CN110662740A - Method for producing epoxy compound - Google Patents
Method for producing epoxy compound Download PDFInfo
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- CN110662740A CN110662740A CN201880030437.6A CN201880030437A CN110662740A CN 110662740 A CN110662740 A CN 110662740A CN 201880030437 A CN201880030437 A CN 201880030437A CN 110662740 A CN110662740 A CN 110662740A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/44—Esterified with oxirane-containing hydroxy compounds
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a method for producing a high-quality epoxy compound suitable for industrial production, which is free from coloring and has high yield without complicated post-treatment. Formula [2]]The method for producing the epoxy compound is characterized in that the compound represented by the formula [1]]The olefin compound, hydrogen peroxide, nitrile compound and alkaline substance are reacted in a solvent. [ formula 1](in the formula, R1And R2Each independently represents an alkyl group having 2 to 27 carbon atoms, R3Represents a hydrogen atom or an alkyl group having 1 to 25 carbon atoms, wherein-CR1R2R3The total number of carbon atoms contained in the group is 10 to 30, R4To R6Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X represents-C (═ O) O-, -CH2O-or-CH2OC (═ O) - (here, indicates bonding at-CR1R2R3Terminal of group), A represents a single bond or an aliphatic hydrocarbon group which may contain an (n +1) -valent ether bond, Z represents a single bond or an oxygen atom, wherein, when A represents a single bond, Z represents a single bond, L represents an alkylene group having 1 to 8 carbon atoms which may contain an ether bond, and n represents an integer of 1 to 8, wherein, when A represents a single bond, n represents 1).
Description
Technical Field
The present invention relates to a novel method for producing an epoxy compound.
Background
Conventionally, as a method for producing an epoxy compound, a method of epoxidizing an olefin compound using hydrogen peroxide as an oxidizing agent and a three-way catalyst containing a tungstate or a molybdate, a quaternary ammonium salt, and a phosphate or a phosphonate as a catalyst has been known (for example, patent document 1). Further, a method of epoxidizing an olefin compound in an aqueous pyrophosphate-pyrophosphoric acid solution in the presence of a nitrile compound using hydrogen peroxide as an oxidizing agent is known (for example, patent document 2).
[ background Art document ]
[ patent document ]
[ patent document 1] Japanese patent laid-open No. 2012 and 25688
[ patent document 2] Japanese patent application laid-open No. 2002-145872
Disclosure of Invention
[ problems to be solved by the invention ]
However, in the method described in patent document 1, it is necessary to remove the catalyst (tungstate, molybdate, quaternary ammonium salt, etc.) remaining in the reaction mixture. Therefore, the production process becomes complicated by the post-treatment using an adsorbent or the like, and the reduction in yield becomes a problem. In addition, since the reaction conditions such as a high reaction temperature are generally severe, there is a problem that the obtained epoxy compound is colored.
On the other hand, patent document 2 does not disclose any application of an olefin compound having a specific branched aliphatic group.
The present invention aims to provide a method for producing a high-quality epoxy compound suitable for industrial production, which is free from coloration and has high yield without requiring complicated post-treatment.
[ means for solving problems ]
As a result of diligent research directed toward solving the above problems, the present inventors have found that an epoxy compound obtained by partially epoxidizing an olefin can be obtained in a high yield by reacting an olefin compound in a solvent containing hydrogen peroxide, a nitrile compound and a basic substance, and that an epoxy compound with little coloration can be obtained by a simple post-treatment, thereby completing the present invention.
That is, the present invention relates to a method for producing an epoxy compound represented by the formula [2] as the 1 st aspect, wherein an olefin compound represented by the formula [1], hydrogen peroxide, a nitrile compound, and a basic substance are reacted in a solvent.
[ solution 1]
(in the formula, R1And R2Each independently represents an alkyl group having 2 to 27 carbon atoms, R3Represents a hydrogen atom or an alkyl group having 1 to 25 carbon atoms, wherein-CR1R2R3The total number of carbon atoms contained in the group is 10 to 30, R4To R6Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X represents-C (═ O) O-, -CH2O-or-CH2OC (═ O) - (here, indicates bonding at-CR1R2R3Terminal of group), A represents a single bond or an aliphatic hydrocarbon group which may contain an (n +1) -valent ether bond, Z represents a single bond or an oxygen atom, wherein, when A represents a single bond, Z represents a single bond, L represents an alkylene group having 1 to 8 carbon atoms which may contain an ether bond, and n represents an integer of 1 to 8, wherein, when A represents a single bond, n represents 1).
[ solution 2]
(in the formula, R1、R2、R3、R4、R5、R6X, A, Z, L and n are as defined above. )
As a2 nd aspect, the present invention relates to the production process as described in the 1 st aspect, wherein X is-CH2O-and said n is an integer from 2 to 8, or said X is-C (═ O) O-or-CH2OC(＝O)。
The 3 rd aspect relates to the production method as described in the 1 st or 2 nd aspect, wherein X is — C (═ O) O-.
The 4 th aspect relates to the production method according to any one of the 1 st to 3 rd aspects, wherein A is an aliphatic hydrocarbon group which may contain an (n +1) -valent ether bond, and n is an integer of 2 to 8.
The 5 th aspect of the present invention relates to the production method according to the 4 th aspect of the present invention, wherein the a is a group derived by removing a part or all of hydroxyl groups from a polyhydric alcohol selected from the group consisting of glycerol, 2-hydroxy-1, 4-butanediol, trimethylolmethane, 1,1, 1-trimethylolethane, 1,1, 1-trimethylolpropane, ditrimethylolpropane, pentaerythritol and dipentaerythritol.
The 6 th aspect relates to the production method according to the 5 th aspect, wherein the polyol is a polyol selected from the group consisting of 1,1, 1-trimethylolpropane and pentaerythritol.
The 7 th aspect relates to the production method as described in the 5 th or 6 th aspect, wherein A is a group derived by removing all hydroxyl groups from the polyol.
The 8 th aspect relates to the production method according to any one of the 1 st to 7 th aspects, wherein L is a methylene group.
The 9 th aspect of the present invention relates to the production method according to any one of the 1 st to 8 th aspects, wherein the-CR1R2R3The radical is a radical having 14 to 26 carbon atoms.
The 10 th aspect relates to the production method according to any one of the 1 st to 9 th aspects, wherein the basic substance is an alkali metal hydroxide.
The 11 th aspect relates to the production method according to any one of the 1 st to 10 th aspects, wherein the solvent is an alcohol.
As a 12 th aspect, there is provided the production method as described in any one of the 1 st to 11 th aspects, wherein the formula [1]]The compound represented by is a compound containing-CR1R2R3Branched fatty acids of radicals or activators thereof or containing-CR1R2R3Reaction products of branched alcohols of the radicals with unsaturated alcohols or unsaturated halides.
[ Effect of the invention ]
According to the production method of the present invention, an epoxy compound can be obtained at a high yield of approximately 80%, and an epoxy compound having a high light transmittance (less coloring) can be produced by a simple post-treatment.
Detailed Description
Method for producing epoxy compound represented by the formula [2]
The present invention is directed to a process for producing an epoxy compound represented by the formula [2], wherein the process for producing an epoxy compound represented by the formula [2] is characterized by reacting an olefin compound represented by the following formula [1], hydrogen peroxide, a nitrile compound and a basic substance in a solvent.
[ solution 3]
(in the formula, R1And R2Each independently represents an alkyl group having 2 to 27 carbon atoms, R3Represents a hydrogen atom or an alkyl group having 1 to 25 carbon atoms, wherein-CR1R2R3The total number of carbon atoms contained in the group is 10 to 30, R4To R6Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X represents-C (═ O) O-, -CH2O-or-CH2OC (═ O) - (here, indicates bonding at-CR1R2R3Terminal group), A represents a single bond or an aliphatic hydrocarbon group which may contain an (n +1) -valent ether bond, and Z represents a single bond or an oxygen atom, wherein A representsWherein Z represents a single bond, L represents an alkylene group having 1 to 8 carbon atoms which may contain an ether bond, and n represents an integer of 1 to 8, wherein when A represents a single bond, n represents 1).
[ solution 4]
(in the formula, R1、R2、R3、R4、R5、R6X, A, Z, L and n are as defined above. )
As said R1And R2The alkyl group having 2 to 27 carbon atoms in (A) may have not only a linear structure but also a branched structure or a cyclic structure.
Specifically, there may be mentioned: linear alkyl groups such as ethyl, propyl, butyl, pentyl (amyl), hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl (myristyl), pentadecyl, hexadecyl (palmityl), heptadecyl (pearlidyl), octadecyl (stearyl), nonadecyl, eicosyl (arachidyl), heneicosyl, docosyl (behenyl), tricosyl, tetracosyl (lignoceryl), pentacosyl, hexacosyl, and heptacosyl; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, sec-isopentyl group, isohexyl group, 1, 2-trimethylpropyl group (thexyl), 4-methylhexyl group, 5-methylhexyl group, 2-ethylpentyl group, heptan-3-yl group, heptan-4-yl group, 4-methylhexan-2-yl group, 3-methylhexan-3-yl group, 2, 3-dimethylpentan-2-yl group, 2, 4-dimethylpentan-2-yl group, 4-dimethylpentan-2-yl group, 6-methylheptyl group, 2-ethylhexyl group, octan-2-yl group, 6-methylheptan-2-yl group, 6-methyloctyl group, 3,5, 5-trimethylhexyl group, Nonan-4-yl, 2, 6-dimethylheptan-3-yl, 3-ethylheptan-3-yl, 3, 7-dimethyloctyl, 8-methylnonyl, 3-methylnonan-3-yl, 4-ethyloctan-4-yl, 9-methyldecyl, undecan-5-yl, 3-ethylnonan-3-yl, 5-ethylnonan-5-yl, 2,4,5, 5-pentamethylhexan-4-yl, 10-methylhexan-4-ylUndecyl, 11-methyldodecyl, tridec-6-yl, tridec-7-yl, 7-ethylundecyl-2-yl, 3-ethylundecyl-3-yl, 5-ethylundecyl-5-yl, 12-methyltridecyl, 13-methyltetradecyl, pentadecyl-7-yl, pentadecyl-8-yl, 14-methylpentadecyl, 15-methylhexadecyl, heptadecyl-8-yl, heptadecyl-9-yl, 3, 13-dimethylpentadecyl-7-yl, 2,4,8,10, 10-hexamethylundec-5-yl, 16-methylheptadecyl, 17-methyloctadecyl, tert-decyl, tert-butyl, nonadecan-9-yl, nonadecan-10-yl, 2,6,10, 14-tetramethylpentadecan-7-yl, 18-methylnonadecanyl, 19-methyleicosyl, eicos-10-yl, 20-methylheneicosyl, 21-methyldocosyl, tricosyl-11-yl, 22-methyltricosyl, 23-methyltetracosyl, pentacosyl-12-yl, pentacosyl-13-yl, 2, 22-dimethyltricosyl-11-yl, 3, 21-dimethyltricosyl-11-yl, 9, 15-dimethyltricosyl-11-yl, 24-methylpentacosyl, 25-methylhexadecyl, a branched alkyl group such as heptacosan-13-yl group; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-tert-butylcyclohexyl, 1, 6-dimethylcyclohexyl, menthyl, cycloheptyl, cyclooctyl, bicyclo [2.2.1]Heptane-2-yl, bornyl, isobornyl, 1-adamantyl, 2-adamantyl, tricyclo [5.2.1.02,6]Decan-4-yl, tricyclo [5.2.1.02,6]An alicyclic alkyl group such as a decan-8-yl group and a cyclododecyl group.
The R is1And R2Each independently is preferably an alkyl group having 4 to 16 carbon atoms, and more preferably an alkyl group having 6 to 10 carbon atoms.
Wherein R is1And R2Each independently is preferably a branched alkyl group, more preferably a branched alkyl group having 4 to 16 carbon atoms, and still more preferably a branched alkyl group having 6 to 10 carbon atoms.
In particular, R1And R2Particular preference is given, independently of one another, to hexyl, heptyl, octyl, nonyl, decyl, 4-methylhexyl, 4-dimethylpentan-2-yl, 6-methylheptan-2-yl, 6-methyloctyl, 3,5, 5-trimethylhexyl, 3, 7-dimethyloctyl.
As said R3Number of carbon atoms of 1 toThe alkyl group of 25 may have not only a linear structure but also a branched or cyclic structure.
As such an alkyl group having 1 to 25 carbon atoms, there may be mentioned: linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl (n-pentyl), hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl (myristyl), pentadecyl, hexadecyl (palmityl), heptadecyl (pearlyl), octadecyl (stearyl), nonadecyl, eicosyl (arachidyl), heneicosyl, docosyl (behenyl), tricosyl, tetracosyl (lignoceryl), and pentacosyl; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, sec-isopentyl group, isohexyl group, 1, 2-trimethylpropyl group (thexyl), 4-methylhexyl group, 5-methylhexyl group, 2-ethylpentyl group, heptan-3-yl group, heptan-4-yl group, 4-methylhexan-2-yl group, 3-methylhexan-3-yl group, 2, 3-dimethylpentan-2-yl group, 2, 4-dimethylpentan-2-yl group, 4-dimethylpentan-2-yl group, 6-methylheptyl group, 2-ethylhexyl group, octan-2-yl group, 6-methylheptan-2-yl group, 6-methyloctyl group, 3,5, 5-trimethylhexyl group, Nonan-4-yl, 2, 6-dimethylheptan-3-yl, 3-ethylheptan-3-yl, 3, 7-dimethyloctyl, 8-methylnonyl, 3-methylnonan-3-yl, 4-ethyloctan-4-yl, 9-methyldecyl, undecan-5-yl, 3-ethylnonan-3-yl, 5-ethylnonan-5-yl, 2,4,5, 5-pentamethylhexan-4-yl, 10-methylundecan, 11-methyldodecyl, tridecan-6-yl, tridecan-7-yl, 7-ethylundecan-2-yl, tridecan, 3-ethylundec-3-yl, 5-ethylundec-5-yl, 12-methyltridec-yl, 13-methyltetradecyl, pentadecyl-7-yl, pentadecyl-8-yl, 14-methylpentadecyl, 15-methylhexadecyl, heptadec-8-yl, heptadec-9-yl, 3, 13-dimethylpentadec-7-yl, 2,4,8,10, 10-hexamethylundec-5-yl, 16-methylheptadecyl, 17-methyloctadecyl, nonadec-9-yl, nonadec-10-yl, 2,6,10, 14-tetramethylpentadecyl-7-yl, 18-methylnonadecyl, and mixtures thereof, 19-methyl eicosyl, eicosan-10-yl, 20-methyl heneicosyl, 21-methyl docosyl, tricosylBranched alkyl groups such as an 11-yl group, a 22-methyltricosyl group, a 23-methyltetracosanyl group, a pentacosan-12-yl group, a pentacosan-13-yl group, a2, 22-dimethyltricosan-11-yl group, a 3, 21-dimethyltricosan-11-yl group, and a 9, 15-dimethyltricosan-11-yl group; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-tert-butylcyclohexyl, 1, 6-dimethylcyclohexyl, menthyl, cycloheptyl, cyclooctyl, bicyclo [2.2.1]Heptane-2-yl, bornyl, isobornyl, 1-adamantyl, 2-adamantyl, tricyclo [5.2.1.02,6]Decan-4-yl, tricyclo [5.2.1.02,6]An alicyclic alkyl group such as a decan-8-yl group and a cyclododecyl group.
Wherein R is3Preferably a hydrogen atom.
With respect to the compound having R1、R2And R3The group of (a): -CR1R2R3A total of 10 to 30 carbon atoms contained in the group, preferably-CR1R2R3The group is a group of 14 to 26 carbon atoms, and a group of 14 to 20 carbon atoms is particularly preferable.
As said-CR1R2R3Specific examples of the group include 3-methylnonan-3-yl, 4-ethyloctan-4-yl, undecan-5-yl, 3-ethylnonan-3-yl, 5-ethylnonan-5-yl, 2,4,5, 5-pentamethylhexan-4-yl, tridecan-6-yl, tridecan-7-yl, 7-ethylundecan-2-yl, 3-ethylundecan-3-yl, 5-ethylundecan-5-yl, pentadecan-7-yl, pentadecan-8-yl, heptadecan-7-yl, heptadecan-8-yl, heptadecan-9-yl, 3, 13-dimethylpentadecan-7-yl, 2,2,4,8,10, 10-hexamethylundec-5-yl, nonadecan-9-yl, nonadecan-10-yl, 2,6,10, 14-tetramethylpentadecan-7-yl, eicosan-10-yl, tricosan-11-yl, pentacosan-12-yl, pentacosan-13-yl, 2, 22-dimethyltricosan-11-yl, 3, 21-dimethyltricosan-11-yl, 9, 15-dimethyltricosan-11-yl, heptacosan-13-yl, nonacosan-14-yl and the like.
As said R4To R6Examples of the alkyl group having 1 to 10 carbon atoms in (A) include methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl and sec-butylT-butyl, cyclobutyl, pentyl (amyl), isopentyl, neopentyl, t-pentyl, sec-isopentyl, cyclopentyl, hexyl, isohexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, and the like.
Among them, R is preferable4To R6Examples thereof include a hydrogen atom.
X represents-C (═ O) O-, -CH2O-or-CH2OC (═ O) -, where preferably X is ═ CH2O-and n is an integer from 2 to 8 or said X is-C (═ O) O-or-CH2OC(＝O)-。
The X is particularly preferably ═ C (═ O) O-.
Examples of the aliphatic hydrocarbon group which may contain an ether bond having a (n +1) valence in A include, for example, an (n +1) valence group derived from the above-mentioned alkyl group having 2 to 27 carbon atoms, alkyl group having 1 to 25 carbon atoms or alkyl group having 1 to 10 carbon atoms with (n) hydrogen atoms removed. In addition, these groups may also contain ether linkages (-O-) between any carbon-carbon bonds.
Specifically, for example, there may be mentioned (n +1) -valent groups derived by removing a part or all of hydroxyl groups from a polyol structure selected from the group consisting of glycerol, 2-hydroxy-1, 4-butanediol, trimethylolmethane, 1,1, 1-trimethylolethane, 1,1, 1-trimethylolpropane, ditrimethylolpropane, pentaerythritol and dipentaerythritol. Among them, the polyol includes a polyol selected from the group consisting of 1,1, 1-trimethylolpropane and pentaerythritol, and a group derived by removing all hydroxyl groups from the polyol structure.
When A is an aliphatic hydrocarbon group which may contain an (n +1) -valent ether bond, n is preferably an integer of 2 to 8.
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 contain an ether bond in the above-mentioned L include methylene, ethylene, trimethylene, methylethylene, tetramethylene, 1-methyltrimethylene, pentamethylene, 2-dimethyltrimethylene, hexamethylene, heptamethylene, octamethylene, 2-oxatetramethylene, 2, 5-dioxaheptamethylene, 2,5, 8-trioxadedecamethylene, 2-oxa-3-methyltetramethylene and 2, 5-dioxa-3, 6-dimethylheptamethylene.
The L is preferably a methylene group, a trimethylene group, a hexamethylene group, or a 2-oxatetramethylene group, and more preferably a methylene group.
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, and for example, the olefin compound, hydrogen peroxide, a nitrile compound, and a basic substance may be put together in a solvent to react. Alternatively, a component other than hydrogen peroxide may be added to the solvent, and then hydrogen peroxide may be added dropwise thereto, followed by reaction.
In the reaction for obtaining the epoxy compound represented by the formula [2] from the olefin compound represented by the formula [1], the amount of hydrogen peroxide to be used is 0.5 to 50 equivalents, or 0.5 to 30 equivalents, or 1 to 10 equivalents relative to 1 equivalent of a double bond in the olefin compound. The hydrogen peroxide may be added to the reaction system in the form of, for example, 35 mass% hydrogen peroxide water.
The hydrogen peroxide may be added at a time, or may be added sequentially by dividing a specific amount of hydrogen peroxide into several times (for example, about 2 to 5 times). The hydrogen peroxide is preferably added by a dropping method, and in this case, the dropping (addition) may be performed 1 time over 1 to 24 hours. Then, after the addition (dropwise addition) is completed, the reaction can be carried out for 1 to 24 hours.
By repeating the combination (dropwise addition and reaction) of the reaction after the addition (dropwise addition) several times (for example, about 2 to 5 times), the yield of the reaction from the olefin to the epoxy group can be improved.
The nitrile compound used in the reaction for obtaining the epoxy compound from the olefin compound includes aliphatic nitriles and aromatic nitriles. The aromatic nitrile may be benzonitrile, and the aliphatic nitrile may be acetonitrile or propionitrile. Aliphatic nitriles are particularly preferred, with acetonitrile being preferred. The amount of the nitrile compound used is 0.5 to 50 equivalents, or 1 to 30 equivalents, or 3 to 15 equivalents relative to 1 equivalent of the double bond in the olefin compound.
Examples of the basic substance used in the reaction for obtaining an epoxy compound from the above-mentioned olefin compound include phosphoric acid compounds, carbonate compounds, and alkali metal hydroxides.
Examples of the phosphoric acid-based compound include phosphoric acid, pyrophosphoric acid, polyphosphoric acid, and salts thereof.
Examples of the carbonate compound include sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and ammonium hydrogen carbonate.
Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide.
Among them, a phosphate, a carbonate, or an alkali metal hydroxide can be particularly preferably used, and examples of the phosphate include sodium phosphate, potassium phosphate, ammonium phosphate, and the like, and examples of the carbonate include sodium carbonate, sodium hydrogen carbonate, and the like, and examples of the alkali metal hydroxide include sodium hydroxide. More preferably an alkali metal hydroxide, and still more preferably sodium hydroxide.
The amount of the basic substance added is 0.01 to 10 equivalents or 0.01 to 2 equivalents relative to 1 equivalent of the double bond in the olefin compound.
The liquid property of the reaction solution during the reaction is preferably 9 to 11 pH, more preferably 9.2 to 10.5 pH, and the alkaline substance is preferably added so that the pH falls within this range.
In the reaction for obtaining an epoxy compound from the above-mentioned olefin compound, an alcohol solvent is used as a solvent for the reaction. As the alcohol solvent, a linear, branched or cyclic alcohol such as methanol, ethanol, 2-propanol, n-butanol, t-amyl alcohol or cyclohexanol is used. Methanol can be particularly preferably used. Further, a non-alcoholic solvent such as toluene may be mixed with the alcoholic solvent.
The reaction for obtaining the epoxy compound from the olefin compound may be carried out at 5 to 60 ℃ for 2 to 48 hours (including the time of adding hydrogen peroxide).
After the reaction, the reaction solution containing the reaction mixture can be purified by a known purification procedure, for example, adding a solvent such as heptane to separate an organic layer, adding an aqueous solution of sodium thiosulfate or ammonium sulfate to the obtained organic layer to wash the organic layer, and then distilling off the solvent to obtain the epoxy compound.
The conversion rate of the olefin to the epoxy group obtained by the production method of the present invention may be 60% or more, for example, 75% or more or 90% or more.
[ olefin Compound represented by the formula [1]
The olefin compound represented by the above formula [1] can be produced by a conventionally known method (for example, a method for producing a compound having an unsaturated bond (intermediate) described in international publication No. 2012/128325, etc.) using a carboxylic acid or an alcohol as a starting material.
For example, in the case of an ester compound in which X represents an X-C (═ O) O-group, one example may be an ester compound containing — CR1R2R3A branched fatty acid or an activated product thereof (e.g., acid halide, acid anhydride, acid azide, active ester) is reacted with an unsaturated alcohol such as allyl alcohol or an unsaturated halide such as allyl halide to obtain a compound represented by the formula [1]]Wherein X represents an ester compound of the group ═ C (═ O) O-.
In addition, X represents a-CH2In the case of an O-based ether compound, for example, the compound can be prepared by allowing a compound containing-CR1R2R3Reacting the branched alcohol of the radical with an unsaturated halide to obtain a compound of the formula [1]Wherein X represents-CH2An O-based ether compound.
Said comprises-CR1R2R3Branched fatty acids of radicals and containing-CR1R2R3As the branched alcohol of the base, commercially available ones can be used.
For example, as the inclusion-CR1R2R3Examples of the branched fatty acids include finexocol (registered trademark) isopalmitic acid, finexocol isostearic acid N, FINEOXOCOL isostearic acid T, FINEOXOCOL isoarachidic acid, which are manufactured by daily chemical industries (stock), and further, activators (derivatives) of these branched fatty acids can be used.
As a stationSaid comprises-CR1R2R3Examples of the branched alcohols include FINOXOCOL (registered trademark) 1600, FINOXOCOL 180, and FINOXOCOL 180N, FINEOXOCOL 180T, FINEOXOCOL 2000 manufactured by Nissan chemical industries, Ltd.
Examples of the unsaturated alcohol include allyl alcohol, glycerol monoallyl ether, glycerol diallyl ether, 2, 4-diallylbutanol, 3, 4-diallylbutanol, 1, 4-diallyloxy-2-butanol, trimethylolmethane monoallyl ether, trimethylolmethane diallyl ether, 1,1, 1-trimethylolethane monoallyl ether, 1,1, 1-trimethylolethane diallyl ether, 1,1, 1-trimethylolpropane monoallyl ether, 1,1, 1-trimethylolpropane diallyl ether, ditrimethylolpropane monoallyl ether, ditrimethylolpropane diallyl ether, ditrimethylolpropane triallyl ether, pentaerythritol monoallyl ether, pentaerythritol diallyl ether, pentaerythritol triallyl ether, dipentaerythritol monoallyl ether, di-trimethylolpropane diallyl ether, and mixtures thereof, Dipentaerythritol diallyl ether, dipentaerythritol triallyl ether, dipentaerythritol tetraallyl ether, dipentaerythritol pentallyl ether, and the like.
Examples of the unsaturated halide include halogenated allyl groups such as allyl chloride, allyl bromide, and allyl iodide, 2-bis (allyloxymethyl) -1-bromobutane, and 1,1, 1-tris (allyloxymethyl) -2-bromoethane.
Commercially available products of these unsaturated alcohols and unsaturated halides can be used.
[ examples ]
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples.
In the examples, the apparatus and conditions used for the preparation of the samples and the analysis of the physical properties were as follows.
(1)1H NMR Spectrum (300MHz)
The device comprises the following steps: JNM-ECP300 manufactured by JEOL RESONANCE
Reference: tetramethylsilane (0.00ppm)
(2)1H NMR Spectrum (400MHz)
The device comprises the following steps: the Varian company manufactures INOVA-400
Reference: tetramethylsilane (0.00ppm)
(3) GC-MS (gas chromatography mass analysis)
The device comprises the following steps: shimadzu corporation (Strand) manufacture GCMS-QP2010 Ultra
Pipe column: agilent Technologies (stock) manufacture Agilent J & W GC column HP-5 (length 30m, inner diameter 0.32mm, film thickness 0.25 μm)
Injection amount: 2.0. mu.L
Injection port temperature: 250 deg.C
Temperature of the pipe column: heating to 300 deg.C and 300 deg.C at 20 deg.C/min (5 min)
(4) GC (gas chromatography)
< System A > (example 1, comparative example 1)
The device comprises the following steps: shimadzu corporation (Strand) manufacture GC-2010Plus
A detector: FID
Pipe column: agilent Technologies (stock) manufacture Agilent J & W GC column HP-1 (length 30m, inner diameter 0.32mm, film thickness 0.25 μm)
Injection amount: 2.0. mu.L
Injection port temperature: 200 deg.C
Temperature of the pipe column: 200 deg.C (5 min), heating to 300 deg.C at 5 deg.C/min (300 deg.C, 5 min)
< System B > (embodiment 2)
The device comprises the following steps: agilent Technologies (stock) makes Agilent 7890A GC system
A detector: FID
Pipe column: agilent Technologies (stock) manufacture Agilent J & W GC column HP-5 (length 30m, inner diameter 0.32mm, film thickness 0.25 μm)
Injection amount: 2.0. mu.L
Injection port temperature: 250 deg.C
Temperature of the pipe column: heating to 300 deg.C and 300 deg.C at 20 deg.C/min (5 min)
(5) Epoxy equivalent
The device comprises the following steps: automatic potential difference titration device AT-710 manufactured by Kyoto electronic industry (Strand)
An electrode: composite glass electrode C-173 made by Kyoto electronic industry
(6) Light transmittance
The device comprises the following steps: ultraviolet visible near infrared spectrophotometer UV-3600Plus manufactured by Shimadzu corporation
The abbreviations indicate the following meanings.
ISA: 2- (4, 4-dimethylpentan-2-yl) -5,7, 7-trimethyloctanoic acid [ FINOXOCOL (registered trademark) isostearic acid manufactured by NIGHTROGICAL CHEMICAL INDUSTRY (JUSTRY) ]
ISOL: 2- (4, 4-dimethylpentan-2-yl) -5,7, 7-trimethyloctan-1-ol [ FINOXOCOL (registered trademark) 180, manufactured by NIGHOGEN CHEMICAL INDUSTRY (USA) ]
AllBr: allyl bromide [ manufactured by Tokyo chemical industry (stock) ]
TMPDA: trimethylolpropane diallyl ether [ NEOALLYL T-20 manufactured by OSAKA SODA ]
DMF: n, N-dimethylformamide
NMP: n-methyl-2-pyrrolidone
THF: tetrahydrofuran (THF)
Production example 1 production of 2- (4, 4-dimethylpentan-2-yl) -5,7, 7-trimethyloctanoic acid 2, 2-bis (allyloxymethyl) butyl ester (ISA2A)
The reaction vessel was charged with 24.0kg (84.4mol) of ISA, 0.185kg of DMF, and 24kg of toluene. To this solution, 10.5kg (88.6mol) of thionyl chloride was added dropwise over 45 minutes at room temperature (approximately 23 ℃) and further stirred for 2 hours. To the reaction mixture, 24kg of toluene was added, and 24kg of the remaining thionyl chloride, solvent and the like were distilled off. 24kg of toluene was again added, and 24kg was distilled off in the same manner as described above.
To the obtained solution, 48kg of toluene and 12.0kg (152mol) of pyridine were added. To this solution, 18.1kg (84.4mol) of TMPDA purified by distillation in advance was added dropwise over 1 hour at room temperature (approximately 23 ℃ C.), and further stirred for 12 hours. The reaction solution was washed with 48.0kg of 1N hydrochloric acid, 36.0kg of a 5 mass% aqueous solution of sodium hydroxide, and ion-exchanged water in this order. The solvent of the organic layer was distilled off, and 40.5kg of 2- (4, 4-dimethylpentan-2-yl) -5,7, 7-trimethyloctanoic acid 2, 2-bis (allyloxymethyl) butyl ester (ISA2A) was obtained as a colorless transparent liquid.
1H NMR(300MHz,CDCl3):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)
Production example 2 production of 2- (4, 4-dimethylpentan-2-yl) -5,7, 7-trimethyloctyl ═ allyl ═ ether (IS1AE)
A reaction flask was charged with 55 mass% sodium hydride [ manufactured by Kanto Chemicals (Ltd.) ]6.45g (0.15mol in the form of NaH) and 80g of THF. 40.0g (0.15mol) of ISOL was added dropwise thereto over 10 minutes, followed by warming to 70 ℃. To this solution, 21.4g (0.18mol) of AllBr was added dropwise over 10 minutes, followed by stirring for 3 hours. To the reaction mixture, 120g of toluene and 40g of ion-exchanged water were added and stirred, and an organic layer was separated. 120g of toluene was added to the organic layer, and the mixture was washed with 40g of ion-exchanged water, and then the solvent was distilled off. The obtained residue was purified by silica gel chromatography (hexane: ethyl acetate 98: 2 (vol)), whereby 35.7g of 2- (4, 4-dimethylpentan-2-yl) -5,7, 7-trimethyloctyl allyl ether (IS1AE) was obtained as a pale yellow transparent liquid.
1H NMR(300MHz,CDCl3):δ＝6.0～5.8(m,1H),5.3(d,J＝17.1Hz,1H),5.2(d,J＝10.5Hz,1H),4.0～3.9(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 ester (ISA2G)
[ solution 5]
A reaction flask was charged with 8.00g (16.6mmol) of ISA2A manufactured according to manufacturing example 1, 9.60g (234mmol) of acetonitrile, and 80g of methanol. The liquid properties of this solution were adjusted to pH 9.5 with an 8 mass% aqueous sodium hydroxide solution, and then the temperature was raised to 40 ℃. The liquid properties of the solution were measured by using 8 mass% sodium hydroxide solutionThe solution was maintained at pH 9.5 and 12.9g (as H) of 35 mass% hydrogen peroxide water was added dropwise over a period of 16 hours2O2Form (d) 133mmol), and further stirred for 11 hours. The total amount of 8 mass% aqueous sodium hydroxide solution used was 17.2 g. The consumption rate of the olefin compound (ISA2A) (i.e., (charged amount-remaining amount) ÷ charged amount × 100) was 97% by GC quantitative analysis of the reaction solution.
To the reaction mixture was added 16g of heptane and stirred, and the organic layer was separated. The organic layer was washed with 16g of a 5 mass% aqueous sodium thiosulfate solution and 16g of a2 mass% aqueous ammonium sulfate solution, and then the solvent was distilled off to obtain 6.71g (epoxy purity 89%, yield 79%) of 2- (4, 4-dimethylpentan-2-yl) -5,7, 7-trimethyloctanoic acid 2, 2-bis (glycidyloxymethyl) butyl ester (ISA2G) as a colorless transparent liquid. Furthermore, the epoxy purity is according to JISK 7236: the epoxy equivalent weight measured in 2009 was calculated as epoxy purity [% ] ═ epoxy equivalent (measured value) ÷ epoxy equivalent (theoretical value) × 100.
Further, the obtained epoxy compound (ISA2G) had a light transmittance at a wavelength of 400nm of 96.8%.
1H NMR(300MHz,CDCl3):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),1.8～0.8(m,40H)(ppm)
GC-MS(CI):m/z＝513(M+1)
Example 2 production of 2- (4, 4-dimethylpentan-2-yl) -5,7, 7-trimethyloctyl ═ glycidyl ═ ether (IS1GE)
[ solution 6]
A reaction flask was charged with 4.00g (12.9mmol) of IS1AE produced in accordance with production example 2, 4.80g (117mmol) of acetonitrile, and 40g of methanol. The liquid properties of this solution were adjusted to pH 9.5 with an 8 mass% aqueous sodium hydroxide solution, and then the temperature was raised to 40 ℃. The solution was kept at pH 9.5 with an 8 mass% aqueous sodium hydroxide solution, and 5.01g of 35 mass% aqueous hydrogen peroxide (as H) was added dropwise over a period of 16 hours2O2Form (d) 51.6mmol), and further stirred for 15 hours. The total amount of 8 mass% aqueous sodium hydroxide solution used was 6.5 g. According to GC quantitative analysis of the reaction solution, the consumption rate of the olefin compound (IS1AE) was 92%. The reaction mixture was worked up in the same manner as in example 1 to give 2- (4, 4-dimethylpentan-2-yl) -5,7, 7-trimethyloctyl ═ glycidyl ═ ether (IS1 GE).
1H NMR(400MHz,CDCl3):δ＝3.67～3.64(m,1H),3.41～3.23(m,3H),3.13(m,1H),2.80～2.77(m,1H),2.61～2.59(m,1H),1.80～0.82(m,35H)(ppm)
GC-MS(CI):m/z＝327(M+1)
Comparative example 1 production of 2- (4, 4-dimethylpentan-2-yl) -5,7, 7-trimethyloctanoic acid 2, 2-bis (glycidyloxymethyl) butyl ester (ISA2G)
Into the reaction vessel, 35.0kg (72.8mol) of ISA2A produced in accordance with production example 1, 3.84kg (11.6mol) of sodium tungstate dihydrate [ manufactured by Wako Pure Chemical industries of optical Pure Chemical industries (now FUJIFILM Wako Pure Chemical Co.) ]]2.79kg (5.81mol) of methyl (trioctyl) ammonium methylsulphate (interphase transfer catalyst) prepared according to J.org.chem.,61,8310(1996), 14.3kg of a 10% by mass aqueous phosphoric acid solution and 35kg of toluene and warmed to 55 ℃. To this solution, 21.2kg (as H) of 35 mass% hydrogen peroxide water was added dropwise over 8 hours2O2In the form of 218mol) and further stirred for 16 hours. According to the GC quantitative analysis of the reaction solution, the consumption rate of the olefin compound (ISA2A) was 97%.
To the reaction mixture was added 35kg of toluene, followed by stirring, and the organic layer was separated. The organic layer was washed with 35kg of a 5 mass% aqueous solution of sodium thiosulfate. Further, after the catalyst (tungstic acid catalyst and phase transfer catalyst) remaining in the solution was removed by adsorbent treatment, the solvent was distilled off to obtain 23.6kg (epoxy purity 90%, yield 63%) of 2- (4, 4-dimethylpentan-2-yl) -5,7, 7-trimethyloctanoic acid 2, 2-bis (glycidyloxymethyl) butyl ester (ISA2G) in the form of a colorless transparent liquid.
Further, the obtained epoxy compound (ISA2G) had a light transmittance at a wavelength of 400nm of 91.2%.
As described above, it was confirmed that the epoxy compound can be obtained with a high yield of approximately 80% by the production method of the present invention, and the epoxy compound having a high light transmittance (less coloring) can be obtained by a simple post-treatment.
Claims (12)
1. A method for producing an epoxy compound represented by the formula [2], characterized in that: reacting an olefin compound represented by the formula [1], hydrogen peroxide, a nitrile compound, and an alkaline substance in a solvent,
[ solution 1]
(in the formula, R1And R2Each independently represents an alkyl group having 2 to 27 carbon atoms, R3Represents a hydrogen atom or an alkyl group having 1 to 25 carbon atoms, wherein-CR1R2R3The total number of carbon atoms contained in the group is 10 to 30, R4To R6Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X represents-C (═ O) O-, -CH2O-or-CH2OC (═ O) - (here, indicates bonding at-CR1R2R3Terminal of group), A represents a single bond or an aliphatic hydrocarbon group which may contain an (n +1) -valent ether bond, Z represents a single bond or an oxygen atom, wherein, when A represents a single bond, Z represents a single bond, L represents an alkylene group having 1 to 8 carbon atoms which may contain an ether bond, n represents an integer of 1 to 8, wherein, when A represents a single bond, n represents 1),
[ solution 2]
(in the formula, R1、R2、R3、R4、R5、R6X, A, Z, L and n represent the same meanings as described).
2. The manufacturing method according to claim 1, wherein the substrate is a glass substrate,wherein X is-CH2O-and said n is an integer from 2 to 8 or said X is-C (═ O) O-or-CH2OC(＝O)。
3. The production method according to claim 1 or 2, wherein X is ═ -C (═ O) O-.
4. The production method according to any one of claims 1 to 3, wherein A is an aliphatic hydrocarbon group which may also contain an (n +1) -valent ether bond and n is an integer of 2 to 8.
5. The production method according to claim 4, wherein A is a group derived by removing a part or all of hydroxyl groups from a polyhydric alcohol selected from the group consisting of glycerol, 2-hydroxy-1, 4-butanediol, trimethylolmethane, 1,1, 1-trimethylolethane, 1,1, 1-trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.
6. The production method according to claim 5, wherein the polyol is a polyol selected from the group consisting of 1,1, 1-trimethylolpropane and pentaerythritol.
7. The production method according to claim 5 or 6, wherein A is a group derived by removing all hydroxyl groups from the polyol.
8. The production method according to any one of claims 1 to 7, wherein the L is a methylene group.
9. The production method according to any one of claims 1 to 8, wherein the-CR1R2R3The radical is a radical having 14 to 26 carbon atoms.
10. The production method according to any one of claims 1 to 9, wherein the basic substance is an alkali metal hydroxide.
11. The production method according to any one of claims 1 to 10, wherein the solvent is an alcohol.
12. The production method according to any one of claims 1 to 11, wherein the formula [1]]The compound represented by is a compound containing-CR1R2R3Branched fatty acids of radicals or activators thereof or containing-CR1R2R3Reaction products of branched alcohols of the radicals with unsaturated alcohols or unsaturated halides.
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| JP2017093057 | 2017-05-09 | ||
| PCT/JP2018/017641 WO2018207735A1 (en) | 2017-05-09 | 2018-05-07 | Method for producing epoxy compound |
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| JP (1) | JPWO2018207735A1 (en) |
| KR (1) | KR20190140474A (en) |
| CN (1) | CN110662740A (en) |
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| WO (1) | WO2018207735A1 (en) |
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| US2965652A (en) * | 1958-05-13 | 1960-12-20 | Monsanto Chemicals | Process of preparing glycidyl ethers |
| JPS56108781A (en) * | 1980-02-01 | 1981-08-28 | Kao Corp | Preparation of glycidyl ether |
| JP2009256260A (en) * | 2008-04-18 | 2009-11-05 | Daiso Co Ltd | Production method of epoxy alcohol |
| EP2354130A1 (en) * | 2010-02-02 | 2011-08-10 | Momentive Specialty Chemicals Research Belgium | Manufacture of an epoxyethyl carboxylate or glycidyl carboxylate |
| JP2011195483A (en) * | 2010-03-18 | 2011-10-06 | Nippon Steel Chem Co Ltd | Process for producing triepoxy ethyl cyclohexane and epoxy resin |
| CN103429632A (en) * | 2011-03-23 | 2013-12-04 | 日产化学工业株式会社 | Polyfunctional epoxy compound |
| EP2687580A1 (en) * | 2012-07-19 | 2014-01-22 | Breitling AG | Clock piece |
| JP2014094937A (en) * | 2012-10-11 | 2014-05-22 | Mitsubishi Chemicals Corp | Novel epoxy compound |
| US20150284372A1 (en) * | 2012-10-25 | 2015-10-08 | Nissan Chemical Industries, Ltd. | Method for producing epoxy compound |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017077846A1 (en) * | 2015-11-05 | 2017-05-11 | 日産化学工業株式会社 | Epoxy-based reactive diluent and epoxy resin composition including same |
| CN108349919B (en) * | 2015-11-05 | 2022-06-03 | 日产化学工业株式会社 | Polyfunctional epoxy compound and curable composition containing the same |
-
2018
- 2018-05-07 KR KR1020197035355A patent/KR20190140474A/en unknown
- 2018-05-07 WO PCT/JP2018/017641 patent/WO2018207735A1/en active Application Filing
- 2018-05-07 CN CN201880030437.6A patent/CN110662740A/en active Pending
- 2018-05-07 JP JP2019517613A patent/JPWO2018207735A1/en not_active Withdrawn
- 2018-05-09 TW TW107115686A patent/TW201900626A/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2965652A (en) * | 1958-05-13 | 1960-12-20 | Monsanto Chemicals | Process of preparing glycidyl ethers |
| JPS56108781A (en) * | 1980-02-01 | 1981-08-28 | Kao Corp | Preparation of glycidyl ether |
| JP2009256260A (en) * | 2008-04-18 | 2009-11-05 | Daiso Co Ltd | Production method of epoxy alcohol |
| EP2354130A1 (en) * | 2010-02-02 | 2011-08-10 | Momentive Specialty Chemicals Research Belgium | Manufacture of an epoxyethyl carboxylate or glycidyl carboxylate |
| JP2011195483A (en) * | 2010-03-18 | 2011-10-06 | Nippon Steel Chem Co Ltd | Process for producing triepoxy ethyl cyclohexane and epoxy resin |
| CN103429632A (en) * | 2011-03-23 | 2013-12-04 | 日产化学工业株式会社 | Polyfunctional epoxy compound |
| EP2687580A1 (en) * | 2012-07-19 | 2014-01-22 | Breitling AG | Clock piece |
| JP2014094937A (en) * | 2012-10-11 | 2014-05-22 | Mitsubishi Chemicals Corp | Novel epoxy compound |
| US20150284372A1 (en) * | 2012-10-25 | 2015-10-08 | Nissan Chemical Industries, Ltd. | Method for producing epoxy compound |
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| Publication number | Publication date |
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| KR20190140474A (en) | 2019-12-19 |
| JPWO2018207735A1 (en) | 2020-03-19 |
| TW201900626A (en) | 2019-01-01 |
| WO2018207735A1 (en) | 2018-11-15 |
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