JP2011136920A - Method for producing alicyclic epoxy compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for epoxidizing an alicyclic compound inexpensively, efficiently and safely by using hydrogen peroxide as an oxidizing agent. <P>SOLUTION: The method for producing an epoxy compound includes contacting a specific alicyclic compound with hydrogen peroxide in the presence of a mixture or a complex compound containing a tungsten compound and a quaternary ammonium salt. Preferably a tungsten atom-containing inorganic acid or its salt is used as the tungsten compound. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing an alicyclic epoxy compound. More specifically, the present invention relates to a method for producing an alicyclic epoxy compound at low cost, efficiently and safely using hydrogen peroxide as an oxidizing agent.

An alicyclic epoxy compound is a substance useful as a plasticizer for a polymer, and a method of epoxidation using perbenzoic acid (MCPBA) is known (Non-patent Document 1). In recent years, alicyclic epoxy compounds have been used not only for plasticizers but also for a wide variety of applications such as sealants, UV inkjet monomers, UV nanoimprint resins, adhesives and coating agents (for example, patents) Reference 1, Patent Document 2, Non-Patent Document 2, and Patent Document 3).

When an alicyclic epoxy compound is used as a monomer for UV cationic polymerization, it is not affected by oxygen polymerization and has a small volume shrinkage. However, it has further high-speed curability and adaptability to non-absorbing substrates. There is a demand for a monomer having a molecular weight (see Non-Patent Document 3). In addition, dual UV curing using light and heat has attracted attention, and an alicyclic epoxy compound having excellent curability is also required (see Patent Document 4). In particular, the general formula (1):

An epoxy compound obtained by epoxidizing (wherein X represents a linking group or a single bond) is useful because it is less irritating to the skin and can give a fast-curing and flexible cured product. However, an epoxy compound obtained by oxidizing a compound having a structure represented by the general formula (1) is susceptible to hydrolysis, and the hydrolyzate may reduce the catalytic activity, thereby suppressing hydrolysis. An efficient manufacturing method is desired.

JP 2002-80557 A JP 2005-187724 A JP 2008-111105 A JP 2009-046565 A

I & EC PRODUCT RESEARCH AND DEVELOPMENT 1965, 4, 231-233 MATERIAL STAGE. 2008, 8, 5-10 J. Jpn. Soc. Color Mater. 2008, 81 (12), 498-503.

Non-Patent Document 1 describes a method of epoxidizing an alicyclic compound using perbenzoic acid, but does not describe other oxidizing agents. Patent Documents 1 to 4 and Non-Patent Documents 2 and 3 describe various alicyclic epoxy compounds, but examples of epoxidation of alicyclic compounds represented by the general formula (1) were performed. There is no. However, perbenzoic acid is a compound that requires attention in handling such as explosiveness, and has a problem that an equimolar amount of waste is generated after the reaction. Furthermore, perbenzoic acid is expensive as an oxidizing agent, and it is not necessarily industrially advantageous from the viewpoint of safety and economy, and an inexpensive and highly efficient production method that can be used industrially has been desired.

Accordingly, an object of the present invention is to provide a method for epoxidizing an alicyclic compound inexpensively, efficiently and safely using hydrogen peroxide as an oxidizing agent.

The inventors of the present invention have made extensive studies to solve the above problems, and found that an epoxy compound having a specific structure can be efficiently obtained by using a tungsten compound and a quaternary ammonium salt. The invention has been completed.

That is, the present invention provides a compound represented by the general formula (1) in the presence of a mixture or a complex compound containing a tungsten compound and a quaternary ammonium salt:

(In the formula, X represents a linking group or a single bond.)
The manufacturing method of the epoxy compound characterized by contacting hydrogen peroxide with the alicyclic compound represented by these.

According to the present invention, an alicyclic epoxy compound having a specific structure can be produced inexpensively, efficiently and safely. These alicyclic epoxy compounds are important substances as plasticizers, encapsulants, or cationic curing resins, such as UV inkjet monomers, UV nanoimprint resins, adhesive / coating agents, and polymer modifiers. The field of application can be used in a wide range.

  The compound used as a substrate in the present invention has the general formula (1):

It is an alicyclic compound represented by these. In addition, as said coupling group X, if it is a coupling group or a single bond, it will not specifically limit, A well-known thing is mentioned. Specifically, for example, an alkylene group having 1 to 20 carbon atoms (for example, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a 2-methylbutane-1,3-diyl group), and a carbon number of 4 to 10 cycloalkylene groups (such as 1,4-cyclohexylene group), arylene groups having 6 to 10 carbon atoms (such as phenylene group and naphthalenediyl group), carbonyl, ester, amide, ether, sulfide, sulfoxide, Examples include sulfone, imine, and urethane bonds. Among these linking groups or single bonds, when a linking group represented by —C (═O) —O—CH ₂ — is used, it has low skin irritation and gives toughness and adhesion to a cured film. preferable.

The hydrogen peroxide used in the present invention is not particularly limited, and a known one can be used. Hydrogen peroxide is preferably used as an aqueous solution from the viewpoint of handleability. The concentration of hydrogen peroxide used in the reaction is not limited, but it is usually used in an amount of about 1 to 100%, and preferably used in an aqueous solution of 10 to 60%.

The amount of the aqueous hydrogen peroxide solution used in the present invention is not limited. Usually, it is about 0.7 to 5.0 equivalents, preferably 0.9 to the carbon-carbon double bond contained in the substrate. 3.5 equivalents.

As a tungsten compound, if it is a compound which produces | generates a tungstate anion in water, it will not specifically limit, A well-known thing can be used. Specific examples include tungstic acid, tungsten trioxide, tungsten trisulfide, phosphotungstic acid, ammonium tungstate, potassium tungstate dihydrate, sodium tungstate dihydrate, and the like. Tungsten oxide, phosphotungstic acid, sodium tungstate dihydrate and the like are preferable. The amount used is usually selected from the range of about 0.0001 to 20 mol%, preferably 0.01 to 10 mol%, relative to the substrate.

Examples of the quaternary ammonium salt include quaternary ammonium salts and nitrogen ring-containing quaternary ammonium salts.

Specific examples of the quaternary ammonium salts include trioctylmethylammonium chloride, trioctylethylammonium chloride, tridecylmethylammonium chloride, dilauryldimethylammonium chloride, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, lauryldimethylbenzylammonium chloride. , Stearyldimethylammonium chloride, tricaprylmethylammonium chloride, tetrabutylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride and the like. These bromides, iodides, sulfites, sulfates or hydrogen sulfates may also be used.

Examples of the nitrogen ring-containing quaternary ammonium salts include quaternary ammonium salts in which the nitrogen ring is a pyridine ring, picoline ring, quinoline ring, imidazoline ring, morpholine ring, or the like. Ammonium compounds are preferred. As a specific example, it has a C8-C20 linear or branched alkyl group. Pyridinium salts (for example, N-laurylpyridinium chloride, N-cetylpyridinium chloride, etc.), picorium salts having a linear or branched alkyl group having 8-20 carbon atoms (for example, N-laurylpicolinium chloride, etc.), carbon number 8 A quinolium chloride having a linear or branched alkyl group of -20, an isoquinolium chloride having a linear or branched alkyl group having 8 to 20 carbon atoms, and a linear or branched alkyl group having 8 to 20 carbon atoms. Examples thereof include hydroxyethyl imidazoline chloride and hydroxymorpholine chloride having a linear or branched alkyl group having 8 to 20 carbon atoms. The nitrogen ring-containing quaternary ammonium salt may be bromide, iodide sulfite, sulfate or hydrogen sulfate of the quaternary ammonium compound. These may be used alone or in combination of two or more. The amount used is usually selected from the range of about 0.0001 to 20 mol%, preferably 0.01 to 10 mol%, relative to the substrate.

The complex compound is, for example, a complex compound formed from a tungsten compound and a quaternary ammonium salt, hydrogen peroxide, and a mineral acid described later, which is used as necessary. Particularly, a complex compound containing a phosphorus atom is preferably used. The

In the reaction of the present invention, a mineral acid may be used as necessary. Examples of the mineral acid include phosphoric acid, sulfuric acid, hydrochloric acid, perchloric acid, hexafluorosilicic acid, nitric acid, tetrafluorosilicic acid and the like, and phosphoric acid and sulfuric acid are preferably used. These mineral acids may be used alone or in combination of two or more. The amount of mineral acid used is preferably about 0.0001 to 15% by weight, more preferably 0.001 to 10% by weight, based on the substrate.

In the present invention, the pH in the reaction system is preferably about 0.1 to 7.0, particularly 1.0 to 4.0 in terms of reaction rate and suppression of the formation of reaction byproducts. Is preferred. Depending on the catalyst composition, when the pH in the reaction system is not within the above range, an acid such as phosphoric acid or a salt thereof, an alkali metal hydroxide such as sodium hydroxide or the like is used as needed. The pH can be adjusted to the above range to carry out the reaction.

Phosphoric acids are phosphoric acids or their salts, and include the following. Examples of phosphoric acids include phosphoric acid, polyphosphoric acid, pyrophosphoric acid, hexametaphosphoric acid, hypophosphorous acid, phosphorous acid, dodecyl phosphoric acid, 2-ethylhexyl phosphoric acid, and the like. Examples of phosphoric acid salts include sodium phosphate. , Potassium phosphate, ammonium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium hydrogen phosphate, ammonium hydrogen phosphate, sodium polyphosphate, sodium hexametaphosphate, acidic sodium hexametaphosphate, sodium polyphosphate, pyrophosphate Examples thereof include sodium, disodium dihydrogen pyrophosphate, sodium hypophosphite, sodium phosphite and the like.

An organic solvent such as toluene may be added to the reaction system as necessary in order to suppress the reaction rate and the production of reaction byproducts. The amount of the organic solvent used is about 1 to 500 mol%, preferably 10 to 300 mol%, based on the substrate.

In the production method of the present invention, the reaction temperature is usually about 0 to 80 ° C, preferably 20 to 60 ° C.

The reaction time in the production method of the present invention may be appropriately determined depending on the amount of catalyst used, reaction temperature, and the like, but is usually about 30 minutes to 24 hours, preferably 2 to 12 hours.

In a general embodiment of the present invention, a tungsten compound, a quaternary ammonium salt, and a hydrogen peroxide solution are mixed in a reactor (adding phosphoric acid or sulfuric acid as necessary), a substrate is added, The reaction is carried out at a temperature of In addition, you may change the addition order of a substrate, a catalyst, and another additive as needed. After completion of the reaction, the target product is obtained by separating and purifying the reaction solution by a known method. If necessary, the remaining hydrogen peroxide may be decomposed with a sodium thiosulfate aqueous solution or the like. The obtained epoxy compound can also be purified by distillation.
When the alicyclic epoxy compound obtained by the present invention uses a compound in which X is represented by —C (═O) —O—CH ₂ —, the general formula (2):

General formula (3):

General formula (4):

It is represented by

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1
In a test tube equipped with a magnetic stir bar, sodium tungstate dihydrate (40 mg, 0.12 mmol), methyl trioctylammonium chloride (50 mg, 0.12 mmol), 42.5 wt% phosphoric acid aqueous solution (7 mg, 0.03 mmol) ), 48.5 wt% dilute sulfuric acid aqueous solution (25 mg, 0.12 mmol) and 35.5% hydrogen peroxide aqueous solution (2.34 g, 24.4 mmol) were added and stirred for 30 minutes, and the temperature was adjusted to 25 ° C. (2 , 2,3-trimethyl-3-cyclopentene-1-ethanol 2,2,3-trimethyl-3-cyclopentene-1-acetate (3.71 g, 12.2 mmol) was added and allowed to react at a stirring speed of 100 rpm for 12 hours. When the organic layer separated from the aqueous layer was analyzed with a gas chromatograph, the conversion was 97 mol% and the selectivity was 99 mol. (Monoepokido 31 mol%, diepoxide 68 mol%) was confirmed to be.

Example 2
When the reaction was carried out under the same conditions as in Example 1 except that 50 wt% of toluene was added, it was confirmed that the conversion was 98 mol% and the selectivity was 99 mol% (monoepoxide 29 mol%, diepoxide 68 mol%).

Comparative Example 1
Reaction was carried out under the same conditions as in Example 1 except that no tungsten compound was used, but formation of epoxide could not be confirmed.

Comparative Example 2
Reaction was carried out under the same conditions as in Example 1 except that no quaternary ammonium salt was used, but formation of epoxide could not be confirmed.

Claims (8)

In the presence of a mixture or complex compound containing a tungsten compound and a quaternary ammonium salt, the general formula (1):

(In the formula, X represents a linking group or a single bond.)
The manufacturing method of the epoxy compound characterized by making the alicyclic compound represented by this, and hydrogen peroxide contact.   The method for producing an epoxy compound according to claim 1, wherein the tungsten compound is an inorganic acid containing a tungsten atom or a salt thereof.   The epoxy according to claim 1 or 2, wherein the inorganic acid or a salt thereof containing a tungsten atom is a tungsten compound which is at least one selected from the group consisting of tungstic acid, sodium tungstate, potassium tungstate, and phosphotungstic acid. A method for producing a compound.   The method for producing an epoxy compound according to any one of claims 1 to 3, wherein the quaternary ammonium salt is a quaternary ammonium halide.   The method for producing an epoxy compound according to any one of claims 1 to 4, wherein the quaternary ammonium salt is at least one quaternary ammonium salt selected from the group consisting of trioctylmethylammonium chloride and tridecylmethylammonium chloride.   The method for producing an epoxy compound according to claim 1, wherein a mineral acid is present in the reaction system.   The method for producing an epoxy compound according to claim 1, wherein the mineral acid is phosphoric acid or sulfuric acid. The linking group X in the alicyclic compound represented by the general formula (1) is an alicyclic compound represented by —C (═O) —O—CH ₂ —. A method for producing an epoxy compound.