JP2010053348A - Method of producing epoxy compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of producing highly selectively producing only diepoxy compounds from unsaturated compounds. <P>SOLUTION: The method of producing diepoxy compound includes oxidizing the double bond part of an organic compound diolefin having in the molecule two C=C double bonds represented by general formula (1) by using a tungsten compound and an oxidizer to produce the diepoxy compound. In formula (1), R<SP>1</SP>and R<SP>2</SP>are each H, alkyl, alkoxy, a univalent alicyclic hydrocarbon, or aromatic hydrocarbon; A is a bivalent functional group; and n is an integer of 1-100. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a method for producing an epoxy compound. More specifically, the present invention relates to an epoxy resin obtained by a method for producing a diepoxy compound that highly selectively oxidizes an organic compound having two C═C double bonds in the molecule.

Conventionally, an epoxy compound is produced by reacting an epihalohydrin with an active hydrogen-containing compound and then dehydrohalogenating the halohydrin intermediate with a basic compound such as an alkali or alkaline earth metal hydroxide. This is well known (Patent Document 1).
However, since this method goes through a halohydrin intermediate, the resulting epoxy compound contains halogen as an impurity. In recent years, a reduction in halogen content has been demanded from the environmental aspect. In particular, in electrical applications and coating materials, an epoxy resin that does not contain an extremely large amount of halogen has been demanded because it adversely affects electrical characteristics and color characteristics.

On the other hand, by oxidizing an organic compound having a C═C double bond in the molecule by using a peracid such as peracetic acid or a relatively expensive organic peroxide such as tert-butylhydroxyperoxide, A method for obtaining a halogen-free epoxy compound is disclosed (Patent Document 2).
However, since reactions using strong oxidizing agents such as peracids and organic peroxides are dangerous, special equipment is required for actual production, and post-treatment of the reaction is also difficult. .

  In addition, since these oxidizing agents are too strong in oxidizing power, the reaction does not stop with the epoxy compound, and the epoxy ring is opened to produce glycol, which makes it impossible to selectively produce only the target epoxy compound. there were.

On the other hand, hydrogen peroxide water is cheap and easy to handle, and is a clean and harmless oxidant that becomes water after the reaction. Molecular oxygen is also attracting attention as a clean oxidant. However, both the hydrogen peroxide solution and molecular oxygen have a low conversion rate of organic compounds having C═C double bonds in the molecule, and the reaction is not limited to epoxy compounds but is ring-opened and converted to glycol. There was a problem such as. (Patent Document 3)

JP 2007-262291 A JP 2003-155280 A JP 2005-161208 A

  Therefore, an inexpensive and versatile oxidation catalyst is used to produce a production method that is highly selective only from a diepoxy compound and substantially free of halogen from an organic compound having two C═C double bonds in the molecule. The purpose is to provide.

The inventors of the present invention have reached the present invention as a result of studies to achieve the above object.
That is, the present invention is an organic compound having two C═C double bonds represented by the general formula (1) or (2) in the molecule using the tungsten compound (C) and the oxidizing agent (D). A process for producing a diepoxy compound (A), wherein the diepoxy compound (A) represented by the general formula (3) or (4) is produced by oxidizing the double bond site of (B); An epoxy resin composition obtained by the method, wherein the content of the diepoxy compound (A) is 70% by weight or more.

[Wherein R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a monovalent alicyclic carbonization having 5 to 20 carbon atoms. It represents a hydrogen group or an aromatic hydrocarbon group having 4 to 20 carbon atoms, and a part of these groups may be further substituted with a carbonyl group, an ester group, a carboxyl group or a base thereof.
A is a divalent group of — (O—R ³ ) _n —, — [O—R ³ —O—C (═O)] _n —, or — [O—C (═O) —R ³ ] _n —. And may be a combination of one or more.
R ³ represents a divalent alkylene group, a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group having 4 to 20 carbon atoms, 5 to 20 carbon atoms having 2 to 20 carbon atoms.
Y ¹ and Y ² are each independently a divalent alkylene group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms, or a divalent aroma having 4 to 20 carbon atoms. Represents a group hydrocarbon group. n represents an integer of 1 to 100. ]

  The method for producing an epoxy resin of the present invention is a method for producing a diepoxy compound substantially free of halogen using an inexpensive and versatile oxidation catalyst. By using this production method, it is possible to extremely suppress glycol by-product. Moreover, since the epoxy resin obtained by this manufacturing method does not contain a halogen substantially, it is excellent in an electrical property.

  The organic compound (B) having two C═C double bonds in the molecule as a raw material used in the method for producing an epoxy compound (A) of the present invention is represented by the following general formula (1) or (2). .

[Wherein R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a monovalent alicyclic carbonization having 5 to 20 carbon atoms. It represents a hydrogen group or an aromatic hydrocarbon group having 4 to 20 carbon atoms, and a part of these groups may be further substituted with a carbonyl group, an ester group, a carboxyl group or a base thereof.
A is a divalent group of — (O—R ³ ) _n —, — [O—R ³ —O—C (═O)] _n —, or — [O—C (═O) —R ³ ] _n —. And may be a combination of one or more.
R ³ represents a divalent alkylene group having 2 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 4 to 20 carbon atoms.
Y ¹ and Y ² are each independently a divalent alkylene group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms, or a divalent aroma having 4 to 20 carbon atoms. Represents a group hydrocarbon group. n represents an integer of 1 to 100. ]

R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon having 5 to 20 carbon atoms, or a carbon number. 4 to 20 aromatic hydrocarbons are represented, and a part of them may be substituted with a carbonyl group, an ester group, a carboxyl group or a base thereof.

  Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, and 2-ethylhexyl group. Nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group and the like.

  Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, t-butoxy group, pentoxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethyl Hexyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, nonadecyloxy group, eicosiloxy group, etc. Can be mentioned.

  Examples of the monovalent alicyclic hydrocarbon having 5 to 20 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cycloundecyl group, a cyclododecyl group, and a cyclotridecyl group. , Cyclotetradecyl group, cyclopentadecyl group, cyclohexadecyl group, cycloheptadecyl group, cyclooctadecyl group, cyclononadecyl group, cycloeicosyl group, norbornyl group and the like.

  Examples of the aromatic hydrocarbon having 4 to 20 carbon atoms include a thienyl group, a pyridyl group, a phenyl group, a bithienyl group, a bipyridyl group, a biphenyl group, a phenanthryl group, a naphthyl group, and an anthranyl group.

  A part of the above alkyl group, alkoxy group, monovalent alicyclic hydrocarbon, and aromatic hydrocarbon may be substituted with a carbonyl group, an ester group, a carboxyl group, or a base thereof.

Examples of those substituted with a carbonyl group include an acetyl group, a cyclohexylcarbonyl group, and a benzoyl group.
Examples of those substituted with an ester group include a methyl ester group, a cyclohexyl ester group, and a benzoic acid ester group.
Examples of those substituted with a carboxyl group include methyl carboxylate, cyclohexane acid, benzoic acid and the like.
Examples of those substituted with carboxylate include sodium salt of methylcarboxylate, sodium salt of cyclohexane acid, sodium salt of benzoic acid and the like.

Preferable examples of R ¹ and R ² include a hydrogen atom, a methyl group, and a methoxy group. Particularly preferred is a hydrogen atom.

A is a divalent group of — (O—R ³ ) _n —, — [O—R ³ —O—C (═O)] _n —, or — [O—C (═O) —R ³ ] _n —. And may be a combination of one or more.
R ³ represents a divalent alkylene group having 2 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 4 to 20 carbon atoms.
Y ¹ and Y ² are each independently a divalent alkylene group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms, or a divalent aroma having 4 to 20 carbon atoms. Represents a group hydrocarbon group.
n represents an integer of 1 to 100.
A in the general formulas (1) and (2) is a repeating unit, and the repeating unit n represents an integer of 1 to 100. A may be a combination of two or more different types.

_{^{- (O-R 3) n}} - as is divalent alkylene group of ^{R 3} is 2 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms, 2 of 4 to 20 carbon atoms -(O-R _< ³ _> ) _{n- of a} valent aromatic hydrocarbon group is mentioned.
n represents an integer of 1 to 100.

In the case where R ³ is a divalent alkylene group having 2 to 20 carbon atoms and n is 1, examples of — (O—R ₃ ) _n — include an oxyethylene group, a 1-oxypropylene group, and 2-oxy Examples thereof include oxyalkylene such as propylene group, 1-oxybutylene group, 1-oxydecylene group, 3-oxydecylene group, 1-oxyeicosyl.

R ³ is a divalent alkylene group having 2 to 20 carbon atoms, n is in the case of _{2~100 - (O-R 3)} n - as, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol And polyoxyalkylene obtained from a polymer, a copolymer of ethylene oxide and propylene oxide, a polymer obtained by repeating oxyalkylene units exemplified when n is 1, and the like.

In the case where R ³ is a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms and n is 1, examples of — (O—R ³ ) _n — include oxycyclopentylene group and oxycyclohexylene. Group, oxycycloheptylene group, oxycyclooctylene group, oxycyclononylene group, oxycyclodecylene group, oxycycloundecylene group, oxycyclododecylene group, oxycyclotridecylene group, oxycyclotetradecylene Groups, oxycyclopentadecylene groups, 2-ethyl-1oxycyclohexylene groups, oxycycloeicosylene groups, 2,4-butyl-1-oxycyclohexylene groups, and the like.

-(O-R ³ ) _n -in the case where R ³ is a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms and n is 2 to 100 includes, for example, repetitive polymerization of the oxycycloalkylene A polymer such as an ethylene oxide addition polymer to cyclohexanediol, a hydrogenated product of a styrene oxide polymer; and an oxycycloalkylene structure represented by the following general formula (5).

[Wherein, X represents a divalent methylene group, 1-methylethane-1,1-diyl group [—C (CH ₃ ) ₂ —], propylene group, sulfone group. ]

R ( ³⁾ is a divalent aromatic hydrocarbon group having 4 to 20 carbon atoms and n is 1, for example,-(O-R ³ ) _n- is, for example, R ³ is a thienylene group, a pyridylene group, a phenylene group, Examples thereof include a bithienylene group, a bipyridylene group, a biphenylene group, a phenanthrylene group, a naphthylene group, and an oxyarylene group that is a divalent aromatic hydrocarbon derived from an anthranylene group.

In the case where R ³ is a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms and n is 2 to 100,-(O-R ³ ) _n- is a repetitive polymer of the oxyarylene group, styrene Represents a polymer of oxide, a polymer such as ethylene oxide addition polymer of bisphenol A; and — (O—R ³ ) _n — represented by the following general formula (6).

  [Wherein, X represents a divalent methylene group, 1-methylethane-1,1-diyl group, propylene group or sulfone group. ]

Preferred examples of — (O—R ³ ) _n — include an oxyethylene group, an oxypropylene group, and those in which X in the above general formula (5) or (6) is a 1-methylethane-1,1-diyl group. Can be mentioned.

As the divalent functional group represented by — [O—R ³ —O—C (═O)] _n —, a (poly) carbonate diol residue having a chemical structure represented by the following general formula (7) Is mentioned.

In the formula, Z ¹ and Z ² each independently represent a divalent hydrocarbon group, for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, hexylene group, Alkyl group such as heptylene group, octylene group, 2-ethylhexylene group, cycloalkylene group such as cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group, thienylene group, pyridylene group, phenylene group, 4, Represents an aromatic hydrocarbon group such as a 4 ′-(propane-2,2-diyl) diphenylene group;

Examples of the divalent functional group represented by — [O—C (═O) —R ³ ] _n — include a (poly) ester diol residue having a chemical structure represented by the following general formula (8). It is done.

Wherein, Z ¹ and Z ² each independently represents a divalent hydrocarbon group such as methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, hexylene group, Alkylene groups such as heptylene group, octylene group, 2-ethylhexylene group, cycloalkylene groups such as cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group, thienylene group, pyridylene group, phenylene group, 4, An aromatic group such as 4 ′-(propane-2,2-diyl) diphenylene group is represented.

Preferable examples of A include oxyethylene group, oxypropylene group, 1,4-oxybutylene group, X in the above general formula (5) is 1-methylethane-1,1-diyl group or propylene group, X in formula (6) is a 1-methylethane-1,1-diyl group or propylene group, polyoxyethylene, polyoxypropylene, a polyester diol residue obtained from adipic acid and ethylene glycol, dimethyl carbonate 1, Examples include polycarbonate diol residues obtained by transesterification of 5-pentanediol. Particularly preferred are oxyethylene group, oxypropyl group, oxybutylene group, polyoxyethylene and polyoxypropylene.

Y ¹ and Y ² are each independently a divalent alkylene group having 1 to 20 carbon atoms, a divalent oxyalkylene group having 1 to 20 carbon atoms, or a divalent alicyclic carbon atom having 5 to 20 carbon atoms. A hydrogen group and a C4-C20 bivalent aromatic hydrocarbon group are represented.

  Examples of the alkylene group having 1 to 20 carbon atoms include methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, hexylene group, heptylene group, octylene group, 2-ethylhexylene group, and nonylene. Group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group, nonadecylene group, eicosylene group, and the like.

  Examples of the divalent oxyalkylene group having 1 to 20 carbon atoms include oxymethylene group, oxyethylene group, oxypropylene group, oxyisopropylene group, oxybutylene group, oxyisobutylene group, oxypentylene group, oxyhexylene group, Oxyheptylene group, oxyoctylene group, oxy-2-ethylhexylene group, oxynonylene group, oxydecylene group, oxyundecylene group, oxide decylene group, oxytridecylene group, oxytetradecylene group, oxypentadecylene group, oxy It represents a hexadecylene group, an oxyheptadecylene group, an oxyoctadecylene group, an oxynonadecylene group, an oxyeicosylene group, or the like.

  Examples of the divalent alicyclic hydrocarbon having 5 to 20 carbon atoms include cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group, cyclononylene group, cyclodecylene group, cycloundecylene group, cyclododecylene group, cyclotridecylene. Group, cyclotetradecylene group, cyclopentadecylene group, cyclohexadecylene group, cycloheptadecylene group, cyclooctadecylene group, cyclononadecylene group, cycloeicosylene group, norbornylene group, and the like. Preferably they are 6-18 bivalent alicyclic hydrocarbons, More preferably, they are 8-16 alicyclic hydrocarbons.

  Examples of the divalent aromatic hydrocarbon having 4 to 20 carbon atoms include a thienylene group, a pyridylene group, a phenylene group, a bithienylene group, a bipyridylene group, a biphenylene group, a phenanthrylene group, a naphthylene group, and an anthranylene group.

Y ¹ and Y ² are each a divalent alkylene group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon having 5 to 20 carbon atoms, and a divalent aromatic hydrocarbon having 4 to 20 carbon atoms. Including those that are combined. For example, 4,4 ′-(propane-2,2′-diyl) dibenzyl, 4,4 ′-(propane-2,2′-diyl) dicyclohexyl and the like.

Preferred examples of Y ¹ and Y ² include a methylene group, an ethylene group, a norbornyl group, a cyclohexylene group, a cyclooctylene group, a phenylene group, a 4,4 ′-(propane-2,2′-diyl) dibenzyl group, 4,4 ′-(propane-2,2′-diyl) dicyclohexyl, ethylcyclohexylene group may be mentioned.
More preferably, methylene group, norbornylene group, 4,4 ′-(propane-2,2′-diyl) dibenzyl group, 4,4 ′-(propane-2,2′-diyl) dicyclohexyl, cyclooctylene group and ethyl A cyclohexylene group is mentioned.
Particularly preferred are 4,4 ′-(propane-2,2′-diyl) dibenzyl group, 4,4 ′-(propane-2,2′-diyl) dicyclohexyl group, cyclooctylene group and ethylcyclohexylene group. .

  Examples of the organic compound (B) having two C═C double bonds represented by the general formula (1) in the molecule include polyethylene glycol diallyl etherate, polypropylene glycol diallyl etherate, and polytetramethylene glycol. Diallyl etherified product, etc .; diallyl etherified product of polyester diol obtained from adipic acid and ethylene glycol, diallyl etherified product of polyester diol obtained from terephthalic acid and 1,4-butanediol, etc .; 1,5-pentanediol of dimethyl carbonate Diallyl etherified product of polycarbonate diol obtained by transesterification, diallyl etherified product of polycarbonate diol obtained from tricyclodecane dimethanol and propylene carbonate, and polycaprola Diallyl ether compound such as tons diols and polycarbonate diols obtained by the dimethyl carbonate transesterification and the like.

Examples of the organic compound (B) having two C═C double bonds represented by the general formula (2) in the molecule include bisphenol A diallyl etherate, hydrogenated bisphenol A diallyl etherate, and bisphenol F Diallyl etherate, diallyl etherate of bisphenol F hydrogenate, diallyl etherate of bisphenol S, diallyl etherate of hydrogenated bisphenol S, etc .; ethylene glycol-bis (2-vinylbicyclo [2.2.1] hept-5 ( 6) -yl) ether and propylene glycol-bis (2-vinylbicyclo [2.2.1] hept-5 (6) -yl) ether, 4-vinyloctenylmethyl-4′-vinyloctenylcarboxylate, Examples include 4-vinyloctene polycarbonate diol adducts. The
Particularly preferred are diallyl etherates of bisphenol A and diallyl etherates of hydrogenated bisphenol A.

  Examples of the method for producing the organic compound (B) having two C═C double bonds in the molecule used in the present invention include ordinary methods such as diallylation with a glycol compound and an allyl halide, and a vinyl group-containing compound. And esterification by condensation of a compound containing vinyl and glycol, and esterification by condensation of a compound containing vinyl group-containing compound and dicarboxylic acid.

  The diepoxy compound (A) produced by the method for producing an epoxy compound in the present invention is a diepoxy compound (A) represented by the following general formula (3) or (4).

  Examples of the diepoxy compound (A) represented by the general formula (3) include polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, and the like; polyester obtained from adipic acid and ethylene glycol Diglycidyl ether of diol, diglycidyl ether of polyester diol obtained from terephthalic acid and 1,4-butanediol, etc .; diglycidyl ether of polycarbonate diol obtained by transesterification of 1,5-pentanediol of dimethyl carbonate, tricyclo Diglycidyl ether of polycarbonate diol obtained from decane dimethanol and propylene carbonate, polycaprolactone diol and dimethyl carbonate Diglycidyl ethers of polycarbonate diols obtained by ether exchange, and the like.

  Examples of the diepoxy compound (A) represented by the general formula (4) include diglycidyl ether of bisphenol A, diglycidyl ether of hydrogenated bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of hydrogenated bisphenol F, and bisphenol. Diglycidyl ether of S and diglycidyl ether of hydrogenated bisphenol S, ethylene glycol-bis (2-epoxybicyclo [2.2.1] hept-5 (6) -yl) ether and propylene glycol-bis (2-epoxy) And bicyclo [2.2.1] hept-5 (6) -yl) ether.

Preferred examples of the diepoxy compound (A) represented by the general formula (3) or (4) include diglycidyl ether of bisphenol A, diglycidyl ether of hydrogenated bisphenol A, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol. Examples include glycidyl ether and ethylene glycol-bis (2-epoxybicyclo [2.2.1] hept-5 (6) -yl) ether.
Particularly preferably, diglycidyl ether of bisphenol A, diglycidyl ether of hydrogenated bisphenol A, ethylene glycol-bis (2-epoxybicyclo [2.2.1] hept-5 (6) -yl) ether, propylene glycol-bis (2-epoxybicyclo [2.2.1] hept-5 (6) -yl) ether.

  Examples of the tungsten compound (C) that is an essential catalyst in the production method of the present invention include tungstic acid (C1) and tungstate (C2).

As tungstic acid (C1), tungstic acid (H ₂ WO ₄ ) silicotungstic acid (H ₄ [SiW ₁₂ O ₄₀ ] .xH ₂ O), phosphotungstic acid (H ₃ [PW ₁₂ O ₄₀ ] .xH ₂ O) ), Phosphovanadotungstic acid (H _{3 + m} [PV _m W _12-m O ₄₀ ] .xH ₂ O), silicoribed tungstic acid (H ₄ [SiMo _m W _12-m O ₄₀ ] .xH ₂ O) , phosphorus molybdate de tungstophosphoric acid _{(H 3 [PMo m W 12} -m O 40] .xH 2 O) ( however, m is an integer of 1 to 11, x is. an integer of 1 or more) and the like .
Among these tungstic acids (C1), tungstic acid (H ₂ WO ₄ ), silicotungstic acid (H ₄ [SiW ₁₂ O ₄₀ ] .xH ₂ O), phosphotungstic acid (H ₃ [PW ₁₂ O ₄₀ ) are preferable. XH ₂ O).

  Examples of the tungstate (C2) include alkali metal salts, alkaline earth metal salts, copper salts, gold salts, gallium salts and ammonium salts of the above tungstic acid.

  Alkali metal salts include lithium, sodium, potassium, rubidium and cesium salts. Alkaline earth metal salts include beryllium, magnesium, calcium, strontium and barium salts. Other salts include copper, gold, gallium and ammonium salts.

  Preferable examples of tungstate (C2) include sodium salts, potassium salts, barium salts, cesium salts, calcium salts, ammonium, and the like of the above preferable tungstic acid. Particularly preferred are sodium, potassium and ammonium salts of silicotungstic acid, sodium, potassium and ammonium salts of phosphotungstic acid.

  Preferable examples of the tungsten compound (C) are tungstic acid, sodium tungstate, ammonium tungstate, and phosphotungstic acid.

  In the oxidation reaction catalyst of the present invention, these tungstic acids (C1) and salts thereof (C2) may be used alone or in combination.

  The catalyst is used in an amount of 0.001 equivalents to 0.1 equivalents, preferably 0.01 equivalents to 0.05 equivalents of tungsten atoms relative to the double bond.

  As the oxidant (D) essential in the production method of the present invention, 1% to 60% by weight of hydrogen peroxide, molecular oxygen, peracetic acid, t-butyl peroxide, perbenzoic acid, metachloroperbenzoic acid, and the like. Among these, a preferable example is 1 to 60% by weight of hydrogen peroxide.

In the production method of the present invention, in addition to the essential components tungsten compound (C) and oxidizing agent (D), an onium salt (E) acting as a phase transfer catalyst may be used in combination in order to further improve the reaction yield. preferable.
Examples of onium salts (E) that can be used for this purpose include quaternary ammonium salts (E1) and phosphonium salts (E1).

As the quaternary ammonium salt (E1), trioctylmethylammonium chloride, trioctylethylammonium chloride, dilauryldimethylammonium chloride, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, lauryldimethylbenzylammonium chloride, stearyldimethylammonium chloride, Chlorides such as tricaprylmethylammonium chloride, didecyldimethylammonium chloride, tetrabutylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride;
Trioctylmethylammonium bromide, trioctylethylammonium bromide, dilauryldimethylammonium bromide, lauryltrimethylammonium bromide, stearyltrimethylammonium bromide, lauryldimethylbenzylammonium bromide, stearyldimethylammonium bromide, tricapryl bromide Bromides such as methylammonium, didecyldimethylammonium bromide, tetrabutylammonium bromide, benzyltrimethylammonium bromide, benzyltriethylammonium bromide;
Trioctylmethylammonium iodide, trioctylethylammonium iodide, dilauryldimethylammonium iodide, lauryltrimethylammonium iodide, stearyltrimethylammonium iodide, lauryldimethylbenzylammonium iodide, stearyldimethylammonium iodide, tricapryl iodide Iodides such as methylammonium, didecyldimethylammonium iodide, tetrabutylammonium iodide, benzyltrimethylammonium iodide, benzyltriethylammonium iodide;
Hydrogenated trioctylmethylammonium phosphate, trioctylethylammonium phosphate, dilauryldimethylammonium phosphate, lauryltrimethylammonium phosphate, stearyltrimethylammonium phosphate, lauryldimethylbenzyl hydrogenphosphate Ammonium, stearyldimethylammonium phosphate, tricaprylmethylammonium phosphate, didecyldimethylammonium phosphate, tetrabutylammonium phosphate, benzyltrimethylammonium phosphate, benzyltriethyl hydrogenphosphate Hydride phosphates such as ammonium;
Trioctylmethylammonium hydrogenate, trioctylethylammonium hydrogenate, dilauryldimethylammonium hydrogenate, lauryltrimethylammonium hydrogenate, stearyltrimethylammonium hydrogenate, lauryldimethylbenzylammonium hydrogenate, stearyl hydrogenate Examples thereof include hydrogen sulfates such as dimethylammonium sulfate, tricaprylmethylammonium sulfate, didecyldimethylammonium sulfate, tetrabutylammonium sulfate, benzyltrimethylammonium sulfate, and benzyltriethylammonium sulfate.

  Examples of the phosphonium salt (E2) include bromides such as tetrabutylphosphonium bromide and tetraphenylphosphonium bromide; chlorides such as tetrabutylphosphonium chloride and tetraphenylphosphonium chloride; iodine such as tetrabutylphosphonium iodide and tetraphenylphosphonium iodide. And phosphoric acid hydrides such as tetrabutylphosphonium hydrophosphate and tetraphenylphosphonium ahydrophosphate; and hydrogen sulfates such as tetrabutylphosphonium hydrosulfate and tetraphenylphosphonium ahydrosulfate.

Preferred examples of these onium salts (E) include trioctylmethylammonium hydrogen sulfate, dilauryldimethylammonium sulfate, lauryltrimethylammonium hydrogensulfate, stearyltrimethylammonium hydrogensulfate, lauryldimethyl hydrogensulfate. Examples thereof include benzylammonium sulfate, stearyldimethylammonium sulfate, tricaprylmethylammonium sulfate, didecyldimethylammonium sulfate, tetrabutylammonium sulfate, benzyltrimethylammonium sulfate, and benzyltriethylammonium sulfate. Particularly preferred are trioctylmethylammonium hydrogensulfate and dilauryldimethylammonium hydrogensulfate.

  In the production method of the present invention, when phosphate (F) is coexisted in addition to the essential components tungsten compound (C) and oxidizing agent (D), a highly active phosphotungsten cluster is obtained in the reaction system. Since speed improves, it is preferable to use together.

As the phosphate (F) that can be used for this purpose, it is sufficient that the anion component is a compound represented by PO ₄ ^3- , and the cation portion is an organic component (F1) and the inorganic component ( F2).

  Examples of the phosphoric acid salt (F) whose cation portion is an organic component (F1) include tri (methyltrioctylammonium phosphate), tri (tetraoctylammonium phosphate), and tri [methyltri (decyl) ammonium phosphate]. , Tri [methyltri (dodecyl) ammonium phosphate, tri [dimethyldi (dodecyl) ammonium] phosphate, tri (lauryldimethylbenzylammonium phosphate), tri (tetrabutylammonium phosphate), tri (benzyltrimethylammonium phosphate), Triphosphoric acid phosphate (N-laurylpyridinium), triphosphoric acid phosphate (N-cetylpyridinium), dihydrogen phosphate (methyltrioctylammonium phosphate), dihydrogen phosphate (tetraoctylammonium phosphate), dihydrogen phosphate (methyltri (decyl)) Ammonium], hydrogen phosphate di [methyltri (do Decyl) ammonium], hydrogen phosphate di [dimethyldi (dodecyl) ammonium], hydrogen phosphate di (lauryldimethylbenzylammonium), hydrogen dihydrogen (tetrabutylammonium), hydrogen dihydrogen (benzyltrimethylammonium), phosphoric acid Hydrogen di (N-laurylpyridinium), dihydrogen phosphate (N-cetylpyridinium), dihydrogen phosphate (methyltrioctylammonium), dihydrogenphosphate (tetraoctylammonium), dihydrogenphosphate [methyltri (decyl) Ammonium], dihydrogen phosphate [methyltri (dodecyl) ammonium], dihydrogen phosphate [dimethyldi (dodecyl) ammonium], dihydrogen phosphate (lauryldimethylbenzylammonium), dihydrogen phosphate (tetrabutylammonium), phosphoric acid Dihydrogen (benzyl) Trimethyl ammonium), dihydrogen phosphate (N- laurylpyridinium), dihydrogen phosphate (N- cetylpyridinium), and the like.

Examples of the phosphoric acid salt (F) whose cation portion is an inorganic component (F2) include polyphosphoric acid, pyrophosphoric acid, sodium phosphate, potassium phosphate, ammonium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, Examples thereof include potassium hydrogen phosphate, potassium dihydrogen phosphate, ammonium hydrogen phosphate, and ammonium dihydrogen phosphate.

Preferred examples of these phosphates (F) include sodium phosphate, potassium phosphate, and ammonium phosphate. Particularly preferred is ammonium phosphate.

Examples of the method for producing the diepoxy compound (A) include: (1) an organic compound (B) having two C═C double bonds in the molecule, a tungsten compound (C), an oxidizing agent (D), and if necessary A method in which onium salt (E) and phosphate (F) are charged into the system at once;
(2) A mixture of (B) and onium salt (E) is prepared in advance and added to a mixture of tungsten compound (C), oxidizing agent (D) and phosphate (F). A method of mixing two or more and introducing the mixture into the system;
(3) Although the method of mixing arbitrary 2 or more and dripping the mixture in a system is mentioned, It does not specifically limit to these.
From the viewpoint of safety, a method of feeding the mixture into the system and a method of dropping the mixture are preferable.

The oxidation reaction may be performed in the presence or absence of a solvent.
The solvent can be appropriately selected depending on the type of organic substrate and target product, its dissolution, boiling point, and the like.
Solvents include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; aliphatic hydrocarbons such as hexane, heptane and octane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; carbon tetrachloride, chloroform, dichloromethane, 1 Halogenated hydrocarbons such as 2-dichloroethane; ketones such as cyclopentanone and cyclohexanone; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; nitriles such as acetonitrile, propionitrile and benzonitrile; diethyl Examples thereof include linear or cyclic ethers such as ether, dibutyl ether, dimethoxyethane, dioxane, tetrahydrofuran, and ethylene glycol monobutyl ether.
These solvents are used alone or in combination of two or more.

  The reaction temperature can be appropriately selected in consideration of the reaction rate and reaction selectivity according to the reaction substrate and the type of reaction, and is, for example, about 0 to 100 ° C., preferably about 50 to 80 ° C. The reaction may be performed at normal pressure or under pressure. The reaction may be performed by any method such as a batch method, a semi-batch method, or a continuous method.

  The compound obtained by the oxidation reaction is purified and separated by a usual method such as extraction, liquid separation, filtration, centrifugation, and distillation. Since the oxidation reaction catalyst of the present invention has high solubility in water and low solubility in a hydrophobic organic solvent, a method using extraction and liquid separation is preferable.

  According to the method for producing a diepoxy resin in the present invention, an epoxy compound substantially free of halogen can be produced with high selectivity using an inexpensive and highly versatile oxidation catalyst.

  In the production method of the present invention, the following impurities (G) are generated in addition to the intended diepoxy compound (A).

As the impurity (G), a compound (G1) represented by the following general formula (9), a compound (G2) represented by the following general formula (10), a compound (G3 represented by the following general formula (11)) ), A compound (G4) represented by the following general formula (12), a compound (G5) represented by the following general formula (13), a compound (G6) represented by the following general formula (14), and the following general formula Examples thereof include the compound (G7) represented by (15), the compound (G8) represented by the following general formula (16), and the compound (G9) represented by the following general formula (17).
In addition, the symbols R ¹ and R ² and Y ¹ and Y ² in the following general formulas (9) to (17) are the same as those defined in the general formulas (1) to (4).

The content of the diepoxy compound (A) in the epoxy resin composition obtained by the production method of the present invention is usually 70% by weight or more, preferably 85 to 100% by weight, particularly preferably 95 to 100% by weight.
The diepoxy compound (A) content in the epoxy resin composition obtained by the production method of the present invention was determined from the following oxidation reaction conversion rate and oxidation reaction selectivity.

<Oxidation conversion rate calculation method>
The oxidation reaction product in the upper layer (organic phase) obtained in Examples and Comparative Examples described later is composed of an organic compound (B) having two C═C double bonds in the molecule and an oxidation reaction product ( The yield was determined from the ratio of the peak of gas chromatography (GC) of A + G) [diepoxy compound (A) and impurity (G)].

Oxidation reaction conversion rate (%) = P _{A + G} × 100 / P _B
However, P _{A + G:} total GC peak diepoxy compound (A) and impurities (G),
P _B : GC peak of the organic compound (B) having two C═C double bonds in the molecule

<Calculation method of diepoxy compound (A) selectivity in oxidation reaction>
The selectivity of the oxidation reaction product in the upper layer (organic phase) obtained in Examples and Comparative Examples described later was determined from the ratio of the GC peaks of the diepoxy compound (A) and the oxidation reaction product (A + G).

Diepoxy compound selectivity _{(%) = P A × 100} / P A + G
However, P _A : GC peak of diepoxy compound (A),
P _{A + G} : Sum of GC peaks of diepoxy compound (A) and impurity (G)

<Calculation method of oxidation reaction yield>
The oxidation reaction products in the upper layer (organic phase) obtained in Examples and Comparative Examples described later are organic compounds (B) and diepoxy compounds (A) having two C═C double bonds in the molecule. The yield was determined from the ratio of the GC peak. The oxidation reaction yield was taken as the content of diepoxy compound (A).

Diepoxy compound yield (%) = P _A × 100 / P _B
= Oxidation conversion rate x diepoxy compound selectivity / 100
= (A) content of diepoxy compound where P _A : GC peak of diepoxy compound (A),
P _B : GC peak of the organic compound (B) having two C═C double bonds in the molecule

  Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these. Hereinafter, unless otherwise specified, “%” represents “% by weight” and “parts” represents “parts by weight”.

[Production Example 1] <Production of organic compound (B-1) having two C = C double bonds in its molecule as an oxidation reaction substrate>
200 parts of methyl ethyl ketone (manufactured by Maruzen Petroleum Co., Ltd.) and 234 parts (1 mole part of hydrogenated bisphenol A (manufactured by Nippon Nippon Chemical Co., Ltd.)) are charged into a reaction vessel equipped with a stirrer, temperature controller and condenser, and stirred at 300 rpm While heating to 50 ° C. 161 parts (2.1 mol parts) of allyl chloride (manufactured by Showa Denko KK) was added dropwise thereto. After completion of dropping, the mixture was aged at 50 ° C. for 3 hours, added with 500 g of water, and allowed to stand at room temperature. After separation, methyl ethyl ketone was removed under reduced pressure at 50 ° C. and 133 Pa to obtain hydrogenated bisphenol A diallyl ether (B-1).

[Production Example 2] <Production of organic compound (B-2) having two C═C double bonds in its molecule as an oxidation reaction substrate>
In a reaction vessel equipped with a stirrer, a temperature controller and a condenser, 62 parts (1 mole part) of ethylene glycol (Mitsubishi Gas Chemical Co., Ltd.) was charged and heated to 60 ° C. while stirring at 300 rpm. 240 parts (2 mole parts) of 5-vinylcyclo [2,2,1] hept-2-ene (manufactured by San Petrochemical Co., Ltd.) was added dropwise. After completion of dropping, the mixture was aged at 60 ° C. for 3 hours, and unreacted substances and ethylene glycol were removed under reduced pressure at 180 ° C. and 133 Pa. Ethylene glycol-bis (5-vinylcyclo [2,2,1] hept-2-ene) ether (B-2) was obtained.

[Examples 1 to 10]
Charge the tungsten compound (C), oxidant (D), and phosphate (F) in this order into a reaction vessel equipped with a stirrer, temperature controller, and reflux condenser, and raise the temperature to 80 ° C. while stirring at 300 rpm. Warm up. The amounts charged are shown in Table 1.
A mixed solution of the solvent in the amount shown in Table 1 and the organic compound (B) having two C═C double bonds in the molecule and onium salt (E) was added dropwise over 2 hours. After completion of dropping, the reaction was allowed to proceed for 2 hours while maintaining the temperature at 80 ° C. After cooling to room temperature and allowing to stand, the upper layer (organic phase) containing the product was separated from the reaction mixture separated into two phases.

In Example 4, polyoxypropylene glycol diallyl ether having a number average molecular weight of 624 was used as a reaction substrate.
In addition, the composition of (B-3) and (B-4) in Table 1 used in Examples 5 and 6 is as follows.
(B-3): Diallyl etherified product of polyester diol obtained from terephthalic acid and 1,4-butanediol (Mn = 1200)
(B-4): Diallyl etherified product of polycarbonate diol obtained by transesterification of 1,5-pentanediol of dimethyl carbonate (Mn = 750)

[Comparative Examples 1 and 2]
In a reaction vessel equipped with a stirrer, a temperature controller, and a reflux condenser, the amounts shown in Table 2 were added to the reaction substrate, base, and solvent, and the temperature was adjusted to 60 ° C. while stirring at 300 rpm.
The charged amount of glycidylation reagent shown in Table 2 was added dropwise over 1 hour. After completion of dropping, the reaction was allowed to proceed for 6 hours while maintaining the temperature at 60 ° C. After cooling to room temperature and slowly adding ion-exchanged water, it was allowed to stand. The upper layer (organic phase) containing the product was separated from the reaction mixture separated into two phases.

[Comparative Examples 3 and 4]
A reaction vessel equipped with a stirrer, a temperature controller, and a reflux condenser was charged with the amounts of reaction substrate and solvent shown in Table 2, and the temperature was adjusted to 40 ° C. while stirring at 300 rpm.
The amount of the oxidizing agent described in Table 2 was dropped over 2 hours. After completion of dropping, the reaction was carried out for 4 hours while maintaining the temperature at 40 ° C. Then, it cooled to room temperature.
In Comparative Example 3, (B-2) obtained in Production Example 2 was used as a reaction substrate. In Comparative Example 4 and the following Comparative Example 5, polyoxypropylene glycol diallyl ether having a number average molecular weight of 624 was used as a reaction substrate.

[Comparative Example 5]
In a pressure-resistant reaction vessel equipped with a stirrer and a temperature controller, the reaction substrate, solvent, catalyst, and gas were charged in the amounts shown in Table 2, and the temperature was adjusted to 100 ° C. and stirred for 4 hours while stirring at 300 rpm. . Then, it cooled to room temperature.

The tungsten catalyst used in Comparative Example 5 in Table 2 Mol. Catal. 32, 107 (1985), and a catalyst represented by the following chemical structural formula.
_{[(n-C 6 H 13} ) 4N] 3 {PO 4 [W (O) (μ-O 2) 2] 4}

  The oxidation reaction conversion rate, oxidation reaction selectivity, oxidation reaction yield, and total chlorine content of Examples 1 to 10 and Comparative Examples 1 to 5 were measured by the above methods. The results are shown in Table 3.

The measurement conditions when the oxidation reaction conversion rate, the oxidation reaction selectivity, and the oxidation reaction yield were determined from the gas chromatography (GC) measurement results were as follows.
<Analysis conditions for oxidation reaction products by GC>
The oxidation reaction substrate and the oxidation reaction product were analyzed by the following GC apparatus and analysis conditions.
Equipment: GC-2014 manufactured by Shimadzu Corporation
Detector: FID
Column: Capillary column Rtx-5 (length 30 m, inner diameter 0.25 mm ID, liquid phase film thickness: 0.25 μM, manufactured by Restek)
Sample injection volume: 1.0 μL
Injection temperature: 200 ° C
Carrier gas He pressure: 129 kPa
Carrier gas He total flow rate: 23.0 mL / min Carrier gas He column flow rate: 1.8 mL / min Linear velocity: 37.8 cm / sec Split ratio: 10.0
Detection temperature: 300 ° C
Make-up gas He pressure: 10.0 kPa
H2 pressure: 60 kPa
Air pressure: 50kPa
Column temperature: 150 ° C. to 10 ° C./min Temperature increase: Maximum temperature reached 300 ° C., retention time 5 minutes

<Total chlorine content>
The total chlorine content was measured according to JIS K7243-3 (total chlorine content).
In Table 3, N.I. D. Represents not detected (below detection limit).

  As is apparent from the results in Table 3, it can be seen that the production methods of Examples 1 to 10 are superior to the production method of the comparative example because all the oxidation reaction yields are high and the total chlorine content is not detected. .

  The diepoxy compound of the present invention does not contain a halogen and is excellent in electrical characteristics and color stability, and thus is useful as a raw material for electrical applications and coating resins. Moreover, since the oxidation catalyst of the present invention is inexpensive and highly versatile, and only the diepoxy compound is produced from an unsaturated compound with high selectivity, the method for producing a diepoxy compound using the oxidation catalyst of the present invention is useful.

Claims (9)

Using the tungsten compound (C) and the oxidizing agent (D), two organic compounds (B) having two C═C double bonds represented by the following general formula (1) or (2) in the molecule A method for producing a diepoxy compound (A), wherein a diepoxy compound (A) represented by the following general formula (3) or (4) is produced by oxidizing a heavy bond site.

[Wherein R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a monovalent alicyclic carbonization having 5 to 20 carbon atoms. It represents a hydrogen group or an aromatic hydrocarbon group having 4 to 20 carbon atoms, and a part of these groups may be further substituted with a carbonyl group, an ester group, a carboxyl group or a base thereof.
A is a divalent group of — (O—R ³ ) _n —, — [O—R ³ —O—C (═O)] _n —, or — [O—C (═O) —R ³ ] _n —. And may be a combination of one or more.
R ³ represents a divalent alkylene group having 2 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 4 to 20 carbon atoms.
Y ¹ and Y ² are each independently a divalent alkylene group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms, or a divalent aroma having 4 to 20 carbon atoms. Represents a group hydrocarbon group. n represents an integer of 1 to 100. ] Y ¹ and Y ^{2 in the} general formulas (2) and (4) are a C 1-20 divalent alkylene group, a C 5-20 divalent alicyclic hydrocarbon group, or a carbon number. The method for producing an epoxy compound (A) according to claim 1, which is a 4-20 divalent aromatic hydrocarbon group.   Furthermore, the manufacturing method of the diepoxy compound (A) of Claim 1 or 2 which uses onium salt (E) together.   Furthermore, the manufacturing method of the diepoxy compound (A) in any one of Claims 1-3 which uses phosphate (F) together.   The method for producing a diepoxy compound (A) according to any one of claims 1 to 4, wherein the tungsten compound (C) is tungstic acid, sodium tungstate, ammonium tungstate or phosphotungstic acid.   The method for producing a diepoxy compound (A) according to any one of claims 1 to 5, wherein the oxidizing agent (D) is hydrogen peroxide.   The method for producing a diepoxy compound (A) according to any one of claims 1 to 6, wherein the onium salt (E) is a quaternary ammonium salt.   The method for producing a diepoxy compound (A) according to any one of claims 1 to 7, wherein the phosphate (F) is ammonium phosphate.   An epoxy resin composition obtained by the production method according to claim 1, wherein the content of the diepoxy compound (A) is 70% by weight or more.