WO2011034114A1 - Composé diépoxy, procédé de production de celui-ci et composition contenant ledit composé diépoxy - Google Patents

Composé diépoxy, procédé de production de celui-ci et composition contenant ledit composé diépoxy Download PDF

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WO2011034114A1
WO2011034114A1 PCT/JP2010/065998 JP2010065998W WO2011034114A1 WO 2011034114 A1 WO2011034114 A1 WO 2011034114A1 JP 2010065998 W JP2010065998 W JP 2010065998W WO 2011034114 A1 WO2011034114 A1 WO 2011034114A1
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formula
alumina
carbon atoms
compound
alkyl group
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PCT/JP2010/065998
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Japanese (ja)
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拓 浅海
誠 板垣
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住友化学株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
    • C07D303/27—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds having all hydroxyl radicals etherified with oxirane containing compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic

Definitions

  • the present invention relates to a diepoxy compound, a production method thereof, and a composition containing the diepoxy compound.
  • Epoxy cured products obtained by curing diepoxy compounds exhibit excellent mechanical and electrical properties in addition to good heat resistance and moisture resistance, and are widely used industrially.
  • Macromol. Chem. Phys. 199, 853-859 (1998) includes the formula (A) And a cured product obtained by curing the diepoxy compound and a curing agent.
  • the present invention [1] Formula (1) (In the formula, R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 5 represents an alkyl group having 2 to 10 carbon atoms.)
  • Formula (2) In the formula, R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 5 represents an alkyl group having 2 to 10 carbon atoms.
  • a dihydroxy compound represented by the formula (3) In the formula, X 1 represents a halogen atom.
  • an epihalohydrin represented by the formula (1) which is reacted in the presence of an ammonium salt and an inorganic base (In the formula, R 1 , R 2 , R 3 , R 4 and R 5 have the same meaning as described above.)
  • Formula (1) (In the formula, R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 5 represents an alkyl group having 2 to 10 carbon atoms.)
  • a composition comprising a diepoxy compound represented by the formula: and a curing agent; [10] The composition according to [9], wherein the curing agent is at least one curing agent selected from the group consisting of an amine curing agent, a phenol curing agent, and an acid anhydride curing agent; [11]
  • the amine curing agent is at least one selected from the group consisting of 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 1,5-diaminonaphthalene and p-pheny
  • the diepoxy compound of the present invention has the formula (1) (Wherein R 1 , R 2 , R 3 And R 4 Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; 5 Represents an alkyl group having 2 to 10 carbon atoms. ) In shown. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group, and a methyl group is preferable.
  • R 1 , R 2 , R 3 And R 4 Are each independently preferably a hydrogen atom or a methyl group; 1 , R 2 , R 3 And R 4 Is more preferably a hydrogen atom.
  • R 5 Represents an alkyl group having 2 to 10 carbon atoms, and examples of the alkyl group having 2 to 10 carbon atoms include an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, and an octyl group. preferably, an ethyl group is more preferable.
  • diepoxy compound (1) As the diepoxy compound represented by the formula (1) (hereinafter abbreviated as diepoxy compound (1)), 2-ethyl-1,4-phenylene-bis ⁇ 4- (2,3-epoxypropoxy) benzoate ⁇ , 2-propyl-1,4-phenylene-bis ⁇ 4- (2,3-epoxypropoxy) benzoate ⁇ , 2-isopropyl-1,4-phenylene-bis ⁇ 4- (2,3-epoxypropoxy) benzoate ⁇ , 2-butyl-1,4-phenylene-bis ⁇ 4- (2,3-epoxypropoxy) benzoate ⁇ , 2-hexyl-1,4-phenylene-bis ⁇ 4- (2,3-epoxypropoxy) benzoate ⁇ , 2-ethyl-1,4-phenylene-bis ⁇ 4- (2,3-epoxypropoxy) -3-methylbenzoate ⁇ , 2-ethyl-1,4-phenylene-bis ⁇ 4- (2,3-
  • the diepoxy compound (1) has the formula (2) (Wherein R 1 , R 2 , R 3 And R 4 Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; 5 Represents an alkyl group having 2 to 10 carbon atoms. )
  • a dihydroxy compound hereinafter abbreviated as compound (2)
  • formula (3) In the formula, X 1 It represents a halogen atom.
  • epihalohydrin (3) an epihalohydrin represented by formula (hereinafter abbreviated as epihalohydrin (3)).
  • X in epihalohydrin (3) 1 Represents a halogen atom, and examples of the halogen atom include a chlorine atom and a bromine atom, with a chlorine atom being preferred.
  • Epihalohydrin (3) includes epichlorohydrin and epibromohydrin, with epichlorohydrin being preferred. Two or more kinds of epihalohydrins (3) may be used in combination.
  • the amount of epihalohydrin (3) to be used is generally 2-200 mol, preferably 5-150 mol, per 1 mol of compound (2).
  • Ammonium salts include tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltributylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, benzyltrimethyl Quaternary ammonium halides such as ammonium bromide, benzyltriethylammonium bromide, tetramethylammonium iodide, tetraethylammonium iodide, tetrabutylammonium iodide, benzyltributylammonium iodide, and the like are preferred.
  • Moniumuburomido and benzyl bromide is more preferable.
  • Two or more ammonium salts may be used in combination.
  • the amount of the ammonium salt to be used is generally 0.0001 to 1 mol, preferably 0.001 to 0.5 mol, per 1 mol of compound (2).
  • the inorganic base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, and alkali metal carbonates such as sodium carbonate and potassium carbonate. Alkali metal hydroxides are preferred, Sodium oxide and potassium hydroxide are more preferred.
  • Two or more inorganic bases may be used in combination.
  • the amount of the inorganic base to be used is generally 0.1 to 20 mol, preferably 0.5 to 10 mol, per 1 mol of compound (2).
  • An inorganic base in the form of a solid such as a granule may be used, or an inorganic base in the form of an aqueous solution having a concentration of about 1 to about 60% by weight may be used.
  • the reaction of compound (2) and epihalohydrin (3) may be performed without a solvent or in the presence of a solvent.
  • solvent methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, ethylene glycol, propylene glycol, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol, 2-heptanol, 3- Heptanol, 2-octanol, 4-decanol, 2-dodecanol, 3-methyl-2-butanol, 3,3-dimethyl-2-butanol, 3-methyl-2-pentanol, 5-methyl-2-hexanol, 4 -Methyl-3-heptanol, 2-methyl-2-propanol, 2-methyl-2-butanol, 2,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 3-methyl-3-pentanol 3-ethyl-3-pentanol, 2,3-dimethyl-3-pentanol Alcohol solvents such as 3-ethyl-2,2-d
  • solvents Two or more kinds of solvents may be used in combination.
  • alcohol solvents are preferable, secondary alcohol solvents such as 2-propanol and 2-butanol, and tertiary alcohol solvents such as 2-methyl-2-propanol and 2-methyl-2-butanol are more preferable, and 2-methyl 2-propanol is particularly preferred.
  • the amount used is usually 0.01 to 100 parts by weight, preferably 0.1 to 50 parts by weight, per 1 part by weight of the compound (2).
  • the reaction may be carried out under normal pressure conditions, under pressure conditions, or under reduced pressure conditions.
  • the reaction is usually carried out by mixing compound (2), epihalohydrin (3), ammonium salt, inorganic base and, if necessary, a solvent.
  • the order of mixing is not limited, the reaction can be performed by mixing compound (2), epihalohydrin (3), and ammonium salt, and further reaction can be performed by mixing the resulting mixture with an inorganic base.
  • the reaction temperature is usually ⁇ 20 ° C. to 150 ° C., preferably ⁇ 10 ° C. to 120 ° C.
  • the reaction time is usually 1 to 150 hours.
  • the reaction is performed by mixing the compound (2), epihalohydrin (3), and ammonium salt, and the reaction is further performed by mixing the resulting mixture with an inorganic base
  • the compound (2) and the epihalohydrin (3 ) And the ammonium salt are preferably mixed at ⁇ 10 ° C. to 150 ° C., more preferably 0 ° C. to 120 ° C.
  • the temperature at which the obtained mixture and inorganic base are mixed is preferably -20 ° C to 120 ° C, more preferably -10 ° C to 80 ° C.
  • the progress of the reaction can be confirmed by ordinary analytical means such as liquid chromatography.
  • an organic layer containing the diepoxy compound (1) is obtained by mixing the reaction mixture, water, and, if necessary, a solvent insoluble in water, and separating the liquid after stirring.
  • the obtained organic layer is washed with water, for example, and then the insoluble matter is removed by filtration as necessary, followed by concentration, whereby the diepoxy compound (1) can be taken out.
  • the taken-out diepoxy compound (1) can be further purified by ordinary purification means such as recrystallization.
  • the diepoxy compound (1) comprises the compound (2) and the formula (6) (In the formula, X 2 It represents a halogen atom.
  • compound (6) (Hereinafter abbreviated as compound (6)) is reacted in the presence of a base to give a compound of formula (7) (Wherein R 1 , R 2 , R 3 , R 4 And R 5 Represents the same meaning as above. ) (Hereinafter abbreviated as compound (7)), and the obtained compound (7) can be oxidized with an oxidizing agent to produce the compound.
  • X in the compound (6) 2 Represents a halogen atom, and examples of the halogen atom include a chlorine atom and a bromine atom.
  • Compound (6) includes allyl chloride and allyl bromide. Two or more compounds (6) may be used in combination.
  • the amount of compound (6) to be used is generally 2-200 mol, preferably 2-100 mol, per 1 mol of compound (2).
  • the base may be an inorganic base or an organic base, and an inorganic base is preferable.
  • the inorganic base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, and alkali metal carbonates such as sodium carbonate and potassium carbonate.
  • the organic base include pyridine. Among these, alkali metal carbonates are preferable, and sodium carbonate and potassium carbonate are more preferable.
  • Two or more bases may be used in combination.
  • the amount of the base to be used is generally 2 to 10 mol per 1 mol of compound (2).
  • reaction of compound (2) and compound (6) may be carried out without solvent, but is preferably carried out in a solvent.
  • the solvent include the same solvents as those used in the reaction of the aforementioned compound (2) and epihalohydrin (3).
  • reaction of a compound (2) and a compound (6) is normally implemented by mixing a compound (2), a compound (6), a base, and a solvent as needed, The mixing order is not restrict
  • the reaction may be carried out under normal pressure conditions, under pressure conditions, or under reduced pressure conditions.
  • reaction temperature is usually ⁇ 20 ° C. to 120 ° C., preferably ⁇ 10 ° C. to 100 ° C.
  • the progress of the reaction can be confirmed by ordinary analytical means such as liquid chromatography, and it is preferable to carry out the reaction until no increase in the amount of compound (7) produced is observed.
  • the obtained reaction mixture containing the compound (7) is usually mixed with an oxidizing agent as it is or after being washed with water, and the reaction between the compound (7) and the oxidizing agent is carried out.
  • the oxidizing agent may be any oxidizing agent capable of converting a carbon-carbon double bond to an epoxy group, and specifically includes a peracid such as m-chloroperbenzoic acid.
  • the amount of the oxidizing agent to be used is generally 2 to 20 mol per 1 mol of compound (7).
  • the reaction between the compound (7) and the oxidizing agent may be carried out under normal pressure, under pressure, or under reduced pressure. Moreover, you may react in inert gas atmosphere, such as nitrogen gas and argon gas.
  • the reaction temperature is usually ⁇ 20 ° C. to 120 ° C., preferably ⁇ 10 ° C. to 100 ° C.
  • the reaction time is usually 0.5 to 72 hours.
  • the diepoxy compound (1) can be taken out by concentrating the reaction mixture.
  • the oxidizing agent remaining in the reaction mixture may be decomposed and then concentrated.
  • the taken-out diepoxy compound (1) can be further purified by ordinary purification means such as recrystallization.
  • Compound (2) is represented by, for example, formula (4) (Wherein R 1 , R 2 , R 3 And R 4 Represents the same meaning as above. ) (Hereinafter abbreviated as compound (4)) and formula (5) (Wherein R 5 Represents the same meaning as above. ) (Hereinafter abbreviated as compound (5)) is allowed to react in the presence of an acid.
  • 4-hydroxybenzoic acid 4-hydroxy-2-methylbenzoic acid, 4-hydroxy-3-methylbenzoic acid, 4-hydroxy-2-ethylbenzoic acid, 4-hydroxy-3-ethyl Benzoic acid, 4-hydroxy-2-isopropylbenzoic acid, 4-hydroxy-3-propylbenzoic acid and 4-hydroxy-3,5-dimethylbenzoic acid, and 4-hydroxybenzoic acid and 4-hydroxy-3- Methylbenzoic acid is preferred.
  • Examples of the compound (5) include 2-ethylhydroquinone, 2-propylhydroquinone, 2-butylhydroquinone, 2-pentylhydroquinone and 2-octylhydroquinone, and 2-ethylhydroquinone and 2-propylhydroquinone are preferred.
  • a commercially available compound (5) may be used, or a known method such as a method of reacting 1,4-cyclohexanedione and an aldehyde in the presence of lithium chloride (Synlet, 1997, 365). You may use what was manufactured according to this.
  • the amount of compound (4) to be used is generally 1 to 10 mol, preferably 2 to 5 mol, per 1 mol of compound (5).
  • Examples of the acid include sulfuric acid and p-toluenesulfonic acid. Two or more acids may be used in combination. The amount of the acid to be used is generally 0.001 to 0.3 mol per 1 mol of compound (4).
  • the reaction between compound (4) and compound (5) is preferably carried out in the presence of a solvent.
  • the solvent include aliphatic hydrocarbon solvents such as hexane, heptane, and octane, and aromatic hydrocarbon solvents such as benzene, toluene, ethylbenzene, xylene, mesitylene, chlorobenzene, and dichlorobenzene.
  • the amount of the solvent to be used is generally 1 to 200 parts by weight, preferably 5 to 100 parts by weight with respect to 1 part by weight of the compound (4).
  • the reaction between the compound (4) and the compound (5) may be performed under normal pressure conditions, may be performed under pressure conditions, or may be performed under reduced pressure conditions. Further, the reaction may be performed under any inert gas atmosphere such as nitrogen gas or argon gas.
  • the reaction temperature is usually 50 to 250 ° C., preferably 60 to 200 ° C.
  • the reaction time varies depending on the reaction temperature, but is usually 0.5 to 72 hours. As the reaction proceeds, water is generated. It is preferable to carry out the reaction while removing the generated water from the reaction system.
  • Examples of a method for removing generated water from the reaction system include a method using a dehydrating agent such as an azeotropic distillation method and molecular sieves. Then, the composition (henceforth the composition X) containing diepoxy compound (1) and a hardening
  • the composition X can contain 2 or more types of diepoxy compounds (1). Moreover, the composition X can contain 2 or more types of hardening
  • the composition X can contain a solvent in addition to the diepoxy compound (1) and the curing agent. In terms of easy preparation, the composition X preferably contains a solvent.
  • Solvents include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, aprotic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone, ester solvents such as butyl acetate, and propylene glycol monomethyl ether And the like, and a ketone solvent is preferable, and methyl isobutyl ketone is more preferable.
  • the diepoxy compound (1) has excellent solubility in methyl isobutyl ketone. Further, the diepoxy compound (1) tends to be excellent in solubility in the above solvents other than methyl isobutyl ketone.
  • Any curing agent may be used as long as it has at least one functional group capable of undergoing a curing reaction with the epoxy group in the diepoxy compound (1) or exhibits a catalytic action in the curing reaction of the diepoxy compound (1).
  • an amine curing agent in which the functional group is an amino group a phenol curing agent in which the functional group is a hydroxyl group, and an acid anhydride curing agent in which the functional group is a group represented by -CO-O-CO- And curing catalysts, with amine curing agents, phenol curing agents and curing catalysts being preferred.
  • amine curing agents include aliphatic polyamines having 2 to 20 carbon atoms such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine, p-xylenediamine, m-xylenediamine, , 5-diaminonaphthalene, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenyl ether, Aromatic polyamines such as 1,1-bis (4-aminophenyl) cyclohexane, 4,4′-diaminodiphenylsulfone, bis (4-aminophenyl) phenylmethane, 4,4′-
  • aromatic polyamines and dicyandiamide are preferable, and 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 1,5-diaminonaphthalene, p-phenylenediamine and dicyandiamide are more preferable.
  • the phenol curing agent include a phenol resin, a phenol aralkyl resin (having a phenylene skeleton, a diphenylene skeleton, etc.), a naphthol aralkyl resin, and a polyoxystyrene resin.
  • phenol resin examples include resol type phenol resins such as aniline-modified resole resin and dimethyl ether resole resin, novolac type phenol resins such as phenol novolac resin, cresol novolac resin, tert-butylphenol novolac resin, nonylphenol novolac resin, and dicyclopentadiene modified. Special phenol resins such as phenol resin, terpene-modified phenol resin, and triphenolmethane type resin can be mentioned.
  • polyoxystyrene resin examples include poly (p-oxystyrene).
  • Examples of the acid anhydride curing agent include maleic anhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride and 5- (2,5-dioxo Tetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride.
  • Examples of the curing catalyst include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-heptadecylimidazole, and benzyldimethylamine. What is necessary is just to select the usage-amount of a hardening
  • the total number of moles of functional groups capable of undergoing a curing reaction with the epoxy group in the curing agent is 0.5 to 1 mole per 1 mole of the epoxy group in the diepoxy compound (1).
  • An amount of 1.5 mol, preferably 0.9 to 1.1 mol is used.
  • the composition X is a compound having another epoxy group unless the desired performance of the cured product obtained by curing the composition X is reduced.
  • Various additives can be included.
  • Other compounds having an epoxy group include bisphenol A type epoxy compounds, orthocresol type epoxy compounds, biphenol diglycidyl ether, 4,4′-bis (3,4-epoxybuten-1-yloxy) phenylbenzoate, naphthalene diene Examples include glycidyl ether and ⁇ -methylstilbene-4,4′-diglycidyl ether.
  • Additives include curing accelerators such as triphenylphosphine, 1,8-azabicyclo [5.4.0] -7-undecene, 2-phenylimidazole; coupling agents such as ⁇ -glycidoxypropyltrimethoxysilane Colorants such as carbon black; low stress components such as silicone oil and silicone rubber; mold release agents such as natural wax, synthetic wax, higher fatty acid or metal salt thereof, paraffin; antioxidant; fused crushed silica powder, fused sphere Silica such as silica powder, crystalline silica powder, secondary agglomerated silica powder; alumina such as ⁇ -alumina or transition alumina ( ⁇ -alumina, ⁇ -alumina, ⁇ -alumina); titanium white; aluminum hydroxide; talc; clay; Mica; and glass fiber.
  • curing accelerators such as triphenylphosphine, 1,8-azabicyclo [5.4.0] -7-undecene, 2-phenylimidazole
  • the composition X preferably contains alumina from the viewpoint of improving the thermal conductivity of a cured product obtained by curing the composition X.
  • curing agent, and an alumina is preferable, and it is preferable that the composition X contains an above-described solvent at the point that the preparation is easy.
  • the content of alumina is usually 75 parts by weight to 95 parts by weight with respect to 100 parts by weight in total of the diepoxy compound (1) and the curing agent.
  • a composition containing 75 parts by weight or more of alumina with respect to a total of 100 parts by weight of the diepoxy compound (1) and the curing agent tends to improve the thermal conductivity of a cured product obtained by curing the composition.
  • a composition in which the amount of alumina is 95 parts by weight or less tends to be easily formed.
  • alumina powdery alumina is preferable, and when the particle diameter (average particle diameter) of the cumulative volume 50% from the fine particle side of the weight cumulative particle size distribution is D50, D50 is 2 ⁇ m or more and 100 ⁇ m or less, and A50 and D50 Is more preferably alumina which is a mixture of alumina B having a diameter of 1 ⁇ m to 10 ⁇ m and alumina C having a D50 of 0.01 ⁇ m to 5 ⁇ m. Further, the proportion of each alumina in the total volume of 100% by volume of alumina A, alumina B and alumina C is 50 to 90% by volume for alumina A, 5 to 40% by volume for alumina B, and 1 to 30% by volume for alumina C.
  • Such alumina can be prepared, for example, by appropriately mixing commercially available alumina having various average particle sizes. Further, the content of alumina contained in the cured product is preferably 50 to 80% by volume with respect to 100% by volume of the cured product.
  • a method for producing a cured product obtained by curing the composition X a method of curing the composition X as it is by heating to a predetermined temperature, a composition X is heated and melted and poured into a mold or the like.
  • a method of forming by heating, a method of melting the composition X, injecting the obtained melt into a preheated mold and curing, partially curing the composition X, and pulverizing the partially cured product obtained After filling the obtained powder into a mold, melt-molding the filled powder, and dissolving the composition X in a solvent as necessary, partially curing while stirring, and casting the resulting solution
  • the substrate is applied or impregnated, and then the obtained substrate is heated to semi-cure the diepoxy compound (1) in the substrate.
  • a prepreg By making it, a prepreg can also be manufactured.
  • a laminate can be obtained by laminating a plurality of prepregs and applying pressure and heating with a press or the like.
  • the base material used for the prepreg include woven or nonwoven fabrics of inorganic fibers such as glass fibers and carbon fibers, and woven or nonwoven fabrics of organic fibers such as polyester.
  • a cured product obtained by curing the composition X is excellent in thermal conductivity, and a cured product obtained by curing the composition X containing alumina is further excellent in thermal conductivity.
  • Example 1 At 0 ° C., 5.0 g of 1,4-cyclohexanedione, 3.93 g of acetaldehyde, 1.89 g of lithium chloride and 18.8 g of 1,3-dimethyl-2-imidazolidinone were added to the autoclave, and the autoclave was sealed. The mixture in the autoclave was stirred at 160 ° C. for 6 hours and then cooled to room temperature (about 25 ° C.). Extraction was performed after adding 100 mL of ion-exchange water and 100 mL of ethyl acetate to the obtained reaction mixture.
  • the obtained organic layer was washed 4 times with 100 mL of saturated aqueous sodium chloride solution.
  • the obtained organic layer was dried over anhydrous magnesium sulfate, and then magnesium sulfate was filtered.
  • the obtained filtrate was concentrated to obtain a crude product.
  • the same operation as described above was further performed three times to obtain crude products.
  • the obtained crude product was mixed and purified by silica gel column chromatography, further washed with hexane, and abbreviated as the compound represented by the above formula (5-1) (hereinafter abbreviated as compound (5-1)). ) Containing 9.96 g of light gray crystals.
  • the crystal was analyzed by gas chromatography, and the area percentage of the obtained chromatograph was calculated to be 92.9%, and the content of the compound (5-1) in the crystal was 92.9% by weight. Assuming that the yield of the compound (5-1) based on 1,4-cyclohexanedione was 38%.
  • a reaction vessel equipped with a Dean-Stark apparatus 8.0 g of 4-hydroxybenzoic acid, 4.0 g of compound (5-1), 0.55 g of p-toluenesulfonic acid and about 60 g of xylene were added at room temperature. Reaction was performed by stirring the obtained mixture under reflux for 26 hours. Water generated as the reaction progressed was continuously removed from the reaction system using a Dean Stark apparatus.
  • the reaction mixture was cooled to room temperature.
  • the precipitated solid was taken out by filtration, washed with 400 mL of methanol, and then dried under reduced pressure at 50 ° C. for 4 hours to obtain 3.90 g of light gray crystals of the compound represented by the above formula (2-1).
  • the area percentage of the peak of the compound represented by the formula (2-1) in the chromatograph was 96.8%. Assuming that the content of the compound represented by the formula (2-1) in the crystal is 96.8% by weight, the yield of the compound represented by the formula (2-1) based on the compound (5-1) is 37%.
  • Example 2 In a reaction vessel equipped with a cooling device, 1.5 g of the compound of the formula (2-1) obtained in Example 1 above, 0.064 g of tetrabutylammonium bromide, 14.7 g of epichlorohydrin and 2 -9.68 g of methyl-2-propanol was added at room temperature. The resulting mixture was stirred at 70 ° C. for 10 hours and then cooled to 18 ° C.
  • the obtained crude product, 8 mL of toluene and 17 mL of 2-propanol were added to a reaction vessel equipped with a cooling device, and the resulting mixture was stirred at 70 ° C. for 1 hour.
  • the obtained mixture was cooled to room temperature, and the precipitated solid was removed by filtration.
  • the extracted solid was washed with 2-propanol and then dried to obtain 1.16 g of white crystals of the compound represented by the above formula (1-1).
  • the area percentage of the peak of the compound represented by the formula (1-1) in the chromatograph was 96.5%.
  • Example 4 In a reaction vessel equipped with a cooling device, 1.50 g of the compound represented by the formula (2-2) obtained in Example 3 above, 0.062 g of tetrabutylammonium bromide, 14.2 g of epichlorohydrin and 2-methyl 9.32 g of 2-propanol was added at room temperature. The resulting mixture was stirred at 70 ° C. for 9 hours and then cooled to 18 ° C. To the obtained mixture, 3.07 g of a 15 wt% aqueous sodium hydroxide solution was gradually added. The resulting mixture was stirred at 18 ° C. for 3 hours and then cooled to 0 ° C.
  • a compound represented by the formula (1-1) can be obtained by mixing the compound represented by the formula (7-1), m-chloroperbenzoic acid and chloroform, and stirring the resulting mixture at a predetermined temperature.
  • Example 6 100 parts by weight of the compound represented by the formula (1-1), 20 parts by weight of 4,4′-diaminodiphenylmethane (manufactured by Wako Pure Chemical Industries, Ltd.) as a curing agent, and N, N-dimethylformamide as a solvent are mixed. As a result, a solution-like composition was obtained. The obtained composition was concentrated with a centrifugal concentrator to obtain a powdery composition. The obtained powdery composition was filled in an alumina pan.
  • the alumina pan filled with the composition was heated using a differential scanning calorimeter (DSC Q2000 manufactured by TA Instruments) to obtain a cured product (curing conditions: after heating at 140 ° C. for 20 minutes in a nitrogen atmosphere, Heat to 180 ° C. at 1 ° C./min and further heat at 200 ° C. for 30 minutes).
  • the obtained cured product was cooled to 20 ° C. It was 144 degreeC when the glass transition point of hardened
  • Example 7 In Example 6, it replaced with 20 weight part of 4,4'- diamino diphenylmethane, and implemented similarly to Example 6 except having used 16 weight part of 1, 5- diamino naphthalene (made by Wako Pure Chemical Industries Ltd.). A solution-like composition was obtained. The obtained solution composition was concentrated with a centrifugal concentrator to obtain a powdery composition. The obtained powdery composition was heated in the same manner as in Example 6 to obtain a cured product. The glass transition point of the cured product was 151 ° C.
  • Example 8 In Example 6, instead of 20 parts by weight of 4,4′-diaminodiphenylmethane, 31 parts by weight of cis-4-cyclohexene-1,2-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used, and a curing accelerator was used. As in Example 6, except that 2.6 parts by weight of 2-phenylimidazole was further added, a solution-like composition was obtained. The obtained solution composition was concentrated with a centrifugal concentrator to obtain a powdery composition. The obtained powdery composition was heated in the same manner as in Example 6 to obtain a cured product. The glass transition point of the cured product was 105 ° C.
  • Example 9 In Example 6, instead of 20 parts by weight of 4,4′-diaminodiphenylmethane, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (Tokyo) This was carried out in the same manner as in Example 6 except that 27 parts by weight of Kasei Kogyo Co., Ltd. and 2.5 parts by weight of 2-phenylimidazole were further added as a curing accelerator to obtain a solution-like composition. The obtained solution composition was concentrated with a centrifugal concentrator to obtain a powdery composition. The obtained powdery composition was heated in the same manner as in Example 6 to obtain a cured product.
  • Tokyo 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride
  • Example 10 In Example 6, instead of 20 parts by weight of 4,4′-diaminodiphenylmethane, 84 parts by weight of a phenol novolak curing agent “MEH-7851H” (manufactured by Meiwa Kasei Co., Ltd.) was used, and triphenylphosphine 3. Except having further added 7 weight part, it implemented similarly to Example 6 and obtained the solution-form composition. The obtained solution composition was concentrated with a centrifugal concentrator to obtain a powdery composition. The obtained powdery composition was heated in the same manner as in Example 6 to obtain a cured product. The glass transition point of the cured product was 103 ° C.
  • Example 11 In Example 6, instead of 20 parts by weight of 4,4′-diaminodiphenylmethane, 10 parts by weight of dicyandiamide (manufactured by Wako Pure Chemical Industries, Ltd.) was used, and 2.2 parts by weight of 2-phenylimidazole was further added as a curing accelerator. It implemented similarly to Example 6 except having added, and obtained the solution-like composition. The obtained solution composition was concentrated with a centrifugal concentrator to obtain a powdery composition. The obtained powdery composition was heated in the same manner as in Example 6 to obtain a cured product. The glass transition point of the cured product was 146 ° C.
  • Example 12 100 parts by weight of the compound represented by the formula (1-1), 16 parts by weight of 1,5-diaminonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.) as a curing agent, and 1071 parts by weight of alumina powder (manufactured by Sumitomo Chemical Co., Ltd.) -Alumina powder: alumina powder A1 having an average particle diameter (D50) measured by laser diffraction method of 18 ⁇ m, alumina powder B1 having an average particle diameter (D50) of 3 ⁇ m, and an average particle diameter (D50) of 0.1.
  • alumina powder A1 having an average particle diameter (D50) measured by laser diffraction method of 18 ⁇ m
  • alumina powder B1 having an average particle diameter (D50) of 3 ⁇ m
  • the solution form of the compositions were prepared.
  • the prepared composition was applied onto a polyethylene terephthalate (PET) film with an applicator so as to have a thickness of 350 ⁇ m.
  • PET film coated with the composition was dried at room temperature for 1 hour and further dried at 120 ° C.
  • the PET film was peeled off to obtain a sheet.
  • the obtained sheet was sandwiched between aluminum foils having a thickness of 40 ⁇ m and subjected to vacuum press molding (press conditions: a vacuum degree of 1 kPa and a press pressure of 6 MPa, raising the temperature from 115 ° C. to 180 ° C. over 60 minutes).
  • the aluminum foil was peeled off to obtain a sheet-like cured product having a thickness of 372 ⁇ m.
  • the thermal conductivity of the cured product was measured by a xenon flash analyzer nanoflash LFA447 manufactured by NETZSCH, it was 9.1 W / (m ⁇ K).
  • the density of the cured product obtained by curing the composition containing the compound represented by the formula (1-1) and 1,5-diaminonaphthalene and not containing the alumina powder is 1.2 g / cm 3 .
  • the density was 3.97 g / cm 3 and the content ratio of the alumina powder in the obtained cured product was calculated, the content ratio of the alumina powder in the cured product was 74% by volume.
  • Example 13 100 parts by weight of the compound represented by the formula (1-1), 16 parts by weight of 1,5-diaminonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.) as a curing agent, 370 parts by weight of methyl isobutyl ketone as a solvent, N,
  • a solution-like composition can be obtained by mixing 60 parts by weight of N-dimethylformamide.
  • a prepreg can be obtained by impregnating the obtained composition into a glass fiber woven fabric having a thickness of 0.2 mm and then drying by heating.
  • a laminate can be obtained by stacking four obtained prepregs and press-molding them for 90 minutes under conditions of a temperature of 175 ° C. and a pressure of 4 MPa.
  • Example 14 100 parts by weight of the compound represented by the formula (1-1), 16 parts by weight of 1,5-diaminonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.) as a curing agent, and 567 parts by weight of alumina powder (manufactured by Sumitomo Chemical Co., Ltd.) -Alumina powder; alumina powder having an average particle diameter (D50) of 18 ⁇ m), 160 parts by weight of methyl isobutyl ketone as a solvent and 60 parts by weight of N, N-dimethylformamide were mixed to prepare a solution-like composition. .
  • the composition prepared with an applicator was applied on a polyethylene terephthalate (PET) film to a thickness of 350 ⁇ m.
  • PET polyethylene terephthalate
  • the PET film coated with the composition was dried at room temperature for 1 hour and further dried at 120 ° C. for 10 minutes, and then the PET film was peeled off to obtain a sheet.
  • the obtained sheet was sandwiched between aluminum foils having a thickness of 40 ⁇ m, and vacuum press molding (press temperature: 140 ° C., vacuum degree: 1 kPa, press pressure: 6 MPa) was performed. Thereafter, the press temperature was raised to 180 ° C. over 40 minutes.
  • the aluminum foil was peeled off to obtain a sheet-like cured product having a thickness of 335 ⁇ m.
  • the heat conductivity of the cured product was measured with a xenon flash analyzer nanoflash LFA447 manufactured by NETZSCH and found to be 5.1 W / (m ⁇ K).
  • the density of the cured product obtained by curing the composition containing the compound represented by the formula (1-1) and 1,5-diaminonaphthalene and not containing the alumina powder is 1.2 g / cm 3 .
  • the density was 3.97 g / cm 3 and the content ratio of the alumina powder in the obtained cured product was calculated, the content ratio of the alumina powder in the cured product was 60% by volume.
  • Examples 6 to 11 a solution was obtained by carrying out in the same manner as in Examples 6 to 11 except that the compound represented by formula (1-2) was used instead of the compound represented by formula (1-1). A composition in the form of a powder, a composition in the form of a powder and a cured product can be obtained.
  • Examples 12-14 alumina was prepared in the same manner as in Examples 12-14 except that the compound represented by formula (1-2) was used instead of the compound represented by formula (1-1). A composition containing a powder and a cured product thereof can be obtained.
  • the diepoxy compound of the present invention is excellent in solubility in methyl isobutyl ketone.
  • a cured product obtained by curing the composition containing the diepoxy compound has high thermal conductivity.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Epoxy Compounds (AREA)
  • Reinforced Plastic Materials (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

L'invention concerne un composé diépoxy représenté par la formule (1) (dans laquelle R1, R2, R3 et R4 représentent chacun indépendamment un atome d'hydrogène ou un groupe alkyle comportant 1-3 atomes de carbone, et R5 représente un groupe alkyle comportant 2-10 atomes de carbone).
PCT/JP2010/065998 2009-09-17 2010-09-09 Composé diépoxy, procédé de production de celui-ci et composition contenant ledit composé diépoxy WO2011034114A1 (fr)

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Cited By (2)

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WO2012086840A1 (fr) * 2010-12-24 2012-06-28 住友化学株式会社 Composé diépoxy et son procédé de production
WO2019021613A1 (fr) * 2017-07-28 2019-01-31 東レ株式会社 Préimprégné et matériau composite renforcé par fibres de carbone

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JP6102744B2 (ja) * 2011-11-02 2017-03-29 日立化成株式会社 樹脂組成物、並びにそれを用いた樹脂シート、プリプレグ、積層板、金属基板、プリント配線板及びパワー半導体装置
JP2013129788A (ja) * 2011-12-22 2013-07-04 Shin Kobe Electric Mach Co Ltd 熱硬化性樹脂組成物、加熱加圧成形用プリプレグ及び積層板
CN108699217B (zh) 2016-02-25 2020-10-30 日立化成株式会社 环氧树脂组合物、半固化环氧树脂组合物、固化环氧树脂组合物、成型物及成型固化物
RU2019133488A (ru) * 2017-03-24 2021-04-27 Торэй Индастриз, Инк. Препрег и армированный углеродным волокном композитный материал
EP3766911A4 (fr) 2018-03-15 2021-03-10 Hitachi Chemical Company, Ltd. Résine époxy, composition de résine époxy, feuille de résine, feuille de stade b, feuille de stade c, objet durci, feuille métallique pourvue de la résine, substrat métallique et dispositif semi-conducteur de puissance
WO2019208242A1 (fr) * 2018-04-27 2019-10-31 東レ株式会社 Préimprégné et matériau composite renforcé par des fibres de carbone

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JPH09176144A (ja) * 1995-10-23 1997-07-08 Nippon Kayaku Co Ltd エポキシ化合物、その製造法、硬化性組成物及び硬化物
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WO2012086840A1 (fr) * 2010-12-24 2012-06-28 住友化学株式会社 Composé diépoxy et son procédé de production
WO2019021613A1 (fr) * 2017-07-28 2019-01-31 東レ株式会社 Préimprégné et matériau composite renforcé par fibres de carbone
JPWO2019021613A1 (ja) * 2017-07-28 2020-05-28 東レ株式会社 プリプレグおよび炭素繊維強化複合材料
US11208541B2 (en) 2017-07-28 2021-12-28 Toray Industries, Inc. Prepreg and carbon fiber reinforced material
JP7206910B2 (ja) 2017-07-28 2023-01-18 東レ株式会社 プリプレグおよび炭素繊維強化複合材料

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