WO2011118368A1 - Composé diépoxy, procédé de fabrication associé, et composition contenant ledit composé diépoxy - Google Patents

Composé diépoxy, procédé de fabrication associé, et composition contenant ledit composé diépoxy Download PDF

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WO2011118368A1
WO2011118368A1 PCT/JP2011/055164 JP2011055164W WO2011118368A1 WO 2011118368 A1 WO2011118368 A1 WO 2011118368A1 JP 2011055164 W JP2011055164 W JP 2011055164W WO 2011118368 A1 WO2011118368 A1 WO 2011118368A1
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compound
formula
alumina
curing agent
reaction
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PCT/JP2011/055164
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English (en)
Japanese (ja)
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拓 浅海
板垣　誠
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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
    • C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
    • C07D303/23—Oxiranylmethyl ethers of compounds having one hydroxy group bound to a six-membered aromatic ring, the oxiranylmethyl radical not being further substituted, i.e.
    • 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.
  • the present invention [1] Formula (1): (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) A diepoxy compound represented by: [2] In the presence of an inorganic base, the formula (2): (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) And a dihydroxy compound represented by the formula (3): (In the formula, X 1 represents a halogen atom.) Formula (1) including the process of making it react with the epihalohydrin shown by: (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 have the same meaning as described above.) A process for producing a diepoxy compound represented by: [3] The production method according to [2], wherein the reaction of the dihydroxy compound represented by the formula (2)
  • composition according to [11]; [13] The composition according to any one of [9] to [12], further comprising alumina; [14]
  • the composition according to [13], comprising 75 parts by weight to 95 parts by weight of alumina with respect to a total of 100 parts by weight of the diepoxy compound represented by formula (1), the curing agent, and alumina; [15]
  • Alumina has an A50 whose D50 (particle diameter of 50% cumulative volume) is 2 ⁇ m or more and 100 ⁇ m or less, an alumina B whose D50 is 1 ⁇ m or more and 10 ⁇ m or less, and an alumina whose D50 is 0.01 ⁇ m or more and 5 ⁇ m or less C is a mixture of alumina A, alumina B and alumina C, and the proportion of each alumina in 100 volume% is 50 to 90 volume% for alumina A, 5 to 40 volume% for alumina B, and alumina C is The composition according to [13] or “14”, which is 1 to
  • the diepoxy compound of the present invention has the formula (1): (Wherein R 1 , R 2 , R 3 , R 4 , R 5 And R 6 Independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ) Indicated by 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. A methyl group and an ethyl group are preferable, and a methyl group is more preferable. R 1 , R 2 , R 3 , R 4 , R 5 And R 6 Are independently preferably a hydrogen atom or a methyl group.
  • R 1 , R 2 , R 3 , R 4 , R 5 And R 6 Preferably, one or two selected from the group consisting of is an alkyl group having 1 to 3 carbon atoms, and the rest are hydrogen atoms, 1 , R 2 , R 3 , R 4 , R 5 And R 6 More preferably, one or two selected from the group consisting of is a methyl group and the rest are hydrogen atoms.
  • R 1 , R 2 , R 3 And R 4 One selected from the group consisting of 1 to 3 is an alkyl group having 1 to 3 carbon atoms, the remaining three are hydrogen atoms, and R 5 And R 6 Is preferably an alkyl group having 1 to 3 carbon atoms and the other is a hydrogen atom.
  • R 1 , R 2 , R 3 And R 4 One selected from the group consisting of is a methyl group, the remaining three are hydrogen atoms, and R 5 And R 6 More preferably, one of these is a methyl group and the other is a hydrogen atom.
  • R 1 , R 2 , R 3 And R 4 One selected from the group consisting of 1 to 3 is an alkyl group having 1 to 3 carbon atoms, the remaining three are hydrogen atoms, and R 5 And R 6 Is preferably a hydrogen atom
  • R 1 , R 2 , R 3 And R 4 One selected from the group consisting of is a methyl group, the remaining three are hydrogen atoms, and R 5 And R 6 Is preferably a hydrogen atom.
  • R 1 , R 2 , R 3 And R 4 Is a hydrogen atom and R 5 And R 6 Is preferably an alkyl group having 1 to 3 carbon atoms and the other is a hydrogen atom.
  • 1 , R 2 , R 3 And R 4 Is a hydrogen atom and R 5 And R 6 More preferably, one of these is a methyl group and the other is a hydrogen atom.
  • diepoxy compound (1) As the diepoxy compound represented by the formula (1) (hereinafter abbreviated as diepoxy compound (1)), R 1 , R 2 , R 3 , R 4 , R 5 And R 6 Diepoxy compound (1) in which is a hydrogen atom, R 1 , R 2 , R 3 And R 4 One selected from the group consisting of is an alkyl group having 1 to 3 carbon atoms, the remaining three are hydrogen atoms, and R 5 And R 6 Diepoxy compound (1) in which is a hydrogen atom, R 1 , R 2 , R 3 And R 4 One selected from the group consisting of is a methyl group, the remaining three are hydrogen atoms, and R 5 And R 6 Diepoxy compound (1) in which is a hydrogen atom, R 1 , R 2 , R 3 And R 4 One selected from the group consisting of is an ethyl group, the remaining three are hydrogen atoms, and R 5 And R 6 Diepoxy compound (1) in which is a hydrogen atom, R 1 Is an alky
  • the diepoxy compound (1) is represented by the formula (2) in the presence of an inorganic base: (Wherein R 1 , R 2 , R 3 , R 4 , R 5 And R 6 Represents the same meaning as above. )
  • a dihydroxy compound hereinafter abbreviated as compound (2)
  • formula (3) (Where X 1 Represents a halogen atom.
  • 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).
  • inorganic bases examples include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and alkali metal hydrogens such as sodium hydride and potassium hydride.
  • alkali metal hydroxides are preferable, and sodium hydroxide and potassium hydroxide are more preferable.
  • 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 a solid form such as a granular material can be used.
  • an aqueous solution having a concentration of about 1 to 60% by weight can be used.
  • the reaction between the compound (2) and the epihalohydrin (3) is preferably carried out in the presence of a quaternary ammonium salt in addition to the inorganic base.
  • the “quaternary ammonium salt” means a salt containing a cation in which four hydrocarbon groups are bonded to a nitrogen atom, and examples of the anion contained in the quaternary ammonium salt include chloride ion, bromide ion, iodine.
  • Halide ions such as halide ions.
  • alkali metal hydroxides and alkali metal carbonates are preferred.
  • quaternary ammonium salts tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltributylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, Quaternary ammonium halides such as benzyltrimethylammonium bromide, benzyltriethylammonium bromide, tetramethylammonium iodide, tetraethylammonium iodide, tetrabutylam
  • Ammonium bromide and benzyl trimethyl ammonium bromide is more preferable.
  • Two or more quaternary ammonium salts may be used in combination.
  • the amount of the quaternary 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 reaction between compound (2) and epihalohydrin (3) is preferably carried out in the presence of an aliphatic alcohol.
  • Examples of the aliphatic alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-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 Examples include ru-3-pentanol, 3-e
  • aliphatic secondary alcohols and aliphatic tertiary alcohols having 4 to 12 carbon atoms Preferred are aliphatic secondary alcohols and aliphatic tertiary alcohols having 4 to 12 carbon atoms, and more preferred are aliphatic tertiary alcohols having 4 to 10 carbon atoms.
  • Two or more aliphatic alcohols may be used in combination.
  • the amount of the aliphatic alcohol 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). Parts by weight.
  • the reaction of compound (2) and epihalohydrin (3) may be performed without a solvent or in the presence of a solvent.
  • Solvents include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, benzonitrile and dimethyl sulfoxide, diethyl ether And ether solvents such as tert-butyl methyl ether, 1,2-dimethoxyethane, 1,4-dioxane, tetrahydrofuran and anisole, and halogenated hydrocarbon solvents such as chloroform, dichloromethane and 1,2-dibromoethane.
  • ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone
  • aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone
  • An aprotic polar solvent is preferred. Two or more solvents may be used in combination.
  • the amount of the solvent to be used is generally 0.01-100 parts by weight, preferably 0.1-50 parts by weight, per 1 part by weight of compound (2).
  • the reaction between the compound (2) and the epihalohydrin (3) may be performed under normal pressure conditions, under pressure conditions, or under reduced pressure conditions. You may implement reaction in inert gas atmosphere, such as nitrogen gas and argon gas.
  • the reaction between compound (2) and epihalohydrin (3) is usually performed by mixing compound (2), epihalohydrin (3), an inorganic base, and, if necessary, a quaternary ammonium salt, an aliphatic alcohol and a solvent. To be implemented.
  • the reaction temperature is usually ⁇ 20 ° C. to 150 ° C., preferably ⁇ 10 ° C. to 120 ° C.
  • the progress of the reaction can be confirmed by analyzing the decreased amount of compound (2) or the amount of diepoxy compound (1) produced by ordinary analytical means such as liquid chromatography, and the formation of diepoxy compound (1). It is preferable to carry out the reaction until no increase in the amount is confirmed.
  • the reaction time is usually 1 to 150 hours.
  • Step (I) preferably includes the following steps (i) and (ii).
  • Step (i) may be performed under normal pressure conditions, may be performed under pressure conditions, or may be performed under reduced pressure conditions. You may implement process (i) in inert gas atmosphere, such as nitrogen gas and argon gas.
  • the reaction temperature in step (i) is usually ⁇ 10 ° C. to 150 ° C., preferably 0 ° C. to 120 ° C.
  • the reaction time in step (i) varies depending on the reaction temperature, but is usually 0.5 to 72 hours.
  • the reaction mixture obtained in step (i) may contain a diepoxy compound (1).
  • Step (ii) may be performed under normal pressure conditions, may be performed under pressure conditions, or may be performed under reduced pressure conditions.
  • Step (ii) may be performed under an inert gas atmosphere such as nitrogen gas or argon gas.
  • the reaction temperature in step (ii) is usually ⁇ 20 ° C. to 120 ° C., preferably ⁇ 10 ° C. to 80 ° C.
  • Step (ii) is preferably carried out until no increase in the amount of diepoxy compound (1) is confirmed, and the reaction time is usually 0.5 to 72 hours, although it varies depending on the reaction temperature.
  • 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. 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.
  • Water-insoluble solvents include halogenated hydrocarbon solvents such as dichloromethane, chloroform, chlorobenzene and dichlorobenzene, ester solvents such as ethyl acetate and butyl acetate, and aromatic hydrocarbon solvents such as benzene, toluene, ethylbenzene, xylene and mesitylene.
  • ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and the amount used is usually 1 to 300 parts by weight, preferably 10 to 200 parts by weight, per 1 part by weight of the diepoxy compound (1).
  • the diepoxy compound (1) is prepared by mixing the compound (2) with the formula (4) (Where X 2 Represents a halogen atom. ) Is reacted with a compound represented by formula (5) (hereinafter abbreviated as compound (4)). (Wherein R 1 , R 2 , R 3 , R 4 , R 5 And R 6 Represents the same meaning as above. ) (Hereinafter abbreviated as compound (5)), and the obtained compound (5) can be produced by a method comprising a step of oxidizing with an oxidizing agent.
  • X in compound (4) 2 Represents a halogen atom, and examples of the halogen atom include a chlorine atom and a bromine atom.
  • Compound (4) includes allyl chloride and allyl bromide. Two or more compounds (4) may be used in combination.
  • the amount of compound (4) 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 used is usually 2 to 10 mol per 1 mol of compound (2).
  • the amount of its use is 2 mol or more normally with respect to 1 mol of compounds (2).
  • an organic base that is liquid under the reaction conditions a large excess of the organic base may be used also as a solvent.
  • the reaction between compound (2) and compound (4) is preferably performed in a solvent. Examples of the solvent include the same solvents as those used in the reaction of the aforementioned compound (2) and epihalohydrin (3).
  • the organic base may be used as a solvent.
  • Reaction of a compound (2) and a compound (4) is normally implemented by mixing a compound (2), a compound (4), 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. 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 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 (5) produced is observed.
  • the obtained reaction mixture containing the compound (5) is usually mixed with an oxidizing agent as it is or after being washed with water, and the reaction between the compound (5) and the oxidizing agent is carried out.
  • the oxidizing agent may be any oxidizing agent that can convert a carbon-carbon double bond to an epoxy group, and specific examples thereof include peracids 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 (5).
  • the reaction between the compound (5) and the oxidizing agent may be performed under normal pressure conditions, under pressure conditions, or under reduced pressure conditions.
  • the reaction may be performed in an inert gas atmosphere such as nitrogen gas or argon gas.
  • the reaction temperature is usually ⁇ 20 ° C.
  • the diepoxy compound (1) can be taken out by concentrating the reaction mixture. After decomposing the oxidizing agent remaining in the reaction mixture, concentration may be performed. The taken-out diepoxy compound (1) can be further purified by ordinary purification means such as recrystallization.
  • Compound (2) is compound of formula (6) in the presence of a base: (Wherein R 1 , R 2 , R 3 And R 4 Represents the same meaning as above, Z 1 Represents an alkyl group having 1 to 5 carbon atoms, and X 3 Represents a halogen atom. )
  • phenol compound (7) a phenol compound represented by formula (8): (Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Z 1 And Z 2 Represents the same meaning as above. ) Can be produced by reacting the resulting compound (8) with a primary amine or ammonia.
  • Z 1 And Z 2 Examples of the alkyl group having 1 to 5 carbon atoms represented by the formula include a methyl group, an ethyl group, a propyl group, and a butyl group, and a methyl group is preferable.
  • X 3 Examples of the halogen atom represented by the formula include a chlorine atom and a bromine atom.
  • Examples of the acid halide (6) include 4-acetoxybenzoic acid chloride, 4-acetoxy-2-methylbenzoic acid chloride, 4-acetoxy-3-methylbenzoic acid chloride, 4-acetoxy-2-ethylbenzoic acid chloride, 4- Examples include acetoxy-3-ethylbenzoic acid chloride, 4-acetoxy-3,5-dimethylbenzoic acid chloride, 4-acetoxybenzoic acid bromide and 4-acetoxy-2-methylbenzoic acid bromide.
  • Acid halide (6) is described in J. Org. Med. Chem. 2007, 50, 5585 and Eur. J. et al. Med. Chem. It can be produced according to the method described in 2009, 44, 772, etc.
  • 4-acyloxybenzoic acid compound obtained by acylating 4-hydroxybenzoic acid compound corresponding to target acid halide (6) such as 4-hydroxybenzoic acid with an acylating agent such as acetic anhydride.
  • the acid halide (6) can be produced by a method of halogenating with a halogenating agent such as thionyl chloride, oxalyl chloride, phosphorus pentachloride or phosphorus tribromide.
  • a halogenating agent such as thionyl chloride, oxalyl chloride, phosphorus pentachloride or phosphorus tribromide.
  • the phenol compound (7) include 4-acetoxy-4′-hydroxy-1,1′-biphenyl, 4-acetoxy-4′-hydroxy-3-methyl-1,1′-biphenyl, and 4-acetoxy-4 ′.
  • the phenol compound (7) has the formula (13): (Wherein R 5 And R 6 Represents the same meaning as above. )
  • an organic base for example, pyridine, etc.
  • a carboxylic acid anhydride for example, acetic anhydride, etc.
  • the biphenol compound represented by the formula (13) can be produced according to a known method such as a method for monoacylation.
  • the amount of the phenol compound (7) to be used is generally 1 to 10 mol, preferably 1 to 5 mol, per 1 mol of the acid halide (6).
  • Examples of the base used for the reaction between the acid halide (6) and the phenol compound (7) include organic bases such as pyridine and triethylamine. The amount used is usually 1 to 50 moles per mole of acid halide (6). Two or more bases may be used in combination.
  • the reaction between the acid halide (6) and the phenol compound (7) is preferably performed in a solvent.
  • the solvent examples include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, benzonitrile and dimethyl sulfoxide, and Examples include ether solvents such as diethyl ether, tert-butyl methyl ether, 1,2-dimethoxyethane, 1,4-dioxane, tetrahydrofuran, and anisole, and ether solvents are preferred.
  • ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone
  • aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, benzonitrile and dimethyl sulfox
  • the amount of the solvent used is usually 1 to 200 parts by weight, preferably 3 to 100 parts by weight per 1 part by weight of the acid halide (6).
  • the reaction between the acid halide (6) and the phenol compound (7) is usually carried out by mixing the acid halide (6), the phenol compound (7), a base, and a solvent as necessary, and the mixing order is limited. Not.
  • the reaction may be performed under normal pressure conditions, may be performed under pressure conditions, or may be performed under reduced pressure conditions. Moreover, you may carry out in inert gas atmosphere, such as nitrogen gas and argon gas.
  • the reaction temperature is usually ⁇ 30 to 150 ° C., preferably ⁇ 30 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 (8) produced is observed.
  • the compound (8) may be taken out from the reaction mixture containing the obtained compound (8) and reacted with a primary amine or ammonia, or the obtained reaction mixture may be used as it is.
  • the reaction may be carried out by mixing with a primary amine or ammonia. Further, the reaction mixture obtained may be washed with water or the like to remove by-produced salts, and then mixed with a primary amine or ammonia to carry out the reaction.
  • the primary amine is preferably a primary amine having 1 to 20 carbon atoms, specifically, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, isopropanol.
  • Examples include pentylamine, neopentylamine, sec-pentylamine, hexylamine, tert-octylamine, undecylamine, 4-phenylbutylamine, cyclohexylamine and benzylamine.
  • ammonia gas may be used, or ammonia water or an alcohol solution of ammonia adjusted to a concentration of about 1 to 60% by weight may be used.
  • the amount of primary amine or ammonia to be used is generally 1-50 mol per 1 mol of compound (8).
  • the reaction of the compound (8) with the primary amine or ammonia may be carried out without a solvent or in the presence of a solvent.
  • Solvents include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol, propylene glycol, 2-methyl-2-propanol, and ketones such as methyl ethyl ketone and methyl isobutyl ketone.
  • Solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, benzonitrile, dimethyl sulfoxide, and diethyl ether, tert-butyl methyl ether, 1, 2 -Ether solvents such as dimethoxyethane, 1,4-dioxane, tetrahydrofuran, and anisole are mentioned, and ether solvents are preferred. Two or more solvents may be used in combination. When a solvent is used, the amount used is usually 0.01 to 100 parts by weight, preferably 0.1 to 50 parts by weight, relative to 1 part by weight of compound (8).
  • aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, benzonitrile, dimethyl sulfoxide, and diethyl ether, tert
  • the reaction temperature in the reaction of the compound (8) with the primary amine or ammonia is usually ⁇ 50 to 150 ° C., preferably ⁇ 30 to 100 ° C.
  • the reaction time varies depending on the reaction temperature and the like, but is usually 0.5 to 72 hours.
  • the compound (2) can be taken out by mixing the obtained reaction mixture and water and then filtering.
  • the extracted compound (2) can be further purified by ordinary purification means such as recrystallization.
  • Compound (2) comprises acid halide (6) and formula (9): (Wherein R 5 Represents the same meaning as above, and X 4 Represents a halogen atom.
  • phenol compound (9) a phenol compound represented by formula (10): (Wherein R 1 , R 2 , R 3 , R 4 , R 5 , Z 1 And X 4 Represents the same meaning as above. )
  • halogen atom represented by the formula include a chlorine atom, a bromine atom and an iodine atom.
  • Examples of the phenol compound (9) include 4-chlorophenol, 4-chloro-2-methylphenol, 4-chloro-2-ethylphenol, 4-chloro-2-propylphenol, 4-chloro-2-isopropylphenol, 4 -Bromophenol, 4-bromo-2-methylphenol, 4-bromo-2-ethylphenol, 4-bromo-2-propylphenol, 4-iodophenol, 4-iodo-2-methylphenol, 2-ethyl-4 -Iodophenol, 4-iodo-2-propylphenol and 4-iodo-2-isopropylphenol.
  • the amount of the phenol compound (9) to be used is generally 1 to 10 mol, preferably 1 to 5 mol, per 1 mol of the acid halide (6).
  • the reaction between the acid halide (6) and the phenol compound (9) can be performed under the same conditions as the reaction between the acid halide (6) and the phenol compound (7).
  • the compound (10) may be taken out from the obtained reaction mixture and reacted with the compound (11), or the obtained reaction mixture may be used as it is for the reaction with the compound (11). Good.
  • the reaction mixture may be washed with water or the like to remove by-produced salts, and then used for the reaction with the compound (11).
  • the amount of compound (11) to be used is generally 1 to 5 mol, preferably 1 to 2 mol, per 1 mol of compound (10).
  • the palladium catalyst include tetrakis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium, tris (dibenzylideneacetone) dipalladium chloroform adduct, bis (1,2-bis (diphenylphosphinoethane)) palladium, Bis (tricyclohexylphosphine) palladium, bis (tri-tert-butylphosphine) palladium, palladium acetate, palladium trifluoroacetate, palladium chloride, palladium bromide, palladium iodide, palladium cyanide, allyl palladium chloride dimer, crotyl palladium Chloride dimer, 2-methylallyl palladium chloride dimer, palladium acety
  • the amount of the palladium catalyst to be used is generally 0.0005 to 0.5 mol in terms of palladium metal with respect to 1 mol of compound (10).
  • a ligand a ligand containing a phosphorus atom is preferable.
  • Examples of the ligand containing a phosphorus atom include triphenylphosphine, tris (2-methylphenyl) phosphine, tris (3-methylphenyl) phosphine, tris (4-methylphenyl) phosphine, tris (pentafluorophenyl) phosphine, and tris.
  • the amount of the ligand used is usually 1 to 10 mol, preferably 1 to 5 mol, per 1 mol of the palladium atom.
  • the tetraalkylammonium fluoride include tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride and tetra-tert-butylammonium fluoride, with tetrabutylammonium fluoride being preferred.
  • the amount of tetraalkylammonium fluoride to be used is generally 1-5 mol, preferably 1-3 mol, per 1 mol of compound (11).
  • the reaction between compound (10) and compound (11) is preferably carried out in a solvent.
  • Solvents include aromatic hydrocarbon solvents such as benzene, toluene and xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile and benzonitrile. And aprotic polar solvents such as dimethyl sulfoxide, and ether solvents such as diethyl ether, tert-butyl methyl ether, 1,2-dimethoxyethane, 1,4-dioxane, tetrahydrofuran, and anisole. A solvent is preferred.
  • the amount of the solvent to be used is generally 1-200 parts by weight, preferably 3-100 parts by weight, per 1 part by weight of compound (10).
  • the reaction between the compound (10) and the compound (11) is usually carried out by mixing the compound (10), the compound (11), a palladium catalyst, a tetraalkylammonium fluoride and, if necessary, a solvent.
  • the order is not limited.
  • the reaction may be performed under normal pressure conditions, may be performed under pressure conditions, or may be performed under reduced pressure conditions. Moreover, you may carry out in inert gas atmosphere, such as nitrogen gas and argon gas.
  • the reaction temperature is usually ⁇ 30 to 200 ° C., preferably ⁇ 30 to 180 ° C.
  • the progress of the reaction can be confirmed by ordinary analytical means such as liquid chromatography, and the reaction is preferably carried out until no increase in the amount of compound (12) produced is observed.
  • the compound (12) may be taken out from the reaction mixture containing the obtained compound (12) and reacted with a primary amine or ammonia, or the obtained reaction mixture may be used as it is.
  • the reaction may be carried out by mixing with a primary amine or ammonia. Further, the reaction mixture obtained may be washed with water or the like to remove by-produced salts, and then mixed with a primary amine or ammonia to carry out the reaction.
  • the reaction between the compound (12) and the primary amine or ammonia can be carried out in the same manner as the reaction between the compound (8) and the primary amine or ammonia. 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.
  • the solvent examples 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 ketone solvents and aprotic polar solvents are preferred. Even if the solvent is removed from the solution obtained by dissolving the diepoxy compound (1) and the curing agent of the present invention in a solvent, a uniform mixture tends to be obtained.
  • 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
  • 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-
  • an amine curing agent, an amine curing agent, a phenol curing agent and a curing catalyst are preferable, and an amine curing agent is more preferable.
  • amine curing agents include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, and other aliphatic polyamines having 2 to 20 carbon atoms, p-xylenediamine, m-xylenediamine, 1 , 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).
  • a curing agent is used in an amount of 1.5 mol, preferably 0.9 to 1.1 mol.
  • the composition X has a desired performance of the cured product obtained by curing the composition X (for example, solubility, heat resistance, thermal conductivity, etc.). As long as it does not cause a decrease, compounds having other epoxy groups can be included.
  • composition X can contain various additives in addition to the diepoxy compound (1), the curing agent and the solvent.
  • 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 can contain an additive in an amount that does not cause a decrease in the desired performance (eg, melting point) of the cured product obtained by curing the composition X.
  • 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 further 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, preferably 83 parts per 100 parts by weight in total of the diepoxy compound (1), the curing agent and alumina. Parts by weight to 90 parts by weight.
  • the 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), the curing agent and alumina improves the thermal conductivity of the cured product obtained by curing the composition.
  • the composition in which the amount of alumina is 95 parts by weight or less tends to be easily formed.
  • alumina granular alumina is preferable, and D50 is 2 ⁇ m or more and 100 ⁇ m or less, where D50 is the particle size of 50% cumulative volume from the fine particle side of the weight cumulative particle size distribution (average particle size measured by laser diffraction method). More preferred is alumina which is a mixture of certain alumina A, alumina B having a D50 of 1 ⁇ m or more and 10 ⁇ m or less, and alumina C having a D50 of 0.01 ⁇ m or more and 5 ⁇ m or less.
  • 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. It is preferable that Such alumina can be prepared, for example, by appropriately mixing commercially available alumina having various average particle sizes. Further, the content ratio of alumina contained in the cured product is preferably 50 to 80% by volume, more preferably 60 to 74% 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 by heating to a predetermined temperature, a composition X is heated and melted and poured into a mold or the like, and the mold is further A method of molding by heating, a method of melting the composition X, a method of injecting and curing the resulting melt into a preheated mold, a partial curing of the composition X, and pulverizing the resulting partially cured product, 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 A method of drying by removing the solvent by ventilation drying or the like, and heating for a predetermined time while applying pressure with a press machine or the like as required.
  • 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 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.
  • the obtained white solid was dissolved in 107 g of tetrahydrofuran to obtain a tetrahydrofuran solution of an acid halide represented by the formula (6-1) (hereinafter abbreviated as acid halide (6-1)).
  • acid halide (6-1) an acid halide represented by the formula (6-1)
  • 22.38 g of phenol (7-1) obtained in [Reference Example 1-1] 24.57 g of pyridine and 107 g of tetrahydrofuran were added and mixed at room temperature (about 25 ° C.). .
  • a tetrahydrofuran solution of acid halide (6-1) was added dropwise over 41 minutes while maintaining the same temperature.
  • the resulting mixture was stirred at 70 ° C. for 14 hours and then cooled to 18 ° C.
  • 42.83 g of a 15 wt% aqueous sodium hydroxide solution was gradually added.
  • the resulting mixture was stirred at 18 ° C. for an additional 3 hours and then cooled to 0 ° C.
  • ion-exchanged water and chloroform were added for liquid separation.
  • the obtained chloroform layer was washed with ion-exchanged water three times, and then insoluble matters were removed by filtration.
  • the obtained filtrate was concentrated to obtain a crude product.
  • the obtained chloroform layer was washed with ion-exchanged water three times, and then insoluble matters were removed by filtration.
  • the obtained filtrate was concentrated to obtain a crude product [1].
  • the obtained crude product [1], 450 mL of toluene and 200 mL of 2-propanol were added to a reaction vessel equipped with a cooling device, and the resulting mixture was heated to 70 ° C. and 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 to obtain a crude product [2].
  • the crude product [2], toluene and 2-propanol were mixed, and the same operation as that for obtaining the crude product [2] from the crude product [1] was performed to obtain the crude product [3].
  • the crude product [3], toluene and 2-propanol were mixed, and the same operation as the operation for obtaining the crude product [2] from the crude product [1] was performed to obtain the crude product [4].
  • the crude product [4], 900 mL of toluene, and 400 mL of chloroform were mixed, and the same operation as the operation for obtaining the crude product [2] from the crude product [1] was performed.
  • the obtained solid was dried to obtain 13.70 g of white crystals containing a diepoxy compound represented by formula (1-1) (hereinafter abbreviated as diepoxy compound (1-1)).
  • the white crystals were analyzed by liquid chromatography, and the area percentage of the peak corresponding to the resulting diepoxy compound (1-1) in the chromatograph was calculated to be 90.4%.
  • the yield of the diepoxy compound (1-1) based on the compound (2-1) was 56%. . Melting point: 160 ° C.
  • the mixture was heated to 70 ° C., stirred at the same temperature for 13 hours, and then cooled to 18 ° C.
  • 3.73 g of a 15 wt% aqueous sodium hydroxide solution was gradually added at 18 ° C.
  • the resulting mixture was stirred at the same temperature for 3 hours and further cooled to 0 ° C. to obtain a reaction mixture.
  • 50 mL of ion exchange water and 100 mL of chloroform were added and separated.
  • the obtained chloroform layer was washed three times with ion exchange water. After removing insolubles contained in the washed chloroform layer by filtration, the obtained filtrate was concentrated to obtain a crude product.
  • the obtained crude product, 33 mL of toluene and 25 mL of 2-propanol were added to a reaction vessel equipped with a cooling device.
  • the resulting mixture was stirred at 70 ° C. for 1 hour and then cooled to room temperature.
  • the precipitated solid was removed by filtration.
  • the taken solid was washed with 2-propanol to obtain a crude product.
  • the obtained crude product, 34 mL of toluene and 15 mL of ethanol were added to a reaction vessel equipped with a cooling device.
  • the resulting mixture was stirred at 70 ° C. for 1 hour and then cooled to room temperature.
  • the precipitated solid was removed by filtration.
  • diepoxy compound (1-2) a diepoxy compound represented by formula (1-2) (hereinafter abbreviated as diepoxy compound (1-2)). It was.
  • the white crystals were analyzed by liquid chromatography, and the area percentage of the peak corresponding to the diepoxy compound (1-2) in the obtained chromatograph was calculated to be 92.7%. Assuming that the content of diepoxy compound (1-2) in the crystal is 92.7% by weight, the yield of diepoxy compound (1-2) based on compound (2-2) was 44%. It was. Melting point: 165 ° C.
  • the obtained mixture was heated to 50 ° C., and 3.68 g of thionyl chloride was added dropwise at 50 ° C. over 10 minutes. The resulting mixture was stirred at 50 ° C. for 3 hours and then cooled to room temperature. The resulting reaction mixture was concentrated under reduced pressure to give a yellow solid. The solid was dissolved in 22 g of tetrahydrofuran to obtain a tetrahydrofuran solution of 4-acetoxy-2-methylbenzoic acid chloride. To a reaction vessel equipped with a cooling device, 5.96 g of phenol (7-1) (content 94.7 wt%), 5.90 g of pyridine and 22 g of tetrahydrofuran were added.
  • the crystals were analyzed by liquid chromatography, and the area percentage of the peak corresponding to the obtained chromatographic compound (8-3) was calculated to be 97.7%. Assuming that the content of the compound (8-3) in the crystal is 97.7% by weight, the yield of the compound (8-3) based on 4-acetoxy-2-methylbenzoic acid is 71%. there were.
  • the obtained mixture was stirred at room temperature for 3 hours, and 5.47 g of 28 wt% aqueous ammonia solution was added. The obtained mixture was stirred for 3 hours, and 5.47 g of 28 wt% aqueous ammonia solution was added. After stirring the resulting mixture for 4 hours, 2.74 g of 28 wt% aqueous ammonia solution was added. The obtained mixture was stirred for 2 hours, and 5.47 g of 28 wt% aqueous ammonia solution was added. The obtained mixture was stirred for 2 hours, and 2.74 g of 28 wt% aqueous ammonia solution was added. The resulting mixture was stirred for 1 hour.
  • the resulting mixture was heated to 70 ° C., stirred at the same temperature for 11 hours, and then cooled to 18 ° C.
  • 5.00 g of a 15 wt% aqueous sodium hydroxide solution was gradually added.
  • the obtained mixture was adjusted to 18 ° C. and stirred for 4 hours, and then cooled to 0 ° C.
  • 50 mL of ion exchange water and 100 mL of chloroform were added and separated to obtain a chloroform layer.
  • the chloroform layer was washed 3 times with ion-exchanged water, and then insoluble matters were removed by filtration.
  • the obtained filtrate was concentrated to obtain a crude product.
  • the obtained crude product, 5 mL of toluene and 15 mL of 2-propanol were added to a reaction vessel equipped with a cooling device.
  • the obtained mixture was heated to 70 ° C. and stirred at the same temperature for 1 hour.
  • the obtained mixture was cooled to room temperature, and the precipitated solid was removed by filtration.
  • the taken solid was washed with 2-propanol to obtain a crude product.
  • the obtained crude product, 13 mL of toluene, and 10 mL of 2-propanol were mixed, and the same stirring, filtration and washing operations were performed as described above. This was abbreviated as 3).
  • the crystals were analyzed by liquid chromatography, and the area percentage of the peak corresponding to the diepoxy compound (1-3) in the obtained chromatograph was calculated to be 90.9%. Assuming that the content of diepoxy compound (1-3) in the crystal is 90.9% by weight, the yield of diepoxy compound (1-3) based on compound (2-3) was 69%. It was. Melting point: 122 ° C.
  • the resulting mixture was stirred at room temperature for 1 hour, and the precipitate [1] was removed by filtration.
  • the precipitate [1], 1.69 L of hexane, and 0.85 L of chloroform were mixed, and the same operation as that for obtaining the precipitate [1] from the crude product was performed to obtain the precipitate [2].
  • the precipitate [2], ethanol (26 mL) and toluene (35 mL) were mixed, and the same operation as that for obtaining the precipitate [1] from the crude product was performed to obtain the precipitate [3].
  • the precipitate [3] was washed with hexane and dried to obtain 12.06 g of white crystals containing a phenol compound represented by the formula (7-2) (hereinafter abbreviated as phenol (7-2)). .
  • the crystals were analyzed by liquid chromatography, and the area percentage of the peak corresponding to phenol (7-2) in the obtained chromatograph was calculated, and it was 95.4%. Assuming that the content of phenol (7-2) in the crystal is 95.4% by weight, the yield of phenol (7-2) based on 3,3′-dimethyl-4,4′-biphenol is 24%.
  • the precipitated solid was removed by filtration, washed with methanol, dried, and 3.85 g of white crystals containing a compound represented by the formula (8-4) (hereinafter abbreviated as compound (8-4)) were obtained. Obtained.
  • the crystals were analyzed by liquid chromatography, and the area percentage of the peak corresponding to the chromatographic compound (8-4) obtained was calculated to be 97.1%. Assuming that the content of the compound (8-4) in the crystal was 97.1% by weight, the yield of the compound (8-4) based on 4-acetoxybenzoic acid was 64%.
  • the crystals were analyzed by liquid chromatography, and the area percentage of the peak corresponding to the obtained chromatograph compound (2-4) was calculated to be 98.7%. Assuming that the content of the compound (2-4) in the crystal was 98.7% by weight, the yield of the compound (2-4) based on the compound (8-4) was 52%.
  • the resulting mixture was stirred at 70 ° C. for 23 hours and then cooled to 18 ° C.
  • 2.40 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.
  • 50 mL of ion exchange water was added, and further 100 mL of chloroform was added, followed by liquid separation.
  • the obtained chloroform layer was washed with ion-exchanged water three times, and then insoluble matters were removed by filtration.
  • the obtained filtrate was concentrated to obtain a crude product.
  • the obtained crude product, 15 mL of toluene and 12 mL of 2-propanol were added to a reaction vessel equipped with a cooling device.
  • the resulting mixture was stirred at 70 ° C. for 1 hour and then cooled to room temperature.
  • the precipitated solid was removed by filtration.
  • the taken-out solid was washed with 2-propanol and dried to obtain 0.86 g of white crystals containing a diepoxy compound represented by the formula (1-4) (hereinafter abbreviated as diepoxy compound (1-4)). It was.
  • the crystals were analyzed by liquid chromatography, and the area percentage of the peak corresponding to the diepoxy compound (1-4) in the obtained chromatograph was calculated to be 93.3%.
  • the obtained mixture was heated to 90 ° C., stirred at the same temperature for 20 hours, and then cooled to 0 ° C. After adding 150 mL of ion-exchanged water to the resulting reaction mixture, 500 mL of ethyl acetate and 91 mL of ion-exchanged water were added and separated at room temperature to obtain an organic layer and an aqueous layer. The obtained aqueous layer was extracted with 500 mL of ethyl acetate to obtain an ethyl acetate layer. The ethyl acetate layer and the previously obtained organic layer were mixed and then washed with saturated aqueous sodium chloride.
  • the precipitated solid was taken out by filtration, washed with methanol, dried, and 0.84 g of white crystals containing a compound represented by the formula (2-5) (hereinafter abbreviated as compound (2-5)) was obtained. Obtained.
  • the crystals were analyzed by liquid chromatography, and the area percentage of the peak corresponding to the obtained chromatograph compound (2-5) was calculated to be 94.8%.
  • the content of the compound (2-5) in the crystal was assumed to be 94.8% by weight.
  • the resulting mixture was heated to 70 ° C., stirred at the same temperature for 19 hours, and then cooled to 18 ° C.
  • 2.00 g of a 15 wt% aqueous sodium hydroxide solution was gradually added.
  • the resulting mixture was stirred at 18 ° C. for 4 hours 30 minutes and then cooled to 0 ° C.
  • 50 mL of ion-exchanged water and 100 mL of chloroform were added and separated.
  • the obtained chloroform layer was washed with ion-exchanged water three times, and then insoluble matters were removed by filtration.
  • the obtained filtrate was concentrated to obtain a crude product [1].
  • the obtained crude product [1], 9 mL of toluene and 8 mL of 2-propanol were added to a reaction vessel equipped with a cooling device.
  • the obtained mixture was heated to 70 ° C., stirred at the same temperature for 1 hour, and then cooled to room temperature.
  • the precipitated solid was removed by filtration to obtain a crude product [2].
  • the crude product [2], 7 mL of toluene, and 6 mL of 2-propanol were mixed, and the same operation as that for obtaining the crude product [2] from the crude product [1] was performed.
  • diepoxy compound (1-5) a diepoxy compound represented by formula (1-5) (hereinafter abbreviated as diepoxy compound (1-5)). It was.
  • the crystals were analyzed by liquid chromatography, and the area percentage of the peak corresponding to the diepoxy compound (1-5) in the obtained chromatograph was calculated to be 93.4%.
  • the yield of the diepoxy compound (1-5) based on the compound (2-5) was 32%. .
  • Melting point 120 ° C.
  • the obtained composition was concentrated with a centrifugal concentrator to obtain a uniform powdery composition.
  • the obtained powdery composition was filled in an alumina pan.
  • the alumina pan filled with the composition was heated with a differential scanning calorimeter (DSC Q2000 manufactured by TA Instruments) to obtain a cured product (curing condition: heated at 140 ° C. for 20 minutes in a nitrogen atmosphere, then 180 ° C. Until heating at 1 ° C./min, and further heating at 200 ° C. for 30 minutes).
  • the obtained cured product was cooled to 20 ° C. When heated to 140 ° C., an exotherm indicating that a curing reaction between the diepoxy compound (1-1) and the curing agent occurred was observed.
  • Example 7 The glass transition point of the cured product was measured with a differential scanning calorimeter (temperature increase rate: 20 ° C./min, measurement temperature range: room temperature to 200 ° C.) and found to be 176 ° C.
  • Example 7 In Example 6, it replaced with 24 weight part of 4,4'- diamino diphenylmethane, and implemented similarly to Example 6 except having used 19 weight part of 1, 5- diamino naphthalene (made by Wako Pure Chemical Industries Ltd.).
  • a solution-like composition was obtained.
  • the obtained solution-like composition was concentrated with a centrifugal concentrator to obtain a uniform powdery composition.
  • the obtained powdery composition was heated in the same manner as in Example 6 to obtain a cured product.
  • Example 6 When heated to 140 ° C., an exotherm indicating that a curing reaction between the diepoxy compound (1-1) and the curing agent occurred was observed. When the glass transition point of hardened
  • Example 8 In Example 6, instead of 24 parts by weight of 4,4′-diaminodiphenylmethane, 36 parts by weight of cis-4-cyclohexene-1,2-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used, and a curing accelerator was used. As in Example 6, except that 2.7 parts by weight of 2-phenylimidazole was further used, a solution-like composition was obtained.
  • the obtained solution-like composition was concentrated with a centrifugal concentrator to obtain a uniform powdery composition.
  • the obtained powdery composition was heated in the same manner as in Example 6 to obtain a cured product.
  • an exotherm indicating that a curing reaction between the diepoxy compound (1-1) and the curing agent occurred was observed.
  • the glass transition point of the cured product was 120 ° C.
  • Example 9 In Example 6, instead of 24 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 31 parts by weight of Kasei Kogyo Co., Ltd. and 2.6 parts by weight of 2-phenylimidazole were further used as a curing accelerator, to obtain a solution-like composition. The obtained solution-like composition was concentrated with a centrifugal concentrator to obtain a uniform powdery composition.
  • Tokyo 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride
  • Example 10 The obtained powdery composition was heated in the same manner as in Example 6 to obtain a cured product. When heated to 140 ° C., an exotherm indicating that a curing reaction between the diepoxy compound (1-1) and the curing agent occurred was observed. The glass transition point of the cured product was 188 ° C.
  • Example 10 instead of 24 parts by weight of 4,4′-diaminodiphenylmethane, 99 parts by weight of a phenol novolac curing agent “MEH-7851H” (Maywa Kasei Co., Ltd.) was used, and triphenylphosphine as a curing accelerator. Except having further used 0 weight part, it implemented similarly to Example 6 and obtained the solution-form composition.
  • the obtained solution-like composition was concentrated with a centrifugal concentrator to obtain a uniform powdery composition.
  • the obtained powdery composition was heated in the same manner as in Example 6 to obtain a cured product.
  • an exotherm indicating that a curing reaction between the diepoxy compound (1-1) and the curing agent occurred was observed.
  • the glass transition point of the cured product was 109 ° C.
  • Example 11 In Example 6, instead of 24 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. Except having used, it implemented similarly to Example 6 and obtained the solution-form composition. The obtained solution-like composition was concentrated with a centrifugal concentrator to obtain a uniform powdery composition. The obtained powdery composition was heated in the same manner as in Example 6 to obtain a cured product.
  • dicyandiamide manufactured by Wako Pure Chemical Industries, Ltd.
  • Example 12 100 parts by weight of diepoxy compound (1-1), 19 parts by weight of 1,5-diaminonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.) as a curing agent, and 1097 parts by weight of alumina powder (alpha-alumina powder by Sumitomo Chemical Co., Ltd.) An alumina powder A1 having an average particle diameter (D50) measured by a laser diffraction method of 18 ⁇ m, an alumina powder B1 having an average particle diameter (D50) of 3 ⁇ m, and an average particle diameter (D50) of 0.4 ⁇ m.
  • D50 average particle diameter
  • Prepared by mixing 530 parts by weight of methyl isobutyl ketone and 60 parts by weight of N, N-dimethylformamide as a solvent Were mixed to prepare a composition.
  • 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 140 ° 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: vacuum degree 1 kPa, press pressure 6 MPa, press temperature 150 ° C., time 20 minutes). Furthermore, the press temperature was raised to 180 ° C. over 40 minutes, and vacuum press molding was performed.
  • the aluminum foil was peeled off to obtain a sheet-like cured product having a thickness of 210 ⁇ m.
  • the heat conductivity of the cured product was measured by a xenon flash analyzer nanoflash LFA447 manufactured by NETZSCH and found to be 10.2 W / (m ⁇ K).
  • the density of the cured product obtained by curing a composition containing the diepoxy compound (1-1) and 1,5-diaminonaphthalene and not containing alumina powder is 1.2 g / cm. 3
  • the density of the alumina powder is 3.97 g / cm 3
  • the content ratio of the alumina powder in the cured product was 74% by volume.
  • Example 13 100 parts by weight of diepoxy compound (1-1), 19 parts by weight of 1,5-diaminonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.) as a curing agent, 380 parts by weight of methyl isobutyl ketone and N, N-dimethylformamide as a solvent
  • a solution-like composition can be prepared by mixing 70 parts by weight.
  • a prepreg can be obtained by impregnating a 0.2 mm-thick glass fiber woven fabric with the resulting composition and then heating.
  • a laminate can be obtained by stacking four prepregs obtained and press-molding at 175 ° C. and 4 MPa for 90 minutes.
  • Example 14 100 parts by weight of diepoxy compound (1-3), 18 parts by weight of 1,5-diaminonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.) as a curing agent, and 1091 parts by weight of alumina powder (alpha-alumina powder by Sumitomo Chemical Co., Ltd.)
  • 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 140 ° 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: vacuum degree 1 kPa, press pressure 6 MPa, press temperature 140 ° C., time 20 minutes). Furthermore, the press temperature was raised to 180 ° C. over 40 minutes, and vacuum press molding was performed.
  • the aluminum foil was peeled off to obtain a sheet-like cured product having a thickness of 313 ⁇ m. When the thermal conductivity of the cured product was measured in the same manner as in Example 12, it was 10.2 W / (m ⁇ K).
  • the density of the cured product obtained by curing a composition containing the diepoxy compound (1-3) and 1,5-diaminonaphthalene and not containing alumina powder is 1.2 g / cm. 3
  • the density of the alumina powder is 3.97 g / cm 3
  • the content ratio of the alumina powder in the cured product was 74% by volume.
  • the diepoxy compound of the present invention has a low melting point, it is easy to handle, and a cured product obtained by curing a 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)
  • Epoxy Resins (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne un composé diépoxy représenté par la formule (1) (dans laquelle R1, R2, R3, R4, R5, et R6 représentent chacun indépendamment un atome d'hydrogène ou un groupe alkyle en C1 à C3).
PCT/JP2011/055164 2010-03-23 2011-02-28 Composé diépoxy, procédé de fabrication associé, et composition contenant ledit composé diépoxy WO2011118368A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2021182280A1 (fr) * 2020-03-11 2021-09-16 住友化学株式会社 Composition de cristaux liquides polymérisable, film de retard, polariseur elliptique et dispositif d'affichage optique

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101139280B1 (ko) * 2012-02-10 2012-04-26 주식회사 신아티앤씨 결정성 에폭시 수지
JP2015155493A (ja) * 2014-02-20 2015-08-27 住友化学株式会社 ジエポキシ化合物及び、該化合物を含む組成物
EP3604407A4 (fr) 2017-03-24 2020-12-23 Toray Industries, Inc. Préimprégné et matériau composite renforcé par des fibres de carbone
JP6819961B2 (ja) * 2017-03-31 2021-01-27 本州化学工業株式会社 新規なジエポキシ化合物

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0284432A (ja) * 1988-06-27 1990-03-26 Idemitsu Kosan Co Ltd 液晶性ポリマー及びその製造に用いられるエポキシ化合物
JPH02240128A (ja) * 1989-01-17 1990-09-25 Dow Chem Co:The メソゲン／剛直棒状部分を含有するビニルエステル樹脂
JPH0841164A (ja) * 1994-07-26 1996-02-13 Dainippon Ink & Chem Inc 高純度エポキシ樹脂の製造方法
JP2002037851A (ja) * 2000-07-28 2002-02-06 Sakamoto Yakuhin Kogyo Co Ltd 新規なエポキシ樹脂の製造法、およびその方法で製造されたエポキシ樹脂を含むエポキシ樹脂組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0284432A (ja) * 1988-06-27 1990-03-26 Idemitsu Kosan Co Ltd 液晶性ポリマー及びその製造に用いられるエポキシ化合物
JPH02240128A (ja) * 1989-01-17 1990-09-25 Dow Chem Co:The メソゲン／剛直棒状部分を含有するビニルエステル樹脂
JPH0841164A (ja) * 1994-07-26 1996-02-13 Dainippon Ink & Chem Inc 高純度エポキシ樹脂の製造方法
JP2002037851A (ja) * 2000-07-28 2002-02-06 Sakamoto Yakuhin Kogyo Co Ltd 新規なエポキシ樹脂の製造法、およびその方法で製造されたエポキシ樹脂を含むエポキシ樹脂組成物

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
GIAMBERINI, M. ET AL.: "Lightly crosslinked liquid-crystalline epoxy resins. The effect of rigid-rod length and applied stress on the state of order of the cured thermoset", MACROMOLECULAR CHEMISTRY AND PHYSICS, vol. 198, no. 10, 1997, pages 3185 - 3196, XP000727218, DOI: doi:10.1002/macp.1997.021981016 *
GIAMBERINI, M. ET AL.: "Liquid crystalline epoxy thermosets", MOLECULAR CRYSTALS AND LIQUID CRYSTALS, vol. 266, 1995, pages 9 - 22 *
SOSETSU EPOXY JUSHI KISO HEN I, 2003, pages 307 - 310 *
SOSETSU EPOXY JUSHI KISO HEN II, 2003, pages 218 *
SOSETSU EPOXY JUSHI OYO HEN I, 2003, pages 134 - 135, 211-212 *
THREE BOND TECHNICAL NEWS, vol. 32, 1990 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2021182280A1 (fr) * 2020-03-11 2021-09-16 住友化学株式会社 Composition de cristaux liquides polymérisable, film de retard, polariseur elliptique et dispositif d'affichage optique

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