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WO2011019061A1 - Procédé de production de composé d'éther polyglycidylique - Google Patents

Procédé de production de composé d'éther polyglycidylique Download PDF

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WO2011019061A1
WO2011019061A1 PCT/JP2010/063658 JP2010063658W WO2011019061A1 WO 2011019061 A1 WO2011019061 A1 WO 2011019061A1 JP 2010063658 W JP2010063658 W JP 2010063658W WO 2011019061 A1 WO2011019061 A1 WO 2011019061A1
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acid
compound
ether compound
producing
polyglycidyl ether
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PCT/JP2010/063658
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Japanese (ja)
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博 内田
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昭和電工株式会社
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    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0237—Amines
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0239—Quaternary ammonium compounds
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0257—Phosphorus acids or phosphorus acid esters
    • B01J31/0259—Phosphorus acids or phosphorus acid esters comprising phosphorous acid (-ester) groups ((RO)P(OR')2) or the isomeric phosphonic acid (-ester) groups (R(R'O)2P=O), i.e. R= C, R'= C, H
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
    • 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
    • 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
    • C07D303/28—Ethers with hydroxy compounds containing oxirane rings
    • C07D303/30—Ethers of oxirane-containing polyhydroxy compounds in which all hydroxyl radicals are etherified with oxirane-containing hydroxy compounds
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B01J2231/72—Epoxidation
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/66—Tungsten

Definitions

  • the present invention relates to a polyglycidyl ether compound in which a carbon-carbon double bond of an allyl group of a compound having a plurality of phenolic hydroxyl groups is epoxidized using hydrogen peroxide as an oxidizing agent in the presence of a tungsten catalyst. It relates to the manufacturing method.
  • Polyglycidyl ether known as an epoxy resin is widely used in various fields, and is industrially produced on a large scale.
  • a method for producing polyglycidyl ether there is a method of obtaining glycidyl ether by reacting bisphenol-A or phenol novolac resin with epichlorohydrin in the presence or absence of a catalyst under basic conditions.
  • the glycidyl ether produced by this production method has a high content of organochlorine compounds that are considered undesirable for electronics applications. Therefore, attempts have been made for a long time to epoxidize the corresponding double bond after allyl etherification of the starting phenolic compound using peracetic acid or hydrogen peroxide.
  • Patent Document 1 discloses a method of performing epoxidation in the presence of molybdenum or a tungsten compound, a quaternary ammonium salt, and phosphoric acid, but the reaction rate, yield, and selectivity are not sufficient. .
  • Patent Document 2 discloses an example in which epoxidation of allyl ether, which is subject to conformational restrictions, is successful, but there are restrictions on allyl ether that can be used, and it is not a method that can be universally adopted industrially. .
  • Patent Document 3 discloses a method using peracid without using hydrogen peroxide.
  • organic peracid which is frequently used in accidents such as explosions. Since the produced carboxylic acid easily reacts with the epoxy resin, there is a problem that it is difficult to isolate the product with a high yield.
  • Patent Document 4 discloses a method of epoxidation using methanol or acetonitrile solvent in the presence of potassium carbonate.
  • Patent Document 5 discloses a method for producing an epoxy compound in which an olefin is reacted with a hydrogen peroxide solution using ⁇ -aminomethylphosphonic acid having a specific structure.
  • the olefins described in Patent Document 5 are mainly low molecular weight olefins, and there is no description or suggestion that they can be similarly applied to polyphenol ethers of polyphenols.
  • the problem to be solved by the present invention is that an allyl group carbon-carbon double bond of a polyallyl ether compound having a plurality of phenolic hydroxyl groups is bonded to an epoxy using hydrogen peroxide as an oxidizing agent under mild conditions. It is an object to provide a method for efficiently converting to a corresponding polyglycidyl ether with less residual organochlorine compound.
  • the present inventors have found that a polyglycidyl ether compound can be efficiently obtained by carrying out the reaction in the presence of a specific catalyst system.
  • the invention has been completed. That is, the present invention includes the following [1] to [12].
  • a carbon-carbon double bond of an allyl group of a polyallyl ether compound of a compound having a plurality of phenolic hydroxyl groups as a starting material is used as an oxidizing agent in the presence of a tungsten compound, a phosphorus compound and a quaternary ammonium salt.
  • a method for producing a polyglycidyl ether compound comprising a step of epoxidation using hydrogen peroxide.
  • the polyallyl ether compound of polyphenol is catechol, resorcinol, hydroquinone, bisphenol A (p, p′-isopropylidenediphenol), bisphenol F (p, p′-methylenediphenol), bisphenol K (p, p'-diphenolcarbonyl), dihydroxymethylstilbene, dihydroxybiphenyl, tetramethyldihydroxybiphenyl, dihydroxynaphthalene, bis (hydroxyphenyl) fluorene, methane type trisphenols, trisphenols, phenol-aldehyde novolac resin, alkyl-substituted phenol- At least one phenol selected from the group consisting of aldehyde novolac resin, polycyclopentadiene-modified phenolic resin, and polyvinylphenol
  • the polyallyl ether compound of polyphenol is a methane type trisphenol obtained by condensing an aromatic hydrocarbon having a phenolic hydroxyl group and an aldehyde compound, a phenol-aldehyde novolak resin, and an alkyl-substituted phenol-aldehyde novolak resin.
  • the polyallyl ether compound of polyphenol is composed of a polycyclopentadiene-modified phenol resin obtained by condensing an aromatic hydrocarbon having a phenolic hydroxyl group and dicyclopentadiene, and polyvinyl phenol obtained by polymerizing vinyl phenol.
  • the phosphorus compound is phosphoric acid, aminomethylphosphonic acid, ⁇ -aminoethylphosphonic acid, ⁇ -aminopropylphosphonic acid, ⁇ -aminobutylphosphonic acid, ⁇ -aminopentylphosphonic acid, ⁇ -aminohexylphosphonic acid, ⁇ -At least one selected from the group consisting of aminoheptylphosphonic acid, ⁇ -aminooctylphosphonic acid, ⁇ -aminononylphosphonic acid, ⁇ -amino- ⁇ -phenylmethylphosphonic acid, and nitrilotris (methylene) trisphosphonic acid
  • a method for producing a polyglycidyl ether compound according to any one of [1] to [5].
  • tungsten compound is at least one selected from the group consisting of tungstic acid, alkali tungstate, ammonium tungstate, phosphotungstic acid, and silicotungstic acid.
  • the molar ratio of the allyl group carbon-carbon double bond to hydrogen peroxide of the polyallyl ether compound of the compound having a plurality of phenolic hydroxyl groups is in the range of 1: 0.5 to 1: 4.
  • -Glycidyl ether which is a useful substance widely used in various industrial fields including chemical industry as a raw material for resist materials) and as a raw material for various polymers such as intermediates for agricultural chemicals and pharmaceuticals, plasticizers, adhesives and paint resins.
  • Type epoxy resin can be produced safely, with good yield and at low cost by a simple operation from the reaction of the corresponding polyallyl ether and hydrogen peroxide solution. Therefore, the present invention has a great industrial effect.
  • the method for producing a polyglycidyl ether compound of the present invention comprises a polyallyl ether compound of a compound having a plurality of phenolic hydroxyl groups using hydrogen peroxide as an oxidizing agent in the presence of a tungsten compound, a phosphorus compound and a quaternary ammonium salt.
  • the carbon-carbon double bond of the allyl group is epoxidized.
  • the concentration of the hydrogen peroxide aqueous solution that is a supply source of hydrogen peroxide used as the oxidizing agent in the production method of the present invention is generally 1 to 80% by mass, preferably 20 to 65% by mass. Selected from a range.
  • hydrogen peroxide is preferably a high concentration, but it is needless to say that it is preferable not to use a high concentration of hydrogen peroxide for safety.
  • the amount of aqueous hydrogen peroxide used is not particularly limited, but at least the molar equivalent of hydrogen peroxide used cannot epoxidize the allyl group. Therefore, when all the carbon-carbon double bonds of the allyl group of the polyallyl ether compound of the compound having a plurality of phenolic hydroxyl groups are epoxidized, the peroxidation is more than equimolar with respect to the carbon-carbon double bond. Although hydrogen is required, when partially epoxidizing, the amount of hydrogen peroxide used may be less than an equimolar amount. In addition, because the reaction system is acidic, the hydrolysis of the epoxy group tends to proceed easily.
  • the amount of hydrogen peroxide depends on the number of phenolic hydroxyl groups that are substrates to be epoxidized.
  • the number of carbon-carbon double bonds of the allyl group of the polyallyl ether compound of the compound is preferably in the range of 0.5 to 10 molar equivalents, more preferably in the range of 0.5 to 4 molar equivalents. And even more preferably in the range of 1 to 4 molar equivalents.
  • Tungsten compounds used as catalysts include compounds that generate tungstate anions in water, such as tungstic acid, tungsten trioxide, tungsten trisulfide, tungsten hexachloride, silicotungstic acid, phosphotungstic acid, ammonium tungstate, and alkali tungstate.
  • tungstic acid tungsten trioxide
  • tungsten trisulfide tungsten hexachloride
  • silicotungstic acid phosphotungstic acid
  • phosphotungstic acid ammonium tungstate
  • alkali tungstate alkali tungstate
  • ammonium tungstate for example, sodium tungstate dihydrate
  • phosphotungstic acid silica Tungstic acid or the like is preferable.
  • These tungsten compounds may be used alone or in combination of two or more.
  • the amount used is 0.001 to 20 mol% of tungsten atoms based on the number of carbon-carbon double bonds of the allyl group of the polyallyl ether compound of the compound having a plurality of phenolic hydroxyl groups as the substrate, preferably 0.8.
  • the range is 1 to 20 mol%.
  • the tungsten compound As a method for adding the tungsten compound to the reaction solution, the tungsten compound is previously dissolved in pure water, and then added in a form mixed with a hydrogen peroxide aqueous solution in a range of 0.5 to 10 times moles of the tungsten compound. It is desirable. If this treatment is not performed, the tungsten compound exists in a solid state depending on the pH of the reaction solution, and the reaction does not proceed immediately after the dropwise addition of the aqueous hydrogen peroxide solution. After the addition, the tungsten compound dissolves and the reaction proceeds suddenly, so that the selectivity may deteriorate.
  • the phosphorus compound examples include phosphoric acid, aminomethylphosphonic acid, ⁇ -aminoethylphosphonic acid, ⁇ -aminopropylphosphonic acid, ⁇ -aminobutylphosphonic acid, ⁇ -aminopentylphosphonic acid, ⁇ -aminohexylphosphonic acid, ⁇ -Aminoheptylphosphonic acid, ⁇ -aminooctylphosphonic acid, ⁇ -aminononylphosphonic acid, ⁇ -amino- ⁇ -phenylmethylphosphonic acid, nitrilotris (methylene) trisphosphonic acid and the like.
  • phosphoric acid, aminomethylphosphonic acid and nitrilotris (methylene) trisphosphonic acid are preferable, aminomethylphosphonic acid and nitrilotris (methylene) trisphosphonic acid are more preferable, and nitrilotris (methylene) trisphosphonic acid is even more preferable.
  • These phosphorus compounds may be used alone or in combination of two or more. If the amount used is small, the effect as an epoxidation catalyst is low, and if it is large, the remaining in the product becomes a problem. Therefore, the carbon-carbon double of the allyl group of the polyallyl ether of the compound having a plurality of phenolic hydroxyl groups of the substrate. A range of 0.001 to 10 mol% is preferable based on the number of bonds, and a range of 0.1 to 5 mol% is more preferable.
  • the ratio of the amount of the tungsten compound and the phosphorus compound used is such that the molar ratio of the tungsten atom to the phosphorus compound in the tungsten compound is in the range of 1: 0.01 to 1: 100, and 1: 0.1 to 1
  • the range of 10 is more preferable.
  • the quaternary ammonium salt acts as a phase transfer catalyst.
  • sulfate, hydrogen sulfate, and nitrate are preferable.
  • examples of the quaternary ammonium ion include tetrahexyl ammonium ion, tetraoctyl ammonium ion, methyl trioctyl ammonium ion, tetrabutyl ammonium ion, ethyl trioctyl ammonium ion, cetyl pyridinium ion, and the like.
  • quaternary ammonium salt tetrahexylammonium hydrogen sulfate, tetraoctylammonium hydrogensulfate, methyltrioctylammonium hydrogensulfate and the like are preferable. These quaternary ammonium hydrogen sulfates may be used alone or in combination of two or more. If the amount used is small, the effect as a phase transfer catalyst is low, and if it is large, the remaining in the product becomes a problem. Therefore, the allyl group carbon-carbon two-carbon compound of the compound having a plurality of phenolic hydroxyl groups of the substrate is used. A range of 0.001 to 10 mol% is preferable based on the number of heavy bonds, and a range of 0.1 to 5 mol% is more preferable.
  • the substrate to be epoxidized is a polyallyl ether compound of a compound having a plurality of phenolic hydroxyl groups, preferably a polyallyl ether compound of polyphenol, specifically catechol, resorcinol, Hydroquinone, bisphenol A (p, p'-isopropylidenediphenol), bisphenol F (p, p'-methylenediphenol), bisphenol K (p, p'-diphenolcarbonyl), dihydroxymethylstilbene, dihydroxybiphenyl, tetra Methyldihydroxybiphenyl, dihydroxynaphthalene, bis (hydroxyphenyl) fluorene, methane type trisphenols, trisphenols, phenol-aldehyde novolac resin, alkyl-substituted phenol- Aldehyde novolak resins, polycyclopentadiene modified phenol resin, and is obtained by allyl etherifying
  • polyphenol polyallyl ether compounds having 3 or more phenolic hydroxyl groups are preferable.
  • examples of such compounds include methane type trisphenols, trisphenols, phenol-aldehyde novolak resins, alkyl-substituted phenol-aldehyde novolak resins, Examples thereof include allyl etherified part or all of phenolic hydroxyl groups such as polycyclopentadiene-modified phenol resin and polyvinylphenol.
  • (Methane-type) trisphenols and (alkyl-substituted) phenol-aldehyde novolak resins can be synthesized by, for example, condensing an aromatic hydrocarbon having a phenolic hydroxyl group with an aldehyde compound or a ketone compound, Widely manufactured industrially.
  • Polycyclopentadiene-modified phenolic resin and polyvinylphenol can also be synthesized according to the following reaction formula and are industrially produced.
  • the polyallyl ether compound of polyphenol can be obtained by allyl etherification of the polyphenol by a known method using allyl chloride, allyl alcohol, and allyl acetate.
  • allyl alcohol Preference is given to using allyl acetate.
  • solvents include aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbon solvents, among which toluene, o-xylene, m-xylene, p-xylene, hexane, octane, cyclohexane, methylcyclohexane Is preferred.
  • concentration to be used if it is used excessively, the substrate concentration becomes dilute and the productivity is low, and the reaction rate is also slowed.
  • the optimum concentration varies depending on the substrate, it is preferably in the range of 5 to 800 parts by weight, more preferably in the range of 30 to 300 parts by weight, based on 100 parts by weight of the polyphenol polyallyl ether compound used.
  • the reaction temperature is usually in the range of 0 to 180 ° C., preferably in the range of 50 to 120 ° C.
  • the addition time of the hydrogen peroxide and the phosphorus compound added as needed varies depending on the reaction scale, but in the case of a 1 liter glass scale, it takes 30 minutes to 2 hours and is 1 in the case of an industrial scale of 10 m 3. It is desirable to perform the addition over a period of 20 hours. After completion of the addition, the reaction is usually terminated by stirring for 1 to 4 hours.
  • FIG. 1 is an example thereof, which can be implemented by the following procedure. (1) The reaction solution is allowed to stand after the epoxidation reaction.
  • the container to be allowed to stand may be a reactor or another container.
  • the container to be allowed to stand may be a reactor or another container.
  • the upper organic layer and the aqueous layer are separated.
  • the separated aqueous layer is concentrated to increase the tungsten catalyst concentration and / or a new catalyst is added.
  • a catalyst is newly added, a phosphorus compound and / or a quaternary ammonium salt and further a tungsten compound are added to the separated aqueous layer as necessary.
  • an aqueous layer containing a newly prepared catalyst can be used instead of the separated aqueous layer.
  • the reason why it is preferable to separate the reaction solution into two layers during the reaction as described above, and to mix the separated organic layer and the aqueous layer with the catalyst concentration readjusted to repeat the reaction is that hydrogen peroxide is removed during the epoxidation reaction.
  • the aqueous layer containing a catalyst such as tungsten is diluted with water contained in the aqueous hydrogen peroxide solution when dropped as an aqueous solution, and the catalytic activity decreases.
  • ⁇ -aminoalkylphosphonic acids are used, they are consumed and decomposed during the reaction, so it is desirable to add them during recycling.
  • FIG. 1 is an example of a method of intermittently separating the aqueous layer and the organic layer of the reaction solution, but the operation can also be carried out continuously using a continuous reactor as shown in FIG.
  • a continuous reactor a tubular reactor can generally be used, and it is more preferable if the organic layer-water layer such as a microreactor is designed to be mixed well.
  • it can implement similarly by extracting continuously, even in a stirring tank, supplying a reaction liquid continuously. After continuously extracting the reaction solution in this way, the organic layer and the aqueous layer are separated into two layers, and then the organic layer is recycled while adding new raw materials and solvents as necessary, and the aqueous layer is necessary.
  • the catalyst components are added and hydrogen peroxide is added and recycled. In this case, a part of the reaction solution is extracted and sent to the next step (reaction tank for increasing the conversion rate to the target value, purification step).
  • an organic solvent such as ethyl acetate, toluene, cyclohexane and hexane is further added as necessary, and the organic layer is treated with a reducing agent such as sodium bisulfite, sodium sulfite and sodium thiosulfate, After decomposing hydrogen peroxide, after washing, extraction, and purification as necessary, the solution is left as it is or in a solution with another solvent by exchanging the solvent, or without solvent.
  • a polyglycidyl ether compound it can be used for a desired use.
  • Example 1 A solution prepared by previously dissolving 0.409 g (1.24 mmol) of sodium tungstate in 0.409 g of pure water and 0.241 g (2.48 mmol) of 35% aqueous hydrogen peroxide was prepared.
  • 10 g of the polyallyl cresol novolak resin obtained in Synthesis Example 1 (0.062 mol as the allyl group)
  • 10 g of toluene 0.290 g (0.620 mmol) of methyl trioctylammonium hydrogen sulfate
  • 0.0688 g (0.620 mmol) of aminomethylphosphonic acid and a tungstic acid solution prepared in advance were added, and the bath temperature was heated to 80 ° C.
  • Examples 2-6 Comparative Examples 1-2
  • the reaction was performed in the same manner as in Example 1 except that the catalysts shown in Table 1 below were used.
  • the results are shown in Table 1 below.
  • Example 7 A solution prepared by previously dissolving 0.438 g (1.33 mmol) of sodium tungstate in 0.438 g of pure water and 0.258 g (2.66 mmol) of 35% aqueous hydrogen peroxide solution was prepared.
  • Example 8 A solution prepared by previously dissolving 0.409 g (1.24 mmol) of sodium tungstate in 0.409 g of pure water and 0.241 g (2.48 mmol) of 35% aqueous hydrogen peroxide was prepared.
  • reaction solution was cooled to room temperature, transferred to a separatory funnel, the aqueous layer was separated, the toluene layer was returned to the reaction flask, 0.0344 g (0.310 mmol) of aminomethylphosphonic acid, The remaining one of the two parts was placed and the bath temperature was reheated to 80 ° C.
  • the bath temperature reached 90 ° C, 12.1 g (0.124 mol) of an aqueous hydrogen peroxide solution was added dropwise over 30 minutes, and then the reaction was continued at a bath temperature of 80 ° C for 4 hours. A part of the reaction solution was sampled, toluene was distilled off, and then the epoxy equivalent was measured.
  • Example 5 shows that epoxidation has progressed.
  • Example 9 A solution prepared by previously dissolving 0.235 g (0.713 mmol) of sodium tungstate in 0.235 g of pure water and 0.139 g (1.43 mmol) of 35% aqueous hydrogen peroxide solution was prepared.
  • 10 g (0.0357 mol) of the diallyl ether distillate of bisphenol-F obtained in Synthesis Example 3 10 g of toluene, 0.167 g (0.357 mmol) of methyltrioctylammonium hydrogensulfate ), 0.0396 g (0.357 mmol) of aminomethylphosphonic acid, and a previously prepared tungstic acid solution were added, and the bath temperature was heated to 80 ° C.
  • Example 10 A solution prepared by previously dissolving 0.214 g (0.648 mmol) of sodium tungstate in 0.214 g of pure water and 0.126 g (1.30 mmol) of 35% aqueous hydrogen peroxide was prepared.
  • Example 11 A solution prepared by previously dissolving 0.214 g (0.648 mmol) of sodium tungstate in 0.214 g of pure water and 0.126 g (1.30 mmol) of 35% aqueous hydrogen peroxide was prepared.
  • Example 12 A solution prepared by previously dissolving 0.214 g (0.648 mmol) of sodium tungstate in 0.214 g of pure water and 0.126 g (1.30 mmol) of 35% aqueous hydrogen peroxide was prepared.
  • Example 13 to 15 The reaction was carried out in the same manner as in Example 6 except that allyl compounds shown in Table 2 below were used. The results are shown in Table 2 below.

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Abstract

Dans le but de proposer un procédé de conversion d'une double liaison carbone-carbone dans un groupe aryle d'un composé d'éther polyarylique qui est un composé polyaryle éthérisé comprenant une pluralité de groupes hydroxyle phénoliques pour obtenir un éther polyglycidylique répondant efficacement au moyen d'une époxydation employant du peroxyde d'hydrogène comme catalyseur dans des conditions douces, l'invention concerne un procédé de production d'un composé d'éther polyglycidylique comprenant une étape d'époxydation d'une double liaison carbone-carbone dans un groupe aryle d'un composé éther polyarylique contenant une pluralité de groupes hydroxyle phénoliques qui est le matériau de départ, ladite époxydation employant du peroxyde d'hydrogène comme agent oxydant en présence d'un sel d'ammonium quaternaire, d'un composé de phosphore et d'un composé de tungstène.
PCT/JP2010/063658 2009-08-13 2010-08-11 Procédé de production de composé d'éther polyglycidylique WO2011019061A1 (fr)

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US20130203068A1 (en) * 2012-02-06 2013-08-08 Perkinelmer Biosignal, Inc. Dual-acceptor time-resolved-fret
JP2014240376A (ja) * 2013-05-13 2014-12-25 昭和電工株式会社 多価グリシジル化合物の製造方法
JP2014240377A (ja) * 2013-05-13 2014-12-25 昭和電工株式会社 多価グリシジル化合物の製造方法
KR20150002630A (ko) 2012-03-30 2015-01-07 미쓰비시 가가꾸 가부시키가이샤 에폭시 화합물의 제조 방법 및 에폭시화 반응용 촉매 조성물
WO2015052925A1 (fr) * 2013-10-09 2015-04-16 日本化薬株式会社 Procédé de production de résine époxy, résine époxy, composition de résine durcissable, et produit durci
JP2016094353A (ja) * 2014-11-12 2016-05-26 昭和電工株式会社 多価グリシジル化合物の製造方法
KR20220157963A (ko) * 2020-03-23 2022-11-29 닛뽄 가야쿠 가부시키가이샤 에폭시 수지, 에폭시 화합물, 에폭시 수지 조성물, 수지 시트, 프리프레그, 탄소 섬유 강화 복합 재료 및, 페놀 수지

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6060123A (ja) * 1983-09-13 1985-04-06 Sumitomo Chem Co Ltd エポキシ化物の製造法
JPH07252373A (ja) * 1994-08-22 1995-10-03 Nippon Petrochem Co Ltd エポキシ樹脂組成物を含浸させた電気絶縁材料用のクロス状またはマット状基材
JPH10511722A (ja) * 1994-12-23 1998-11-10 ザ ダウ ケミカル カンパニー エポキシ化合物の製造方法
JP2002517387A (ja) * 1998-05-29 2002-06-18 ザ ダウ ケミカル カンパニー アリールアリルエーテルのエポキシ化法
JP2002317021A (ja) * 2001-01-15 2002-10-31 Rp Topla Ltd ラジカル硬化性樹脂組成物、その製造方法および該組成物からなる成形品
DE10136884A1 (de) * 2001-07-24 2003-02-13 Inst Angewandte Chemie Berlin Phosphonsäurestabilisierte Peroxowolfram-Katalysatoren und deren Verwendung
WO2003029322A1 (fr) * 2001-09-28 2003-04-10 Mitsui Chemicals, Inc. Composition d'agent de durcissement pour resines epoxy, composition de resine epoxy et son utilisation
JP2003292583A (ja) * 2002-03-29 2003-10-15 Hitachi Chem Co Ltd エポキシ樹脂成形材料及び電子部品装置
JP2010053348A (ja) * 2008-07-30 2010-03-11 Sanyo Chem Ind Ltd エポキシ化合物の製造方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3662038B2 (ja) * 1994-07-14 2005-06-22 三井化学株式会社 エポキシ化合物の製造方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6060123A (ja) * 1983-09-13 1985-04-06 Sumitomo Chem Co Ltd エポキシ化物の製造法
JPH07252373A (ja) * 1994-08-22 1995-10-03 Nippon Petrochem Co Ltd エポキシ樹脂組成物を含浸させた電気絶縁材料用のクロス状またはマット状基材
JPH10511722A (ja) * 1994-12-23 1998-11-10 ザ ダウ ケミカル カンパニー エポキシ化合物の製造方法
JP2002517387A (ja) * 1998-05-29 2002-06-18 ザ ダウ ケミカル カンパニー アリールアリルエーテルのエポキシ化法
JP2002317021A (ja) * 2001-01-15 2002-10-31 Rp Topla Ltd ラジカル硬化性樹脂組成物、その製造方法および該組成物からなる成形品
DE10136884A1 (de) * 2001-07-24 2003-02-13 Inst Angewandte Chemie Berlin Phosphonsäurestabilisierte Peroxowolfram-Katalysatoren und deren Verwendung
WO2003029322A1 (fr) * 2001-09-28 2003-04-10 Mitsui Chemicals, Inc. Composition d'agent de durcissement pour resines epoxy, composition de resine epoxy et son utilisation
JP2003292583A (ja) * 2002-03-29 2003-10-15 Hitachi Chem Co Ltd エポキシ樹脂成形材料及び電子部品装置
JP2010053348A (ja) * 2008-07-30 2010-03-11 Sanyo Chem Ind Ltd エポキシ化合物の製造方法

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130203068A1 (en) * 2012-02-06 2013-08-08 Perkinelmer Biosignal, Inc. Dual-acceptor time-resolved-fret
KR20150002630A (ko) 2012-03-30 2015-01-07 미쓰비시 가가꾸 가부시키가이샤 에폭시 화합물의 제조 방법 및 에폭시화 반응용 촉매 조성물
US9650353B2 (en) 2012-03-30 2017-05-16 Mitsubishi Chemical Corporation Method for producing epoxy compound and catalyst composition for epoxidation reaction
US10730846B2 (en) 2012-03-30 2020-08-04 Mitsubishi Chemical Corporation Method of producing epoxy compound and catalyst composition for epoxidation reaction
JP2014240376A (ja) * 2013-05-13 2014-12-25 昭和電工株式会社 多価グリシジル化合物の製造方法
JP2014240377A (ja) * 2013-05-13 2014-12-25 昭和電工株式会社 多価グリシジル化合物の製造方法
WO2015052925A1 (fr) * 2013-10-09 2015-04-16 日本化薬株式会社 Procédé de production de résine époxy, résine époxy, composition de résine durcissable, et produit durci
JPWO2015052925A1 (ja) * 2013-10-09 2017-03-09 日本化薬株式会社 エポキシ樹脂の製造方法、エポキシ樹脂、硬化性樹脂組成物、及び、硬化物
JP2016094353A (ja) * 2014-11-12 2016-05-26 昭和電工株式会社 多価グリシジル化合物の製造方法
KR20220157963A (ko) * 2020-03-23 2022-11-29 닛뽄 가야쿠 가부시키가이샤 에폭시 수지, 에폭시 화합물, 에폭시 수지 조성물, 수지 시트, 프리프레그, 탄소 섬유 강화 복합 재료 및, 페놀 수지
EP4130088A4 (fr) * 2020-03-23 2024-04-17 Nippon Kayaku Kabushiki Kaisha Résine époxyde, composés époxyde, composition de résine époxyde, feuille de résine, préimprégné, matériau composite renforcé par des fibres de carbone et résine phénolique
KR102787108B1 (ko) 2020-03-23 2025-03-25 닛뽄 가야쿠 가부시키가이샤 에폭시 수지, 에폭시 수지 조성물, 수지 시트, 프리프레그 및, 탄소 섬유 강화 복합 재료

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