KR20190140474A - Method of producing epoxy compound - Google Patents

Abstract

(식 중, R¹ 및 R²는 각각 독립적으로, 탄소원자수 2 내지 27의 알킬기를 나타내고, R³은 수소원자 또는 탄소원자수 1 내지 25의 알킬기를 나타내고, 단 -CR¹R²R³기에 포함되는 탄소원자의 수의 합계는 10 내지 30이고, R⁴ 내지 R⁶은 각각 독립적으로, 수소원자 또는 탄소원자수 1 내지 10의 알킬기를 나타내고, X는, *-C(=O)O-, *-CH₂O- 또는 *-CH₂OC(=O)-를 나타내고(여기서 *은 -CR¹R²R³기에 결합하는 단을 나타낸다.), A는 단결합, 또는 (n+1)가의 에테르결합을 포함하고 있을 수도 있는 지방족 탄화수소기를 나타내고, Z는 단결합 또는 산소원자를 나타내고, 단 A가 단결합을 나타낼 때 Z는 단결합을 나타내고, L은 에테르결합을 포함하고 있을 수도 있는 탄소원자수 1 내지 8의 알킬렌기를 나타내고, n은 1 내지 8의 정수를 나타내고, 단 A가 단결합을 나타낼 때 n은 1을 나타낸다.)[PROBLEMS] To provide a method for producing a high-quality epoxy compound having high yield, suitable for industrial production, and requiring no complicated post-treatment and without coloring.
[Solution] A method for producing an epoxy compound represented by formula [2], wherein the olefin compound represented by formula [1], hydrogen peroxide, a nitrile compound, and an alkaline substance are reacted in a solvent.

(Wherein R ¹ and R ² each independently represent an alkyl group having 2 to 27 carbon atoms, R ³ represents a hydrogen atom or an alkyl group having 1 to 25 carbon atoms, provided that they are included in the group -CR ¹ R ² R ³ ) The sum of the number of carbon atoms to be used is 10 to 30, R ⁴ to R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X represents * -C (= O) O-, *- CH ₂ O— or * —CH ₂ OC (═O) —, where * represents a group which binds to a —CR ¹ R ² R ³ group, and A is a single bond or a (n + 1) valent ether An aliphatic hydrocarbon group which may contain a bond, Z represents a single bond or an oxygen atom, provided that when A represents a single bond, Z represents a single bond and L represents a carbon atom that may contain an ether bond 1 N represents an alkylene group of 8 to 8, n represents an integer of 1 to 8, provided that n represents 1 when A represents a single bond. Indicates.)

Description

Method of producing epoxy compound

The present invention relates to a novel process for the preparation of epoxy compounds.

Until now, the olefin compound was epoxy-based using a hydrogen peroxide as an oxidizing agent and a three-way catalyst containing tungstate or molybdate, quaternary ammonium salt, and phosphate or phosphonate as a catalyst. The method of converting (for example, patent document 1) is known. Moreover, the method (for example, patent document 2) which uses hydrogen peroxide as an oxidizing agent and epoxidizes an olefin compound in the pyrroline-pyrroline aqueous solution in the presence of a nitrile compound is known.

Japanese Patent Application Laid-Open No. 2012-25688 Japanese Patent Application Laid-Open No. 2002-145872

However, in the method described in Patent Document 1, it was necessary to remove the catalyst (tungstate salt, molybdate salt, quaternary ammonium salt, etc.) remaining in the reaction mixture. As a result, the post-treatment using an adsorbent or the like has complicated the manufacturing process, and a reduction in yield has been a problem. Moreover, since reaction conditions are normally severe, such as high reaction temperature, there existed a subject that the epoxy compound obtained will color.

On the other hand, patent document 2 does not disclose at all about the application to the olefin compound which has a specific branched aliphatic group.

An object of the present invention is to provide a method for producing a high-quality epoxy compound having high yield, suitable for industrial production, and requiring no complicated post-treatment, and without coloring.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, this inventor reacts an olefin compound in the solvent containing hydrogen peroxide, a nitrile compound, and an alkaline substance, and the epoxy compound which the olefin part epoxidized in high yield is obtained, Furthermore, it discovered that the epoxy compound with little coloring is obtained by simple post-processing, and completed this invention.

That is, this invention is a manufacturing method of the epoxy compound represented by Formula [2] characterized by making the olefin compound, hydrogen peroxide, nitrile compound, and alkaline substance which are represented by Formula [1] react in a solvent as a 1st viewpoint. It is about.

[Formula 1]

(Wherein R ¹ and R ² each independently represent an alkyl group having 2 to 27 carbon atoms, R ³ represents a hydrogen atom or an alkyl group having 1 to 25 carbon atoms, provided that they are included in the group -CR ¹ R ² R ³ ) The sum of the number of carbon atoms to be used is 10 to 30, R ⁴ to R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X represents * -C (= O) O-, *- CH ₂ O— or * —CH ₂ OC (═O) —, where * represents a group which binds to a —CR ¹ R ² R ³ group, and A is a single bond, or (n + 1) ) Represents an aliphatic hydrocarbon group which may contain an ether bond, Z represents a single bond or an oxygen atom, provided that when A represents a single bond, Z represents a single bond, and L may contain an ether bond. N represents an alkylene group having 1 to 8 carbon atoms, n represents an integer of 1 to 8, provided that n represents a single bond 1 is displayed.)

[Formula 2]

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , X, A, Z, L and n represent the same meanings as above).

As a second aspect, the X is * -CH ₂ O- and n is an integer of 2 to 8, or the X is * -C (= 0) O- or * -CH ₂ OC (= 0) The manufacturing method which concerns on phosphorus and a 1st viewpoint.

As a 3rd viewpoint, it is related with the manufacturing method as described in a 1st viewpoint or a 2nd viewpoint whose said X is * -C (= O) O-.

As a 4th viewpoint, said A is an aliphatic hydrocarbon group which may contain the (n + 1) valent ether bond, and manufacture as described in any one of the 1st viewpoint thru | or 3rd viewpoint that said n is an integer of 2-8. It is about a method.

As a fifth aspect, A is glycerin, 2-hydroxy-1,4-butanediol, trimethylolmethane, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, ditrimethylolpropane The manufacturing method as described in a 4th viewpoint is a group derived by removing all or a hydroxyl group from the polyol selected from the group which consists of a pentaerythritol and dipentaerythritol.

As a 6th viewpoint, it is related with the manufacturing method as described in a 5th viewpoint that the said polyol is a polyol chosen from the group which consists of 1,1,1-trimethylol propane and pentaerythritol.

As a 7th viewpoint, the said A is group which is derived by removing all the hydroxyl groups from the said polyol, It is related with the manufacturing method as described in a 5th viewpoint or a 6th viewpoint.

As an 8th viewpoint, it is related with the manufacturing method in any one of a 1st viewpoint thru | or a 7th viewpoint which L is a methylene group.

As a 9th viewpoint, the said -CR <^1> R <^2> R <^3> group is group of 14-26 carbon atoms, It is related with the manufacturing method in any one of 1st-8th viewpoint.

As a 10th viewpoint, it is related with the manufacturing method in any one of a 1st viewpoint thru | or a ninth viewpoint whose said alkaline substance is alkali metal hydroxide.

As a 11th viewpoint, it is related with the manufacturing method in any one of a 1st viewpoint thru | or a 10th viewpoint that the said solvent is alcohol.

Claim 12 as a viewpoint, the compound represented by the above formula ^{[1], -CR 1 R 2} R 3 which comprises a branched fatty acid or its active material, or -CR, unsaturated alcohols and branched alcohols containing an ¹ R ² R ³ Or it is related with the manufacturing method in any one of a 1st viewpoint thru | or an 11th viewpoint which is a reaction product with unsaturated halide.

According to the production method of the present invention, an epoxy compound can be obtained with a high yield close to 80%, and an epoxy compound having a high light transmittance (low coloration) can be produced by simple post-treatment.

<Method for Producing Epoxy Compound Represented by Formula [2]>

This invention is the manufacturing method of the epoxy compound represented by Formula [2] characterized by making the olefin compound, hydrogen peroxide, nitrile compound, and alkaline substance which are represented by following formula [1] react in a solvent.

[Formula 3]

(Wherein R ¹ and R ² each independently represent an alkyl group having 2 to 27 carbon atoms, R ³ represents a hydrogen atom or an alkyl group having 1 to 25 carbon atoms, provided that they are included in the group -CR ¹ R ² R ³ ) The number of carbon atoms to be added is 10 to 30, R ⁴ to R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X represents * -C (= 0) O- or * -CH. ₂ O- or * -CH ₂ OC (= O)-(where * represents a group bonded to a -CR ¹ R ² R ³ group), A is a single bond or a (n + 1) valent ether bond Represents an aliphatic hydrocarbon group which may contain, Z represents a single bond or an oxygen atom, provided that when A represents a single bond, Z represents a single bond, and L represents from 1 to 4 carbon atoms which may contain an ether bond. 8 represents an alkylene group, n represents an integer of 1 to 8, provided that n represents 1 when A represents a single bond It produces another.)

[Formula 4]

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , X, A, Z, L and n represent the same meanings as above).

The alkyl group having 2 to 27 carbon atoms in R ¹ and R ² may have not only a linear structure but also a branched structure and a cyclic structure.

Specifically, ethyl group, propyl group, butyl group, pentyl group (amyl group), hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group (lauryl group), tridecyl group, tetra Decyl group (myristyl group), pentadecyl group, hexadecyl group (palmyl group), heptadecyl group (margaryl group), octadecyl group (stearyl group), nonadecyl group, isocyl group (aralkyl group), hen Linear alkyl groups such as an isocyl group, a docosyl group (behenyl group), a tricosyl group, a tetracosyl group (lignoceyl group), pentacosyl group, hexacosyl group, and heptacosyl group; Isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, sec-isoamyl group, isohexyl group, texyl group, 4-methylhexyl group, 5-methylhexyl group, 2-ethylpentyl group, heptane-3-yl group, heptane-4-yl group, 4-methylhexane-2-yl group, 3-methylhexane-3-yl group, 2,3-dimethylpentane-2 -Yl group, 2,4-dimethylpentan-2-yl group, 4,4-dimethylpentan-2-yl group, 6-methylheptyl group, 2-ethylhexyl group, octan-2-yl group, 6-methylheptan-2- Diary, 6-methyloctyl group, 3,5,5-trimethylhexyl group, nonan-4-yl group, 2,6-dimethylheptan-3-yl group, 3,6-dimethylheptan-3-yl group, 3-ethylheptane -3-yl group, 3,7-dimethyloctyl group, 8-methylnonyl group, 3-methylnonan-3-yl group, 4-ethyloctan-4-yl group, 9-methyldecyl group, undecane-5-yl group, 3-ethylnonan-3-yl group, 5-ethylnonan-5-yl group, 2,2,4,5,5-pentamethylhexan-4-yl group, 10-methyl undecyl group, 11-methyldodecyl group, tridecane -6-yl group, tridecane-7-yl group, 7-ethyl undecane-2-yl group, 3-ethyl undecane-3-yl group, 5- Tilundecane-5-yl, 12-methyltridecyl, 13-methyltedecyl, pentadecane-7-yl, pentadecane-8-yl, 14-methylpentadecyl, 15-methylhexadecyl, Heptadecan-8-yl, heptadecan-9-yl, 3,13-dimethylpentadecan-7-yl, 2,2,4,8,10,10-hexamethylundec-5-yl, 16-methyl Heptadecyl, 17-methyloctadecyl, nonadecan-9-yl, nonadecan-10-yl, 2,6,10,14-tetramethylpentadedecane-7-yl, 18-methylnonadecyl, 19 -Methylicosyl group, henicosan-10-yl group, 20-methylhenicosyl group, 21-methyldocosyl group, tricosane-11-yl group, 22-methyltricosyl group, 23-methyltetracosyl group, pentacoic acid-12 -Diary, pentacoic acid-13- diary, 2,22- dimethyl tricoic acid-11- diary, 3,21- dimethyl tricoic acid-11- diary, 9,15- dimethyl tricoic acid-11- yl, 24-methylpenta Branched chain alkyl groups such as a kosyl group, a 25-methylhexacosyl group, and a heptaconic acid-13-yl group; Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 4-tert-butylcyclohexyl group, 1,6-dimethylcyclohexyl group, menthyl group, cycloheptyl group, cyclooctyl group, bicyclo [2.2. 1] heptan-2-yl, carbonyl, isobonyl, 1-adamantyl, 2-adamantyl, tricyclo [5.2.1.0 ^2,6 ] decan-4-yl, tricyclo [5.2.1.0 ^{2 And} alicyclic alkyl groups such as a ^6- decane-8-yl group and a cyclododecyl group.

R ¹ and R ² are each independently, preferably an alkyl group having 4 to 16 carbon atoms, and more preferably an alkyl group having 6 to 10 carbon atoms.

Among these, R ¹ and R ² are each independently preferably a branched alkyl group, more preferably a branched alkyl group having 4 to 16 carbon atoms, still more preferably a branched alkyl group having 6 to 10 carbon atoms. .

Specifically, R ¹ and R ² are each independently hexyl group, heptyl group, octyl group, nonyl group, decyl group, 4-methylhexyl group, 4,4-dimethylpentan-2-yl group, 6-methylheptane It is especially preferable that they are a 2-yl group, a 6-methyl octyl group, a 3,5, 5- trimethylhexyl group, and a 3,7- dimethyl octyl group.

The alkyl group having 1 to 25 carbon atoms in R ³ may have not only a linear structure but also a branched structure and a cyclic structure.

Examples of the alkyl group having 1 to 25 carbon atoms include methyl, ethyl, propyl, butyl, pentyl (amyl), hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl groups Uryl group), tridecyl group, tetradecyl group (myristyl group), pentadecyl group, hexadecyl group (palmityl group), heptadecyl group (margaryl group), octadecyl group (stearyl group), nonadecyl group Linear alkyl groups such as an icosyl group (aralkyl group), a hencosyl group, a docosyl group (behenyl group), a tricosyl group, a tetracosyl group (lignoseryl group), and a pentacosyl group; Isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, sec-isoamyl group, isohexyl group, texyl group, 4-methylhexyl group, 5-methylhexyl group, 2-ethylpentyl group, heptane-3-yl group, heptane-4-yl group, 4-methylhexane-2-yl group, 3-methylhexane-3-yl group, 2,3-dimethylpentane-2 -Yl group, 2,4-dimethylpentan-2-yl group, 4,4-dimethylpentan-2-yl group, 6-methylheptyl group, 2-ethylhexyl group, octan-2-yl group, 6-methylheptan-2- Diary, 6-methyloctyl group, 3,5,5-trimethylhexyl group, nonan-4-yl group, 2,6-dimethylheptan-3-yl group, 3,6-dimethylheptan-3-yl group, 3-ethylheptane -3-yl group, 3,7-dimethyloctyl group, 8-methylnonyl group, 3-methylnonan-3-yl group, 4-ethyloctan-4-yl group, 9-methyldecyl group, undecane-5-yl group, 3-ethylnonan-3-yl group, 5-ethylnonan-5-yl group, 2,2,4,5,5-pentamethylhexan-4-yl group, 10-methyl undecyl group, 11-methyldodecyl group, tridecane -6-yl group, tridecane-7-yl group, 7-ethyl undecane-2-yl group, 3-ethyl undecane-3-yl group, 5- Tilundecane-5-yl, 12-methyltridecyl, 13-methyltedecyl, pentadecane-7-yl, pentadecane-8-yl, 14-methylpentadecyl, 15-methylhexadecyl, Heptadecan-8-yl, heptadecan-9-yl, 3,13-dimethylpentadecan-7-yl, 2,2,4,8,10,10-hexamethylundec-5-yl, 16-methyl Heptadecyl, 17-methyloctadecyl, nonadecan-9-yl, nonadecan-10-yl, 2,6,10,14-tetramethylpentadedecane-7-yl, 18-methylnonadecyl, 19 -Methylicosyl group, henicosan-10-yl group, 20-methylhenicosyl group, 21-methyldocosyl group, tricosane-11-yl group, 22-methyltricosyl group, 23-methyltetracosyl group, pentacoic acid-12 Branched chain alkyl groups, such as a -group, a pentacoic acid- 13- yl group, a 2,22- dimethyl tricosic acid 11- yl group, a 3,21- dimethyl tricosic acid 11- yl group, and a 9,15- dimethyl tricoic acid 11- yl group ; Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 4-tert-butylcyclohexyl group, 1,6-dimethylcyclohexyl group, menthyl group, cycloheptyl group, cyclooctyl group, bicyclo [2.2. 1] heptan-2-yl, carbonyl, isobonyl, 1-adamantyl, 2-adamantyl, tricyclo [5.2.1.0 ^2,6 ] decan-4-yl, tricyclo [5.2.1.0 ^{2 And} alicyclic alkyl groups such as a ^6- decane-8-yl group and a cyclododecyl group.

Among these, R ³ is preferably a hydrogen atom.

The group having R ¹ , R ² and R ³ : -CR ¹ R ² R ³ group, the sum of the number of carbon atoms contained in this group is 10 to 30, preferably -CR ¹ R ² R ³ group is the number of carbon atoms It is group of 14-26, Especially preferably, it is group of 14-20 carbon atoms.

Specific examples of the -CR ¹ R ² R ³ group include 3-methylnonan-3-yl group, 4-ethyloctan-4-yl group, undecane-5-yl group, 3-ethylnonan-3-yl group, 5 -Ethylnonan-5-yl group, 2,2,4,5,5-pentamethylhexan-4-yl group, tridecane-6-yl group, tridecane-7-yl group, 7-ethyl undecane-2-yl group, 3-ethylundecane-3-yl, 5-ethylundecane-5-yl, pentadecane-7-yl, pentadecane-8-yl, heptadecan-7-yl, heptadecan-8-yl, heptadecane -9- diary, 3, 13- dimethylpentadecane-7- diary, 2, 2, 4, 8, 10, 10- hexamethyl undecane-5- diary, nonadecan-9- diary, nonadecan-10- Diary, 2,6,10,14-tetramethylpentadecan-7-diary, henicosan-10-diary, trichoic acid-11-diary, pentacoic acid-12-diary, pentacoic acid-13-diary, 2, 22-dimethyltricoic acid-11-yl group, 3,21-dimethyltricoic acid-11-yl group, 9,15-dimethyltricoic acid-11-yl group, heptacoic acid-13-yl group, nonacosan-14-yl group, etc. Can be mentioned.

Examples of the alkyl group having 1 to 10 carbon atoms in R ⁴ to R ⁶ include methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, pentyl group (amyl group), isopentyl group, neopentyl group, tert-pentyl group, sec-isoamyl group, cyclopentyl group, hexyl group, isohexyl group, cyclohexyl group, Heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, etc. are mentioned.

Among these, as a suitable R <^4> -R <^6> , a hydrogen atom is mentioned.

X represents * -C (= O) O-, * -CH ₂ O- or * -CH ₂ OC (= O)-, wherein X is * -CH ₂ O- and n is an integer of from 2 to 8, or, wherein X is * -C (= O) O- or _{* -CH 2 OC (= O)} - is preferably a.

It is preferable that especially said X is * -C (= O) O-.

As an aliphatic hydrocarbon group which may contain the (n + 1) valent ether bond in said A, it is the said C2-C27 alkyl group, the C1-C25 alkyl group, or C1-C1 carbon atom, for example. From the alkyl group of 10, the (n + 1) valence group derived by further removing (n) hydrogen atoms is mentioned. Moreover, these groups may contain the ether bond (-O-) between arbitrary carbon-carbon bonds.

Specifically, for example, glycerin, 2-hydroxy-1,4-butanediol, trimethylolmethane, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, ditrimethylolpropane, (N + 1) valent groups derived by removing some or all of the hydroxy groups from a polyol structure selected from the group consisting of pentaerythritol and dipentaerythritol. Among these, as said polyol, the polyol selected from the group which consists of 1,1,1- trimethylol propane and pentaerythritol is mentioned, Moreover, group derived by removing all the hydroxyl groups from the said polyol structure is mentioned. .

Moreover, when said A is an aliphatic hydrocarbon group which may contain the (n + 1) valent ether bond, it is preferable that n is an integer of 2-8.

On the other hand, when A represents a single bond, Z represents a single bond, and n represents 1.

Examples of the alkylene group having 1 to 8 carbon atoms which may include the ether bond in L include methylene group, ethylene group, trimethylene group, methylethylene group, tetramethylene group, 1-methyltrimethylene group and penta. Methylene group, 2,2-dimethyltrimethylene group, hexamethylene group, heptamethylene group, octamethylene group, 2-oxatetramethylene group, 2,5-dioxaheptamethylene group, 2,5,8-trioxadeca Methylene group, 2-oxa-3-methyltetramethylene group, 2,5-dioxa-3,6-dimethylheptamethylene group, etc. are mentioned.

As said L, Preferably a methylene group, trimethylene group, hexamethylene group, 2-oxa tetramethylene group, More preferably, a methylene group is mentioned.

The procedure for producing the epoxy compound represented by the formula [2] from the olefin compound represented by the formula [1] is not particularly limited. For example, the olefin compound, the hydrogen peroxide, the nitrile compound and the alkaline substance are collectively added to the solvent. And react. In addition, after adding components other than hydrogen peroxide to a solvent, hydrogen peroxide may be dripped here, and you may react after that.

The amount of hydrogen peroxide used in the reaction for obtaining the epoxy compound represented by the formula [2] from the olefin compound represented by the formula [1] is 0.5 to 50 equivalents, or 1 equivalent of the double bond in the olefin compound. 0.5 to 30 equivalents, or 1 to 10 equivalents. Hydrogen peroxide can be added to the reaction system, for example, as 35 mass% hydrogen peroxide.

Although addition of hydrogen peroxide can also be added at once, the method of dividing a predetermined addition amount into several times (for example, about 2-5 times), and adding sequentially can be used. The addition of hydrogen peroxide can preferably be performed by the dropping method, and in this case, one dropping (addition) can be performed over 1 to 24 hours. And after completion | finish of addition (dropping), reaction for 1 to 24 hours can be performed.

After this addition (dropping), the combination (dropping and reaction) which performs a reaction is repeated several times (for example, about 2 to 5 times), and the yield of reaction from an olefin to an epoxy group can be improved.

As a nitrile compound used at the time of obtaining an epoxy compound from the said olefin compound, an aliphatic nitrile and an aromatic nitrile are mentioned. Examples of the aromatic nitriles include benzonitrile and the like, and examples of the aliphatic nitriles include acetonitrile and propionitrile. Especially aliphatic nitrile is preferable and acetonitrile is used preferably. The usage-amount of a nitrile compound is 0.5-50 equivalent, 1-30 equivalent, or 3-15 equivalent with respect to 1 equivalent of the double bond in an olefin compound.

As an alkaline substance used at the time of reaction which obtains an epoxy compound from the said olefin compound, a phosphoric acid type compound, a carbonate type compound, an alkali metal hydroxide, etc. are mentioned.

Examples of the phosphoric acid compound include phosphoric acid, pyrroline acid, polyphosphoric acid, and salts thereof.

Examples of the carbonate compound include sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium bicarbonate and the like.

Examples of the alkali metal hydroxides include sodium hydroxide and potassium hydroxide.

Among these, in particular, phosphates, carbonates, or alkali metal hydroxides can be preferably used, and as the phosphate, sodium phosphate, potassium phosphate, ammonium phosphate, and the like, as the carbonate, sodium carbonate, sodium hydrogen carbonate and the like, and the alkali Examples of the metal hydroxides may include sodium hydroxide. More preferably, it is alkali metal hydroxide, and sodium hydroxide is further more preferable.

The addition amount of these alkaline substances is 0.01-10 equivalent or 0.01-2 equivalent with respect to 1 equivalent of double bond in an olefin compound.

On the other hand, the liquidity of the reaction liquid at the time of the said reaction becomes like this. Preferably it is pH 9-11, More preferably, it is pH 9.2-10.5, and it is preferable to add the said alkaline substance so that pH may become this range.

Alcohol solvent is used for the solvent used at the time of reaction which obtains an epoxy compound from the said olefin compound. As this alcohol solvent, linear, branched, cyclic alcohols such as methanol, ethanol, 2-propanol, n-butanol, tert-amyl alcohol and cyclohexanol are used. In particular, methanol can be used preferably. Moreover, you may mix non-alcoholic solvents, such as toluene, with this alcohol solvent.

Reaction which obtains an epoxy compound from the said olefin compound can be performed in 5 to 60 degreeC for 2 to 48 hours (including time to add hydrogen peroxide), for example.

After the completion of the reaction, the reaction solution containing the reaction mixture is subjected to a known purification operation, for example, a solvent such as heptane, to separate the organic layer, and then to the obtained organic layer, aqueous sodium thiosulfate solution, aqueous ammonium sulfate solution, and the like. After adding and washing an organic layer, a solvent is distilled off and an epoxy compound can be obtained.

The conversion from olefins to epoxy groups by the production process of the invention is obtained at 60% or more, for example 75% or more, or 90% or more.

<Olefin compound represented by Formula [1]>

The olefin compound represented by the formula [1] is a compound (intermediate) having a unsaturated bond as described in the prior art (for example, disclosed in International Publication No. 2012/128325, etc.), using carboxylic acids or alcohols as starting materials. Manufacturing method).

For example, in the case of an ester compound in which X represents a * -C (= O) O- group, as an example, a branched fatty acid or an activator thereof including an -CR ¹ R ² R ³ group (an acid halide, an acid anhydride, Acid azide, active esters, etc.), unsaturated alcohols such as allyl alcohol, or unsaturated halides such as allyl halide, whereby X represents a * -C (= O) O- group in formula [1]. Can be obtained.

In addition, in the case of an ether compound in which X represents a * -CH ₂ O- group, for example, a branched alcohol containing a -CR ¹ R ² R ³ group and an unsaturated halide are reacted to form X in formula [1]. it is possible to obtain an ether compound represented group * -CH ₂ O-.

The -CR ¹ R ² R ³ -CR branched fatty acids and branched alcohols containing an ¹ R ² R ³ comprises a group may be used a commercially available product.

For example, as a branched fatty acid containing the said -CR <^1> R <^2> R <^3> group, the fine oxocol (trademark) isopalmitic acid, the isostearic acid, and the isostearic acid manufactured by Nissan Chemical Industries, Ltd. N, copper isostearic acid T, copper isoarachinic acid, etc. can be mentioned, and also the activator (derivative) of these branched fatty acids can be used.

As branched alcohol containing the said -CR <^1> R <^2> R <^3> group, Pineoxocol (trademark) 1600, copper 180, copper 180N, copper 180T, copper 2000 etc. by Nissan Chemical Industries, Ltd. are mentioned.

Examples of the unsaturated alcohols include allyl alcohol, glycerin monoallyl ether, glycerin diallyl ether, 2,4-diallyloxybutanol, 3,4-diallyloxybutanol, and 1,4-diallyloxy-2. Butanol, trimethylol methane monoallyl ether, trimethylol methane diallyl ether, 1,1,1-trimethylol ethane monoallyl ether, 1,1,1-trimethylol ethanediallyl ether, 1,1,1-trimethyl All propane monoallyl ether, 1,1,1-trimethylol propane diallyl ether, ditrimethylol propane monoallyl ether, ditrimethylol propane diallyl ether, ditrimethylol propane triallyl ether, pentaerythritol monoallyl ether, penta Erythritol diallyl ether, pentaerythritol triallyl ether, dipentaerythritol monoallyl ether, dipentaerythritol diallyl ether, dipentaerythritol triallyl ether, dipentaerythritol tetraallyl ether, dipentaerythritol The other may be an allyl ether.

Moreover, as said unsaturated halide, allyl halides, such as allyl chloride, allyl bromide, and allyl iodide, for example, 2, 2-bis (allyloxymethyl) -1-bromobutane, 1,1,1-tris (Allyloxymethyl) -2-bromoethane etc. are mentioned.

A commercial item can be used for these unsaturated alcohols and unsaturated halides.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

In addition, in the Example, the apparatus and conditions used for preparation of a sample and the analysis of a physical property are as follows.

(1) ¹ H NMR spectrum (300MHz)

Device: JNM-ECP300 made by JEOL RESONANCE

Reference: Tetramethylsilane (0.00 ppm)

(2) ¹ H NMR spectrum (400 MHz)

Device: INOVA-400 made by Varian

Reference: Tetramethylsilane (0.00 ppm)

(3) GC-MS (gas chromatograph mass spectrometry)

Device: GCMS-QP2010 Ultra manufactured by Shimadzu Corporation

Column: Agilent J & W GC Column HP-5 (30m long, 0.32mm inner diameter, 0.25μm thick)

Injection volume: 2.0 μL

Inlet temperature: 250 ℃

Column temperature: 40 ° C. (5 minutes), 20 ° C./min to 300 ° C., 300 ° C. (12 minutes)

(4) GC (gas chromatograph)

<System A> (Example 1, Comparative Example 1)

Equipment: GC-2010 Plus manufactured by Shimadzu Corporation

Detector: FID

Column: Agilent J & W GC Column HP-1 (30 m long, 0.32 mm inner diameter, 0.25 μm thick)

Injection volume: 2.0 μL

Inlet temperature: 200 ℃

Column temperature: 200 ° C. (5 minutes), 5 ° C./min to 300 ° C., 300 ° C. (5 minutes)

<System B> (Example 2)

Device: Agilent 7890A GC System from Agilent Technologies, Inc.

Detector: FID

Column: Agilent J & W GC Column HP-5 (30m long, 0.32mm inner diameter, 0.25μm thick)

Injection volume: 2.0 μL

Inlet temperature: 250 ℃

Column temperature: 40 ° C. (5 minutes), 20 ° C./min to 300 ° C., 300 ° C. (12 minutes)

(5) epoxy equivalent

Equipment: Potentiometer automatic titrator AT-710 manufactured by Kyoto Electronics Co., Ltd.

Electrode: Composite Glass Electrode C-173 manufactured by Kyoto Electronics Co., Ltd.

(6) light transmittance

Device: UV-visible infrared spectrophotometer UV-3600 Plus manufactured by Shimadzu Corporation

In addition, a symbol shows the following meanings.

ISA: 2- (4,4-dimethylpentan-2-yl) -5,7,7-trimethyloctanoic acid [Fineoxocol (registered trademark) isostearic acid manufactured by Nissan Chemical Industries, Ltd.]

ISOL: 2- (4,4-dimethylpentan-2-yl) -5,7,7-trimethyloctan-1-ol [fine oxocol (registered trademark) 180 manufactured by Nissan Chemical Industries, Ltd.]

AllBr: allyl bromide (manufactured by Tokyo Chemical Industries, Ltd.)

TMPDA: trimethylolpropanediallyl ether [neoallyl T-20 made by Osaka soda Co., Ltd.]

DMF: N, N-dimethylformamide

NMP: N-methyl-2-pyrrolidone

THF: tetrahydrofuran

Preparation Example 1 Preparation of 2- (4,4-dimethylpentan-2-yl) -5,7,7-trimethyloctanoic acid 2,2-bis (allyloxymethyl) butyl (ISA2A)

Into the reactor, 24.0 kg (84.4 mol) of ISA, 0.185 kg of DMF, and 24 kg of toluene were added. 10.5 kg (88.6 mol) of thionyl chlorides were dripped at this solution over 45 minutes at room temperature (about 23 degreeC), and also it stirred for 2 hours. After adding 24 kg of toluene to this reaction mixture, 24 kg of excess thionyl chloride, a solvent, etc. were combined and distilled away. Again, 24 kg of toluene was added and 24 kg was distilled off similarly to the above.

To the obtained solution, 48 kg of toluene and 12.0 kg (152 mol) of pyridine were added. 18.1 kg (84.4 mol) of TMPDA distilled and purified previously was dripped at this solution over 1 hour at room temperature (about 23 degreeC), and it stirred for 12 hours again. The reaction solution was washed with 48.0 kg of 1N hydrochloric acid, 36.0 kg of 5 mass% aqueous sodium hydroxide solution, and ion-exchanged water. The solvent of this organic layer was distilled off, and 40.5 kg of 2- (4,4- dimethylpentan-2-yl) -5,7,7-trimethyloctanoic acid 2,2-bis (allyloxymethyl) butyl (ISA2A) were colorless. Obtained as a transparent liquid.

¹ H NMR (300MHz, CDCl ₃ ): δ = 6.0 ~ 5.8 (m, 2H), 5.3 ~ 5.1 (m, 4H), 4.1 ~ 3.9 (m, 6H), 3.4 ~ 3.2 (s, 4H), 2.2 ~ 0.8 (m, 40H) (ppm)

GC-MS (CI): m / z = 481 (M + 1)

Preparation Example 2 Preparation of 2- (4,4-dimethylpentan-2-yl) -5,7,7-trimethyloctyl = allyl = ether (IS1AE)

6.45 g (0.15 mol as NaH) of 55 mass% sodium hydride [manufactured by Kanto Chemical Co., Ltd.] and 80 g of THF were added to the reaction flask. ISOL 40.0g (0.15mol) was dripped here over 10 minutes, and it heated up at 70 degreeC after that. 21.4 g (0.18 mol) of AllBr was dripped at this solution over 10 minutes, and also it stirred for 3 hours. 120 g of toluene and 40 g of ion-exchange water were added to this reaction mixture, and the organic layer was separated. 120 g of toluene was added to this organic layer, and after wash | cleaning with 40 g of ion-exchange water, the solvent was distilled off. The obtained residue was purified by silica gel chromatography (hexane: ethyl acetate = 98: 2 (volume ratio)) to thereby give 2- (4,4-dimethylpentan-2-yl) -5,7,7-trimethyloctyl = allyl = 35.7 g of ether (IS1AE) was obtained as a pale yellow transparent liquid.

¹ H NMR (300 MHz, CDCl ₃ ): δ = 6.0 to 5.8 (m, 1H), 5.3 (d, J = 17.1 Hz, 1H), 5.2 (d, J = 10.5 Hz, 1H), 4.0 to 3.9 (m , 2H), 3.4 ~ 3.2 (m, 2H), 2.2 ~ 0.8 (m, 35H) (ppm)

GC-MS (CI): m / z = 311 (M + 1)

Example 1 Preparation of 2- (4,4-dimethylpentan-2-yl) -5,7,7-trimethyloctanoic acid 2,2-bis (glycidyloxymethyl) butyl (ISA2G)

[Formula 5]

Into the reaction flask, 8.00 g (16.6 mmol) of ISA2A, 9.60 g (234 mmol) of acetonitrile, and 80 g of methanol were prepared. The liquidity of this solution was adjusted to pH9.5 with 8 mass% sodium hydroxide aqueous solution, and it heated up at 40 degreeC after that. While maintaining the liquidity of this solution at pH9.5 in an 8 mass% sodium hydroxide aqueous solution, 12.9 g of 35 mass% hydrogen peroxide water (133 mmol as H ₂ O ₂ ) was added dropwise over 16 hours, followed by stirring for 11 hours. The total used amount of the 8 mass% sodium hydroxide aqueous solution was 17.2 g. From the GC quantitative analysis of the reaction solution, the consumption rate of the olefin compound (ISA2A) (= (injection amount-residual amount) ÷ input amount x 100) was 97%.

16 g of heptane was added to the reaction mixture, and the organic layer was separated. The organic layer was washed with 16 g of 5 mass% sodium thiosulfate aqueous solution and 16 g of 2 mass% ammonium sulfate aqueous solution, and then the solvent was distilled off to remove 2- (4,4-dimethylpentan-2-yl) -5,7,7-. 6.71 g (89% epoxy purity, 79% yield) of trimethyloctanoic acid 2,2-bis (glycidyloxymethyl) butyl (ISA2G) were obtained as a colorless transparent liquid. On the other hand, epoxy purity was calculated as epoxy purity [%] = epoxy equivalent (measured value) ÷ epoxy equivalent (theoretical value) x 100 from the epoxy equivalent measured according to JIS K7236: 2009.

Moreover, the light transmittance of wavelength 400nm of the obtained epoxy compound (ISA2G) was 96.8%.

¹ H NMR (300MHz, CDCl ₃ ): δ = 4.0 (m, 2H), 3.7 (m, 2H), 3.5 ~ 3.3 (m, 6H), 3.1 (m, 2H), 2.8 (m, 2H), 2.6 (m, 2H), 1.8 to 0.8 (m, 40H) (ppm)

GC-MS (CI): m / z = 513 (M + 1)

Example 2 Preparation of 2- (4,4-dimethylpentan-2-yl) -5,7,7-trimethyloctyl = glycidyl = ether (IS1GE)

[Formula 6]

4.00 g (12.9 mmol) of IS1AE, 4.80 g (117 mmol) of acetonitrile, and 40 g of methanol were added to the reaction flask. The liquidity of this solution was adjusted to pH9.5 with 8 mass% sodium hydroxide aqueous solution, and it heated up at 40 degreeC after that. While maintaining the liquidity of this solution at pH9.5 in an 8 mass% aqueous sodium hydroxide solution, 5.01 g of 35 mass% hydrogen peroxide solution (51.6 mmol as H ₂ O ₂ ) was added dropwise over 16 hours, followed by further stirring for 15 hours. The total used amount of the 8 mass% sodium hydroxide aqueous solution was 6.5 g. From the GC quantitative analysis of the reaction solution, the consumption rate of the olefin compound (IS1AE) was 92%. This reaction mixture was worked up in the same manner as in Example 1 to obtain 2- (4,4-dimethylpentan-2-yl) -5,7,7-trimethyloctyl = glycidyl = ether (IS1GE).

¹ H NMR (400 MHz, CDCl ₃ ): δ = 3.67 to 3.64 (m, 1H), 3.41 to 3.23 (m, 3H), 3.13 (m, 1H), 2.80 to 2.77 (m, 1H), 2.61 to 2.59 ( m, 1H), 1.80-0.82 (m, 35H) (ppm)

GC-MS (CI): m / z = 327 (M + 1)

Comparative Example 1 Preparation of 2- (4,4-dimethylpentan-2-yl) -5,7,7-trimethyloctanoic acid 2,2-bis (glycidyloxymethyl) butyl (ISA2G)

35.0 kg (72.8 mol) of ISA2A and sodium tungstate dihydrate [made by Wako Pure Chemical Industries, Ltd. (current Fujifilm Wako Pure Chemical Industries, Ltd.)] in the reactor, 3.84 kg (11.6 mol), J 2.79 kg (5.81 mol) of methyl methyl sulfate (trioctyl) ammonium (phase transfer catalyst) prepared according to .Org.Chem., 61,8310 (1996), 14.3 kg of 10 mass% aqueous solution of phosphate, and 35 kg of toluene were added thereto. It heated up at 55 degreeC. To the solution, it is added dropwise over a 35 mass% hydrogen peroxide 21.2kg (218mol as H ₂ O ₂₎ to 8 hours, and the resulting mixture was stirred for 16 hours. From the GC quantitative analysis of the reaction solution, the consumption rate of the olefin compound (ISA2A) was 97%.

Toluene 35 kg was added to the reaction mixture, the mixture was stirred, and the organic layer was separated. The organic layer was washed with 35 kg of 5 mass% sodium thiosulfate aqueous solution. After removing the catalyst (tungstic acid catalyst and phase transfer catalyst) remaining in the solution by adsorbent treatment, the solvent is distilled off, and 2- (4,4-dimethylpentan-2-yl) -5,7,7- 23.6 kg of trimethyloctanoic acid 2,2-bis (glycidyloxymethyl) butyl (ISA2G) (90% epoxy purity, 63% yield) were obtained as a colorless transparent liquid.

In addition, the light transmittance of wavelength 400nm of the obtained epoxy compound (ISA2G) was 91.2%.

As mentioned above, according to the manufacturing method of this invention, it was confirmed that an epoxy compound is obtained by a high yield near 80%, and the epoxy compound with a high light transmittance (little coloring) is obtained by simple post-processing.

Claims (12)

A method for producing an epoxy compound represented by formula [2], wherein the olefin compound, hydrogen peroxide, nitrile compound, and alkaline substance represented by formula [1] are reacted in a solvent.
[Formula 1]

(Wherein R ¹ and R ² each independently represent an alkyl group having 2 to 27 carbon atoms, R ³ represents a hydrogen atom or an alkyl group having 1 to 25 carbon atoms, provided that they are included in the group -CR ¹ R ² R ³ ) The sum of the number of carbon atoms to be used is 10 to 30, R ⁴ to R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X represents * -C (= O) O-, *- CH ₂ O— or * —CH ₂ OC (═O) —, where * represents a group which binds to a —CR ¹ R ² R ³ group, and A is a single bond or a (n + 1) valent ether An aliphatic hydrocarbon group which may contain a bond, Z represents a single bond or an oxygen atom, provided that when A represents a single bond, Z represents a single bond, and L represents a carbon atom that may contain an ether bond 1 N represents an alkylene group of 8 to 8, n represents an integer of 1 to 8, provided that n represents 1 when A represents a single bond. Indicates.)
[Formula 2]

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , X, A, Z, L and n represent the same meanings as above). The method of claim 1,
And said X is * -CH ₂ O- and n is an integer of 2 to 8, or said X is * -C (= 0) O- or * -CH ₂ OC (= 0). The method according to claim 1 or 2,
Wherein X is * -C (= 0) O-. The method according to any one of claims 1 to 3,
The said A is the aliphatic hydrocarbon group which may contain the (n + 1) valent ether bond, and said n is an integer of 2-8. The method of claim 4, wherein
A is glycerin, 2-hydroxy-1,4-butanediol, trimethylolmethane, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, ditrimethylolpropane, pentaerythritol, and A method for producing a compound obtained by removing part or all of hydroxyl groups from a polyol selected from the group consisting of dipentaerythritol. The method of claim 5,
The polyol is a polyol selected from the group consisting of 1,1,1-trimethylolpropane and pentaerythritol. The method according to claim 5 or 6,
The said A is a group derived from the removal of all the hydroxyl groups from the said polyol. The method according to any one of claims 1 to 7,
L is a methylene group. The method according to any one of claims 1 to 8,
The -CR ¹ R ² R ³ group is a group having 14 to 26 carbon atoms, the production method. The method according to any one of claims 1 to 9,
The alkaline substance is an alkali metal hydroxide. The method according to any one of claims 1 to 10,
And the solvent is an alcohol. The method according to any one of claims 1 to 11,
The formula is a compound represented by ^{[1], -CR 1 R 2} R 3 and branched alcohols containing branched fatty acid or its active material, or -CR ¹ R ² R ³ groups, including groups, and the unsaturated alcohol or an unsaturated halide The reaction product of, the production method.