Classifications

• • 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
  • C08G59/02—Polycondensates containing more than one epoxy group per molecule
  • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
  • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
  • C08G59/08—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols from phenol-aldehyde condensates
• • 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
  • C08G59/50—Amines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material

Definitions

• the present invention relates to epoxy resins, curable resin compositions, and their cured products, as well as carbon fiber reinforced composite materials.
• CFRP Carbon fiber reinforced composites
• JP 2010-275492 A Japanese Patent Application Laid-Open No. 2022-173168 Japanese Patent Application Laid-Open No. 2007-211254
• the present invention was made in consideration of the above circumstances, and aims to provide epoxy resins and curable resin compositions with high heat resistance and high flexural modulus, as well as cured products and carbon fiber reinforced composite materials.
• the present invention can provide epoxy resins, curable resin compositions, and cured products thereof, as well as carbon fiber reinforced composite materials, whose cured products have high heat resistance and a high flexural modulus.
• Example 1 The evaluation results of Example 1 and Comparative Examples 1 and 2 are shown below.
• n is the average number of repetitions and is a real number in the range 1 ⁇ n ⁇ 15.
• n can be calculated from the number average molecular weight determined by measuring the epoxy resin using gel permeation chromatography (GPC, detector: RI), or from the area ratio of each separated peak.
• n is preferably a real number in the range 1 ⁇ n ⁇ 15, more preferably 1 ⁇ n ⁇ 10, and particularly preferably 1 ⁇ n ⁇ 5.
• the epoxy equivalent of the epoxy resin of this embodiment is preferably 228 g/eq. or more and 237 g/eq. or less, more preferably 230 g/eq. or more and 236 g/eq. or less, and even more preferably 231 g/eq. or more and 235 g/eq. or less.
• An epoxy equivalent of 228 g/eq. or more will result in high heat resistance, while an epoxy equivalent of 237 g/eq. or less will result in a high flexural modulus.
• an epoxy equivalent of 228 g/eq. or more and 237 g/eq. or less will achieve both high heat resistance and a high flexural modulus.
• the softening point of the epoxy resin represented by formula (1) is preferably 67°C or higher and 100°C or lower, and more preferably 70°C or higher and 80°C or lower.
• a softening point of 67°C or higher is preferable for storage and handling, as resins do not block with each other even without refrigeration and can be stored at room temperature.
• a softening point higher than 100°C makes it difficult to mix uniformly with curing agents, polymerization initiators, fillers, etc., and is prone to poor curing.
• a/b is preferably 3.0 or greater and 3.4 or less, and more preferably 3.1 or greater and 3.3 or less.
• the epoxy equivalent is low compared to a certain softening point, resulting in high curing density and good heat resistance, thermal decomposition resistance, and elastic modulus.
• the softening point becomes too high compared to the epoxy equivalent, restricting molecular movement during the curing reaction and resulting in partial insufficient curing, resulting in reduced heat resistance and thermal decomposition resistance.
• the ratio is 3.0 to 3.4, a balance between curing density and curing reaction is achieved, allowing for the development of excellent properties.
• the biomass degree of the epoxy resin of this embodiment is preferably 50% or more.
• the biomass degree can be 100%, but in terms of the balance with the cured physical properties, it is preferably 80%.
• a high biomass degree can also reduce the amount of fossil resource-based materials used, such as petroleum, and is therefore beneficial in terms of sustainable resource use. Therefore, it is preferable that the biomass degree of the curable resin composition after mixing with other materials is also high; specifically, it is preferably 20% or more, and more preferably 30% or more.
• the biomass degree of this embodiment is measured by the method described in the Examples below.
• the epoxy resin represented by formula (1) above can be obtained by reacting a phenolic resin represented by formula (2) below with epihalohydrin.
• n is the average number of repetitions and is a real number in the range 1 ⁇ n ⁇ 15.
• the epihalohydrin is readily available on the market.
• the amount of epihalohydrin used is preferably 2.0 to 10 moles, more preferably 3.0 to 8.0 moles, and even more preferably 3.5 to 6.0 moles per mole of hydroxyl groups in the raw material phenol mixture.
• Preferred epihalohydrins that can be used in this embodiment include epichlorohydrin, ⁇ -methylepichlorohydrin, ⁇ -methylepichlorohydrin, and epibromohydrin, with epichlorohydrin being particularly preferred as it is easily available industrially.
• an alkali metal hydroxide can be used as a catalyst to promote the epoxidation step.
• Usable alkali metal hydroxides include sodium hydroxide and potassium hydroxide.
• a solid or an aqueous solution thereof may be used, but in this embodiment, the use of a solid formed into flakes is particularly preferred from the standpoints of solubility and handling.
• the amount of alkali metal hydroxide used is preferably 0.90 to 1.5 mol, more preferably 0.95 to 1.25 mol, and even more preferably 0.99 to 1.15 mol per mol of hydroxyl groups in the raw material phenol mixture.
• quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, or trimethylbenzylammonium chloride may be added as a catalyst.
• the amount of quaternary ammonium salt used is preferably 0.1 to 15 g, and more preferably 0.2 to 10 g, per mole of hydroxyl groups in the raw material phenol mixture.
• the reaction temperature is preferably 30 to 90°C, more preferably 35 to 80°C. In particular, in this embodiment, a temperature of 50°C or higher is preferred for higher purity epoxidation, with 60°C or higher being particularly preferred.
• the reaction time is preferably 0.5 to 10 hours, more preferably 1 to 8 hours, and particularly preferably 1 to 3 hours. A short reaction time will not allow the reaction to proceed fully, while a long reaction time is undesirable as it will result in the formation of by-products.
• the reaction products of these epoxidation reactions are washed with water, or without washing, and then heated under reduced pressure to remove epihalohydrin and solvent.
• the recovered epoxy resin can be dissolved in a ketone compound having 4 to 7 carbon atoms (e.g., methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.) as a solvent, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to carry out the reaction, ensuring ring closure.
• a ketone compound having 4 to 7 carbon atoms e.g., methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.
• the amount of alkali metal hydroxide used is preferably 0.01 to 0.3 mol, more preferably 0.05 to 0.2 mol, per 1 mol of hydroxyl groups in the raw phenol mixture used in the epoxidation.
• the reaction temperature is preferably 50 to 120°C, and the reaction time is preferably 0.5 to 2 hours.
• the salt produced is removed by filtration, washing with water, etc., and the solvent is then distilled off under heating and reduced pressure to obtain the epoxy resin of this embodiment.
• Phenols include disubstituted phenols such as catechol, resorcinol, and hydroquinone, and monosubstituted phenols such as phenol, cresol, and xylenol, and may be used alone or in combination of two or more types.
• Solvents include, but are not limited to, methanol, ethanol, propanol, isopropanol, toluene, and xylene, and may be used alone or in combination of two or more. When a solvent is used, the amount used is preferably 5 to 500 parts by weight, more preferably 10 to 300 parts by weight, per 100 parts by weight of phenol.
• a base catalyst is preferably used in the above condensation reaction. Polycondensation is possible with an acidic catalyst, but reactions between furfurals occur, resulting in increased by-products. Alternatively, an organometallic compound can be used, but this is cost-inefficient.
• Specific examples of base catalysts include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, and potassium tert-butoxide; and alkaline earth metal alkoxides such as magnesium methoxide and magnesium ethoxide.
• the amount of catalyst used is preferably 0.005 to 2.0 moles, more preferably 0.01 to 1.1 moles, per mole of phenol.
• the condensation reaction in the presence of these base catalysts is preferably carried out in the range of 40 to 180°C, particularly preferably in the range of 80 to 165°C, and the reaction time can be selected preferably in the range of 0.5 to 10 hours.
• the reaction product thus obtained is neutralized to neutralize the system or repeatedly washed with water in the presence of a solvent, after which the water is separated and drained, and the solvent and unreacted materials are removed under heating and reduced pressure to obtain the phenolic resin represented by formula (2).
• the curable resin composition of this embodiment contains a curing agent.
• curing agents that can be used include amine-based curing agents, acid anhydride-based curing agents, amide-based curing agents, and phenol-based curing agents.
• aniline novolak orthoethylaniline novolak
• aniline resins obtained by reacting aniline with xylylene chloride and aniline resins obtained by polycondensation of aniline with substituted biphenyls (such as 4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl) or substituted phenyls (such as 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene).
• substituted biphenyls such as 4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl
• substituted phenyls such as 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(
• acid anhydride curing agents examples include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.
• Amide-based curing agents include dicyandiamide or polyamide resins synthesized from a linolenic acid dimer and ethylenediamine.
• Suitable phenols include phenolic resins obtained by condensation with hydroxybenzaldehyde and furfural, ketones (p-hydroxyacetophenone and o-hydroxyacetophenone), or dienes (dicyclopentadiene and tricyclopentadiene); phenolic resins obtained by polycondensation of the above phenols with substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl), or substituted phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene); modified products of the above phenols and/or the above phenolic resins; and halogenated phenols such as tetrabromobisphenol A and brominated phenolic resins.
• the phenolic resin represented by formula (2) is also preferable to use as the entire curing agent or as part of it.
• the amount of curing agent used is preferably 0.7 to 1.2 equivalents per equivalent of epoxy groups in the epoxy resin. If the amount is less than 0.7 equivalents per equivalent of epoxy groups or more than 1.2 equivalents, curing may be incomplete and good cured physical properties may not be obtained.
• the curable resin composition of this embodiment may also contain a curing accelerator, if necessary.
• the gelation time can also be adjusted by using a curing accelerator.
• curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole; tertiary amines such as 2-(dimethylaminomethyl)phenol and 1,8-diaza-bicyclo[5.4.0]undecene-7; phosphines such as triphenylphosphine; and metal compounds such as tin octoate.
• the curing accelerator is used in an amount of 0.01 to 5.0 parts by weight per 100 parts by weight of the epoxy resin, as needed.
• the curable resin composition of this embodiment may contain other epoxy resins.
• specific examples include phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, etc.).
• epoxy resins examples include polycondensates of bisphenols and aldehydes (e.g., 4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl), phenolic resins obtained by polycondensation of phenols and substituted biphenyls (e.g., 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, and 1,4-bis(hydroxymethyl)benzene), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidylating alcohols, alicyclic epoxy resins such as 4-vinyl-1-cyclohexene diepoxide and 3,4-epoxycyclohexylmethyl-3,4'-epoxycyclohexanecarboxylate, glycidylamine epoxy resins such as
• the curable resin composition of this embodiment can contain known additives as needed.
• usable additives include active ester compounds, phenolic resins, compounds having ethylenically unsaturated bonds, isocyanate resins, polyamide resins, benzoxazine compounds, polybutadiene and modified products thereof, modified acrylonitrile copolymers, polyphenylene ether compounds, polystyrene and modified products thereof, polyethylene and modified products thereof, polyimide resins, fluororesins, maleimide compounds, cyanate ester resins, silicone gels, silicone oils, inorganic fillers such as silica, alumina, calcium carbonate, quartz powder, aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride, asbestos, mica, and glass powder, surface treatment agents for fillers such as silane coupling agents, mold release agents, and colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.
• active ester compounds include phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds.
• Maleimide compounds include 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, and 1,3-bis(4-maleimidophenoxy) benzene, Zylok-type maleimide compounds (Anilix Maleimide, manufactured by Mitsui Fine Chemicals, Inc.), biphenylaralkyl-type maleimide compounds (solidified by distilling off the solvent under reduced pressure from a resin solution containing the maleimide compound
• Cyanate ester resins include dicyanatobenzene, tricyanatobenzene, dicyanatonaphthalene, dicyanatobiphenyl, 2,2'-bis(4-cyanatophenyl)propane, bis(4-cyanatophenyl)methane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanatophenyl)propane, 2,2'-bis(4-cyanatophenyl)ethane, 2,2'-bis(4-cyanatophenyl)hexafluoropropane, bis(4-cyanatophenyl)sulfone, bis(4-cyanatophenyl)thioether, phenol novolac cyanate, and phenol-dicyclopentadiene co-condensates in which the hydroxyl groups have been converted to cyanate groups.
• Polyimide resins include those prepared by combining the above diamines with tetracarboxylic dianhydrides (4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2-dicarboxylic anhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyl ...
• tetracarboxylic dianhydrides (4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)
• diphthalic dianhydride 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylidene-4,4'-diphthalic dianhydride, 2,2'-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-di Phthalic dianhydride, 4,4'-oxydiphthalic dianhydride, thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride
• SEP styrene-ethylene propylene copolymer: Septon ethylene-butylene-styrene block copolymer: Septon 8004, Septon 8006, Septon 8007L, all manufactured by Kuraray Co., Ltd.
• SEEPS-OH styrene-ethylene/ethylene-propylene-styrene block copolymer with a hydroxyl group at the end: Septon HG252, manufactured by Kuraray Co., Ltd.
• SIS styrene-isoprene-styrene block copolymer: Septon 5125, Septon 5127, all manufactured by Kuraray Co., Ltd.
• hydrogenated SIS hydrogenated styrene-isoprene-styrene block copolymer: Hybrar 7125F, Hybrar 7311F, all manufactured by Kuraray Co., Ltd.
• SIBS styrene-isobutylene
• suitable copolymers include ethylene
• the curable resin composition of this embodiment can be made into a varnish-like composition (hereinafter simply referred to as "varnish") by adding an organic solvent.
• solvents that can be used include amide-based solvents such as gamma-butyrolactones, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and N,N-dimethylimidazolidinone; sulfones such as tetramethylene sulfone; ether-based solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and propylene glycol monobutyl ether; ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; and aromatic solvents such
• the curable resin composition of the present embodiment can also be used as a resin sheet, a prepreg, or a carbon fiber reinforced composite material.
• the curable resin composition of this embodiment may be applied to one or both sides of a support substrate and used as a resin sheet. Examples of application methods include casting, extruding the resin through a nozzle or die using a pump or extruder, adjusting the thickness with a blade, adjusting the thickness by calendaring with a roll, and spraying using a sprayer.
• the layer formation process may be performed while heating within a temperature range that can avoid thermal decomposition of the curable resin composition. If necessary, rolling, grinding, or the like may also be performed.
• the prepreg of this embodiment can be obtained by heating and melting the curable resin composition and/or resin sheet of this embodiment to reduce its viscosity and then impregnating the fiber substrate.
• the prepreg of this embodiment can be obtained by impregnating a fiber substrate with a varnish-like curable resin composition and heating and drying it. The prepreg is then cut into the desired shape, laminated, and the curable resin composition is heated and cured while applying pressure to the laminate using a press molding method, autoclave molding method, sheet winding molding method, or the like, to obtain the carbon fiber reinforced composite material of this embodiment. Copper foil or an organic film can also be laminated when laminating the prepreg.
• the carbon fiber reinforced composite material of this embodiment can be obtained by molding using known methods other than the above-mentioned methods.
• a resin transfer molding technique RTM method
• a carbon fiber substrate usually a carbon fiber fabric
• a preform a preform before being impregnated with a resin
• the preform is placed in a mold, the mold is closed, resin is injected to impregnate the preform, and the resin is cured, and the mold is then opened to remove the molded product.
• RTM methods such as the VaRTM method, the SCRIMP (Seeman's Composite Resin Infusion Molding Process), and the CAPRI (Controlled Atmospheric Pressure Resin Infusion) method, which is described in JP-A-2005-527410, in which a resin supply tank is evacuated to a pressure lower than atmospheric pressure, cyclic compression is used, and the net molding pressure is controlled to more appropriately control the resin injection process, particularly the VaRTM method.
• Further methods that can be used include the film stacking method, in which the fiber substrate is sandwiched between resin sheets (films), the method of attaching powdered resin to the reinforced fiber substrate to improve impregnation, the molding method (Powder Impregnated Yarn) that uses a fluidized bed or fluid slurry method in the process of mixing the resin into the fiber substrate, and the method of blending resin fibers into the fiber substrate.
• Carbon fibers include acrylic, pitch, and rayon carbon fibers, with acrylic carbon fibers being preferred due to their high tensile strength.
• the carbon fiber can be in the form of twisted yarn, untwisted yarn, or untwisted yarn, but untwisted yarn or untwisted yarn is preferred due to the good balance between the formability and strength properties of the fiber-reinforced composite material.
• Epoxy equivalent Measured by the method described in JIS K-7236, and expressed in g/eq.
• Softening point Measured according to a method in accordance with JIS K-7234, and the unit is °C.
• -Biomass analysis (accelerator mass spectrometry) Measurements were carried out in accordance with ASTM D6866-21 and calculations were made in units of %.
• ⁇ GPC gel permeation chromatography
• Manufacturer Waters Column: Guard column SHODEX GPC KF-601 (2 columns), KF-602, KF-602.5, KF-603 Flow rate: 1.23ml/min. Column temperature: 25°C Solvent used: THF (tetrahydrofuran)
• Detector RI (differential refractive index detector)
• the mixture was neutralized by adding 4 parts by weight of phosphoric acid and 63 parts by weight of 35% hydrochloric acid. After repeated water washing, unreacted phenol was distilled off under reduced pressure with heating to obtain 205 parts by weight of the phenolic resin represented by the formula (2). 78 parts by weight of the obtained phenolic resin represented by formula (2) were charged into a reaction vessel with 254 parts by weight of epichlorohydrin (ECH), 64 parts by weight of dimethyl sulfoxide (DMSO), and 13 parts by weight of water. After heating, stirring, and dissolution, 23 parts by weight of flaky sodium hydroxide were added in portions over 2 hours while maintaining the temperature at 45°C. The reaction was then continued for 2 hours at 45°C and 60 minutes at 70°C.
• ECH epichlorohydrin
• DMSO dimethyl sulfoxide
• the mixture was neutralized by adding 4 parts by weight of phosphoric acid and 63 parts by weight of 35% hydrochloric acid. After repeated water washing, unreacted phenol was distilled off under reduced pressure with heating to obtain 205 parts by weight of the phenolic resin represented by the formula (2). 78 parts by weight of the resulting phenolic resin represented by formula (2) were charged to a reaction vessel with 181 parts by weight of ECH, 64 parts by weight of DMSO, and 13 parts by weight of water. After heating, stirring, and dissolution, 23 parts by weight of flaky sodium hydroxide were added in portions over 2 hours while maintaining the temperature at 45°C. The reaction was then continued for 2 hours at 45°C and 60 minutes at 70°C.
• the mixture was neutralized by adding 4 parts by weight of phosphoric acid and 63 parts by weight of 35% hydrochloric acid. After repeated water washing, unreacted phenol was distilled off under reduced pressure with heating to obtain 120 parts by weight of the phenolic resin represented by the formula (2).
• To 78 parts by weight of the resulting phenolic resin 254 parts by weight of the resulting phenolic resin, 254 parts by weight of ECH, 64 parts by weight of DMSO, and 13 parts by weight of water were charged into a reaction vessel. After heating, stirring, and dissolution, 23 parts by weight of flaky sodium hydroxide was added in portions over 2 hours while maintaining the temperature at 45°C. The reaction was then continued for 2 hours at 45°C and 60 minutes at 70°C.
• Example 1 Comparative Examples 1 and 2
• the epoxy resins obtained in Synthesis Examples 1 to 3 were used as the base resin, and 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane (abbreviation: TEDDM, manufactured by Tokyo Chemical Industry Co., Ltd., active hydrogen equivalent: 78 g/eq.) was used as the curing agent.
• TEDDM 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane
• active hydrogen equivalent 78 g/eq.
• Tg Heat resistance
• TMA Thermomechanical measurement apparatus
• TMA Q400EM Temperature rise rate: 2°C/min Measurement temperature range: 25°C to 300°C Tg: The point at which the thermal expansion coefficient changes was taken as Tg.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Materials Engineering (AREA)
• Epoxy Resins (AREA)
• Reinforced Plastic Materials (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (1)

Family

ID=96699704

Family Applications (1)

Country Status (3)

Citations (4)

Family Cites Families (2)

• 2025
  • 2025-01-24 JP JP2025536255A patent/JPWO2025169748A1/ja active Pending
  • 2025-01-24 WO PCT/JP2025/002147 patent/WO2025169748A1/ja active Pending
  • 2025-01-24 TW TW114103350A patent/TW202532493A/zh unknown

Patent Citations (4)

Also Published As

Similar Documents

Legal Events