JP2010106009A - Method for producing epoxy compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an epoxy compound from an organic compound having one or more C=C double bonds in the molecule by using a highly versatile oxidation catalyst available at a low cost and keeping high catalytic activity. <P>SOLUTION: The method for producing the epoxy compound (A) by oxidizing all double bond sites of the organic compound (B) having one or more C=C double bonds in the molecule comprises addition and reaction of an organic phase comprising the organic compound (B) as a starting material and an onium salt (D) to an aqueous phase containing a tungsten compound (C), ammonium phosphate and hydrogen peroxide. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing an epoxy compound. More specifically, the present invention relates to a method for oxidizing an organic compound having a C═C double bond in the molecule and epoxidizing the compound in a high yield.

Various reactions for epoxidizing an organic compound having one or more C═C double bonds in the molecule with a tungsten compound and hydrogen peroxide have been known. For example, a method of epoxidation using α-aminomethylphosphonic acid and a phase transfer catalyst (Non-Patent Document 1) is known.
As another method, an aqueous phase containing a tungsten compound, an 85% phosphoric acid aqueous solution and a hydrogen peroxide solution is replaced with an organic compound having a C═C double bond in the molecule and an organic phase containing a quaternary ammonium salt. A method (Patent Document 1) in which the organic compound is epoxidized by dropping over a period of time is known.

However, in the former method, the appearance of a new oxidation catalyst that is inexpensive, highly versatile, and has high catalytic activity is desired because α-aminomethylphosphonic acid, which is an essential component, is expensive although it has high activity. It was.
In the latter method, since an aqueous phosphoric acid solution is used as a pH adjuster, it is considered that a tungsten catalyst having activity for epoxidation does not exist stably in the system.
The above tungsten catalyst is strongly dependent on pH and can exist only in a specific pH range. When an aqueous phosphoric acid solution is used, the pH in the system increases with time, so that the active species related to epoxidation decreases with time, and the reaction rate of epoxidation decreases with time. Conceivable. For this reason, in the latter method, the pH increased during the reaction, and the epoxidation reaction was extremely slow before the epoxidation sufficiently proceeded, resulting in an insufficient epoxy compound yield.

Bull. Chem. Soc. Jpn. , 70, 905 (1997).

JP 2003-192679 A

  An object of this invention is to provide the manufacturing method of the epoxy compound which is excellent in an epoxy compound yield by maintaining the active species of the catalyst regarding epoxidation among tungsten compounds in a system.

The inventors of the present invention have reached the present invention as a result of studies to achieve the above object.
That is, this invention oxidizes the double bond part of the organic compound (B) which has one or more C = C double bonds represented by the following general formula (1) in the molecule, and the following general formula (2) In the production method of the epoxy compound (A) represented by the formula (1), the organic compound (B) and the onium salt (D) are contained in an aqueous phase containing a tungsten compound (C), ammonium phosphate and hydrogen peroxide. It is a manufacturing method of the epoxy compound (A) characterized by adding an organic phase and making it react.

[Wherein, R ¹ , R ² and R ³ 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 ring having 5 to 20 carbon atoms. Represents a hydrocarbon group and an aromatic hydrocarbon group having 4 to 20 carbon atoms, a part of which may be substituted with a carbonyl group, an ester group, a carboxyl group or a base thereof. R ⁴ is 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 group having 5 to 20 carbon atoms, or an aromatic carbon atom having 4 to 20 carbon atoms. A hydrogen group, an optionally substituted alkenyl group having one or more C═C double bonds (provided that a plurality of C═C double bonds in the group are non-conjugated to each other, and the C═C The double bond is in a non-conjugated relationship with the C═C double bond in the formula), and a part of them may be substituted with an ether group, a carbonyl group, an ester group, a carboxyl group or a base thereof. . R ⁵ is 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 group having 5 to 20 carbon atoms, or an aromatic carbon atom having 4 to 20 carbon atoms. Represents a hydrogen group, an organic group substituted by an epoxy group by reaction of a C═C double bond of R ⁴ , a part of which is substituted with an ether group, a carbonyl group, an ester group, a carboxyl group or its base May be. R ¹ and R ³ , R ² and R ⁴ , R ² and R ⁵ may be bonded to form a ring. ]

  In the method for producing an epoxy resin of the present invention, an organic compound (B) having a C═C double bond in the molecule and an onium salt (D) in an aqueous phase containing a tungsten compound, ammonium phosphate and hydrogen peroxide. ) Is added and reacted. By using this production method, the epoxidation reaction can be stably performed at a high yield.

In the production of the epoxy compound (A) by oxidizing the double bond site of the organic compound (B) having a C═C double bond in the molecule of the present invention,
(I) For the aqueous phase containing the tungsten compound (C), ammonium phosphate and hydrogen peroxide,
(Ii) A method for producing an epoxy compound (A), characterized by adding an organic phase comprising an organic compound (B) having a C═C double bond in the molecule and an onium salt (D) and reacting them. .

  The organic compound (B) having one or more C═C double bonds in the molecule used in the method for producing an epoxy compound of the present invention is an organic compound (B) represented by the following general formula (1). is there.

[Wherein, R ¹ , R ² and R ³ 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 ring having 5 to 20 carbon atoms. Represents a hydrocarbon group and an aromatic hydrocarbon group having 4 to 20 carbon atoms, a part of which may be substituted with a carbonyl group, an ester group, a carboxyl group or a base thereof.
R ⁴ is 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 group having 5 to 20 carbon atoms, or an aromatic carbon atom having 4 to 20 carbon atoms. A hydrogen group, an optionally substituted alkenyl group having one or more C═C double bonds (provided that a plurality of C═C double bonds in the group are non-conjugated to each other, and the C═C The double bond is in a non-conjugated relationship with the C═C double bond in the formula), and a part of them may be substituted with an ether group, a carbonyl group, an ester group, a carboxyl group or a base thereof. .
Further, R ¹ and R ^3, R ² and R ⁴ may bond together to form a ring. ]

R ¹ , R ² and R ³ 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. Represents hydrogen, an aromatic hydrocarbon having 4 to 20 carbon atoms, and a part of them is 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. To express.

  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.

R ¹ , R ² and R ³ are not limited to the above monovalent hydrocarbon group itself, but a part thereof may be substituted with a carbonyl group, an ester group, a carboxyl group or a base thereof.
Examples of those partially 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 residues of methyl carboxylate, cyclohexane acid, and benzoic acid.
Examples of those substituted with the base include sodium salts of substituted methyl carboxylates, sodium salts of cyclohexane acid, sodium salts of benzoic acid, and the like.
Among these, preferred examples include a hydrogen atom, a norbornyl group, a hexyl group, a cyclohexyl group, an octyl group, and a cyclooctyl group.

R ⁴ represents an optionally substituted alkenyl group having one or more C═C double bonds, in addition to the substituent such as the hydrocarbon group exemplified in the description of R ¹ , R ² and R ³ ; A part of which is substituted with an ether group, a carbonyl group, an ester group or a carboxyl group, or a base thereof. That is, when R ⁴ is optionally substituted alkenyl group having 1 or more C = C double bonds, an organic compound as a whole (B) has two or more C = C double bonds.
However, the C═C double bonds existing in the alkenyl group are not conjugated to each other, and the C═C double bond existing in the alkenyl group and the C═C double bond in the above general formula (1). It is not conjugated with a bond.

  Examples of such an alkenyl group include an allyl group, a methallyl group, a prenyl group, a 7-octenyl group, a neryl group, and a geranyl group. In addition, the following general formula (3) and general formula (4) An organic group is mentioned.

[In the formulas (3) and (4), X ¹ , X ² and X ³ 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 5 to 5 carbon atoms. 20 monovalent alicyclic hydrocarbon groups and aromatic hydrocarbon groups having 4 to 20 carbon atoms, part of which may be substituted with a carbonyl group, an ester group, a carboxyl group or a base thereof.
Y ¹ , Y ² and Y ³ 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 ring having 5 to 20 carbon atoms. Represents an aromatic hydrocarbon group, a divalent aromatic hydrocarbon group having 4 to 20 carbon atoms, or a carbonyl group.
OA is-(O-R ⁶ ) _n -,-[O-R ⁶ -OC (= O)] _n- , or-[O-C (= O) -R ⁶ ] _n- in the chain. It may be a combination of one or more types. R ⁶ 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.
n represents an integer of 0 to 100. Further, X ¹ and X ³ , a part of Y ² and X ² , a part of Y ³ and X ² may be bonded to form a ring. ]

X ¹ , X ² and X ³ are substituents exemplified in the description of R ¹ , R ² and R ³ in the general formula (1) of the organic compound (B) having a C═C double bond in the molecule. is there.

Y ¹ , Y ² and Y ³ 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 ring having 5 to 20 carbon atoms. Represents a hydrocarbon group, a divalent aromatic hydrocarbon group having 4 to 20 carbon atoms, or a carbonyl group as a linking group.

  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 Examples include a hexadecylene group, an oxyheptadecylene group, an oxyoctadecylene group, an oxynonadecylene group, and an oxyeicosylene group.

  The divalent alicyclic hydrocarbon having 5 to 20 carbon atoms includes 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 divalent aromatic hydrocarbon having 4 to 20 carbon atoms include thienyl group, pyridyl group, phenyl group, bithienyl group, bipyridyl group, biphenyl group, phenanthryl group, naphthyl group, and anthranyl group.

Preferable examples of Y ¹ , Y ² and Y ³ include a methylene group, an ethylene group, a norbornyl group, a cyclohexyl group, a cyclooctyl group and a phenyl group. Particularly preferred is a methylene group.
X ¹ and X ³ , a part of Y ² in Formula (3) and X ² , or a part of Y ³ in Formula (4) and X ² may combine to form a ring.

  Examples of such an organic group include a cyclohexenyl group, a cyclooctenyl group, a cyclododecenyl group, a cyclohexadienyl group, a cyclooctadienyl group, a 2-methylcyclohexenyl group, and a 2-isopropyl-5-methylcyclohexenyl group. Forming a cycloolefin ring; Forming an alkoxycycloolefin ring such as a 2-methoxy-4-cyclohexenyl group; Forming an ester-type cycloolefin ring such as a 2-acetoxy-3-cyclohexenyl group And those that form a ketone-type cycloolefin ring such as a 2-acetyl-3-cyclohexenyl group.

OA is-(O-R ⁶ ) _n -,-[O-R ⁶ -OC (= O)] _n- , or-[O-C (= O) -R ⁶ ] _n- in the chain. It may be a combination of one or more types. R ⁶ 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.

As-(O-R ⁶ ) _n- , R ⁶ is a divalent alkylene group having 2 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms, or 2 having 4 to 20 carbon atoms. -(O-R _< ⁶ _> ) _{n- of a} valent aromatic hydrocarbon group is mentioned.
n represents an integer of 1 to 100.

R ⁶ is a divalent alkylene group having 2 to 20 carbon atoms, n is in the case of _{^{1 - (O-R 6)}} n - as, for example, oxyethylene group, 1-oxypropylene group, 2-oxy Examples thereof include oxyalkylene such as propylene group, 1-oxybutylene group, 1-oxydecylene group, 3-oxydecylene group, 1-oxyeicosyl.

When R ⁶ is a divalent alkylene group having 2 to 20 carbon atoms and n is 2 to 100, examples of — (O—R ⁶ ) _n — include polyethylene glycol, polypropylene glycol, and 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.

R ⁶ is a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms, n is in the case of _{^{1 - (O-R 6)}} n - as, for example, oxy cyclopentylene group, oxy cyclohexylene 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.

In the case where R ⁶ is a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms and n is 2 to 100,-(O-R ⁶ ) _n- is, for example, repeated 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. ]

As R ⁶ is a divalent aromatic hydrocarbon group having 4 to 20 carbon atoms and n is 1, as — (O—R ⁶ ) _n —, for example, R ⁶ 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 ⁶ is a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms and n is 2 to 100,-(O-R ⁶ ) _n- is a repeating 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 ⁶ ) _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 ⁶ ) _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.

^{- [O-R 6 -O-} C (= O)] n - in the divalent functional group represented, having a chemical structure represented by the following general formula (7) (poly) carbonate diol residues 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 ⁶ ] _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 OA 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.

In addition, the alkenyl group as R ⁴ in the chemical formula (1) representing the organic compound (B) having a C═C double bond in the molecule is represented by the above general formula (3) or general formula (4). As an example of the compound containing such an alkenyl group, an organic group capable of
For example, bisphenol A diallyl etherate, hydrogenated bisphenol A diallyl etherate, bisphenol F diallyl etherate, hydrogenated bisphenol F diallyl etherate, bisphenol S diallyl etherate, hydrogenated bisphenol S diallyl etherate, etc. ;
(1) diallyl etherified product of polyethylene glycol, diallyl etherified product of polypropylene glycol, diallyl etherified product of polytetramethylene glycol, etc .;
Diallyl etherified product of polyester diol obtained from adipic acid and ethylene glycol, and diallyl etherified product of polyester diol obtained from terephthalic acid and 1,4-butanediol;
(2) Diallyl etherified product of polycarbonate diol obtained by transesterification of 1,5-pentanediol of dimethyl carbonate, diallyl etherified product of polycarbonate diol obtained from tricyclodecane dimethanol and propylene carbonate, and polycaprolactone diol and dimethyl carbonate Diallyl etherified product of polycarbonate diol obtained by transesterification;
(3) 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 and the like.

Among these R ⁴ , preferred examples include a hydrogen atom, a norbornyl group, a hexyl group, a cyclohexyl group, an octyl group, a cyclooctyl group, an allyl group, a group represented by the above general formula (5), a general formula ( And the group represented by 6).

Further, R ¹ and R ³ , R ² and R ⁴ in formula (1) may be bonded to form a ring.
Examples of such cyclic unsaturated compounds include cyclohexene, cyclooctene, cyclododecene, cyclohexadiene, cyclooctadiene, 1-methylcyclohexene, 4-isopropyl-1-methylcyclohexene, 1,5-dimethylcyclooctene, 1, Cycloolefins such as 2,3,3-tetramethylcyclohexene; alkoxycycloolefins such as 1-methoxy-3-cyclohexene; ester-type cycloolefins such as 1-acetoxy-2-cyclohexene; 1-acetyl-2-cyclohexene And ketone type cycloolefin.

  Examples of the organic compound (B) having one or more C═C double bonds in the molecule represented by the general formula (1) include linear monoolefin, branched monoolefin, ether type olefin, ester type Olefins, linear non-conjugated dienes, aromatic olefins, ketone olefins, cycloolefin diallyl ether compounds, polyoxyalkylene glycol allylates, polyester diol allylates, polycarbonate diol allylates, cycloolefin divinyl compounds , Diene-based cycloolefin, alkoxycycloalkene, ester-type cycloalkene, and ketone-type cycloalkene.

  Examples of the linear monoolefin include 1-hexene, 2-hexene, 3-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 2-octene, 3-octene and 4-octene. Examples include octene.

  Examples of branched monoolefins include 3,3-dimethyl-1-butene, 4-methyl-2-pentene, 2-methyl-2-pentene, 3-methyl-2-pentene, and 2,3-dimethyl-2-butene. 2,4,4-trimethyl-2-pentene and 2-methyl-2-heptene, 2,3,4-trimethyl-2-pentene, and the like.

As ether type olefins, alcohol type olefins such as geraniol, nerol, linalool, citronellol, lavandulol, phytol, and isophytol;
Examples include diprenyl ether, diisoprenyl ether and methylgeranyl ether.

  Ester olefins include geranyl acetate, neryl acetate, citronellyl acetate, lavandulyl acetate, isophytol acetate, methyl acrylate, methyl methacrylate, geranyl acetate, neryl acetate, citronellyl acetate, farnesyl acetate, isophytyl acetate and cinnamic acid And methyl.

  Examples of the linear non-conjugated diene include 1,5-hexadiene, 1,7-octadiene and 1,9-decadiene.

  Examples of aromatic olefins include styrene and 1-phenyl-1-propene.

  Examples of the ketone-based olefin include methyl vinyl ketone, ethyl propenyl ketone, and methyl allyl ketone.

  Examples of cycloolefin diallyl ethers include cyclohexane diallyl ether, bisphenol A diallyl etherate, hydrogenated bisphenol A diallyl etherate, bisphenol F diallyl etherate, hydrogenated bisphenol F diallyl etherate, bisphenol S diallyl ether And diallyl etherified products of hydrogenated bisphenol S

  Examples of the allyl compound of polyoxyalkylene glycol include diallyl etherified product of polyethylene glycol, diallyl etherified product of polypropylene glycol, and diallyl etherified product of polytetramethylene glycol.

  Examples of the allylated product of polyester diol include diallyl etherified product of polyester diol obtained from adipic acid and ethylene glycol, and diallyl etherified product of polyester diol obtained from terephthalic acid and 1,4-butanediol.

  Polyallyldiol allylic compounds include diol carbonate diallyl etherate obtained by transesterification of 1,5-pentanediol of dimethyl carbonate, diallyl etherate of polycarbonate diol obtained from tricyclodecane dimethanol and propylene carbonate, and polycaprolactone. Examples thereof include diallyl etherified products of polycarbonate diol obtained by transesterification of diol and dimethyl carbonate.

  Divinyl compounds of cycloolefin include ethylene glycol-bis (2-vinylbicyclo [2.2.1] hept-5 (6) -yl) ether and propylene glycol-bis (2-vinylbicyclo [2.2.1]. And hept-5 (6) -yl) ether.

  Examples of the diene-based cycloolefin include cyclohexene, cyclooctene, cyclododecene, cyclohexadiene, cyclooctadiene, 1-methylcyclohexene, 4-isopropyl-1-methylcyclohexene, 1,5-dimethylcyclooctene and 1,2,3,3. Examples include 3-tetramethylcyclohexene.

  Examples of the alkoxycycloalkene include 1-methoxy-3-cyclohexene and 3-methoxy-5-methyl-3-cyclohexene.

  Examples of the ester type cycloalkene include 1-acetoxy-2-cyclohexene and 1-propoxy-3-cyclohexene.

  Examples of the ketone type cycloalkene include 1-acetyl-2-cyclohexene and 1-butyryl-5-norbornene.

  Preferable examples of the organic compound (B) having one or more C═C double bonds in the molecule include 1-octene, 2-octene, cyclooctene, cyclooctadiene, diallyl etherate of bisphenol A, hydrogen Diallyl etherate of bisphenol A, diallyl etherate of polyethylene glycol and ethylene glycol-bis (2-vinylbicyclo [2.2.1] hept-5 (6) -yl) ether and propylene glycol-bis (2-vinyl) Bicyclo [2.2.1] hept-5 (6) -yl) ether.

  The epoxy compound (A) produced by the method for producing an epoxy compound in the present invention is an epoxy compound (A) having one or more epoxy groups in the molecule represented by the following general formula (2).

[Wherein, R ¹ , R ² and R ³ 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 ring having 5 to 20 carbon atoms. Represents a hydrocarbon group and an aromatic hydrocarbon group having 4 to 20 carbon atoms, a part of which may be substituted with a carbonyl group, an ester group, a carboxyl group or a base thereof.
R ⁵ is 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 group having 5 to 20 carbon atoms, or an aromatic carbon atom having 4 to 20 carbon atoms. hydrogen group, an organic group of C = C double bond R ⁴ is substituted with an epoxy group reacts, some of them are carbonyl group, it may be substituted by an ester group or a carboxyl group or its bases .
R ¹ and R ³ , R ² and R ⁵ may be bonded to form a ring. ]

R ¹ , R ² and R ³ are the same substituents as those exemplified in the description of the general formula (1) of the organic compound (B) having a C═C double bond as a raw material in the molecule.

R ⁵ represents C═C 2 in the alkenyl group exemplified in the description of R ^{4 in} the general formula (1) in addition to the substituent such as the hydrocarbon group exemplified in the description of R ¹ , R ² and R ^3. An organic group in which a heavy bond is epoxidized and substituted with an epoxy group.
In R ⁵ , X ¹ , X ² , X ³ , Y ¹ , Y ² , Y ³ , AO which are the substituents and repeating units in the general formula (3) and the general formula (4) used in the description of R ⁴ And n are the same and represent an organic group in which the C═C double bond present in the general formula (3) and the general formula (4) is epoxidized and substituted with an epoxy group.

Examples of the target epoxy compound containing an organic group in which the C═C double bond of the alkenyl group is epoxidized and substituted with the epoxy group include diglycidyl ether of bisphenol A, diglycidyl ether of hydrogenated bisphenol A, Epoxy resins produced from diallyl ethers such as diglycidyl ether of bisphenol F, diglycidyl ether of hydrogenated bisphenol F, diglycidyl ether of bisphenol S and diglycidyl ether of hydrogenated bisphenol S;
Epoxy resins made from polyalkylene glycol diallyl ethers such as diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, and diglycidyl ether of polytetramethylene glycol;
Epoxy resins produced from polyester diallyl ethers such as diglycidyl ether of polyester diol obtained from adipic acid and ethylene glycol and diglycidyl ether of polyester diol obtained from terephthalic acid and 1,4-butanediol;
Diglycidyl ether of polycarbonate diol obtained by transesterification of 1,5-pentanediol of dimethyl carbonate, diglycidyl ether of polycarbonate diol obtained from tricyclodecane dimethanol and propylene carbonate, and transesterification of polycaprolactone diol with dimethyl carbonate An epoxy resin produced from polycarbonate diallyl ether such as diglycidyl ether of polycarbonate diol obtained;
Ethylene glycol-bis (2-epoxybicyclo [2.2.1] hept-5 (6) -yl) ether and propylene glycol-bis (2-epoxybicyclo [2.2.1] hept-5 (6)- Yl) ether.

Preferred examples of R ^{5 in} the general formula (2) include a hydrogen atom, a norbornyl group, a hexyl group, a cyclohexyl group, an octyl group, a cyclooctyl group, a 2-epoxypropyl group, and the above-described general formula (7). Carbonate groups, and ester group carbonate groups represented by the general formula (8).

R ¹ and R ³ , R ² and R ⁵ may be bonded to form a ring.
Examples of such cyclic epoxy compounds include epoxycyclohexane, epoxycyclooctane, epoxycyclododecane, diepoxycyclohexane, diepoxycyclooctane, 1-methylepoxycyclohexane, 4-isopropyl-1-methylepoxycyclohexane, 1,5 An epoxy compound produced from a cycloolefin such as dimethyl epoxycyclooctane or 1,2,3,3-tetramethylepoxycyclohexane; an epoxy compound produced from an alkoxycycloolefin such as 1-methoxy-3-epoxycyclohexane; Epoxy compound produced from ester type cycloolefin such as 1-acetoxy-2-cyclohexene; produced from ketone type cycloolefin such as 1-acetyl-2-cyclohexene Epoxy compounds and the like.

Examples of the epoxy compound (A) represented by the general formula (2) include (1) 1-epoxyhexane, 2-epoxyhexane, 3-epoxyhexane, 1-epoxyheptane, 2-epoxyheptane, 3- Epoxy compounds produced from linear olefins such as epoxyheptane, 1-epoxyoctane, 2-epoxyoctane, 3-epoxyoctane, 4-epoxyoctane;
(2) 3,3-dimethyl-1-epoxybutane, 2-epoxy-4-methylpentane, 2-epoxy-2-methylpentane, 2-epoxy-3-methylpentane, 2,3-dimethyl-2-epoxy Epoxy compounds produced from branched olefins such as butane, 2-epoxy-2,4,4-trimethylpentane, 2-epoxy-2-methylheptane, 2-epoxy-2,3,4-trimethylpentane;
(3) Epoxy compounds produced from alcohol-type olefins such as epoxygeraniol, epoxynerol, epoxylinalool, epoxycitronellol, epoxylavandolol, epoxyphytol and epoxyisophytol;
(4) Epoxy compounds produced from ether type olefins such as diepoxypropyl ether, diepoxy isopropyl ether, epoxy methylgeranyl ether; epoxy geranyl acetate, epoxy neryl acetate, epoxy citronellyl acetate, epoxy lavandulyl acetate, epoxy iso Epoxy compounds produced from ester-type olefins such as phytoacetate;
(5) a diepoxy compound produced from a linear non-conjugated diene such as 1,5-diepoxyhexane, 1,7-diepoxyoctane, 1,9-diepoxydecane;
(6) Epoxy compounds produced from aromatic olefins such as styrene oxide and 1-phenyl-1-epoxypropane;
(7) Methyl acrylate epoxide, methyl methacrylate epoxidation, geranyl acetate epoxidation, neryl acetate epoxidation, citronellyl acetate epoxidation, farnesyl acetate epoxidation, isophytyl acetate epoxidation, methyl cinnamate An epoxy compound produced from an ester-type olefin such as an epoxidized product of
(8) Epoxy compounds produced from ketone-type olefins such as methyl-epoxy ethyl ketone;
(9) Diglycidyl ether of bisphenol A, diglycidyl ether of hydrogenated bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of hydrogenated bisphenol F, diglycidyl ether of bisphenol S and diglycidyl ether of hydrogenated bisphenol S Epoxy resins produced from diallyl ethers such as
(10) Epoxy resins produced from polyalkylene glycol diallyl ethers such as polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polytetramethylene glycol diglycidyl ether;
(11) An epoxy resin produced from polyester diallyl ether such as diglycidyl ether of polyester diol obtained from adipic acid and ethylene glycol and diglycidyl ether of polyester diol obtained from terephthalic acid and 1,4-butanediol;
(12) Diglycidyl ether of polycarbonate diol obtained by transesterification of 1,5-pentanediol of dimethyl carbonate, diglycidyl ether of polycarbonate diol obtained from tricyclodecane dimethanol and propylene carbonate, and polycaprolactone diol and dimethyl carbonate An epoxy resin produced from polycarbonate diallyl ether such as diglycidyl ether of polycarbonate diol obtained by transesterification;
(13) Ethylene glycol-bis (2-epoxybicyclo [2.2.1] hept-5 (6) -yl) ether and propylene glycol-bis (2-epoxybicyclo [2.2.1] hept-5 ( 6) -yl) ether and the like.

  Among the above epoxy compounds, preferable examples include 1-epoxyoctane, 2-epoxyoctane, epoxycyclooctane, diepoxycyclooctane, diglycidyl ether of bisphenol A, diglycidyl ether of hydrogenated bisphenol A, and polyethylene glycol. Diglycidyl ether, ethylene glycol-bis (2-epoxybicyclo [2.2.1] hept-5 (6) -yl) ether and propylene glycol-bis (2-epoxybicyclo [2.2.1] hept-5 (6) -yl) ether.

  The tungsten compound (C), which is an essential catalyst in the production method of the present invention, includes a tungsten compound (C1) composed of a tungstic acid compound and tungsten oxide, a tungstate (C2), and two or more polyatoms (W, Mo). , V), and the like.

Examples of the tungsten compound (C1) include tungstic acid compounds; tungstic acid (H ₂ WO ₄ ), phosphotungstic acid (H ₃ [PW ₁₂ O ₄₀ ] .xH ₂ O), silicotungstic acid (H ₄ [SiW ₁₂ O _40). ] .XH ₂ O), borotungstic acid (H ₅ [BW ₁₂ O ₄₀ ] .xH ₂ O), where x represents an integer of 1 or more, and tungsten oxide (WO ₃ ).
Preferred among these tungstic acid _(H 2 _WO 4), a phosphotungstic acid _{(H 3 [PW 12 O 40} ] .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.

  The composite tungsten compound (C3) is a tungsten compound having tungsten and yet another kind of poly atom (Mo, V). Examples thereof include phosphovanadotungstic acid, silico-molybdotungstic acid, and phosphomolybdo-tungsten. And complex tungsten compounds such as acids; and salts of the above complex tungsten compounds.

Examples of the salt of the composite tungsten compound include the same alkali metal salts, alkaline earth metal salts, copper salts, gold salts, gallium salts, ammonium salts and the like as those exemplified for the tungstate.

  A preferred example of the composite tungsten compound (C3) is phosphomolybdotungstic acid.

These tungsten compounds (C) may be used as single compounds, or between tungsten compounds (C1), between tungstates (C2), between composite tungsten compounds (C3), or between tungsten compounds (C1) and tungstic acid. A salt (C2) may be mixed and used, or a tungsten compound (C1), a tungstate (C2), and a composite tungsten compound (C3) may be mixed.
Preferably, the tungsten compound (C1) and the tungstate (C2) are mixed and used from the viewpoint of catalytic activity.

  As for the usage-amount of a tungsten compound (C), the equivalent of a tungsten atom is 0.001-0.1 equivalent with respect to a double bond, Preferably it is 0.01-0.05 equivalent.

  Hydrogen peroxide essential in the production method of the present invention is used as an oxidizing agent. Usually, hydrogen peroxide is used as an aqueous solution, and its concentration is 1 to 60% by weight from the viewpoint of safety. A preferable concentration range is 5 to 40% by weight, and more preferably 10 to 30% by weight.

  In the production method of the present invention, by using ammonium phosphate in combination, a highly active tungsten compound can be obtained in the reaction system, and a tungsten catalyst having activity for the epoxidation reaction can be maintained by the action of ammonium phosphate. Used as an essential component.

The ammonium phosphate that works to maintain the structure of the tungsten catalyst having activity for the epoxidation reaction here is different from other phosphoric acids.
For example, when phosphoric acid is used, the pH increases as the reaction time elapses. As a result, in the tungsten compound, the structure of the tungsten catalyst having activity in epoxidation changes, and the structure becomes inactive with respect to epoxidation. However, when ammonium phosphate is used, the increase in pH can be suppressed, and the structure of a tungsten catalyst having activity in epoxidation can be maintained even if the reaction time elapses. This makes it possible to find characteristics that are not found in other phosphorus compounds.

In the production method of the present invention, an organic phase composed of an olefin (B) and an onium salt (D) is added to an aqueous phase containing a tungsten compound (C), ammonium phosphate and hydrogen peroxide, and epoxidized. .
In the preparation of the aqueous phase composed of the tungsten compound (C), the ammonium phosphate, and the hydrogen peroxide aqueous solution, the order in which the reaction vessel is charged may be any order. However, it is not preferable to put the tungsten compound before the aqueous hydrogen peroxide solution. Preferably, hydrogen peroxide solution, tungsten compound, and ammonium phosphate are added in this order.
It is not preferable to add the hydrogen peroxide solution and the tungsten compound simultaneously.

In the production method of the present invention, the organic phase is composed of an organic compound (B) having a C═C double bond in the molecule and an onium salt (D).
The onium salt (D) acts as a phase transfer catalyst in order to improve the reaction yield.
Examples of the onium salt (D) of the present invention include a quaternary ammonium salt (D1) and a phosphonium salt (D2).

As the quaternary ammonium salt (D1),
(1) Trioctylmethylammonium chloride, trioctylethylammonium chloride, dilauryldimethylammonium chloride, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, lauryldimethylbenzylammonium chloride, stearyldimethylammonium chloride, tricaprylmethylammonium chloride, dichloride Chlorides such as decyldimethylammonium chloride, tetrabutylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride;
(2) Trioctylmethylammonium bromide, trioctylethylammonium bromide, dilauryldimethylammonium bromide, lauryltrimethylammonium bromide, stearyltrimethylammonium bromide, lauryldimethylbenzylammonium bromide, stearyldimethylammonium bromide, odor Bromides such as tricaprylmethylammonium bromide, didecyldimethylammonium bromide, tetrabutylammonium bromide, benzyltrimethylammonium bromide, benzyltriethylammonium bromide;
(3) Trioctylmethylammonium iodide, trioctylethylammonium iodide, dilauryldimethylammonium iodide, lauryltrimethylammonium iodide, stearyltrimethylammonium iodide, lauryldimethylbenzylammonium iodide, stearyldimethylammonium iodide, iodine Iodides such as tricaprylmethylammonium iodide, didecyldimethylammonium iodide, tetrabutylammonium iodide, benzyltrimethylammonium iodide, benzyltriethylammonium iodide;
(4) Hydrogenated trioctylmethylammonium phosphate, trioctylethylammonium phosphate, dilauryldimethylammonium phosphate, lauryltrimethylammonium phosphate, stearyltrimethylammonium phosphate, hydrogenated hydrogen phosphate Lauryldimethylbenzylammonium phosphate, stearyldimethylammonium phosphate, tricaprylmethylammonium phosphate, didecyldimethylammonium phosphate, tetrabutylammonium phosphate, benzyltrimethylammonium phosphate, hydrogen phosphate Hydrogen phosphates such as benzyltriethylammonium fluoride;
(1) Trioctylmethyl ammonium hydrogen sulfate, trioctyl ethyl ammonium hydrogen sulfate, dilauryl dimethyl ammonium hydrogen sulfate, lauryl trimethyl ammonium hydrogen sulfate, stearyl trimethyl ammonium hydrogen sulfate, lauryl dimethyl benzyl ammonium hydrogen sulfate, sulfuric acid Examples include hydrogen sulfates such as stearyldimethylammonium hydrogenate, tricaprylmethylammonium hydrogensulfate, didecyldimethylammonium hydrogensulfate, tetrabutylammonium hydrogensulfate, benzyltrimethylammonium hydrogensulfate, and benzyltriethylammonium hydrogensulfate. It is done.

Examples of the phosphonium salt (D2) include (1) bromides such as tetrabutylphosphonium bromide and tetraphenylphosphonium bromide;
(2) Chlorides such as tetrabutylphosphonium chloride and tetraphenylphosphonium chloride;
Iodides such as tetrabutylphosphonium iodide and tetraphenylphosphonium iodide;
(3) Phosphoric acid hydrides such as tetrabutylphosphonium hydrophosphate and tetraphenylphosphonium ahydrophosphate;
(4) Hydrogen sulfate such as tetrabutylphosphonium hydrosulfate and tetraphenylphosphonium ahydrosulfate.

Preferred examples of these onium salts (D) include trioctylmethylammonium hydrogen sulfate, dilauryldimethylammonium hydrogensulfate, lauryltrimethylammonium hydrogensulfate, stearyltrimethylammonium hydrogensulfate, lauryldimethylbenzylammonium hydrogensulfate. , Stearyldimethylammonium hydrogen sulfate, tricaprylmethylammonium hydrogensulfate, didecyldimethylammonium hydrogensulfate, tetrabutylammonium hydrogensulfate, benzyltrimethylammonium hydrogensulfate, and benzyltriethylammonium hydrogensulfate. Particularly preferred are trioctylmethylammonium hydrogensulfate and dilauryldimethylammonium hydrogensulfate.

The organic phase of the present invention may contain a solvent in addition to the organic compound (B) having an C═C double bond in the molecule and the onium salt (D).
The solvent can be appropriately selected depending on the kind of the organic compound (B) and the target product.
As a solvent, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene;
Aliphatic hydrocarbons such as hexane, heptane, octane;
Cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane;
Halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane;
Ketones such as cyclopentanone and cyclohexanone;
Amides such as N, N-dimethylformamide, N, N-dimethylacetamide;
Nitriles such as acetonitrile, propionitrile, benzonitrile;
Examples thereof include linear or cyclic ethers such as diethyl ether, dibutyl ether, dimethoxyethane, dioxane, tetrahydrofuran, and ethylene glycol monobutyl ether. These solvents are used alone or in combination of two or more.

In the production method of the present invention, an organic phase is added to an aqueous phase, and an organic compound (B) having a C═C double bond in the molecule is epoxidized.
Examples of the method for adding the organic phase to the aqueous phase include batch charging, dropping, and continuous charging. Preferably, from the viewpoint of reaction temperature, the organic phase is added dropwise. In addition, as an unpreferable addition method, it is the method of batch injection from a viewpoint of reaction temperature.

  The method of adding the aqueous phase to the organic phase is as follows: (1) charging a hydrogen peroxide aqueous solution, a tungsten compound and a mixture of three kinds of phosphoric acid or phosphate; or (2) adding a tungsten compound and phosphoric acid or phosphate. There is a method in which an aqueous solution and an aqueous hydrogen peroxide solution are added over the same time.

In the case of (1), the hydrogen peroxide concentration is decomposed into water by contact with the tungsten compound, and the concentration of hydrogen peroxide is different between the initial stage of dropping and the latter stage of dropping. Absent.
In the case of (2), since two aqueous solutions are dropped in the organic phase without mixing, the lifetime of hydrogen peroxide is long, but it is difficult to produce a tungsten compound that is a tungsten catalyst having an activity for epoxidation. . Accordingly, the reaction time becomes long and the yield becomes unfavorable.

  The time for adding the organic phase dropwise to the aqueous phase is 1-5 hours. Preferably it is 1.5 to 2.5 hours.

  The reaction temperature of epoxidation can be appropriately selected in consideration of the reaction rate and reaction selectivity according to the organic compound (B), the type of reaction, and the like. is there. Epoxidation may be performed at normal pressure or under pressure. Moreover, you may carry out by any methods, such as a batch type, a semibatch type, and a continuous type.

  The obtained epoxy compound (A) 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.

  In the method for producing an epoxy compound by oxidation of an organic compound, it is desired that the epoxy compound yield is high. The epoxy compound yield represents how efficiently the epoxy compound (A) is produced with respect to the organic compound (B) having a C═C double bond in the molecule as a reaction substrate.

The reaction rate and selectivity of the epoxy compound are determined by quantitatively analyzing the oxidation reaction product in the organic phase by gas chromatography (GC), in addition to the monoepoxy compound and the diepoxy compound in the case where the starting material is diene. The content ratio (%) of other by-product components other than the target product such as a ring-opened product (diol, tetraol, etc.) of the epoxy compound with water is obtained.
In the examples described later, the analysis values (%) are shown in Table 1.

  According to the present invention described in detail above, the target epoxy compound yield is high, and the epoxy compound can be produced while keeping the tungsten catalyst highly active.

  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 Example 1 of Raw Material Hydrogenated Bisphenol A Diallyl Ether (B-1)>
A reaction vessel equipped with a stirrer, a temperature controller and a condenser was charged with 200 parts of methyl ethyl ketone and 234 parts (1 mol part of hydrogenated bisphenol A (“Rikabinol HB” manufactured by Shin Nippon Chemical Co., Ltd.)) and stirred at 300 rpm. The mixture was heated to 50 ° C. 161 parts (2.1 mole parts) of allyl chloride 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 10 Torr to obtain hydrogenated bisphenol A diallyl ether (B-1).

[Production Example 2] <Production Example 2 of Raw Material Ethylene Glycol-bis (5-vinylcyclo [2,2,1] hept-2-ene) ether (B-2)>
A reaction vessel equipped with a stirrer, a temperature controller and a condenser was charged with 62 parts (1 mol part) of ethylene glycol 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 the dropping, the mixture was aged at 60 ° C. for 3 hours, and unreacted substances and ethylene glycol were removed under reduced pressure at 150 ° C. and 1 Torr, and ethylene glycol-bis (5-vinylcyclo [2,2,1] hept-2-ene) ether ( B-2) was obtained.

[Example 1]
Table 1 shows tungstic acid (C-1), sodium tungstate (C-2), 30% aqueous hydrogen peroxide, and ammonium phosphate in a reaction vessel equipped with a stirrer, a temperature controller, and a reflux condenser. An aqueous phase was prepared by charging at a weight ratio. The temperature was adjusted to 80 ° C. while stirring at 300 rpm.
The amount of 1-octene, dilauryldimethylammonium hydrogen sulfate (D-1) and toluene described in Table 1 were mixed to prepare an organic phase. This organic phase was added dropwise to the aqueous phase previously prepared in the reaction vessel over 2 hours. The pH of the aqueous phase after the dropwise addition was 2.8.
After completion of dropping, the reaction was allowed to proceed for 3 hours while maintaining the temperature at 80 ° C. The pH after the reaction was 3.0. 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. Table 1 shows the analytical value (%) by GC of the oxidation reaction product in the organic phase in this production method.

[Example 2]
In Example 1, except that 1-octene was changed to cyclooctene, the same operation as Example 1 was performed and epoxy cyclooctane was obtained. In addition, the amount of preparation and the analytical value of the obtained oxidation reaction product are as shown in Table 1 (the same applies to the following examples).
The pH of the aqueous phase after the dropwise addition was 2.8, and the pH after the reaction was 3.1.

[Example 3]
In Example 1, except that 1-octene was changed to cyclooctadiene, the same operation as in Example 1 was performed to obtain diepoxycyclooctane.
The pH of the aqueous phase after the dropwise addition was 2.8, and the pH after the reaction was 3.1.

[Example 4]
In Example 1, hydrogenated bisphenol A diglycidyl ether was obtained in the same manner as in Example 1 except that 1-octene was changed to hydrogenated bisphenol A diallyl ether (B-1) of Production Example 1. .
The pH of the aqueous phase after the dropwise addition was 2.8, and the pH after the reaction was 3.1.

[Example 5]
Example 1 and Example 1 except that 1-octene was changed to ethylene glycol-bis (5-vinylcyclo [2,2,1] hept-2-ene) ether (B-2) of Production Example 2. The same operation was performed to obtain ethylene glycol-bis (5-epoxycyclo [2,2,1] hept-2-ene) ether.
The pH of the aqueous phase after the dropwise addition was 2.8, and the pH after the reaction was 3.0.

[Example 6]
In Example 1, except that the combination of tungstic acid (C-1) and sodium tungstate (C-2) was changed to a combination of sodium tungstate (C-2) and phosphotungstic acid (C-3). The same operation as in Example 1 was performed to obtain 1-epoxyoctane.
The pH of the aqueous phase after the dropping was 2.7, and the pH after the reaction was 3.0.

[Example 7]
In Example 1, except that the concentration of the aqueous hydrogen peroxide solution was changed from 30% to 6%, the same operation as in Example 1 was performed to obtain 1-epoxyoctane.
The pH of the aqueous phase after dropping was 3.0, and the pH after reaction was 3.0.

[Example 8]
In Example 1, the same operation as in Example 1 was performed, except that dilauryldimethylammonium hydrogensulfate (D-1) onium salt was changed to trioctylmethylammonium hydrogensulfate (D-2). Epoxy octane was obtained.
The pH of the aqueous phase after the dropwise addition was 2.8, and the pH after the reaction was 3.2.

[Example 9]
In Example 1, except for using only tungstic acid (C-1) as a tungsten compound, the same operation as Example 1 was performed and 1-epoxyoctane was obtained.
The pH of the aqueous phase after the dropping was 2.5, and the pH after the reaction was 3.8.

[Comparative Example 1]
A reaction vessel equipped with a stirrer, a temperature controller and a reflux condenser was charged with 1-octene, dilauryldimethylammonium hydrogensulfate (D-1) and toluene in the weight ratio shown in Table 2 to prepare an organic phase. did. The temperature was adjusted to 80 ° C. while stirring at 300 rpm.
The amount of tungstic acid (C-1) described in Table 2, 30% aqueous hydrogen peroxide solution and 85% aqueous phosphoric acid solution were mixed to prepare an aqueous phase. Unlike the Example, this aqueous phase was dripped at the organic phase previously prepared to the reaction tank over 2 hours. The pH of the aqueous phase after dropping was 2.5.
After completion of dropping, the reaction was allowed to proceed for 3 hours while maintaining the temperature at 80 ° C. The pH of the aqueous phase after the reaction was 6.6. 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. The analytical values of the oxidation reaction product in the organic phase in the production method for comparison are shown in Table 2.
In addition to 1-epoxyoctane (A), 12% of by-products such as unreacted 1-octene and 1-epoxyoctane ring-opening by-products were present.

[Comparative Example 2]
In Comparative Example 1, except that the tungsten compound was sodium tungstate (C-2), the same operation as in Comparative Example 1 was performed to obtain 1-epoxyoctane. In addition, the analytical value of the charged amount and the oxidation reaction product in the organic phase is as shown in Table 2 (the same applies to the following comparative examples).
In addition to 1-epoxyoctane, 25% of byproducts such as unreacted 1-octene and 1-epoxyoctane ring-opening side reaction products were present.
The pH of the aqueous phase after the dropwise addition was 3.8, and the pH after the reaction was 6.3.

[Comparative Example 3]
In Comparative Example 1, the same operation as in Comparative Example 1 was performed except that the 85% aqueous phosphoric acid solution was changed to sodium phosphate. In addition to 1-epoxyoctane, there were 29% by-products such as unreacted 1-octene and 1-epoxyoctane ring-opening by-products.
The pH of the aqueous phase after the dropping was 3.0, and the pH after the reaction was 6.5.

[Comparative Example 4]
In Comparative Example 1, the same operation as in Comparative Example 1 was performed except that 1-octene was changed to cyclooctene. In addition to 1-epoxycyclooctane, by-products such as unreacted cyclooctene and 1-epoxycyclooctane ring-opening by-reactant were present in a total amount of 10%.
The pH of the aqueous phase after the dropping was 2.5, and the pH after the reaction was 6.5.

[Comparative Example 5]
In Comparative Example 1, the same operation as in Comparative Example 1 was performed except that 1-octene was changed to cyclooctadiene. In addition to diepoxycyclooctane, the total amount of unreacted cyclooctadiene and by-products such as epoxy ring-opening side reaction products is 3%, and monoepoxycyclohexane in which only one C = C double bond is oxidized. There was 15% octene.
The pH of the aqueous phase after the dropping was 2.5, and the pH after the reaction was 6.5.

[Comparative Example 6]
In Comparative Example 1, the same operation as in Comparative Example 1 was performed except that 1-octene was replaced with hydrogenated bisphenol A diallyl ether (B-1). In addition to hydrogenated bisphenol A diallyl ether, by-products such as unreacted hydrogenated bisphenol A diallyl ether and epoxy compound ring-opening by-products are 15% in total, and there is only one C = C double bond. 15% of the monoepoxy compound of hydrogenated bis A diallyl ether which was not oxidized was present.
The pH of the aqueous phase after the dropping was 2.5, and the pH after the reaction was 6.6.

[Comparative Example 7]
1-octene (B), dilauryldimethylammonium hydrogensulfate (D) and toluene are charged in a reaction tank equipped with a stirrer, a temperature controller and a reflux condenser to prepare an organic phase. did. The temperature was adjusted to 80 ° C. while stirring at 300 rpm.
The amount of tungstic acid (C-1) described in Table 2, 30% aqueous hydrogen peroxide solution and 85% aqueous phosphoric acid solution were mixed to prepare an aqueous phase. The pH of the aqueous phase was adjusted from 2.5 to 3.0 using sulfuric acid as a pH adjuster. As in Comparative Example 1, this aqueous phase was added dropwise to the organic phase previously prepared in the reaction vessel over 2 hours. The pH of the aqueous phase after dropping was 2.5. After completion of dropping, the reaction was allowed to proceed for 24 hours while maintaining the temperature at 80 ° C.
Unlike Comparative Example 1, in order to adjust the pH in the reaction system, the pH of the aqueous phase was analyzed every 30 minutes, and the pH was adjusted to 2.5 to 3.5 using sulfuric acid as a pH adjuster each time. It adjusted so that it might enter in the area of. The pH of the aqueous phase after the reaction was 3.3. 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. The oxidation reaction product in the organic phase in this production method was analyzed.
Although 1-epoxycyclooctane is obtained in a high yield of 97%, this requires complicated pH adjustment as described above and a long-time (24 hours) reaction.

<Analysis conditions for oxidation reaction products by GC>
The reaction product was 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
INJ 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
DET temperature: 300 ° C
Make-up gas He pressure: 10.0 kPa
H2 pressure: 60 kPa
Air pressure: 50kPa
Column temperature: 50 ° C. to 10 ° C./min.

  As is clear from the results of Tables 1 and 2, the production methods of Examples 1 to 9 are both unreacted C = C doubles in the oxidation reaction product as compared with the production methods of Comparative Examples 1 to 6. The content of the organic compound or other component having a bond in the molecule is small, and the ratio of the target epoxy compound is high. In particular, even in the case of epoxidation by an oxidation reaction from an organic compound having two C═C double bonds in the molecule as in Examples 3, 4, and 5, unlike the comparative examples 5 and 6, the monoepoxy compound Thus, the diepoxy compound is obtained efficiently. Moreover, the Example of this invention does not require complicated operation, such as carrying out reaction, pH analysis, and pH adjustment like the comparative example 7, and reaction time does not take long. Therefore, it turns out that the manufacturing method of Examples 1-9 is simple and excellent compared with the manufacturing method of Comparative Examples 1-7.

The method for producing an epoxy compound of the present invention is very useful for industrial production because of its high oxidation reaction yield and simple production method. In addition, the epoxy resin obtained by the production method of the present invention is inexpensive and can be used for electronic material applications where electrical characteristics are important.

Claims (5)

An epoxy compound represented by the following general formula (2) by oxidizing the double bond site of the organic compound (B) having at least one C = C double bond in the molecule represented by the following general formula (1) In the production method of (A), an organic phase composed of the organic compound (B) and the onium salt (D) is added to the aqueous phase containing the tungsten compound (C), ammonium phosphate and hydrogen peroxide, The manufacturing method of the epoxy compound (A) characterized by making it react.
[Wherein, R ¹ , R ² and R ³ 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 ring having 5 to 20 carbon atoms. Represents a hydrocarbon group and an aromatic hydrocarbon group having 4 to 20 carbon atoms, a part of which may be substituted with a carbonyl group, an ester group, a carboxyl group or a base thereof. R ⁴ is 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 group having 5 to 20 carbon atoms, or an aromatic carbon atom having 4 to 20 carbon atoms. A hydrogen group, an optionally substituted alkenyl group having one or more C═C double bonds (provided that a plurality of C═C double bonds in the group are non-conjugated to each other, and the C═C The double bond is in a non-conjugated relationship with the carbon-carbon double bond in the formula), and a part of them may be substituted with an ether group, a carbonyl group, an ester group, a carboxyl group or a base thereof. . R ⁵ is 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 group having 5 to 20 carbon atoms, or an aromatic carbon atom having 4 to 20 carbon atoms. Represents a hydrogen group, an organic group substituted by an epoxy group by reaction of a C═C double bond of R ⁴ , a part of which is substituted with an ether group, a carbonyl group, an ester group, a carboxyl group or its base May be. R ¹ and R ³ , R ² and R ⁴ , R ² and R ⁵ may be bonded to form a ring. ]   The epoxy compound according to claim 1, wherein the tungsten compound (C) is one or more tungsten compounds (C1) selected from the group consisting of tungstic acid, phosphotungstic acid, silicotungstic acid, borotungstic acid and tungsten oxide. A) production method.   The method for producing an epoxy compound (A) according to claim 2, wherein the tungsten compound (C1) according to claim 2 and the tungstate (C2) are used in combination.   The method for producing an epoxy compound (A) according to claim 3, wherein the tungstate (C2) is at least one tungstate selected from the group consisting of sodium tungstate, ammonium tungstate and potassium tungstate.   The method for producing an epoxy compound (A) according to any one of claims 1 to 4, wherein the onium salt (D) is a quaternary ammonium salt.