Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
  • C07C69/12—Acetic acid esters
  • C07C69/21—Acetic acid esters of hydroxy compounds with more than three hydroxy groups
• • 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
  • C08G59/40—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 curing agents used

Definitions

• the present invention relates to a novel polyacyloxymethyl-4,4'-acyloxybiphenyl compound.
• Epoxy resins are well-balanced in various properties such as moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to inserts, and are widely used in various industrial fields such as electricity, paints, and adhesives. Used.
• Various types of curing agents can be used for the epoxy resin, and the curing properties vary greatly depending on the selection of the curing agent. Therefore, the curing agents are properly used according to the purpose of each application.
• general curing agents for epoxy resins phenolic curing agents, amide curing agents, imidazole curing agents, active ester curing agents, etc. are known. In addition, it is widely used due to its low cost and other advantages.
• a phenolic curing agent In general, a phenolic curing agent often shows a solid property due to hydrogen bonding of a phenolic hydroxyl group, and when it is highly crystalline, it is hardly compatible with the epoxy resin composition and the fluidity of the epoxy resin composition There is a problem that it decreases.
• means for preventing or inhibiting hydrogen bonding by a hydroxyl group of a phenolic curing agent is used.
• phenol derivatives in which a phenolic hydroxyl group is partially or completely protected with a silyl group see Patent Document 1
• means for introducing a substituent at the ortho-position of a phenolic hydroxyl group, and the like are used (see Patent Document 2). ).
• the present invention has been made in view of the above-described circumstances, and is a novel compound that can be easily dissolved in a liquid epoxy resin, and can be a curing agent for an epoxy resin that gives a cured product having excellent heat resistance and chemical resistance.
• the purpose is to provide.
• the present inventors have conducted intensive studies to solve the above problems, and as a result, have found a novel compound in which a plurality of acyloxymethyl groups are substituted on the 4,4'-acyloxybiphenyl skeleton, and have completed the present invention.
• a polyacyloxymethyl-4,4′-acyloxybiphenyl compound represented by the following formula (1) (Wherein, R 1 , R 2 , R 3 and R 4 each independently represent an alkyl group having 1 to 8 carbon atoms, and R 5 and R 6 each independently represent an alkyl group having 1 to 8 carbon atoms.
• R 1 , R 2 , R 3 and R 4 each independently represent an alkyl group having 1 to 8 carbon atoms
• R 5 and R 6 each independently represent an alkyl group having 1 to 8 carbon atoms.
• n and m each independently represent any of 0, 1, 2, and 3.
• the polyacyloxymethyl-4,4′-acyloxybiphenyl compound of the present invention has a lower melting point than a conventional curing agent having a biphenol skeleton for an epoxy resin. It can be mixed with the components. Accordingly, an effect that a solvent for dissolving the curing agent is not required, or even when a solvent is used, the solubility in the solvent is high and the amount of the solvent used can be greatly reduced. Furthermore, since the polyacyloxymethyl-4,4′-acyloxybiphenyl compound of the present invention is a compound having many functional groups, it greatly contributes to improving the heat resistance and chemical resistance of the epoxy resin film, Very useful. Further, the polyacyloxymethyl-4,4′-acyloxybiphenyl compound of the present invention is also useful as a raw material for a phenol compound.
• the compound of the present invention is a polyacyloxymethyl-4,4′-acyloxybiphenyl compound represented by the following formula (1).
• R 1 , R 2 , R 3 and R 4 each independently represent an alkyl group having 1 to 8 carbon atoms
• R 5 and R 6 each independently represent an alkyl group having 1 to 8 carbon atoms.
• n and m each independently represent any of 0, 1, 2, and 3.
• R 1 to R 6 or R 7 is an alkyl group having 1 to 8 carbon atoms
• a linear or branched alkyl group is included.
• Preferred alkyl groups are straight-chain or branched-chain alkyl groups having 1 to 5 carbon atoms, and specifically, methyl, ethyl, n-propyl, i-propyl, n-butyl Group, i-butyl group, t-butyl group, n-pentyl group, i-pentyl group, t-pentyl group and the like.
• a methyl group, an ethyl group, or an n-propyl group is preferable.
• a substituent may be bonded to the alkyl group as long as the effects of the present application are not impaired.
• examples of such a substituent include a phenyl group and an alkoxy group.
• R 5 and R 6 are acyloxymethyl groups (—CH 2 OCOR 7 )
• the substitution position is preferably the ortho position of the acyloxy group.
• n and m are preferably each independently 1, 2, and 3, and particularly preferably, n and m are 1.
• the production method of the polyacyloxymethyl-4,4′-acyloxybiphenyl compound represented by the formula (1) of the present invention is not particularly limited, and can be produced by a known method.
• a biphenol such as 4,4'-dihydroxybiphenyl is reacted with a secondary amine compound such as dimethylamine and formalin (aqueous formaldehyde solution) to introduce a disubstituted aminomethyl group (Step 1).
• a secondary amine compound such as dimethylamine and formalin (aqueous formaldehyde solution) to introduce a disubstituted aminomethyl group (Step 1).
• an acid anhydride such as acetic anhydride (Step 2).
• the above-mentioned biphenols include, for example, 4,4′-dihydroxybiphenyl, 3,3′-dimethyl-4,4′-dihydroxybiphenyl, 2,2 ′, 3 , 3 ', 5,5'-Hexamethyl-4,4'-dihydroxybiphenyl and the like.
• the secondary amine include dimethylamine, diethylamine, and morpholine. Among them, dimethylamine can be suitably used in reactivity and handling.
• the acid anhydride include acetic anhydride, propionic anhydride, butyric anhydride, and pivalic anhydride.
• the compound is represented by the formula (1) of the present invention.
• a production method for obtaining a polyacyloxymethyl-4,4′-acyloxybiphenyl compound can be mentioned.
• the amount of the secondary amine compound and formalin (formaldehyde aqueous solution) used in Step 1 is 6 to 8 moles, preferably 6.4 to 7 moles per mole of the raw material biphenols.
• the amount of formaldehyde is 6 to 8 times by mole, preferably 6.5 to 7 times by mole.
• the reaction temperature in Step 1 is preferably from 60 to 85 ° C, more preferably from 70 to 80 ° C.
• reaction temperature is lower than 60 ° C., the reaction is slowed down due to precipitation of raw materials and products, and if it is higher than 85 ° C., countermeasures against odor of the secondary amine compound are required, which is not preferable.
• the reaction pressure may be any of normal pressure, increased pressure, and reduced pressure, but the reaction is preferably performed under normal pressure.
• a catalyst may be used as necessary. When a catalyst is used, it is preferable to use about 1 mole of the catalyst per 1 mole of the secondary amine compound. Acetic acid is preferred as the catalyst in step 1.
• Step 1 is preferably performed in a solvent.
• solvent used examples include ether solvents such as diethyl ether, dipropyl ether, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran, 1,4-dioxane, diisobutyl ether and diphenyl ether, or methanol, ethanol, 1-propanol , 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, 2-methyl-2-propanol, cyclohexanol, ethylene glycol, ethylene glycol monomethyl ether, diethylene glycol, and other alcohol solvents, benzene, toluene, xylene, ethyl alcohol Aromatic solvents such as benzene and mesitylene; ketones such as acetone, 2-butanone, 3-pentanone, cyclohexanone and methyl isobutyl ketone.
• ether solvents such as diethyl ether, diprop
• acetic acid selected from among a carboxylic acid solvents such as acetic acid and propionic acid, may be used as a mixture thereof.
• Acetic acid may be used as a reaction solvent also as a catalyst.
• a solvent such as toluene that separates from water and water are added to the reaction-completed mixture, and the mixture is stirred and allowed to stand to remove an aqueous layer.
• the organic layer may be neutralized if necessary, or water may be added to the obtained organic layer, stirred and allowed to stand, and a water washing operation for removing the aqueous layer may be further performed several times. Water is removed from the obtained organic layer using a Dean-Stark apparatus or the like to obtain a solution containing the target substance, which can be used in the next step 2.
• the amount of the acid anhydride used in the step 2 is 7.5 to 12 times, preferably 8 to 9 times the molar amount of 1 mol of the biphenol as the raw material in the step 1. If the amount of the acid anhydride is less than 7.5 mole times, the reaction tends to be slow and the amount of by-products tends to increase. If the amount is more than 12 mole times, many unreacted substances remain, and post-treatment is complicated. Become.
• the reaction temperature in step 2 is preferably from 100 to 130 ° C, more preferably from 115 to 125 ° C.
• reaction temperature is lower than 100 ° C., the reaction is slowed down due to precipitation of raw materials and products, and if it is higher than 130 ° C., the target substance is decomposed by heat, which is not preferable.
• the reaction pressure may be any of normal pressure, increased pressure, and reduced pressure, but the reaction is preferably performed under normal pressure.
• a catalyst may be used as necessary. When a catalyst is used, the catalyst is used in an amount of about 0.1 mol per 1 mol of the biphenols used as the raw material in Step 1. Is preferred.
• sodium acetate is suitable.
• Step 2 is preferably performed in a solvent. It is preferable to use the aromatic hydrocarbon-based solvent, such as toluene, which is used for the post-reaction treatment in step 1 and separates from water as the reaction solvent.
• the post-processing method of Step 2 in the above manufacturing method will be described below.
• the end point of the reaction may be confirmed by liquid chromatography or gas chromatography analysis. It is preferable that the time when the increase in the target polyacyloxymethyl-4,4′-acyloxybiphenyl compound is not observed is determined as the end point of the reaction.
• unreacted acid anhydride is distilled off by distillation under reduced pressure or the like, and an organic solvent and water that separate from water are added to the residue.
• the mixture is left standing to remove an aqueous layer. Water may be added to the obtained oil layer, stirred, left standing, and the washing operation of removing the water layer may be performed several times as needed.
• the solvent is added to the distillation residue and dissolved by heating, cooled, and the precipitated crystals are filtered and dried to obtain the desired product in high purity or crude. Can be obtained as crystals.
• the target product obtained above can be further purified by recrystallization using a solvent.
• alcohols such as butanol, ethers such as tetrahydrofuran and dioxolan
• saturated aliphatic hydrocarbons such as hexane, heptane, and cyclohexane.
• the polyacyloxymethyl-4,4′-acyloxybiphenyl compound represented by the formula (1) of the present invention obtained by the above production method or the like has a lower melting point than conventional curing agents for epoxy resins, It has excellent miscibility with other components at the curing reaction temperature and can be suitably used as a curing agent for epoxy resins.
• the polyacyloxymethyl-4,4′-acyloxybiphenyl compound represented by the formula (1) of the present invention is used as a curing agent for an epoxy resin due to its chemical structure having many functional groups, This is useful because it can contribute to improvement in heat resistance and chemical resistance of the film.
• Example 1 Production of 4,4′-diacetoxy-3,3 ′, 5,5′-tetra (acetoxymethyl) biphenyl 4,4 ′ was placed in a 3 liter four-necked flask equipped with a thermometer, stirrer, dropping funnel and condenser. 285 g (1.53 mol) of '-dihydroxybiphenyl, 285 g of isopropanol, and 880.4 g (10.3 mol) of 35% formalin (aqueous formaldehyde solution) were charged. It was dropped while keeping it. Thereafter, the mixture was stirred for 2 hours while maintaining the internal temperature at 80 to 85 ° C. (Step 1).
• reaction-terminated liquid is subjected to distillation under reduced pressure to distill unreacted acetic anhydride and the like.After that, toluene and water are added, and an operation of separating an aqueous layer after stirring is performed. Distilled. Thereafter, 178.5 g of methanol was added at an internal temperature of 40 to 50 ° C., and the precipitated crystals were separated by filtration to obtain 4,4′-diacetoxy-3,3 ′, 5,5′-tetra (acetoxy). 598.2 g of methyl) biphenyl were obtained.
• Carbon-13 nuclear magnetic resonance spectrum (400 MHz, solvent CDCl 3 , standard TMS): 20.4 ppm, 20.7 ppm, 61.2 ppm, 129.4 ppm, 129.7 ppm, 138.2 ppm, 147.4 ppm, 169.1 ppm, 170 0.4 ppm.
• the melting point of 4,4′-diacetoxy-3,3 ′, 5,5′-tetra (acetoxymethyl) biphenyl obtained in Example 1 was 116.2 ° C. as described above.
• the melting point of 4,4′-di (acetoxy) biphenyl used as a curing agent for an epoxy resin is 163 ° C. That is, it is apparent that the polyacyloxymethyl-4,4′-acyloxybiphenyl compound represented by the formula (1) of the present invention is characterized in that the melting point is greatly reduced due to the chemical structure having a plurality of acyloxymethyl groups. became.
• the solvent solubility of the polyacyloxymethyl-4,4′-acyloxybiphenyl compound represented by the formula (1) of the present invention will be examined.
• the solubility of the polyacyloxymethyl-4,4′-acyloxybiphenyl compound of the present invention represented by the formula (1) in a solvent is greatly improved due to the chemical structure having a plurality of acyloxymethyl groups. Became clear.
• the polyacyloxymethyl-4,4′-acyloxybiphenyl compound of the present invention represented by the formula (1) has a lower melting point than a conventional curing agent having a biphenol skeleton for an epoxy resin, and thus has a lower epoxy resin curing reaction temperature. Since it can be mixed with other components at about 140 ° C., a solvent for dissolving the curing agent is not required. In addition, since the compound has high solubility in a solvent, even when a solvent is used, the amount of the solvent used can be greatly reduced, which is very useful.

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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)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Epoxy Resins (AREA)
• Epoxy Compounds (AREA)

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• 2019
  • 2019-07-03 CN CN201980045765.8A patent/CN112384492B/zh active Active
  • 2019-07-03 WO PCT/JP2019/026532 patent/WO2020017331A1/ja not_active Ceased
  • 2019-07-03 US US16/973,398 patent/US11932598B2/en active Active
  • 2019-07-03 JP JP2020531228A patent/JP7280262B2/ja active Active
  • 2019-07-03 KR KR1020207037666A patent/KR102660466B1/ko active Active
  • 2019-07-12 TW TW108124701A patent/TWI799615B/zh active

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