristics after monomer polymerization using the synthesized ruthenium carbene complex catalyst. According to the study of the present inventor, in the disclosed ruthenium carbene complex catalyst, the reaction as described above is not performed. It was not possible to simultaneously control the progress and the polymerization conversion of the monomer. JP-T-2001-503434
  • Non-Patent Document 1 also discloses a ruthenium carbene complex catalyst having a chelating carbene ligand.
  • a catalyst disclosed in Non-Patent Document 1 it has been impossible to achieve both a rise in viscosity due to the passage of time of the polymerizable composition and a high polymerization conversion rate.
  • Non-Patent Document 1 discusses that an equilibrium reaction occurs in which a compound in which a carbene substituent of a ruthenium carbene complex catalyst is chelated becomes an unchelated compound in the presence of tricyclohexylphosphine.
  • the method described in Non-Patent Document 1 allows an equilibrium reaction between compounds having structures represented by Formula (A1) and Formula (A2) described later. I could not confirm what would happen. Therefore, in the method of Non-Patent Document 1, the composition of the ruthenium carbene complex catalyst cannot be controlled.
  • An object of the present invention is to obtain a resin molded article suitable as an electric material used for an electric circuit board and the like, and a polymerizable composition that achieves both suppression of increase in viscosity over time and high polymerization conversion, and production thereof It is to provide a method. Further, a resin molded body obtained by using the polymerizable composition, a method for producing the same, a crosslinked resin molded body having excellent electrical insulation, adhesion, mechanical strength, heat resistance, dielectric properties, and the like, and production thereof It is to provide a method.
  • a ruthenium carbene complex catalyst having a chelate coordination structure [ruthenium having a structure represented by the formula (A1) described later] is used in the production of a polymerizable composition.
  • a mixture of a carbene complex catalyst (A1)] and a ruthenium carbene complex catalyst [ruthenium carbene complex catalyst (A2) having a structure represented by the formula (A2) described later] having no chelate coordination structure It is possible to simultaneously satisfy the two contradictory properties of suppressing the increase in viscosity over time and obtaining a high monomer polymerization conversion rate, whereby the fibrous composition can be uniformly impregnated with the polymerizable composition.
  • the cross-linked resin molded body and the cross-linked resin excellent in electrical insulation, adhesion, mechanical strength, heat resistance, dielectric properties, etc. It has been found that a fat composite can be produced stably.
  • the present inventor further found out a production method that is excellent in productivity of the polymerizable composition by preparing the mixture of ruthenium carbene complex catalyst at once.
  • the present invention has been completed based on these findings.
  • L 1 and L 2 are neutral electron donating ligands;
  • X 1 and X 2 are anionic ligands;
  • R 1 represents a hydrogen atom, a carbon atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms substituted with a group containing any of a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom Is;
  • A is a divalent or trivalent organic group;
  • Z is an electron donating group.
  • L 1 and L 2 are neutral electron donating ligands;
  • X 1 and X 2 are anionic ligands;
  • R 1 represents a hydrogen atom, a carbon atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms substituted with a group containing any of a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom Is;
  • A is a divalent or trivalent organic group;
  • Z is an electron donating group.
  • [6] A method for producing a resin molded body comprising a step of subjecting the polymerizable composition according to [5] to metathesis bulk polymerization.
  • [7] A method for producing a crosslinked resin molded product, comprising a step of crosslinking the resin molded product obtained by the production method according to [6].
  • [8] A ruthenium carbene complex catalyst (A1) and a ruthenium carbene complex catalyst (A2) defined in the above [1] by reacting the compound (B) and the compound (C) defined in the above [2]. ) And a step of mixing the ruthenium carbene complex catalyst mixture with a cycloolefin monomer.
  • a resin molded body obtainable by the production method according to [6].
  • [10] A crosslinked resin molded article obtainable by the production method according to [7].
  • the polymerizable composition of the present invention can simultaneously satisfy two contradictory properties of suppressing the increase in viscosity over time and increasing the polymerization conversion rate of the monomer, and can uniformly impregnate the fibrous reinforcement. It is.
  • the polymerizable composition of the present invention is bulk polymerized and then crosslinked, a crosslinked resin molded article excellent in properties such as electrical insulation, adhesion, mechanical strength, heat resistance, and dielectric properties can be stably produced.
  • a polymerizable composition is prepared by using a mixture of ruthenium carbene complex catalysts prepared in a lump by the production method of the present invention, the polymerizable composition having the above-described characteristics can be produced with high productivity.
  • the cross-linked resin molded product and the cross-linked resin composite obtained using the polymerizable composition of the present invention are suitable as an electric material used for an electric circuit board.
  • the polymerizable composition of the present invention contains a mixture of a ruthenium carbene complex catalyst and a cycloolefin monomer.
  • the cycloolefin monomer constituting the polymerizable composition of the present invention is a compound having a ring structure formed of carbon atoms and having a carbon-carbon double bond in the ring. The carbon-carbon double bond is a bond that can be opened by a metathesis reaction to form a polymer.
  • Examples of cycloolefin monomers include norbornene monomers.
  • the norbornene-based monomer is a cycloolefin monomer containing a norbornene ring.
  • the norbornene monomer has a hydrocarbon group having 1 to 20 carbon atoms such as an alkyl group, an alkenyl group, an alkylidene group, and an aryl group, and a polar group such as a carboxyl group or an acid anhydride group as a substituent. May be.
  • a polar group such as a carboxyl group or an acid anhydride group as a substituent. May be.
  • the norbornene ring double bond it may further have a double bond.
  • norbornene-based monomers that do not contain a polar group that is, are composed only of carbon atoms and hydrogen atoms are preferable.
  • the number of rings constituting the norbornene-based monomer is preferably 3 to 6, more preferably 3 or 4, and particularly preferably 4.
  • the content of the norbornene monomer in the cycloolefin monomer is not particularly limited, but is preferably 60% by weight or more, more preferably 80% by weight or more. Further, the total amount of the cycloolefin monomer may be a norbornene monomer.
  • Norbornenes having 2 rings such as -2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-propenyl-2-norbornene;
  • the number of rings such as 5-cyclohexyl-2-norbornene, 5-cyclopentyl-2-norbornene, 5-cyclohexenyl-2-norbornene, 5-cyclopentenyl-2-norbornene, 5-phenyl-2-norbornene is 3 Norbornenes; dicyclopentadiene, methyldicyclopentadiene, dihydrodicyclopentadiene (also referred to as tricyclo [5.2.1.0 2,6 ] dec-8-ene), etc. Pentadienes;
  • Examples of norbornene-based monomers containing a polar group include tetracyclo [6.2.1.1 3,6 . 0 2,7 ] methyl dodeca-9-ene-4-carboxylate, tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-9-ene-4-methanol, tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-9-ene-4-carboxylic acid, tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-9-ene-4,5-dicarboxylic acid, tetracyclo [6.2.1.1 3,6 .
  • dodec-9-ene-4,5-dicarboxylic anhydride methyl 5-norbornene-2-carboxylate, methyl 2-methyl-5-norbornene-2-carboxylate, 5-norbornene-2 acetate -Yl, 5-norbornene-2-methanol, 5-norbornene-2-ol, 5-norbornene-2-carbonitrile, 2-acetyl-5-norbornene, 7-oxa-2-norbornene and the like.
  • monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclooctene, cyclododecene, 1,5-cyclooctadiene, and derivatives thereof having a substituent are added to the norbornene-based monomer for polymerization.
  • the above cycloolefin monomers can be used alone or in combination of two or more. It is possible to control the glass transition temperature and the melting temperature of the resulting resin molded article by using two or more monomers together and changing the quantity ratio.
  • the addition amount of the monocyclic cycloolefins and their derivatives is usually 40% by weight or less, preferably 20% by weight or less, based on the total amount of the cycloolefin monomer. When the addition amount exceeds 40% by weight, the heat resistance of the polymer obtained by bulk polymerization tends to be insufficient.
  • the mixture of the ruthenium carbene complex catalyst constituting the polymerizable composition of the present invention includes a ruthenium carbene complex catalyst (A1) having a chelate-coordinated ring structure having a structure represented by the following formula (A1): And a ruthenium carbene complex catalyst (A2) having a structure represented by the formula (A2) and having no chelate coordination ring structure.
  • Z is chelate-coordinated to Ru, that is, Z is coordinated to Ru via a lone pair as a ligand, and C, A, Z and Ru Thus, a chelate coordination ring structure is formed.
  • R 1 is a hydrogen atom, a carbon atom, a halogen atom, or a group containing any of a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom.
  • X 1 and X 2 each independently represents an arbitrary anionic ligand.
  • L 1 and L 2 each independently represent a neutral electron donating ligand.
  • A represents a divalent or trivalent organic group.
  • An organic group is an atomic group containing a carbon atom. The organic group is not particularly limited.
  • Z is an electron donating group.
  • the electron donating group is an atomic group composed of at least one atom having an unshared electron pair.
  • Examples of the electron donating group include an atomic group having a structure represented by OR 2 , O, PR 3 R 4 , or NR 5 R 6 .
  • R 2 to R 6 each independently represents a hydrocarbon group having 1 to 20 carbon atoms.
  • Anionic ligands are ligands that have a negative charge when pulled away from the central metal.
  • the anionic ligand include halogen atoms such as F, Cl, Br, and I. Among these, Cl (chlorine atom) is preferable.
  • a neutral electron donating ligand is a ligand that has a neutral charge when pulled away from the central metal.
  • the neutral electron donating ligand is not particularly limited, and examples thereof include carbene compounds, carbonyls, amines, pyridines, ethers, nitriles, esters, phosphines, thioethers, aromatic compounds, olefins. , Isocyanides, thiocyanates and the like.
  • carbene compounds, phosphines, ethers, and pyridines are preferable, carbene compounds are more preferable, and heteroatom-containing carbene compounds are particularly preferable.
  • the heteroatom in the heteroatom-containing carbene compound means an atom belonging to Group 15 and Group 16 of the periodic table (according to the long-period type periodic table; the same shall apply hereinafter).
  • O, P, S, As, Se, etc. can be mentioned.
  • N, O, P, and S are preferable, and N (nitrogen atom) is more preferable.
  • the heteroatom-containing carbene compound preferably has a structure in which heteroatoms are adjacently bonded to both sides of the carbene carbon atom, and further comprises a heterocycle comprising the carbene carbon atom and heteroatoms on both sides thereof. It is more preferable. Moreover, it is preferable that the hetero atom adjacent to the carbene carbon atom has a bulky substituent.
  • heteroatom-containing carbene compound examples include compounds represented by the following formula (D) or formula (E).
  • R 7 to R 10 are each independently a hydrogen atom, a halogen atom, or a carbon atom that may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. This represents a hydrocarbon group of 1 to 20. R 7 to R 10 may be bonded to each other in any combination to form a ring.
  • Examples of the divalent or trivalent organic group represented by A in the formula (A1) and the formula (A2) include a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. Examples thereof may include a divalent or trivalent hydrocarbon group having 1 to 20 carbon atoms.
  • the “hydrocarbon group” may be a chain hydrocarbon group or a cyclic hydrocarbon group.
  • a preferable example of A is a cyclic hydrocarbon group containing one nitrogen atom, and the cyclic hydrocarbon bonded to the carbene carbon bonded to the ruthenium atom at the nitrogen atom.
  • Specific examples of such cyclic hydrocarbon groups include groups having the following structures.
  • the combination of the ruthenium carbene complex catalyst (A1) and the ruthenium carbene complex catalyst (A2) is, for example, (1,3-dimesityl-4- Imidazoline-2-ylidene) (2-pyrrolidone-1-ylmethylene) (tricyclohexylphosphine) ruthenium dichloride and (1,3-dimesityl-4-imidazoline-2-ylidene) (2-pyrrolidone-1-ylmethylene) ruthenium dichloride (1,3-dimesityl-4-imidazoline-2-ylidene) (2-phthalimido-1-ylmethylene) (tricyclohexylphosphine) ruthenium dichloride and (1,3-dimesityl-4-imidazoline-2-ylidene) ( 2-phthalimido-1-ylmethyl (Len) ruthen
  • the amount ratio of the ruthenium carbene complex catalyst (A1) and (A2) is in this range, the two contradictory properties of suppressing the increase in viscosity with time and increasing the polymerization conversion of the monomer are further satisfied at the same time. This is preferable.
  • the use amount of the ruthenium carbene complex catalyst as the mixture of the polymerizable composition of the present invention is usually 1: 2,000 to 1: 2,000,000 in terms of a molar ratio of (ruthenium atom: cycloolefin monomer).
  • the range is preferably 1: 5,000 to 1: 1,000,000, more preferably 1: 10,000 to 1: 500,000.
  • the ruthenium carbene complex catalyst can be used, if desired, dissolved or suspended in a small amount of an inert solvent.
  • solvents include chain aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, liquid paraffin, mineral spirits; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane , Cycloaliphatic hydrocarbons such as decahydronaphthalene, dicycloheptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene, xylene and indene; nitrogen-containing compounds such as nitromethane, nitrobenzene and acetonitrile Hydrocarbons; oxygen-
  • reaction (a) In the formulas (B) and (C), L 1 , L 2 , X 1 , X 2 , R 1 , A, and Z are the same as described in the formulas (A1) and (A2). Reaction (a) is performed as follows. The compound (B) having a structure represented by the formula (B) and the compound (C) having a structure represented by the formula (C) are dissolved in a solvent.
  • the amount of compound (C) added is usually in the range of 2 to 30 equivalents, preferably 5 to 25 equivalents, more preferably 10 to 20 equivalents, relative to compound (B).
  • the solvent is capable of dissolving the ruthenium carbene complex catalysts (A1) and (A2) and the compounds (B) and (C), and is preferably inert to the ruthenium carbene complex catalyst.
  • Specific examples of the solvent include toluene, benzene, tetrahydrofuran, dichloromethane, and chloroform. Of these, tetrahydrofuran and benzene are preferable, and tetrahydrofuran is more preferable.
  • the amount of the solvent is not particularly limited as long as the ruthenium carbene complex catalysts (A1) and (A2) and the compounds (B) and (C) are dissolved, but usually 50 parts per 100 parts by weight of the compound (B). It is in the range of ⁇ 300 parts by weight, preferably 80 to 200 parts by weight. When the amount of the solvent is within this range, the compounds (B) and (C) are sufficiently dissolved, and the efficiency of drying the solvent described later is excellent and preferable.
  • the reaction system is preferably filled with an inert gas so that the compound (B) does not decompose. Specifically, nitrogen or argon gas is usually selected as the inert gas.
  • the dissolution temperature is usually in the range of ⁇ 60 to + 20 ° C., preferably ⁇ 50 to 0 ° C., more preferably ⁇ 40 to ⁇ 10 ° C. When the dissolution temperature is within this range, the compound (B) does not decompose and is excellent in workability.
  • a reaction accelerator for reaction (a) such as CH 3 CN and a compound having a structure represented by CH ⁇ CR 11 are added. It is preferable to start the reaction for producing the ruthenium carbene complex catalyst mixture by increasing the temperature in the container.
  • R 11 is not particularly limited, and examples thereof include alkyl groups, alkenyl groups, aryl groups, alkoxy groups, ether bond-containing groups, amino groups, nitrile groups, thiol groups, carbonyl groups, aldehyde groups, ketone groups, carboxyl groups, and esters. Examples thereof include a bond-containing group and an amide group. Preferably, it is a carboxyl group.
  • the reaction temperature is usually ⁇ 20 to + 50 ° C., preferably 0 to 40 ° C. When the reaction temperature is within this range, it is preferable that the compound (B) does not decompose and the reaction proceeds without delay.
  • the amount ratio of the ruthenium carbene complex catalysts (A1) and (A2) in the mixture can be controlled to a desired value, and the ruthenium carbene can be efficiently performed in one reaction. Mixtures of complex catalysts can be produced. Within this range, particularly when the reaction temperature is high, the ratio of the ruthenium carbene complex catalyst (A1) can be increased in the mixture of the ruthenium carbene complex catalyst (A1) and (A2) to be produced.
  • the ratio of the ruthenium carbene complex catalyst (A2) can be increased.
  • the reaction time is appropriately selected depending on the purpose, but is usually in the range of 20 minutes to 3 hours, preferably 1 hour to 2 hours.
  • X ⁇ 1 >, X ⁇ 2 >, L ⁇ 1 > and L ⁇ 2 > substitution for raising polymerization activity is usually performed, and the structure of a ruthenium carbene complex catalyst can be changed to a more preferable aspect.
  • X 1 and X 2 can be replaced with the desired halogen atom by reaction with HF, HCl, HBr, or HI.
  • L 1 and L 2 can be substituted with a heteroatom-containing carbene or the like in the presence of potassium-t-butoxide or the like.
  • the ruthenium carbene complex catalyst can be substituted with a desired structure, and a more suitable mixture of the ruthenium carbene complex catalyst (A1) and (A2) can be produced.
  • the produced mixture of the ruthenium carbene complex catalysts (A1) and (A2) is isolated from other compounds in the reaction system according to a usual method.
  • the isolation method include methods such as adsorption of impurities, recrystallization, and precipitation with a poor solvent, usually after drying the solvent used in the reaction under reduced pressure and passing through a column containing silica.
  • precipitation with a poor solvent is preferable because of excellent workability.
  • the poor solvent is not particularly limited as long as it does not dissolve the ruthenium carbene complex catalyst, and examples thereof include methanol, ethanol, n-pentane, and n-hexane.
  • the temperature at which the ruthenium carbene complex catalyst is precipitated with a poor solvent is preferably lower.
  • a mixture of the ruthenium carbene complex catalysts (A1) and (A2) can be obtained.
  • a mixture is dissolved or dispersed in an appropriate solvent to prepare a catalyst solution, which is used for polymerization of cycloolefin monomer.
  • a catalyst solution which is used for polymerization of cycloolefin monomer.
  • the cycloolefin monomer can be polymerized while maintaining the quantitative ratio of the ruthenium carbene complex catalysts (A1) and (A2) in the obtained mixture.
  • the polymerizable composition of the present invention is obtained.
  • the mixing ratio of the mixture and the cycloolefin monomer may be appropriately determined in consideration of the amount of the ruthenium carbene complex catalyst used.
  • the manufacturing method of the polymeric composition containing the mixture of the ruthenium carbene complex catalyst (A1) and (A2) of this invention includes the process of manufacturing this mixture collectively, it has high productivity.
  • the polymerizable composition of the present invention comprises, for example, a ruthenium carbene complex catalyst (A1) and (A2) with reference to a known production method of a ruthenium carbene complex catalyst and a method described in Example 3 described later. It can also be prepared by preparing separately and mixing them to obtain a mixture of ruthenium carbene complex catalysts which are mixed with cycloolefin monomer.
  • additives such as polymerization reaction retarders, chain transfer agents, crosslinking agents, radical crosslinking retarders, modifiers, antioxidants, difficulty A flame retardant, a filler, a colorant, a light stabilizer and the like can be contained. These can be used by, for example, dissolving or dispersing in advance in a monomer liquid or a catalyst liquid when the polymerizable composition of the present invention is produced.
  • polymerization reaction retarder examples include phosphines such as triphenylphosphine, tributylphosphine, trimethylphosphine, and triethylphosphine; Lewis bases such as aniline and pyridine.
  • phosphines are preferred because the pot life of the polymerizable composition of the present invention can be controlled efficiently and the inhibition of the polymerization reaction is small.
  • cycloolefin monomers a monomer having a 1,5-diene structure or a 1,3,5-triene structure in the molecule also functions as a polymerization reaction retarder. Examples of such compounds include 1,5-cyclooctadiene and 5-vinyl-2-norbornene.
  • chain olefins which may have a substituent can be usually used. Specifically, aliphatic olefins such as 1-hexene and 2-hexene; olefins having an aromatic group such as styrene, divinylbenzene and stilbene; olefins having an alicyclic hydrocarbon group such as vinylcyclohexane; Vinyl ethers such as ethyl vinyl ether; vinyl ketones such as methyl vinyl ketone, 1,5-hexadien-3-one, 2-methyl-1,5-hexadien-3-one; styryl acrylate, ethylene glycol diacrylate; allyltri Vinylsilane, allylmethyldivinylsilane, allyldimethylvinylsilane; glycidyl acrylate, allylglycidyl ether; allylamine, 2- (diethylamino) ethanol vinyl ether, 2- (diethylamino)
  • chain transfer agents compounds represented by the formula (F): CH 2 ⁇ CH—Y—OCO—CR 12 ⁇ CH 2 are preferable.
  • Y in the formula (F) is an alkylene group, and R 12 is a hydrogen atom or a methyl group.
  • the number of carbon atoms of the alkylene group is not particularly limited, but is usually 1 to 20, preferably 4 to 12.
  • Examples of the compound represented by the formula (F) include allyl methacrylate, 3-buten-1-yl methacrylate, allyl acrylate, 3-buten-1-yl acrylate, undecenyl methacrylate, hexenyl methacrylate, and the like. It is done. Of these, undecenyl methacrylate and hexenyl methacrylate are particularly preferred.
  • the addition amount of the chain transfer agent is usually 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the total amount of the cycloolefin monomer.
  • the addition amount of the chain transfer agent is within this range, a resin molded product having a high metathesis polymerization reaction rate and capable of being crosslinked by the crosslinking agent can be efficiently obtained.
  • the soot polymerizable composition further contains a crosslinking agent in order to obtain a resin molded body that can be crosslinked after bulk polymerization.
  • the crosslinking agent is a compound that can induce a crosslinking reaction in the resin molded body.
  • examples of the crosslinking agent include radical generators, epoxy compounds, isocyanate group-containing compounds, carboxyl group-containing compounds, acid anhydride group-containing compounds, amino group-containing compounds, Lewis acids, and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.
  • radical generators epoxy compounds, isocyanate group-containing compounds, carboxyl group-containing compounds, and acid anhydride group-containing compounds
  • radical generators epoxy compounds, and isocyanate group-containing compounds
  • carboxyl group-containing compounds, and acid anhydride group-containing compounds are preferred, and the use of radical generators, epoxy compounds, and isocyanate group-containing compounds is more preferred.
  • the use of radical generators is particularly preferred.
  • radical generator examples include organic peroxides, diazo compounds, and nonpolar radical generators.
  • organic peroxide examples include hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide; dicumyl peroxide, t-butylcumyl peroxide, ⁇ , ⁇ '-bis (t- Butylperoxy-m-isopropyl) benzene, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, 2,5-dimethyl-2,5-di ( dialkyl peroxides such as t-butylperoxy) hexane; diacyl peroxides such as dipropionyl peroxide and benzoyl peroxide; 2,2-di (t-butylperoxy) butane, 1,1-di (t-hexylperoxy)
  • diazo compound examples include 4,4′-bisazidobenzal (4-methyl) cyclohexanone, 4,4′-diazidochalcone, 2,6-bis (4′-azidobenzal) cyclohexanone, and 2,6-bis.
  • Nonpolar radical generators used in the present invention include 2,3-dimethyl-2,3-diphenylbutane, 2,3-diphenylbutane, 1,4-diphenylbutane, 3,4-dimethyl-3,4- Diphenylhexane, 1,1,2,2-tetraphenylethane, 2,2,3,3-tetraphenylbutane, 3,3,4,4-tetraphenylhexane, 1,1,2-triphenylpropane, 1 1,1,2-triphenylethane, triphenylmethane, 1,1,1-triphenylethane, 1,1,1-triphenylpropane, 1,1,1-triphenylbutane, 1,1,1-triphenyl And phenylpentane, 1,1,1-triphenyl-2-propene, 1,1,1-triphenyl-4-pentene, 1,1,1-triphenyl-2-phenylethane, etc. .
  • radical generators may be used alone or in combination of two or more. It is possible to control the glass transition temperature and the molten state of the resin molded body and cross-linked resin molded body obtained by using two or more kinds of radical generators together and changing the quantity ratio thereof.
  • the amount of the crosslinking agent is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the cycloolefin monomer. If the amount of the crosslinking agent is too small, crosslinking may be insufficient, and a crosslinked product having a high crosslinking density may not be obtained. When the amount of the crosslinking agent is too large, the crosslinking effect is saturated, but there is a possibility that a resin molded body and a crosslinked resin molded body having desired physical properties cannot be obtained.
  • crosslinking aids include hydrocarbon compounds having two or more isopropenyl groups such as diisopropenylbenzene; methacrylate compounds such as lauryl methacrylate and trimethylolpropane trimethacrylate; cyanuric acids such as triallyl cyanurate and triallyl isocyanurate Compounds; imide compounds such as maleimide; and the like.
  • the amount of the crosslinking aid is not particularly limited, but is usually 0 to 100 parts by weight, preferably 0 to 50 parts by weight with respect to 100 parts by weight of the cycloolefin monomer.
  • radical crosslinking retarders examples include alkoxyphenols, catechols, and benzoquinones, and alkoxyphenols such as 3,5-di-t-butyl-4-hydroxyanisole are preferred.
  • flame retardants examples include phosphorus flame retardants, nitrogen flame retardants, halogen flame retardants, metal hydroxide flame retardants such as aluminum hydroxide, and antimony compounds such as antimony trioxide. Although a flame retardant may be used independently, you may use it in combination of 2 or more type.
  • filler various materials can be used regardless of whether they are organic or inorganic as long as they are insoluble in the cycloolefin monomer and the solvent used as required.
  • a filler is suitably selected according to the use of the resin molding obtained and a crosslinked resin molding.
  • the average particle diameter is not particularly limited, it is usually a median diameter containing 50% by volume of the total filler measured with a laser scattering diffraction particle size distribution meter, and is usually 0.001 to 70 ⁇ m, preferably 0.01 to 50 ⁇ m, more The thickness is preferably 0.05 to 15 ⁇ m.
  • the inorganic filler include glass, ceramic, silica and the like.
  • the organic filler include polyolefin, various elastomers, waste plastics and the like.
  • short fiber fillers such as chopped strands and milled fibers can also be used.
  • the fiber examples include inorganic fibers such as glass fibers, carbon fibers, and metal fibers, or organic fibers such as aramid fibers, nylon fibers, jute fibers, kenaf fibers, bamboo fibers, polyethylene fibers, and polypropylene fibers.
  • these fillers may be used alone or in combination of two or more.
  • the filler one that has been surface-treated with a silane coupling agent or the like can also be used.
  • the amount of the filler is usually 0 to 600 parts by weight, preferably 50 to 500 parts by weight, and more preferably 50 to 300 parts by weight with respect to 100 parts by weight of the cycloolefin monomer.
  • colorant dyes, pigments and the like are used. There are various kinds of dyes, and known dyes can be appropriately selected and used.
  • the polymerizable composition of the present invention is prepared by preparing a liquid (catalyst liquid) in which a ruthenium carbene complex catalyst is dissolved or dispersed in an appropriate solvent, and separately adding other additives to a cycloolefin monomer as required ( It is preferable to prepare a monomer liquid) by adding a catalyst liquid to the monomer liquid and stirring.
  • a catalyst liquid to the monomer liquid and stirring.
  • the addition of the ruthenium carbene complex catalyst is preferably performed immediately before the bulk polymerization described below.
  • the chain transfer agent, radical generator, radical crosslinking retarder, etc. may be added in advance to the monomer liquid and / or catalyst liquid before mixing the monomer liquid and catalyst liquid, or the monomer liquid and catalyst liquid. May be added simultaneously with or after mixing.
  • the resin molded product of the present invention can be obtained by bulk polymerization of the polymerizable composition substantially without using a solvent.
  • a method of coating the polymerizable composition on a support, and then bulk polymerization for example, (a) a method of coating the polymerizable composition on a support, and then bulk polymerization, (b) Examples thereof include a method in which the polymerizable composition is injected into the space of the mold and then bulk polymerization, and (c) a method in which the fibrous composition is impregnated with the polymerizable composition and then bulk polymerization.
  • the polymerizable composition of the present invention has a low viscosity, the application in the method (a) can be smoothly carried out, and the injection in the method (b) does not rapidly cause foaming even in a complex-shaped space.
  • the fibrous reinforcing material can be impregnated quickly and uniformly.
  • a resin molded body such as a film or plate
  • the thickness of the molded body is usually 15 mm or less, preferably 5 mm or less, more preferably 0.5 mm or less, and most preferably 0.1 mm or less.
  • the support include films and plates made of resins such as polyethylene terephthalate, polypropylene, polyethylene, polycarbonate, polyethylene naphthalate, polyarylate, and nylon; iron, stainless steel, copper, aluminum, nickel, chromium, gold, and silver.
  • films and plates made of metal materials such as Especially, use of metal foil or a resin film is preferable.
  • the thickness of these metal foils or resin films is usually 1 to 150 ⁇ m, preferably 2 to 100 ⁇ m, more preferably 3 to 75 ⁇ m from the viewpoint of workability and the like.
  • Examples of the method for applying the polymerizable composition of the present invention on the support include known coating methods such as spray coating, dip coating, roll coating, curtain coating, die coating, and slit coating. .
  • the polymerizable composition coated on the support is optionally dried and then bulk polymerized.
  • the polymerizable composition is heated for bulk polymerization.
  • a heating method a method of placing and heating the polymerizable composition applied to a support on a heating plate, a method of heating while applying pressure using a press (hot pressing), a method of pressing a heated roller, Examples include a method using a heating furnace.
  • the shape of the resin molding obtained by the method of (b) can be arbitrarily set by a molding die.
  • a film shape, a column shape, other arbitrary three-dimensional shapes, etc. are mentioned.
  • the shape, material, size, etc. of the mold are not particularly limited.
  • a conventionally known mold for example, a split mold structure, that is, a mold having a core mold and a cavity mold; a mold having a spacer between two plates; and the like can be used.
  • the pressure (injection pressure) for injecting the polymerizable composition of the present invention into the space (cavity) of the mold is usually 0.01 to 10 MPa, preferably 0.02 to 5 MPa. If the injection pressure is too low, the filling may be insufficient and the transfer surface formed on the inner surface of the cavity may not be transferred well. If the injection pressure is too high, the mold may have high rigidity. Needed and not economical.
  • the mold clamping pressure is usually in the range of 0.01 to 10 MPa.
  • Bulk polymerization can be performed by heating the polymerizable composition filled in the heel space.
  • Examples of the method for heating the polymerizable composition include a method using a heating means such as an electric heater and steam disposed in a mold, and a method for heating the mold in an electric furnace.
  • Examples of the resin molded product obtained by the method of c) (c) include a prepreg formed by filling a bulk polymer with a gap between fibrous reinforcing materials.
  • fibrous reinforcing material inorganic and / or organic fibers can be used, such as glass fibers, metal fibers, ceramic fibers, carbon fibers, aramid fibers, polyethylene terephthalate fibers, vinylon fibers, polyester fibers, amide fibers, And known ones such as liquid crystal fibers such as polyarylate. These may be used individually by 1 type and may be used in combination of 2 or more type.
  • Examples of the shape of the fibrous reinforcing material include mats, cloths, and nonwoven fabrics.
  • a predetermined amount of the polymerizable composition is poured onto a fibrous reinforcing material cloth, mat, etc. It can be performed by stacking protective films and pressing with a roller or the like from above.
  • a prepreg impregnated with a resin can be obtained by impregnating the polymerizable composition into a fibrous reinforcing material and then heating to a predetermined temperature to cause the resulting impregnated product to undergo bulk polymerization.
  • a heating method for example, a method in which an impregnated material is placed on a support and heated as in the method (a) above, a fibrous reinforcing material is set in a mold in advance, and a polymerizable composition is used. After impregnation, a method of heating as in the method (b) is used.
  • the heating temperature for bulk polymerization of the polymerizable composition is usually 30 to 250. ° C, preferably 50 to 200 ° C.
  • the polymerization time may be appropriately selected, but is usually 1 second to 20 minutes, preferably 10 seconds to 5 minutes or less.
  • the bulk polymerization reaction is started by heating the polymerizable composition to a predetermined temperature.
  • the temperature of the polymerizable composition rapidly increases due to the heat of reaction, and reaches the peak temperature in a short time (eg, about 10 seconds to 5 minutes). Further, the bulk polymerization reaction proceeds, but the polymerization reaction gradually stops and the temperature decreases. It is preferable to control the peak temperature so as to be equal to or higher than the glass transition temperature of the polymer constituting the resin molded body obtained by this polymerization reaction, since the polymerization proceeds completely.
  • the peak temperature can be controlled by the heating temperature.
  • the polymerization reaction rate of a polymer is 80% or more normally, Preferably it is 90% or more, More preferably, it is 95% or more.
  • the polymerization reaction rate of the polymer can be determined, for example, by analyzing a solution obtained by dissolving the polymer in a solvent by gas chromatography. A polymer in which bulk polymerization has proceeded almost completely has little residual monomer and substantially no odor.
  • the peak temperature during the bulk polymerization reaction becomes too high, not only the bulk polymerization reaction but also the crosslinking reaction may progress all at once. Therefore, in order to completely advance only the bulk polymerization reaction and prevent the crosslinking reaction from proceeding, it is usually preferable to control the peak temperature of the polymerizable composition in the bulk polymerization to less than 200 ° C. However, from the viewpoint of productivity and the like, the bulk polymerization reaction and the crosslinking reaction may proceed simultaneously.
  • the peak temperature in bulk polymerization is not more than the 1 minute half-life temperature of the radical generator.
  • the crosslinked resin molded article of the present invention is obtained by heating and crosslinking the resin molded article of the present invention obtained using a polymerizable composition containing a crosslinking agent.
  • the temperature at which the resin molded body is crosslinked by heating is usually 170 to 250 ° C., preferably 180 to 220 ° C. This temperature is preferably higher than the peak temperature in the bulk polymerization, and more preferably 20 ° C. or higher.
  • the time for crosslinking by heating is not particularly limited, but is usually 1 minute to 10 hours.
  • the method for heating and crosslinking the plastic molded body is not particularly limited.
  • the resin molded body is in the form of a film
  • a method of laminating a plurality of sheets if desired and applying pressure simultaneously with heating by hot pressing is preferable.
  • the pressure during hot pressing is usually 0.5 to 20 MPa, preferably 3 to 10 MPa.
  • the bulk polymerization reaction and the crosslinking reaction may be simultaneously performed to obtain a crosslinked resin molded body directly from the polymerizable composition.
  • the method for heating, polymerizing and crosslinking the polymerizable composition is not particularly limited.
  • a method of injecting a polymerizable composition into a mold and applying pressure simultaneously with heating by a hot press is preferable.
  • the pressure during hot pressing is usually 0.5 to 20 MPa, preferably 3 to 10 MPa.
  • the resin molded body or the crosslinked resin molded body may be used as a laminate.
  • the laminate has a constituent layer composed of the resin molded body or the crosslinked resin molded body, more specifically, has at least two or more layers, and at least one of the layers is the resin molded body or the crosslinked resin. It is formed of a molded body.
  • a more specific example of such a laminate includes a laminate including a base material such as a copper foil and a constituent layer formed from the resin molded body or the crosslinked resin molded body of the present invention.
  • the laminated body may be a composite material in which a base material such as a copper foil and a resin layer made of a resin molded body or a crosslinked resin molded body are alternately laminated like a multilayer laminated substrate.
  • a base material such as a copper foil
  • a resin layer made of a resin molded body or a crosslinked resin molded body are alternately laminated like a multilayer laminated substrate.
  • the composition of each resin layer may be the same or different.
  • the base material examples include metal foils such as copper foil, aluminum foil, nickel foil, chrome foil, gold foil, and silver foil; substrates for manufacturing printed wiring boards; polytetrafluoroethylene (PTFE) films, conductive polymer films, etc. Resin film; Noise suppression sheet, radio wave absorber and the like.
  • the surface of the base material may be treated with a silane coupling agent, a thiol coupling agent, a titanate coupling agent, various adhesives, or the like.
  • a resin molded product obtained using the polymerizable composition of the present invention is suitable.
  • a laminate may be obtained by superimposing on a base material, or a laminate may be obtained by superimposing resin molded bodies on each other.
  • a polymerizable composition can be coated on a suitable base material or resin molded body, and the polymerizable composition can be polymerized to obtain a laminate.
  • the laminated body containing the structural layer which consists of the crosslinked resin molding of this invention for example, (1) The resin molding obtained using the polymeric composition containing a crosslinking agent is used for base material. Superposed, then heated to crosslink, (2) Laminate polymerizable composition on substrate material, proceed with bulk polymerization and crosslinking reaction, (3) Obtained using polymerizable composition containing crosslinking agent There is a method in which two or more obtained resin molded bodies are superposed and then heated to crosslink.
  • a resin molded body and a metal foil as a base material are overlapped and heated by hot pressing or the like to be cross-linked and firmly adhered to the metal foil.
  • a metal foil-clad laminate can be obtained.
  • the peel strength of the metal foil of the obtained metal foil-clad laminate is a value measured based on JIS C 6481, using a surface-treated F0 copper foil having a thickness of 12 ⁇ m, More than 0.2 kN / m, preferably more than 0.4 kN / m, more preferably more than 0.6 kN / m.
  • the bulk polymerization temperature of the polymerizable composition is set high and heating is performed at a temperature at which a crosslinking reaction occurs.
  • the peel strength at the interface increases.
  • a plurality of such laminates may be further laminated.
  • a laminate in which a metal foil, a crosslinked resin molded product, and a resin molded product are laminated in this order is used, a multilayer circuit board can be easily obtained.
  • a conductive circuit is formed by patterning the metal foil layer of the laminate.
  • the method for patterning the metal foil is not particularly limited, and examples thereof include a photolithography method and a laser processing method.
  • a via hole is formed through the cross-linked body layer and the resin molded body layer and exposing the conductor circuit on the bottom surface. Then, a conductor is provided to the via hole and a wiring electrically connected from the conductor circuit to the resin molded body layer side is provided to obtain a single-sided circuit board for a multilayer circuit board.
  • a method for forming the via hole is not particularly limited, and examples thereof include a laser drilling method and a paste printing method. After forming the via hole, a permanganate desmear method can be performed in order to remove laser smear generated by the laser drilling method.
  • a method for applying a conductor to the via hole is not particularly limited, and a method of filling the via hole with a conductive paste by a screen printing method may be used.
  • a conductive bump in which the conductive paste protrudes from the surface of the resin molded body layer can be formed.
  • the height of the conductive bump is usually 5 to 100 ⁇ m.
  • a conductor may be applied to the via hole by plating.
  • a multilayer circuit board having an inner layer wiring and a surface wiring can be obtained by stacking two or more single-sided circuit boards for the multilayer circuit board or by stacking them with another circuit board and hot pressing.
  • the hot press By the hot press, the resin molded body layer is melted and deformed according to the unevenness of the circuit board.
  • the resin molded body layer is further heated, a cross-linking reaction proceeds and adhesion is improved.
  • the resin molded body and the crosslinked resin molded body of the present invention can be produced by bulk polymerization and have an advantage that they can be produced very easily because a step of evaporating a large amount of solvent as in the conventional casting method is unnecessary.
  • the polymerizable composition of the present invention can be polymerized at a high polymerization conversion rate, the produced resin molded article has no stickiness and excellent workability, and has no odor derived from the monomer and excellent in the use environment. .
  • the polymerizable composition of the present invention has a very small increase in viscosity over time, and can uniformly impregnate a fibrous reinforcing material, and can always produce a resin molded product having stable properties.
  • the polymerizable composition of the present invention is produced with high productivity while using a plurality of ruthenium carbene complex catalysts by collectively producing a mixture of two types of ruthenium carbene complex catalysts having a specific structure. be able to.
  • the resin molded body and cross-linked resin molded body of the present invention have excellent electrical characteristics such as low dielectric loss tangent, and have a lower linear expansion coefficient and higher mechanical strength than conventional resin molded bodies, etc. Adhesion to other supports such as foil is also high.
  • the resin molded body and the crosslinked resin molded body of the present invention having such characteristics include a prepreg; a copper foil with resin; a printed wiring board, an insulating sheet, an interlayer insulating film, an overcoat, an antenna substrate, an electromagnetic wave absorber, an electromagnetic wave shield, and the like. It is suitable as an electronic component material.
  • Polymerization conversion A part of the central part of the prepreg was cut out and dissolved in toluene, and then the dissolved components were extracted, and the residual monomer amount was measured by gas chromatography. The polymerization conversion rate was calculated from the measured residual monomer amount and evaluated according to the following evaluation criteria. (Evaluation criteria) A: Polymerization conversion rate is 98% or more B: 95% or more, less than 98% C: 90% or more, less than 95% D: less than 90%
  • the ruthenium carbene complex catalyst mixture (powder) was dissolved in CDCl 3 and calculated from the area ratio of hydrogen peaks of the carbene part of the ruthenium carbene complex catalyst (A1) and the ruthenium carbene complex catalyst (A2) using 1 H-NMR. did.
  • Example 1 In a glass flask whose inside was a nitrogen atmosphere, 2.3 parts of (bistricyclohexylphosphine) ruthenium dichloride hydride complex powder was added, and 200 parts of tetrahydrofuran was added thereto with a syringe. Using a thermostatic bath, the temperature in the glass flask was adjusted to 0 ° C., 0.3 parts of acetonitrile, 0.2 parts of propiolic acid, 3.3 parts of 1N hydrogen chloride / ethanol solution, and N-vinylpyrrolidone 3. Seven parts were added sequentially. This was stirred for 3 hours to react.
  • a mixture of the ruthenium carbene complex catalyst was dissolved in tetrahydrofuran in nitrogen to prepare a catalyst solution having a ruthenium concentration of 0.05 mol / liter.
  • Table 1 shows the evaluation results of the rate of increase in the viscosity of the polymerizable composition after 60 minutes, the impregnation into glass cloth, and the polymerization conversion rate of the monomers used for preparing the prepreg.
  • Example 2 A ruthenium carbene complex catalyst (A1) (1,3-dimesityl-4-imidazoline-) was obtained in the same manner as in Example 1 except that the reaction temperature during the preparation of the ruthenium carbene complex catalyst mixture was changed from 0 ° C. to 40 ° C. 2-Ilidene) (2-pyrrolidone-1-ylmethylene) ruthenium dichloride and ruthenium carbene complex catalyst (A2) (1,3-dimesityl-4-imidazoline-2-ylidene) (2-pyrrolidone-1-ylmethylene) A mixture with (tricyclohexylphosphine) ruthenium dichloride was obtained.
  • Example 3 10 parts of the ruthenium carbene complex catalyst mixture obtained in Example 1 and 2 parts of CuCl were dissolved in 200 parts of methylene chloride and stirred at room temperature for 2 hours.
  • the ruthenium carbene complex catalyst (A2) phosphine coordinated to ruthenium and CuCl reacted to precipitate a solid product. This was filtered, dried under reduced pressure, and isolated with methanol as a poor solvent to obtain (1,3-dimesityl-4-imidazoline-2-ylidene) (2-pyrrolidone-1) which is a ruthenium carbene complex catalyst (A1).
  • -Ilmethylene) ruthenium dichloride was obtained.
  • Benzylidene-bis (tricyclohexylphosphine) ruthenium dichloride (Grubbs Catalyst 1st Generation; Sigma Aldrich) 2.3 parts, 1,3-dimesitylimidazolidine chloride 3 parts, and potassium-t-butoxide 0.2 part, tetrahydrofuran Dissolved in and stirred at room temperature for 2 hours.
  • 3.7 parts of N-vinylpyrrolidone was dissolved, stirred at 40 ° C. for 3 hours, and then dried under reduced pressure. The temperature was set to ⁇ 80 ° C., n-pentane was added, the complex was precipitated, and collected by filtration in the atmosphere.
  • the ruthenium carbene complex catalyst (A2) ruthenium carbene complex catalyst (1,3-dimesityl-4-imidazoline- 2-Ilidene) (2-pyrrolidone-1-ylmethylene) (tricyclohexylphosphine) ruthenium dichloride was obtained.
  • a catalyst solution having a concentration of 0.05 mol / liter was prepared. Except for the above, a polymerizable composition was prepared in the same manner as in Example 1 to obtain a prepreg. The evaluation results are shown in Table 1.
  • the laminated body is obtained by sandwiching the prepared prepreg sheet and heating press at 3 MPa for 20 minutes at 205 ° C., all such laminated bodies are excellent as electrical materials used for the electric circuit board, It exhibits adhesion, mechanical strength, heat resistance, and dielectric properties.
  • the temperature is set to ⁇ 80 ° C., n-pentane is added, the complex is precipitated, and is collected by filtration under the atmosphere, and is ruthenium carbene complex catalyst (A2) (1,3-dimesityl-4-imidazoline-2-ylidene) (2-Pyrrolidone-1-ylmethylene) (tricyclohexylphosphine) ruthenium dichloride was obtained.
  • the obtained ruthenium carbene complex catalyst was dissolved in tetrahydrofuran in nitrogen to prepare a catalyst solution having a ruthenium concentration of 0.05 mol / liter.
  • a polymerizable composition was prepared in the same manner as in Example 1 except that the above-described catalyst solution was used for the ruthenium carbene complex catalyst.
  • the viscosity of the polymerizable composition became too high after 60 minutes from the preparation, so that the glass cloth could not be impregnated and a prepreg could not be produced. Therefore, the polymerization conversion rate could not be measured.
  • the evaluation results are shown in Table 2.
  • the polymerizable composition was too high in viscosity to impregnate glass cloth, and a prepreg could not be produced. Therefore, the polymerization conversion rate could not be measured.
  • the evaluation results are shown in Table 2.
  • the obtained ruthenium carbene complex catalyst was dissolved in tetrahydrofuran in nitrogen to prepare a catalyst solution having a ruthenium concentration of 0.05 mol / liter.
  • a polymerizable composition was prepared in the same manner as in Example 1 except that the above catalyst solution was used as the catalyst solution for the ruthenium carbene complex catalyst.
  • polymerization did not proceed even after heating, and a prepreg could not be produced.
  • the evaluation results are shown in Table 2.

Abstract

Cette invention concerne une composition polymérisable qui peut donner un article moulé en résine utilisable à titre de matériau électrique pour carte de circuit électrique ou autre, dont l'accroissement de la viscosité dans le temps est supprimé et qui a un taux de conversion par polymérisation élevé ; un procédé de production de la composition polymérisable ; un article moulé en résine produit au moyen de la composition polymérisable ; un procédé de production de l'article moulé en résine ; un article moulé en résine réticulée ayant d'excellentes propriétés d'isolation électrique, adhésivité, résistance mécanique, résistance à la chaleur, propriétés diélectriques et autres ; et un procédé de production dudit article moulé en résine réticulée.
PCT/JP2009/056707 2008-03-31 2009-03-31 Composition polymérisable, article moulé en résine et article moulé en résine réticulée WO2009123209A1 (fr)

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WO2012121342A1 (fr) 2011-03-08 2012-09-13 日本ゼオン株式会社 Composition polymérisable, résine moulée et stratifié
WO2024085044A1 (fr) * 2022-10-20 2024-04-25 Rimtec株式会社 Composition polymérisable et résine de norbornène
WO2024085043A1 (fr) * 2022-10-20 2024-04-25 Rimtec株式会社 Liquide catalyseur et composition polymérisable

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