WO2011078060A1 - グリシジルエーテル化合物の製造方法及びモノアリルモノグリシジルエーテル化合物 - Google Patents

グリシジルエーテル化合物の製造方法及びモノアリルモノグリシジルエーテル化合物 Download PDF

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WO2011078060A1
WO2011078060A1 PCT/JP2010/072715 JP2010072715W WO2011078060A1 WO 2011078060 A1 WO2011078060 A1 WO 2011078060A1 JP 2010072715 W JP2010072715 W JP 2010072715W WO 2011078060 A1 WO2011078060 A1 WO 2011078060A1
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compound
ether
carbon atoms
allyl
producing
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PCT/JP2010/072715
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French (fr)
Japanese (ja)
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博 内田
良和 新井
一彦 佐藤
健文 千代
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昭和電工株式会社
独立行政法人産業技術総合研究所
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Priority to KR1020127016471A priority Critical patent/KR101415113B1/ko
Priority to CN201080058513.8A priority patent/CN102666518B/zh
Priority to JP2011547508A priority patent/JPWO2011078060A1/ja
Publication of WO2011078060A1 publication Critical patent/WO2011078060A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
    • C07D303/27—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds having all hydroxyl radicals etherified with oxirane containing compounds

Definitions

  • the present invention relates to a method for producing a glycidyl ether compound and a monoallyl monoglycidyl ether compound. More specifically, the present invention relates to an efficient epoxidation by oxidizing a carbon-carbon double bond of the allyl group of a compound having an allyl ether bond with hydrogen peroxide by using a predetermined catalyst. The present invention relates to a method for producing a characteristic glycidyl ether compound, and a monoallyl monoglycidyl ether compound produced by oxidation of a carbon-carbon double bond of the allyl group of a compound having an allyl ether bond with hydrogen peroxide.
  • Glycidyl ether known as a raw material for epoxy resins, is industrially produced on a large scale and is widely used in various fields.
  • Patent Document 1 Japanese Patent Laid-Open No. 10-511722
  • Patent Document 2 Japanese Patent Laid-Open No. 60-60123
  • diallyl ether of bisphenol-A or polyallyl ether of novolac type phenol resin is added to toluene or the like.
  • a method of epoxidation with hydrogen peroxide in the presence of a quaternary ammonium salt using sodium tungstate and a phosphoric acid catalyst in an organic solvent is disclosed. This method requires a very large amount of tungsten compound, and the epoxidation rate is not sufficient, so that it cannot be carried out as an industrial production method.
  • Patent Document 3 US Pat. No. 5,633,391
  • an olefin is epoxidized by contacting the olefin with bis (trimethylsilyl) peroxide as an oxidizing agent in an organic solvent in the presence of a rhenium oxide catalyst.
  • bis (trimethylsilyl) peroxide as an oxidizing agent in an organic solvent in the presence of a rhenium oxide catalyst.
  • Patent Document 4 Japanese Patent Laid-Open No. 7-145221
  • Patent Document 5 Japanese Patent Laid-Open No. 58-173118
  • a phenol novolak resin is allyl etherified with an allyl halide and then peroxygenated in an organic solvent.
  • a method for epoxidation is disclosed, it is necessary to use peracids which are highly hazardous.
  • Patent Document 6 Japanese Patent Publication No. 2002-526383 discloses a method of epoxidation with hydrogen peroxide in the presence of a titanium-containing zeolite catalyst, a tertiary amine, a tertiary amine oxide, or a mixture thereof.
  • a titanium-containing zeolite catalyst a tertiary amine, a tertiary amine oxide, or a mixture thereof.
  • a substrate having a high molecular weight such as phenyl ether has poor catalytic efficiency and cannot be applied.
  • the problem to be solved by the present invention is to provide a method for efficiently producing a glycidyl ether compound from a compound having an allyl ether bond using hydrogen peroxide as an oxidizing agent under mild conditions.
  • the present inventor used a tungsten compound, a tertiary organic amine, and phenylphosphonic acid as a catalyst to produce an aqueous hydrogen peroxide solution and an allyl ether compound.
  • a tungsten compound a tertiary organic amine, and phenylphosphonic acid as a catalyst to produce an aqueous hydrogen peroxide solution and an allyl ether compound.
  • the present invention is as follows. [1] In a method for producing a corresponding glycidyl ether compound by reacting a compound having an allyl ether bond with hydrogen peroxide and epoxidizing the carbon-carbon double bond of the allyl group, tungsten as a reaction catalyst A method for producing the glycidyl ether compound, comprising using a compound, a tertiary amine, and phenylphosphonic acid.
  • the compound having an allyl ether bond is represented by the following formula (1): ⁇ Wherein R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a carbon number. R 1 and R 2 may be taken together to form an alkylidene group having 2 to 6 carbon atoms or a cycloalkylidene group having 3 to 12 carbon atoms.
  • R 3 , R 4 , R 5 , and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or An aryl group having 6 to 10 carbon atoms, and n represents an integer of 0 or 1.
  • the compound having an allyl ether bond is composed of diallyl ether of bisphenol-A, diallyl ether of bisphenol-F, and 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-diallyl ether.
  • the compound having an allyl ether bond is a C 2-20 ⁇ , ⁇ -polyalkylene glycol diallyl ether, 1,4-cyclohexanedimethanol diallyl ether, and tricyclo [5.2.1.0 2, 6 ]
  • R 7 , R 8 , R 9 , and R 10 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a cyclohexane having 3 to 10 carbon atoms.
  • An alkyl group or an aryl group having 6 to 10 carbon atoms is shown.
  • the monoallyl monoglycidyl ether compound which has a biphenyl frame
  • the method for producing a glycidyl ether compound of the present invention by using a tungsten compound, a tertiary organic amine, and phenylphosphonic acid as a catalyst, and reacting hydrogen peroxide with an allyl ether compound, the corresponding glycidyl ether is obtained.
  • Epoxy resins which are useful substances widely used in various industrial fields including the chemical industry as raw materials for various polymers such as electronic materials and adhesives and paint resins, can be produced. It is possible to manufacture safely, with good yield, and at low cost by a simple operation while minimizing the mixing of impurities. Therefore, the method for producing a glycidyl ether compound of the present invention has a great industrial effect.
  • the monoallyl monoglycidyl ether compound according to the present invention has an allyl group, it can be hydrosilylated with a compound having an Si—H group, and biphenyl can be added to various compounds having an Si—H group. Since a glycidyl ether group can be introduced, it is extremely useful as a raw material for epoxy resins used for resists and sealing materials.
  • FIG. 1 shows the 1 H-NMR measurement result of the product obtained in Example 16.
  • FIG. 2 shows the results of 13 C-NMR measurement of the product obtained in Example 16.
  • FIG. 3 shows the result of mass spectrometry (MS) measurement of the product obtained in Example 16.
  • FIG. 4 shows the 1 H-NMR measurement result of the product obtained in Example 17.
  • FIG. 5 shows the results of 13 C-NMR measurement of the product obtained in Example 17.
  • FIG. 6 shows the 29 Si-NMR measurement result of the product obtained in Example 17.
  • FIG. 7 shows the results of mass spectrometry (MS) measurement of the product obtained in Example 17.
  • hydrogen peroxide is used as an oxidizing agent.
  • Hydrogen peroxide can be used as an aqueous hydrogen peroxide solution.
  • the concentration of hydrogen peroxide is not particularly limited, but is generally selected from the range of 1 to 80%, preferably 5 to 80%, more preferably 10 to 60%. From the viewpoint of industrial productivity and the energy cost of separation, hydrogen peroxide is preferred to have a high concentration, but excessively high concentration and / or excessive hydrogen peroxide is not used. This is preferable from the viewpoints of economy and safety. Reactivity is low when the concentration of hydrogen peroxide is less than 1%.
  • the amount of hydrogen peroxide used is not particularly limited, but is 0.5 to 10 equivalents, preferably 0 to the carbon-carbon double bond of the allyl group of the compound having an allyl ether bond to be epoxidized. Selected from the range of 8 to 2 equivalents. If it is out of this range, one raw material will remain excessively, which is not economical.
  • tungsten compound used as a catalyst in the method for producing a glycidyl ether compound of the present invention a compound that generates a tungstate anion in water is suitable.
  • tungstic acid, tungsten trioxide, tungsten trisulfide, tungsten hexachloride, phosphorus examples include tungstic acid, ammonium tungstate, potassium tungstate dihydrate, sodium tungstate dihydrate, and the like. Tungstic acid, tungsten trioxide, phosphotungstic acid, sodium tungstate dihydrate, and the like are preferable. These tungsten compounds may be used alone or in combination of two or more.
  • tungstic acid and an alkali metal salt of tungstic acid may be mixed in the above ratio, or tungstic acid and an alkali compound (alkali metal or alkaline earth metal hydroxide) may be used. , Carbonates, etc.) or a combination of alkali metal or alkaline earth metal salts of tungstic acid and acidic compounds such as mineral acids such as phosphoric acid and sulfuric acid. Partially neutralized salts of acids can be formed. Specific examples of these include a mixture of sodium tungstate and tungstic acid, a mixture of sodium tungstate and mineral acid, or a mixture of tungstic acid and an alkali compound.
  • the amount of the tungsten compound used as a catalyst is 0.0001 to 20 mol%, preferably 0.01 to 0.01%, based on the number of carbon-carbon double bonds of the allyl group of the compound having an allyl ether bond as a substrate. It is selected from the range of 20 mol%. If it is less than 0.0001 mol%, the reactivity is low, and if it is more than 20 mol%, it is economically disadvantageous.
  • the tertiary amine used as the catalyst is a tertiary organic amine (trialkylamine) having a total of 6 or more, preferably 10 or more carbon atoms of the alkyl group bonded to the nitrogen atom, and has a high epoxidation reaction activity. preferable.
  • Such tertiary organic amines include triethylamine, tributylamine, tri-n-octylamine, tri- (2-ethylhexyl) amine, N, N-dimethyloctylamine, N, N-dimethyllaurylamine, N, N -Dimethylmyristylamine, N, N-dimethylpalmitylamine, N, N-dimethylstearylamine, N, N-dimethylbehenylamine, N, N-dimethylcocoalkylamine, N, N-dimethyl tallow alkylamine, N, N-dimethyl-cured tallow alkylamine, N, N-dimethyloleylamine, N, N-diisopropyl-2-ethylhexylamine, N, N-dibutyl-2-ethylhexylamine, N-methyldioctylamine, N-methyldidecylamine
  • the total number of carbon atoms of the alkyl group bonded to the nitrogen atom of the tertiary amine is preferably 50 or less, more preferably 30 or less, considering the solubility of the compound having an allyl ether bond as a reaction substrate. .
  • tertiary amines may be used alone or in combination of two or more.
  • the amount used is preferably from 0.0001 to 10 mol%, more preferably from 0.01 to 10 mol%, based on the number of carbon-carbon double bonds of the allyl group of the compound having an allyl ether bond of the substrate. It is. If it is less than 0.0001 mol%, the reactivity is low, and if it is more than 10 mol%, it is economically disadvantageous.
  • phenylphosphonic acid is further used as a (co-) catalyst.
  • the amount used is preferably from 0.0001 to 10 mol%, more preferably from 0.01 to 10 mol%, based on the number of carbon-carbon double bonds of the allyl group of the compound having an allyl ether bond of the substrate. It is. If it is less than 0.0001 mol%, the reactivity is low, and if it is more than 10 mol%, it is economically disadvantageous.
  • the substrate for epoxidation in the method for producing a glycidyl ether compound of the present invention is not particularly limited as long as it is a compound having an allyl ether bond, and the number of allyl ether bonds contained in the compound may be one. And two or more.
  • Compounds having one allyl ether bond include phenyl allyl ether, o-, m-, p-cresol monoallyl ether, biphenyl-2-ol monoallyl ether, biphenyl-4-ol monoallyl ether, butyl allyl ether, Examples thereof include cyclohexyl allyl ether and cyclohexane methanol monoallyl ether.
  • the compounds having two allyl ether bonds include 1,5-pentanediol diallyl ether, 1,6-hexanediol diallyl ether, 1,9-nonanediol diallyl ether, 1,10-decanediol diallyl ether, neopentyl glycol ⁇ , ⁇ -alkylenediol diallyl ethers having 2 to 20 carbon atoms such as diallyl ether, ⁇ , ⁇ -polyalkylene glycol diallyl ethers having 2 to 20 carbon atoms, 1,4-cyclohexanedimethanol diallyl ether, tricyclo [ 5.2.1.0 2,6 ] decanedimethanol diallyl ether and the following general formula (1): ⁇ Wherein R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having
  • R 6 may be an aryl group having 6 to 10 carbon atoms, or R 1 and R 2 may be combined to form an alkylidene group having 2 to 6 carbon atoms or a cycloalkylidene group having 3 to 12 carbon atoms.
  • R 3 , R 4 , R 5 , and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or An aryl group having 6 to 10 carbon atoms, and n represents an integer of 0 or 1. ⁇ The compound represented by this is mentioned.
  • R 1 to R 6 are each independently a hydrogen atom or a methyl group, and n is more preferably 1 or 0.
  • Such compounds include bisphenol-A diallyl ether, bisphenol-F diallyl ether, 2,6,2 ′, 6′-tetramethylbisphenol-A diallyl ether, and 2,2′-diallyl.
  • Examples of the compound having three or more allyl ether bonds include phenol-formaldehyde / allyl alcohol polycondensate or cresol-formaldehyde / allyl alcohol polycondensate.
  • These substrates can be used without an organic solvent or with an organic solvent if necessary, by mixing an aqueous hydrogen peroxide solution and the above-described catalyst to allow the epoxidation reaction to proceed, without using an organic solvent.
  • Performing the epoxidation reaction is advantageous in terms of reduction of production cost, simplification of production equipment (for example, omission of explosion-proof equipment, etc.), waste disposal, and improvement of work environment.
  • the reaction rate becomes slow and, depending on the solvent, an undesirable reaction such as a hydrolysis reaction may easily proceed.
  • a minimum necessary organic solvent may be used.
  • the organic solvent that can be used is preferably an aromatic hydrocarbon, an aliphatic hydrocarbon or an alicyclic hydrocarbon, and examples thereof include toluene, xylene, hexane, octane, and cyclohexane. It is advantageous in terms of production cost to keep the amount used to the minimum necessary, and it is preferably used at 50 parts by mass or less, more preferably 30 parts by mass or less with respect to 100 parts by mass of the compound having an allyl ether bond. The When the amount of the organic solvent used exceeds 50 parts by mass with respect to 100 parts by mass of the compound having an allyl ether bond, the substrate concentration decreases and the reactivity decreases.
  • the catalyst and substrate are first charged into the reactor, and hydrogen peroxide is consumed in the reaction while keeping the reaction temperature as constant as possible. It is better to add gradually while confirming that it is.
  • the amount of hydrogen peroxide accumulated is small and the pressure rise can be minimized.
  • reaction temperature is preferably selected in the range of ⁇ 10 to 120 ° C., more preferably 20 ° C. to 100 ° C.
  • an organic extraction solvent is prepared by mixing the aqueous layer with a saturated aqueous solution of an inorganic compound and making a difference in specific gravity with the organic layer. Two-layer separation can be carried out without using.
  • the specific gravity of the tungsten compound is heavy, in order to bring the aqueous layer to the lower layer, a tungsten compound exceeding the above-mentioned usage amount that is originally necessary as a catalyst may be used. In this case, it is desirable to increase the efficiency of the tungsten compound by reusing the tungsten compound from the aqueous layer.
  • the specific gravity of the organic layer may be close to 1.2.
  • water is added to bring the specific gravity of the aqueous layer closer to 1, so that It is also possible to bring an organic layer under the layer.
  • the extraction of the reaction solution can also be carried out using an organic solvent such as toluene, cyclohexane, hexane, methylene chloride, etc., and an optimal separation method can be selected according to the situation.
  • the obtained glycidyl ether compound can be taken out by normal methods, such as distillation, chromatographic separation, recrystallization, and sublimation.
  • the compound having an allyl ether bond is a compound having two allyl ether bonds
  • a monoallyl monoglycidyl ether compound in which only one allyl ether bond is epoxidized from the reaction product by performing the above separation and purification operation Can be isolated.
  • the organic layer contains monoallyl monoglycidyl ether, diglycidyl ether, and unreacted diallyl ether compound, which are described later in Example 16.
  • the following general formula (2) ⁇
  • R 7 , R 8 , R 9 , and R 10 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a cyclohexane having 3 to 10 carbon atoms.
  • An alkyl group or an aryl group having 6 to 10 carbon atoms is shown.
  • R 7 , R 8 , R 9 , and R 10 can be methyl groups.
  • Example 1 To a 300 mL three-necked flask equipped with a dropping funnel and a Dimroth condenser, 0.950 g (2.88 mmol) of sodium tungstate (manufactured by Nippon Inorganic Chemical Co., Ltd.), 0.720 g of tungstic acid (manufactured by Nippon Inorganic Chemical Co., Ltd.) ( 2.88mmol), Trioctylamine (Guangei Chemical Co., Ltd.) 2.04g (5.76mmol), Phenylphosphonic acid (Nissan Chemical Co., Ltd.) 0.911g (5.76mmol), Allyl phenyl ether 80g (0.576mol) While stirring with a magnetic stirrer, the mixture was heated to 70 ° C.
  • Conversion rate (%) (1 ⁇ number of moles of raw material remaining / number of moles of raw material used) ⁇ 100
  • Selectivity (%) ⁇ (number of moles of target compound / number of moles of raw material used) ⁇ 10000 ⁇ / conversion rate (%)
  • Example 2 to 10 The epoxidation reaction was carried out in the same manner as in Example 1 with the catalyst components and the charged molar ratios shown in Table 1 below. The results are also shown in Table 1 below.
  • the distillate was a solid having a melting point of 51.7 ° C., and the viscosity at 60 ° C. was 29 mPa ⁇ s (measured with a B-type viscometer (DV-E (model: LVDV-E) manufactured by BROOKFIELD)).
  • the reaction temperature was gradually raised, the temperature was raised to 70 ° C. over 3 hours, and the reaction was further continued for 17 hours.
  • the reaction solution was cooled to room temperature, 200 ml of toluene was added to extract the reaction product, and the organic layer was washed twice with pure water. After distilling off toluene with an evaporator, the initial fraction was removed by distillation under reduced pressure to obtain 84.6 g of a distillate having a boiling point of 80.4 ° C./28 Pa (diallyl ether 94%, the rest being monoallyl ether). These analyzes were performed by gas chromatography. The viscosity of the distillate at 25 ° C. was 8.5 mPa ⁇ s (measured with a B-type viscometer (DV-E (model: LVDV-E) manufactured by BROOKFIELD)).
  • the reaction temperature was gradually raised as the reaction proceeded, the temperature was raised to 70 ° C. over 2 hours, and the reaction was further continued for 10 hours.
  • the reaction solution was cooled to room temperature, 200 ml of toluene was added to extract the reaction product, and the organic layer was washed twice with pure water. After distilling off toluene with an evaporator, the initial distillation was removed by distillation under reduced pressure to obtain 84.6 g of a distillate having a boiling point of 72 ° C./133 Pa (diallyl ether 97%, the rest being monoallyl ether). These analyzes were performed by gas chromatography.
  • the viscosity of the distillate at 25 ° C. was 2.3 mPa ⁇ s (measured with a B-type viscometer (DV-E (model: LVDV-E) manufactured by BROOKFIELD)).
  • Example 11 to 15 The epoxidation reaction was carried out in the same manner as in Example 1 except that allyl phenyl ether in Example 1 was replaced with the compounds shown in Table 2 below. The results are also shown in Table 2 below.
  • Example 16 Monoglycidyl monoallyl ether was isolated from the product obtained in Example 13 and identified in this example. The experimental procedure is described below. To a 300 mL three-necked flask equipped with a dropping funnel and a Dimroth condenser, 0.950 g (2.88 mmol) of sodium tungstate (manufactured by Nippon Inorganic Chemical Co., Ltd.), 0.720 g of tungstic acid (manufactured by Nippon Inorganic Chemical Co., Ltd.) ( 2.88 mmol), trioctylamine (manufactured by Guangei Chemical Co., Ltd.) 2.04 g (5.76 mmol), phenylphosphonic acid (manufactured by Nissan Chemical Co., Ltd.) 0.911 g (5.76 mmol), 3,3 ′, 5,5′- 92.9 g (0.288 mol) of tetramethylbiphenyl-4,4′-diallyl ether was added and heated
  • Example 17 In a 50 ml three-necked flask equipped with a reflux condenser, a thermometer, a stirrer, and a serum cap, 0.1 g (0.30 mmol) of monoallyl monoglycidyl ether synthesized in Example 16, 1,1,1,3,5 , 5,5-heptamethyltrisiloxane 0.077 g (0.35 mmol) and toluene 1 ml were added, and the mixture was stirred at room temperature under an argon stream.
  • a glycidyl ether compound of the present invention by using a tungsten compound, a tertiary organic amine, and phenylphosphonic acid as a catalyst, and reacting hydrogen peroxide with an allyl ether compound, the corresponding glycidyl ether is obtained.
  • Epoxy resins which are useful substances widely used in various industrial fields including the chemical industry as raw materials for various polymers such as electronic materials and adhesives and paint resins, can be produced. It is possible to manufacture safely, with good yield, and at low cost by a simple operation while minimizing the mixing of impurities.
  • the monoallyl monoglycidyl ether compound of the present invention can introduce a biphenyl glycidyl ether group into a compound having various Si—H groups by a hydrosilylation reaction with a compound having an Si—H group. It is useful for synthesizing epoxy resins used for resists and sealing materials having high properties and etching resistance.

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PCT/JP2010/072715 2009-12-24 2010-12-16 グリシジルエーテル化合物の製造方法及びモノアリルモノグリシジルエーテル化合物 WO2011078060A1 (ja)

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WO2014123005A1 (ja) * 2013-02-08 2014-08-14 三菱瓦斯化学株式会社 新規アリル化合物及びその製造方法
JP2018100236A (ja) * 2016-12-20 2018-06-28 Dic株式会社 ナフタレン型エポキシ化合物の製造方法及びナフタレン型エポキシ化合物
JP2021046449A (ja) * 2020-12-25 2021-03-25 Dic株式会社 ナフタレン型エポキシ化合物の製造方法及びナフタレン型エポキシ化合物
US11773207B2 (en) 2019-01-07 2023-10-03 Shikoku Chemicals Corporation Thiol compound, method for synthesizing same, and uses for said thiol compound

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JP6634178B1 (ja) * 2018-07-30 2020-01-22 花王株式会社 エポキシアルカンの製造方法、及び固体酸化触媒

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