JP2009285583A - Catalyst for oxidation reaction - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst for the oxidation reaction which maintains the reactive activities for a long term and is stably usable. <P>SOLUTION: The catalyst for the oxidation reaction is comprised of heteropoly acid or its salt (A) and a salt (B) consisting of one or more of cation components selected from the group consisting of imidazolium ions, imidazolium and pyrimidinium ions and at least one of anion components selected from the group consisting of phosphoric acid anions, alkyl phosphoric acid anions, carboxylic anions, boric acid anions and alkyl boric acid anions. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an oxidation reaction catalyst. Specifically, the present invention relates to a heteropolyacid-based oxidation reaction catalyst and an organic compound oxidation method using the oxidation reaction catalyst.

Heteropolyacids or salts thereof are widely used industrially as catalysts effective for esterification of a hydroxyl group-containing compound and a carboxyl group-containing compound, epoxidation reaction of an olefin compound, hydration reaction, oxidation reaction of methacryloline, and the like. However, most of the heteropolyacids or their salts are soluble in polar solvents such as water and alcohol, and when used as a catalyst in a medium containing a polar solvent, elution occurs and cannot be used continuously for a long time. Was.

In contrast, a method for preparing a catalyst in which heteropolyacid or a salt thereof is supported on inorganic fine particles such as silica (see Patent Document 1), a method of treating with a fluorine-containing quaternary ammonium salt and a heteropolyacid (see Patent Document 2). Is disclosed.

JP 2002-79088 A Japanese Patent Laid-Open No. 2004-868

However, all of them have low reaction activity and have a problem in industrial use. Further, the durability of the catalyst was insufficient due to desorption and elution.
The present invention has been made to solve the above-described problems, and provides a catalyst that maintains a reaction activity over a long period of time and can be used stably, and a method for producing the catalyst. Objective.

The inventors of the present invention have intensively studied to solve the above problems, and have reached the present invention.
That is, the present invention is a heteropolyacid and / or a salt thereof (A), and the cation component is at least one selected from the group consisting of imidazolinium ion, imidazolium ion and pyrimidinium ion, and the anion component is phosphoric acid. Catalyst for oxidation reaction as an essential component containing salt (B) which is a combination of one or more selected from an anion, alkyl phosphate anion, carboxyl anion, borate anion and alkyl borate anion; Organic using the oxidation reaction catalyst This is a method for oxidizing a compound.

  The catalyst for oxidation reaction of the present invention maintains reaction activity over a long period of time and can be used stably.

The heteropolyacid (A ₀ ) used in the catalyst of the present invention is composed of a peripheral element in which a central element and oxygen are bonded. The central element is preferably silicon or phosphorus, but is not limited thereto, and may be any one selected from elements of Groups 1 to 17 of the periodic table.

    Central elements include divalent beryllium, zinc, cobalt or nickel ions; trivalent boron, aluminum, gallium, iron, cerium, arsenic, antimony, phosphorus, bismuth, chromium or rhodium ions; tetravalent silicon, germanium, tin , Titanium, zirconium, vanadium, sulfur, tellurium, manganese, nickel, platinum, thorium, hafnium, cerium ions and other rare earth ions; pentavalent phosphorus, arsenic, vanadium, antimony ions; hexavalent tellurium ions; An iodine ion etc. can be mentioned. Of these, silicon and phosphorus are preferred.

    Examples of peripheral elements to which oxygen is bonded include oxides such as tungsten, molybdenum, vanadium, niobium, and tantalum. Of these, oxides of tungsten and molybdenum are preferable. The chemical formula can be represented by MxOy (M represents a peripheral element, O represents oxygen), and preferably x = 5 to 15 and y = 30 to 50.

A heteropolyacid (A ₀ ) consisting of 12 elements in which a central element and oxygen are bonded is known as a “polyoxoanion”, “polyoxometal salt” or “metal oxide cluster”. Some structures of well-known anions are known as, for example, Keggin, Wells-Dawson and Anderson-Evans-Pairov structures.
Heteropolyacids usually have a molecular weight in the range of 700-8,500 and include not only the monomers but also dimeric complexes.

Examples of heteropolyacids (A ₀ ) include silicotungstic acid (H ₄ [SiW ₁₂ O ₄₀ ] .xH ₂ O), phosphotungstic acid (H ₃ [PW ₁₂ O ₄₀ ] .xH ₂ O), phosphomolybdic acid (H ₃ [PMo ₁₂ O ₄₀ ] .xH ₂ O), silicomolybdic acid (H ₄ [SiMo ₁₂ O ₄₀ ] .xH ₂ O), and caivanadotungstic acid (H _{4 + n} [SiV _n W _12-n O ₄₀ ] .xH ₂ O), phosphovanad tungstic acid (H _{3 + n} [PV _n W _12-n O ₄₀ ] .xH ₂ O), phosphovanadmolybdic acid (H _{3 + n} [PV _n Mo _12-n O ₄₀ ] .xH ₂ O), silicovanadmolybdic acid (H _{4 + n} [SiV _n Mo _12-n O ₄₀ ] .xH ₂ O), silicoribed tungstic acid (H ₄ [SiMo _n W _12-n O ₄₀₎ ] .xH ₂ O), phosphorus molybdate de tungstophosphoric acid _{(H 3 [PMo n W 12} -n O 40] .xH 2 O) ( where, n is an integer of 1 to 11, x Represents an integer of 1 or more).
Of these, silicotungstic acid (H ₄ [SiW ₁₂ O ₄₀ ] .xH ₂ O), phosphotungstic acid (H ₃ [PW ₁₂ O ₄₀ ] .xH ₂ O), and phosphomolybdic acid (H ₃ [PMo] are preferred. ₁₂ O ₄₀ ] .xH ₂ O) and silicomolybdic acid (H ₄ [SiMo ₁₂ O ₄₀ ] .xH ₂ O).

The method for synthesizing such a heteropolyacid (A ₀ ) is not particularly limited. For example, a method of mixing tungsten oxide, molybdenum oxide, and vanadium oxide with silicic acid, phosphoric acid, and alkali metal salts and ammonium salts thereof, There is a method in which tungstic acid or molybdic acid is mixed with silicic acid, phosphoric acid and alkali metal salts or ammonium salts thereof.
When mixing with silicic acid, phosphoric acid and their alkali metal salts and ammonium salts, the molar ratio of metal elements (tungsten, molybdenum and vanadium) to silicon and phosphorus atoms is charged to 12: 1 to 13: 1. And an aqueous solution of about pH 1 to pH 2 and mixed at 5 to 60 ° C. The produced heteropolyacid aqueous dispersion can be used for the oxidation reaction as it is, but the heteropolyacid catalyst may be once isolated from the aqueous solution. To isolate the heteropolyacid (A0) from the aqueous solution, there is a method of crystallization separation.
Specific examples thereof are described on page 1413 of “New Experimental Chemistry Lecture 8 Synthesis of Inorganic Compounds (III)” (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd., August 20, 1984, 3rd edition). However, it is not limited to this. In addition, the Keggin structure of the synthesized heteropolyacid can be confirmed by X-ray diffraction, UV and IR measurements in addition to chemical analysis.

Examples of the heteropolyacid salt (A ₁ ) include alkali metal salts, alkaline earth metal salts, copper salts, gold salts, gallium salts, and ammonium salts of the heteropolyacid (A ₀ ).

  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.

The method for synthesizing these heteropolyacid salts (A ₁ ) is not particularly limited. For example, a method of mixing the heteropolyacid (A ₀ ) with an acid salt containing the metal, a hydroxide containing the metal, or the like, There is a method of mixing tungsten, molybdenum oxide, vanadium oxide and an acid salt containing the above metal.

  Acid salts containing the above metals include nitric acid, sulfuric acid, acetic acid, carbonic acid, hydrochloric acid, hydrogen carbonate, dihydrogen phosphate, hydrogen carbonate and citric acid alkali metals, alkaline earth metals, copper, gold, gallium and ammonium salts. Can be mentioned.

  Examples of the hydroxide containing the metal include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, Examples thereof include copper hydroxide and gallium hydroxide.

The heteropolyacid (A ₀ ) and the acid salt or hydroxide are mixed at 5 ° C. to 60 ° C. with an aqueous solution of about pH 1 to pH 2. The aqueous solution of the produced heteropolyacid salt (A ₁ ) can be used for the oxidation reaction as it is, but the heteropolyacid salt (A ₁ ) may be once isolated from the aqueous dispersion. In order to isolate the heteropolyacid salt (A ₁ ) from the aqueous solution, there is a method of crystallization separation.
Specific examples thereof are described on page 1413 of “New Experimental Chemistry Lecture 8 Synthesis of Inorganic Compounds (III)” (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd., August 20, 1984, 3rd edition). However, it is not limited to this. The Keggin structure of the synthesized heteropolyacid salt (A1) can be confirmed by X-ray diffraction, UV and IR measurements in addition to chemical analysis.

Preferable examples of the heteropolyacid salt (A ₁ ) include the sodium salt, potassium salt, barium salt, cesium salt, calcium salt and the like of the above preferable heteropolyacid (A ₀ ). Particularly preferred are sodium tungstic acid sodium salt, potassium salt, phosphotungstic acid sodium salt and potassium salt.

In the oxidation reaction catalyst of the present invention, these heteropolyacids (A ₀ ) and salts thereof (A ₁ ) may be used alone or in combination.

The salt (B), which is another essential component of the oxidation reaction catalyst of the present invention, is a salt of a combination of a cation component and an anion component, and the cation component includes imidazolinium ions, imidazolium ions, and pyrimidides. One or more selected from the group consisting of nium ions.
Examples of the imidazolinium ion include 1,2,3-trimethylimidazolinium, 1,2,3,4-tetramethylimidazolinium, 1,3,4-trimethyl-2-ethylimidazolinium, 3-dimethyl-2,4-diethylimidazolinium, 1,2-dimethyl-3,4-diethylimidazolinium, 1,2-dimethyl-3-ethylimidazolinium, 1-ethyl-3-methylimidazoli 1-methyl-3-ethylimidazolinium, 1,2,3,4-tetraethylimidazolinium, 1,2,3-triethylimidazolinium, 4-cyano-1,2,3-trimethylimidazolium Ni, 2-cyanomethyl-1,3-dimethylimidazolinium, 4-acetyl-1,2,3-trimethylimidazolinium, 3-acetylmethyl 1,2-dimethylimidazolinium, 4-methylcarboxymethyl-1,2,3-trimethylimidazolinium, 3-methoxy-1,2-dimethylimidazolinium, 4-formyl-1,2,3-trimethyl Examples include imidazolinium, 4-formyl-1,2-dimethylimidazolinium, 3-hydroxyethyl-1,2,3-trimethylimidazolinium and 3-hydroxyethyl-1,2-dimethylimidazolinium. .

  Examples of imidazolium ions include 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1-methyl-3-ethylimidazolium, 1,2,3-trimethylimidazolium, 1,2,3, 4-tetramethylimidazolium, 1,3-dimethyl-2-ethylimidazolium, 1,2-dimethyl-3-ethylimidazolium, 1-ethyl-3-methylimidazolium, 1-methyl-3-ethylimidazolium 1,2,3-triethylimidazolium, 1,2,3,4-tetraethylimidazolium, 1,3-dimethyl-2-phenylimidazolium, 1,3-dimethyl-2-benzylimidazolium, 1-benzyl -2,3-dimethylimidazolium, 4-cyano-1,2,3-trimethylimidazolium, 3-cyanomethyl Ru-1,2-dimethylimidazolium, 4-acetyl-1,2,3-trimethylimidazolium, 3-acetylmethyl-1,2-dimethylimidazolium, 4-carboxymethyl-1,2,3-trimethylimidazole 4-methoxy-1,2,3-trimethylimidazolium, 4-formyl-1,2,3-trimethylimidazolium, 3-formylmethyl-1,2-dimethylimidazolium, 3-hydroxyethyl-1, 2-dimethylimidazolium, 2-hydroxyethyl-1,3-dimethylimidazolium, N, N'-dimethylbenzimidazolazolim, N, N'-diethylbenzimidazolazolim and N-methyl-N'-ethylbenzo Examples include imidazolium.

  The pyrimidinium ions include 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium and 1-methyl. -1,8-diazabicyclo [5.4.0] undecene-7, 1-methyl-1,5-diazabicyclo [4.3.0] nonene-5 and the like.

  Examples of the anion component of the salt (B) include a phosphate anion, an alkyl phosphate anion, a carboxyl anion, a borate anion, and an alkyl borate anion.

  As an anion of an alkyl phosphate, an anion of an alkyl phosphate whose alkyl group is a C1-C18 hydrocarbon group can be mentioned. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, Of alkyl phosphoric acid having an alkyl group such as octadecyl group, oleyl group, 10-undecenyl group, 2-ethyl-hexyl group, isononyl group, isodecyl group, 2-methyl-undecyl group, 5-methyl-tetradecyl group, cyclohexyl group, etc. Anions.

  Examples of the carboxyl anion include monocarboxylic acid, dicarboxylic acid, tricarboxylic acid, and aromatic carboxylic acid anions.

Monocarboxylic acids include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid and lactic acid Of the anion.
Examples of the dicarboxylic acid include oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, phthalmalic acid, maleic acid and malic acid.
Examples of the tricarboxylic acid include citric acid and aconitic acid.
Examples of the aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, mellitic acid, and cinnamic acid. Of these, phosphoric acid and monocarboxylic acid anions are preferable.

  As an alkyl borate anion, the anion of the alkyl borate whose alkyl group is a C1-C18 hydrocarbon group is mentioned. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, Anion of alkylboric acid having an alkyl group such as octadecyl group, oleyl group, 10-undecenyl group, 2-ethyl-hexyl group, isononyl group, isodecyl group, 2-methyl-undecyl group, 5-methyl-tetradecyl group, cyclohexyl group, etc. Is mentioned.

Of these anion components, phosphate anions, carboxyl anions, and borate anions are preferred. These may be used in combination.

  The catalyst for oxidation reaction of the present invention may be used as a catalyst that has been isolated after previously mixing (A) and (B), provided that (A) and (B) are present in the oxidation reaction system. Alternatively, an aqueous solution obtained by dissolving (B) in an aqueous solution or aqueous dispersion of (A) may be used. Further, it is possible to simply charge (A) and (B) so as to have the following predetermined ratio when the oxidation reaction raw material is charged.

  As for the mixing ratio of (A) and (B), the total of (B) is 0.1 to 1.5 equivalents relative to 1 equivalent of the heteropolyacid or its salt (A). 3 equivalents or more are preferable, and 1.2 equivalents or less are preferable from the viewpoint of durability.

When preparing the aqueous solution or aqueous dispersion of (A), a method in which the heteropolyacid (A ₀ ) and the heteropolyacid salt (A ₁ ) are added and dissolved and dispersed, the acid salt in the aqueous solution of the heteropolyacid (A ₀ ) And a method of obtaining an aqueous solution or aqueous dispersion of the heteropolyacid salt (A ₁ ) by reacting and reacting. The solid content concentration of the aqueous solution or aqueous dispersion is usually 10 to 60% by weight, preferably 30 to 50% by weight.

The oxidation reaction catalyst of the present invention can be used for a normal oxidation reaction.
Examples of oxidation reactions include: (1) epoxidation, dihydroxylation, Wacker oxidation when using olefin as the reaction substrate, (2) aldehyde formation or ketination using alcohol as the reaction substrate, (3) Examples include, but are not limited to, esterification when a ketone is used as a reaction substrate, and (4) an oxidation reaction such as sulfonation or sulfoxidation when sulfide is used as a reaction substrate.
The catalyst of the present invention can be particularly preferably used for olefin epoxidation from the viewpoint of high selectivity.

Examples of the olefin as a reaction substrate include alkenes and cycloalkenes. Examples of alkenes include ethene, propene, 1-butene, 2-butene, 1-pentene, 2-pentene, 3-methyl-1-butene, 1-hexene, 2-hexene, 3-hexene, 1-heptene, 2 -Linear or branched carbon such as heptene, 1-octene, 2-octene, 1-decene, 1-undecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-icocene, 1-triacontene Alkenes having a number of about 1 to 30 (preferably about 2 to 20) are listed.
Alkenes also include alkapolyenes (for example, alkadienes such as butadiene).

Examples of the cycloalkene include cycloalkene having about 3 to 30 carbon atoms such as cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, and cyclooctadecene.
Cycloalkenes also include cycloalkapolyenes such as cycloalkadienes.

These alkenes and cycloalkenes may have various substituents in the molecule.
Examples of such substituents include halogen atoms, hydroxyl groups, substituted oxy groups (eg, alkoxy groups, cycloalkyloxy groups, aryloxy groups, acyloxy groups, silyloxy groups), alkylene ether groups, mercapto groups, substituted thios. Group (eg, alkylthio group, cycloalkylthio group, arylthio group, etc.), carboxyl group, substituted oxycarbonyl group (eg, alkyloxycarbonyl group, aryloxycarbonyl group, etc.), substituted or unsubstituted carbamoyl group, cyano group, acyl group , Formyl group, nitro group, substituted or unsubstituted amino group, cycloalkyl group, cycloalkenyl group, aryl group, heterocyclic group and the like.

  Specific examples of the alkene having a substituent include, for example, styrene derivatives such as styrene and methylstyrene; α, β-unsaturated esters such as ethyl acrylate; α, β-unsaturated nitriles such as acrylonitrile; α, such as acrolein; β-unsaturated aldehyde; α, β-unsaturated acetal such as acrolein diethyl acetal; α, β-unsaturated ketone such as vinyl methyl ketone, terminal allyl etherified product of polyethylene polyol, terminal allyl etherified product of polypropylene polyol, bisphenol A Diallyl etherates, bisphenol F diallyl etherates, hydrogenated bisphenol A diallyl etherates, hydrogenated bisphenol F diallyl aleates, allyl compounds such as triallyl isocyanurate; Vinyl etherified product, polypropylene polyol both-end divinyl etherified product, bisphenol A divinyl etherified product, bisphenol F divinyl etherified product, hydrogenated bisphenol A divinyl etherified product, hydrogenated bisphenol F divinyl etherified product, trivinyl isocyanurate, etc. Vinyl compound: dipropenyl etherification product of both ends of polyethylene polyol, dipropenyl etherification product of both ends of polypropylene polyol, dipropenyl etherification product of bisphenol A, dipropenyl etherification product of bisphenol F, dipropenyl etherification product of hydrogenated bisphenol A, water Propenyl ether compounds such as dipropenyl etherified bisphenol F and tripropenyl isocyanurate; 5-vinylcyclo [ 2,2,1] hept-2-ene, 1-methyl-5-vinylcyclo [2,2,1] hept-2-ene, 3a, 4,7,7a-tetrahydroindene, 4-vinyl-1-cyclohexene And modified products thereof (for example, dimerized with ethylene glycol or methyl hydrogen siloxane). Preferred organic substrates include cycloalkenes such as cyclopentene, diallyl etherates of hydrogenated bisphenol A, triallyl isocyanurate, 5-vinylcyclo [2,2,1] hept-2-ene, 5-vinylcyclo [2,2, 1] Ethylene glycol modified product of hept-2-ene, methylhydrogensiloxane modified product of 5-vinylcyclo [2,2,1] hept-2-ene.

As the reaction substrate alcohol, primary alcohol or secondary alcohol is used.
As primary alcohol, methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-decanol, 1-eicosanol, 3-methyl-1-butanol 3,3-dimethyl-1-butanol, 4-methyl-1-pentanol, 2-methyl-1-pentanol, 2,2-dimethyl-1-pentanol, 5-methyl-1-hexanol, 3- Monoalcohols such as chloro-1-propanol, benzyl alcohol, 2-phenylethanol and 2- (p-chlorophenyl) ethanol; ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neo Pentyl glycol, cyclohexane dimethyl Dihydric alcohol, such as cyclohexanol and cyclohexylene glycol.

  Secondary alcohols include 2-propanol, 2-butanol, 2-pentanol, 2-hexanol, 2-heptanol, 2-decanol, 2-eicosanol, 3-pentanol, 3-hexanol, 3-heptanol, 3- Decanol, 3-eicosanol, 4-heptanol, 4-decanol, 4-eicosanol, 3-methyl-2-butanol, 3,3-dimethyl-2-butanol, 4-methyl-2-pentanol, 2-methyl-3 -Pentanol, 2,2-dimethyl-3-pentanol, 5-methyl-3-hexanol, 1-chloro-2-propanol, 1-bromo-2-propanol, 1-methoxy-2-propanol, 1-phenoxy 2-propanol, 1-acetoxy-2-propanol, 1-phenylethanol, Dehydrol, 1- (p-tolyl) ethanol, 1- (p-chlorophenyl) ethanol, 1- (p-bromophenyl) ethanol, 1- (p-methoxyphenyl) ethanol, 1- (p-phenoxyphenyl) ethanol, 1- (p-acetoxyphenyl) ethanol, 1-phenyl-2-propanol, 1- (p-tolyl) -2-propanol, 1- (p-chlorophenyl) -2-propanol, 1- (p-bromophenyl) 2-propanol, 1- (p-methoxyphenyl) -2-propanol, 1- (p-phenoxyphenyl) -2-propanol, 1- (p-acetoxyphenyl) -2-propanol, cyclopentanol, cyclohexanol , Cycloheptanol, cyclooctanol, cyclododecanol, exo-no Borneol, endo- norborneol, 1-indanol, 1-tetralol, 9-fluorenol, and the like.

  Further, an alcohol obtained by addition polymerization of alkylene oxide to the above alcohol may also be used. Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2- or 1,4-butylene oxide, styrene oxide, and a combination of two or more thereof (block addition or random addition). The added mole number of alkylene oxide is usually 2 to 500. A preferred alcohol is a secondary alcohol.

Examples of the ketone as the reaction substrate include aromatic ketones, aliphatic ketones, arylalkyl ketones, and cyclic ketones.
Specific examples of ketones include aromatic ketones such as benzophenone, dinaphthyl ketone, and benzopinacolone; aliphatic ketones such as acetone, methyl ethyl ketone, methyl tert-butyl ketone, methyl vinyl ketone, and diethyl ketone; methyl phenyl ketone, butyrophenone, isobutyrophenone Arylalkyl ketones such as valerophenone and benzoylacetone; cyclic ketones such as cyclopentanone, cyclohexanone and cyclooctanone.

<I'm sorry for the details, but in [0033], examples of sulfides that are sulfonated and sulfoxidized reaction substrates include aromatic sulfides, aliphatic sulfides, arylalkyl sulfides, and cyclic sulfides.
Aromatic sulfides such as diphenyl sulfide and phenyl-1-methylphenyl sulfide; fats such as dimethyl sulfide, diethyl sulfide, dipropyl sulfide, dicyclohexyl sulfide, ethylbutyl sulfide, 1-chloro-2- (ethylsulfanyl) ethane and tetrahydrothiophene Group sulfides and the like; and arylalkylthioethers such as phenylmethyl sulfide and phenylethyl sulfide.

In the oxidation reaction using the oxidation reaction catalyst of the present invention, any of hydrogen peroxide, molecular oxygen, organic peroxide, inorganic peroxide and the like may be used as an oxidizing agent. From the viewpoint of safety, hydrogen peroxide and molecular oxygen are preferable, and hydrogen peroxide water is particularly preferable.
Usually, hydrogen peroxide diluted to water at a concentration of 35% or less is used. The amount of the oxidizing agent used can be selected according to the type of the organic substrate, and is usually 0.5 mol or more (for example, 1 mol or more), preferably 1 to 100 mol, more preferably 1 mol of the organic substrate. Is about 1 to 50 mol.
In the oxidation reaction, these oxidizing agents and the heteropolyacid and / or its salt (A) which are oxidation reaction catalysts may be mixed in advance, or the oxidation reaction catalyst aqueous solution and (B) and oxidation reaction of the present invention. These oxidizing agents may be added dropwise to a homogeneous mixed solution or dispersion solution composed of a substrate solution.

The oxidation reaction may be performed in the presence or absence of a solvent.
The solvent can be appropriately selected depending on the type of organic substrate and target product.
Solvents include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; aliphatic hydrocarbons such as hexane, heptane and octane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; carbon tetrachloride, chloroform, dichloromethane, 1 Halogenated hydrocarbons such as 2-dichloroethane; carboxylic acids such as acetic acid, propionic acid and butyric acid; ketones such as acetone, methyl ethyl ketone, cyclopentanone and cyclohexanone; esters such as methyl acetate, ethyl acetate, isopropyl acetate and butyl acetate; Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; Nitriles such as acetonitrile, propionitrile and benzonitrile; Diethyl ether, dibutyl ether, dimethoxyethane, dioxane, tetra Dorofuran, chain or cyclic ethers such as ethylene glycol monobutyl ether; methanol, ethanol, isopropanol, etc. alcohols such as 2-ethylhexyl alcohol. These solvents are used alone or in combination of two or more.

  The reaction temperature can be appropriately selected according to the reaction substrate, the type of reaction, and the like, taking into consideration the reaction rate and reaction selectivity, and is, for example, about 0 to 200 ° C, preferably about 10 to 150 ° C. The reaction may be carried out at normal pressure or under pressure. The reaction may be performed by any method such as a batch method, a semi-batch method, or a continuous method.

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

  The catalyst for oxidation reaction in the present invention maintains reaction activity over a long period of time and can be used stably.

Hereinafter, although it demonstrates further as a usage example of the catalyst for oxidation reactions of this invention, this invention is not limited to this. In the following description, “parts” represents parts by weight and “%” represents% by weight.

Hereinafter, production examples of the catalyst of the present invention will be described.
[Production method of catalyst 1]
A heteropolyacid aqueous solution was prepared by dissolving 182 g of silicomolybdic acid (H ₃ SiMo ₁₂ O ₄₀ ) (A-1) in 500 g of water. To this was added 51 g of 1-ethyl-3-methylimidazolium acetate (B-1) to obtain an aqueous dispersion of 1-ethyl-3-methylimidazolium salt of silicomolybdic acid, which is catalyst 1 of the present invention. It was.

[Method for producing catalyst 2]
A heteropolyacid aqueous solution was prepared by dissolving 288 g of phosphotungstic acid (H ₃ PW ₁₂ O ₄₀ ) (A-2) in 1000 g of water. 1-methyl-1,8-diazabicyclo [5.4.0] undecene-7 salt obtained from methyl phosphate and 1,8-diazabicyclo "5.4.0" undecene-7 (B -2) 68 g was charged to obtain an aqueous solution of 1-methyl-1,8-diazabicyclo [5.4.0] undecene-7 salt of phosphotungstic acid.
Next, this aqueous solution was dried with a circulating dryer at 120 ° C. for 8 hours, and 1-methyl-1,8-diazabicyclo [5.4.0] undecene-7 salt of phosphotungstic acid, which is catalyst 2 of the present invention, was obtained. Obtained.

[Method for producing catalyst 3]
Phosphotungstic acid (H ₃ PW ₁₂ O ₄₀ ) (A-2) (288 g) and 1-ethyl-3-methylimidazolium phosphate (B-3) (60 g) were dissolved in 10% hydrogen peroxide water (500 g) to obtain the present invention. Thus, a hydrogen peroxide aqueous solution of 1-ethyl-3-methylimidazolium phosphate of phosphotungstic acid as catalyst 3 was obtained.

[Catalyst 4: Method for Producing Silica Support of Phosphotungstic Acid (H3PW12O40) (A-20)]
As a carrier, 300 parts of synthetic silica gel (CariACT Q-10 manufactured by Fuji Silysia Chemical Co., Ltd.) (specific surface area 219.8 m ² / g, pore volume 0.660 cm ³ / g) was adjusted to 110 ° C. with hot air drying. And dried for 4 hours.
300 parts of phosphotungstic acid was weighed, and all the dried synthetic silica gel was put into an aqueous solution to which 500 ml of pure water was added, and stirred well. The carrier impregnated with this aqueous solution was air-dried for 1 hour and then dried for 5 hours with a drier adjusted to 150 ° C. to obtain a silica-supported catalyst of phosphotungstic acid, which is catalyst 4 for comparison.

[Catalyst 5: Method for producing reaction product of phosphotungstic acid (H ₃ PW ₁₂ O ₄₀ ) (A-2) and fluorine-containing ammonium]
Below, the manufacturing method of the catalyst 5 which is a catalyst for a comparison combined with fluorine-containing ammonium as (B) component is described.
First, 1H, 1H, 7H-dodecafluoroheptyltrimethylammonium chloride, which is a fluorine-containing ammonium compound, was synthesized by the following method.

Under a nitrogen atmosphere, a 1 L four-necked flask equipped with a stirrer, a thermometer and two dropping funnels was charged with 42 g of 2-nitrobenzenesulfonyl chloride and 278 g of methylene chloride, and then 20 g of triethylamine, 1H, 1H, 66 g of 7H-dodecafluoroheptanol was charged.
While stirring, the flask was cooled so that the temperature of the reaction solution became 0 ° C., and triethylamine was added dropwise over about 10 minutes while maintaining the temperature at 0 ° C. Next, while maintaining the temperature at 0 ° C., 1H, 1H, 7H-dodecafluoroheptanol was added dropwise over about 40 minutes and stirred for 4 hours. After completion of the reaction, the flask temperature was returned to room temperature, and 300 ml of water was added for hydrolysis. The solution was transferred to a 1 L separatory funnel, and after separating the reaction solution, 40 ml of methylene chloride was added to the aqueous layer, and the aqueous layer was washed three times. The obtained methylene chloride layer and the organic layer were combined, dried over anhydrous magnesium sulfate, the anhydrous magnesium sulfate was removed by filtration, and the methylene chloride was removed by evaporation to remove 1H, 1H, 7H-dodecafluoroheptyl-2. -98 g (yield 95%) of nitrobenzenesulfonate was obtained as a pale yellow solid.

    Next, 95 g of synthesized 1H, 1H, 7H-dodecafluoroheptyl 2-nitrobenzenesulfonate and 77 g of dimethylbenzylamine were added to a 300 ml four-necked flask equipped with a magnetic stir bar, thermometer, and Dimroth condenser in a nitrogen atmosphere. Was charged. While stirring, the flask was heated so that the temperature of the reaction liquid reached the reflux temperature (150 to 160 ° C.), and stirred for 45 hours while maintaining the temperature at 150 to 160 ° C. After the completion of the reaction, the reaction mixture was allowed to cool to precipitate a solid. After separating this, by distillation of the mother liquor, the target low-boiling compound group containing a fluorine-containing tertiary amine and dimethylbenzylamine (boiling point 183 ° C.) were fractionated. Ether was added to the obtained distillate, and the aqueous phase was removed by chlorinating dimethylbenzylamine contained in a trace amount by washing with 3% aqueous hydrochloric acid. The aqueous hydrochloric acid layer was washed 3 times with 20 ml of ether and added to the ether layer. Next, 10% aqueous hydrochloric acid was added to the ether layer and the mixture was shaken. This time, the fluorine-containing tertiary amine was converted to hydrochloric acid to remove the organic layer containing reaction byproducts. When this aqueous hydrochloric acid layer was made alkaline by adding sodium hydroxide little by little, an oily substance appeared. This was extracted with ether, dried over anhydrous magnesium sulfate, filtered to remove anhydrous magnesium sulfate, evaporated to remove ether, and dimethyl 1H, 1H, 7H-dodecafluoroheptylamine as a colorless liquid (37 g) Rate 56%).

    Next, 30 g of the above dimethyl 1H, 1H, 7H-dodecafluoroheptylamine and 67 g of methyl iodide were charged into a 200 ml two-necked flask equipped with a magnetic stir bar, thermometer and Dimroth condenser. While stirring, the flask was heated so that the temperature of the reaction liquid reached the reflux temperature (45 ° C.), and stirred for 10 hours while maintaining the temperature at 45 ° C. After completion of the reaction, the flask temperature was returned to room temperature, the precipitated solid was filtered off, and washed 5 times with 5 ml of diethyl ether. The washed solid was dried to obtain 40 g (yield 94%) of 1H, 1H, 7H-dodecafluoroheptyltrimethylammonium iodide as a white solid.

In a 500 ml eggplant flask equipped with a magnetic stirring bar, 5.01 g of the above-mentioned 1H, 1H, 7H-dodecafluoroheptyltrimethylammonium iodide, ion exchange resin Amberlite IRA-400 (Rohm and Haas, USA) 50 ml of distilled water and 250 ml of distilled water were charged. The reaction solution was stirred for 16 hours while maintaining the temperature of the reaction solution at room temperature (20 to 25 ° C.). After completion of the reaction, the ion exchange resin was removed by filtration, and the ion exchange resin was washed 5 times with 25 ml of distilled water.
After removing water by evaporation, 4.01 g of 1H, 1H, 7H-dodecafluoroheptyltrimethylammonium chloride, which is a fluorine-containing ammonium compound to be combined with (A-2), was obtained as a white solid. It was.

Separately, 1.250 g of tungstic acid (H ₂ WO ₄ ) and 3.00 mL of 35% hydrogen peroxide solution were added to a 50 ml eggplant flask equipped with a Dimroth cooler and a stirrer, and stirred at 60 ° C. for 3 hours. The resulting white suspension was cooled to room temperature, and 0.114 g (0.4 mmol) of 85% phosphoric acid (H ₃ PO ₄ ) and 15 mL of water were added.
To this solution was added dropwise a solution of 1.02 g (2.50 mmol) of 1H, 1H, 7H-dodecafluoroheptyltrimethylammonium chloride in methylene chloride (20 mL) over 2 minutes. After further stirring for 15 minutes, methylene chloride was distilled off at 50 ° C., and the remaining solid was collected by filtration. The solid was washed with water and dried to give 1.71 g (90.) of a mixture of phosphotungstic acid and 1H, 1H, 7H-dodecafluoroheptyltrimethylammonium chloride, which is catalyst 5 for Comparative Example, as a pale yellow solid. 3%).

[Production Example 1] <Production Example 1 of Olefin as Oxidation Reaction Substrate>
In a reaction vessel equipped with a stirrer, a temperature controller and a condenser, 200 parts of methyl ethyl ketone (manufactured by Maruzen Petroleum Corporation) and 234 parts (1 mole part) of hydrogenated bisphenol A (manufactured by Nippon Nippon Chemical Co., Ltd.) are charged at 300 rpm. Heat to 50 ° C. with stirring. 161 parts (2.1 mol parts) of allyl chloride (manufactured by Showa Denko KK) was added dropwise thereto. After completion of dropping, the mixture was aged at 50 ° C. for 3 hours, added with 500 g of water, and allowed to stand at room temperature. After separation, methyl ethyl ketone was removed under reduced pressure at 50 ° C. and 1 Torr to obtain hydrogenated bisphenol A diallyl ether (c-1).

[Production Example 2] <Production Example 2 of Olefin as Oxidation Reaction Substrate>
In a reaction vessel equipped with a stirrer, a temperature controller and a condenser, 62 parts (1 mole part) of ethylene glycol (Mitsubishi Gas Chemical Co., Ltd.) was charged and heated to 60 ° C. while stirring at 300 rpm. 240 parts (2 mole parts) of 5-vinylcyclo [2,2,1] hept-2-ene (manufactured by San Petrochemical Co., Ltd.) was added dropwise. After completion of dropping, the mixture was aged at 60 ° C. for 3 hours, and unreacted substances and ethylene glycol were removed under reduced pressure at 180 ° C. and 1 Torr, and ethylene glycol-bis (5-vinylcyclo [2,2,1] hept-2-ene) ether ( c-2) was obtained.

[Examples 1-7]
An epoxy resin was produced by the following method using the catalysts 1 to 3 of the present invention.
A reactor equipped with a stirrer, a temperature controller, and a reflux condenser is charged with the amount (weight) of the oxidation reaction catalyst 1 to 3, 85% phosphoric acid aqueous solution, oxidizing agent, and phase transfer catalyst described in Table 1. The temperature was adjusted to 60 ° C. while stirring at 300 rpm.
A mixed solution of the solvent and the oxidation reaction substrate in the amounts shown in Table 1 was added dropwise over 1 hour. After completion of dropping, the reaction was allowed to proceed for 20 hours while maintaining the temperature at 60 ° C. Cooled to room temperature and allowed to stand. The upper layer (organic phase) was separated from the reaction mixture separated into two phases.

[Comparative Examples 1 to 7]
In accordance with Table 2, the reaction vessel was charged and reacted in the same manner as in Examples 1-7. Since Comparative Examples 3 and 6 were separated into three phases including the catalyst phase, the lower layer (aqueous phase) and the catalyst phase (intermediate phase) were separated.

  The oxidation reaction yield, catalyst recovery rate, and catalyst activity retention rate of Examples 1 to 7 and Comparative Examples 1 to 7 were measured by the following methods. The results are shown in Table 3.

<Calculation method of oxidation reaction yield>
The yield of the oxidation reaction product in the upper layer (organic phase) obtained in the above Examples and Comparative Examples was determined from the ratio of the peak of the oxidation reaction substrate and the oxidation reaction product in gas chromatography (GC). . The results are shown in Table 3.
Oxidation reaction yield (%) = oxidation reaction product × 100 / oxidation reaction substrate

<Analysis conditions for oxidation reaction products by GC>
The oxidation reaction product was analyzed using the following GC apparatus and analysis conditions.
Equipment: GC-1700, 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: 300 ° 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 temperature rise; maximum temperature reached 280 ° C., holding time 5 minutes

<Measuring method of metal element content>
Measurement was performed using an ICP emission spectrometer (ICP-OES).
2.00 g of a measurement sample is weighed into a plastic sample tube, and 18.00 g of dimethylformamide is added to dilute it 10 times. A calibration curve is used at 10 ppb, 50 ppb, and 100 ppb using the standard solution XSTC-622 for ICP emission analysis manufactured by SPEC as a standard substance, and ICP-OES measurement is performed under normal conditions.

  There are 35 elements that can be measured with XTSC-622, Li, B, Na, Mg, Al, Si, P, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga , Ge, As, Se, Rb, Sr, Zr, Mo, Ag, Cd, Sn, Sb, Cs, Ba, W, and Pb. Accordingly, the metal element refers to 28 types excluding B, Si, P, Ge, As, Se, and Sb.

<Catalyst recovery>
Tungsten or molybdenum, which is a metal in the catalyst heteropolyacid, was subjected to partition analysis by ICP emission analysis. The recovery rate of the catalyst was determined by the following formula and listed in Table 3.
Catalyst recovery (%) = [(a)-(b)] 100 / (a)
However, (a) represents the charged metal content (ppm), and (b) represents the metal content (ppm) in the organic phase after liquid separation.
Here, the metal refers to tungsten or molybdenum in the heteropolyacid. As the charged metal content, a calculated value obtained from the structural formula was used.

<Activity retention of catalyst>
To the aqueous phase (or aqueous phase and catalyst phase) obtained in the above Examples and Comparative Examples, the oxidizing agent used was added and stirred and heated again. When the temperature was raised to 60 ° C., each was used. A solution obtained by dissolving the oxidation reaction substrate in the organic solvent was added dropwise over 1 hour, and reacted for 20 hours. By this method, the catalyst could be recovered. After repeating this 10 times, the activity retention calculated by the following formula was obtained. It described in Table 3.
Activity retention (%) = Oxidation reaction yield after 10 cycles / First oxidation reaction yield

  As is clear from the results in Table 3, the oxidation reaction catalysts used in Examples 1 to 7 all have high oxidation reaction yields (catalytic activity), and high catalyst recovery and activity retention, It turns out that it is superior to the catalyst for oxidation reaction of a comparative example.

The oxidation reaction catalyst of the present invention maintains the reaction activity over a long period of time and can be used stably. Therefore, the expensive heteropolyacid catalyst or a salt thereof can be repeatedly used without being discarded, and the oxidation reaction is inexpensive. Can be done.

Claims (5)

  Heteropolyacid and / or salt thereof (A), and the cation component is at least one selected from the group consisting of imidazolinium ion, imidazolium ion and pyrimidinium ion, and the anion component is phosphate anion, alkyl phosphate An oxidation reaction catalyst comprising, as an essential component, a salt (B) which is a combination of one or more selected from an anion, a carboxyl anion, a borate anion, and an alkyl borate anion. The heteropolyacid is H ₄ [SiW ₁₂ O ₄₀ ]. _{xH 2 O, H 3 [PW} 12 O 40]. _{xH 2 O, H 3 [PMo} 12 O 40]. _{xH 2 O, H 4 [SiMo} 12 O 40]. _{xH 2 O, H 4 + n} [SiV n W 12-n O 40]. _{xH 2 O, H 3 + n} [PV n W 12-n O 40]. _{xH 2 O, H 3 + n} [PV n Mo 12-n O 40]. _{xH 2 O, H 4 + n} [SiV n Mo 12-n O 40]. xH ₂ O, H ₄ [SiMo _n W _12-n O ₄₀ ]. xH ₂ O, and _{H 3 [PMo n W 12-} n O 40]. The catalyst for oxidation reaction according to claim 1, which is at least one selected from the group consisting of xH ₂ O (where n is an integer of 1 to 11, and x is an integer of 1 or more).   2. The oxidation reaction according to claim 1, wherein the salt of the heteropolyacid is at least one salt selected from the group consisting of alkali metal salts, alkaline earth metal salts, copper salts, gold salts, gallium salts and ammonium salts. catalyst.   An oxidation reaction method of an organic compound, characterized in that the oxidation reaction catalyst according to any one of claims 1 to 3 is used and hydrogen peroxide or molecular oxygen is used as an oxidizing agent.   The oxidation reaction method according to claim 4, wherein the organic compound is an olefin and the oxidation reaction is epoxidation.