JPS6058916B2 - Unsaturated dicarboxylic acid glycidyl ester and its production method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel unsaturated dicarboxylic acid glycidyl ester and a method for producing the same.

More specifically, the present invention relates to glycidyl ester of α-methylene-δ-methyladipic acid and a method for producing the same.

α-Methylene-δ-methyldimethyl adipate is produced by heating methyl methacrylate in the presence of a polymerization inhibitor, and is also a by-product in the production of methyl methacrylate using acetone cyanohydrin as a starting material. is J. W. CCrawfOrd (Journal, of,
Society, chemicals, industry? 155C47
)) study and CJ Albisetti et al. (Journal of Chemical Society, 472C56))
It is known from the research results of

Furthermore, regarding the synthesis of alkyl derivatives of α-methylene-δ-methyladipate, there is a proposal by Kambara et al.

(JP-A-52-133916) However, no proposal has been made so far to introduce other useful functional groups into the ester group of α-methylene-δ-methyladipic acid.

As a result of intensive study on introducing useful functional groups into ester groups, the present inventors discovered that a new compound can be produced by introducing a (methyl)glycidyl group,
The present invention has been achieved.

That is, an object of the present invention is to provide a useful glycidyl ester of α-methylene-δ-methyladipic acid and a method for producing the same.

The present invention is represented by the general formula (in the formula, at least one of X. It relates to unsaturated dicarboxylic acid glycidyl esters.

The present invention also relates to an α-methylene-δ-methyladipate diester represented by (wherein R″ and R″ represent an alkyl group having 1 to 4 carbon atoms)
The present invention relates to a method for producing a-methylene-δ-methyladipate glycidyl ester represented by the general formula (1), which comprises reacting an alcohol represented by the following formula (wherein R represents hydrogen or a methyl group).

Furthermore, the present invention provides an alkali metal salt of α-methylene-δ-methyladipic acid represented by (wherein Z represents sodium or potassium) (wherein R represents hydrogen or a methyl group) ( The present invention relates to a method for producing α-methylene-δ-methyladipate glycidyl ester represented by the general formula (1), which comprises reacting with methyl)epichlorohydrin.

As the α-methylene-δ-methyladipate diester used as one of the starting materials in the present invention, an alkyl group having 1 to 4 carbon atoms can be used, but dimethyl ester having 1 carbon number can be used as the reaction proceeds. This is the most preferred ester because the resulting alcohol can be easily distilled off from the system, and also from the viewpoint of availability.

The reaction molar ratio between diester and (methyl)glycidol can usually be varied between 0.25 and 5, and when the molar ratio of (methyl)glycidol to diester is large, the formation of mono(methyl)glycidyl is small. In the opposite case, the formation of di(methyl)glycidyl compound increases, so conditions can be freely selected depending on the purpose.

As the transesterification catalyst, it is possible to use a general transesterification catalyst, but it is particularly preferable to use a quaternary ammonium salt.

The amount used is preferably 0.1 mol% or more based on the ester.
It is also possible to use an inert solvent such as benzene, toluene, etc. in the reaction, and the reaction temperature is usually 80 to 120°C, and the reaction proceeds while the lower alcohol produced is distilled out of the system under normal pressure or reduced pressure.

Further, it is preferable to add a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether or phenothiazine to the reaction system. After the esterification reaction, the reaction solution is distilled as it is or after washing with water to remove unreacted starting materials to obtain the target product. Further, α-methylene-δ-methyladipate sodium salt, which is another starting material used in the present invention, can be obtained by the neutralization reaction of α-methylene-δ-methyladipate with an alkali metal hydroxide or by the neutralization reaction of α-methylene-δ-methyladipate with an alkali metal hydroxide. It is easily produced by the saponification reaction of dimethyl adipate with an alkali metal hydroxide.

For example, α-methylene-δ-methyl dimethyl adipate and a predetermined amount of aqueous sodium chloride solution are mixed with a polymerization inhibitor for 55 minutes.
The reaction is carried out at 0 to 110°C, and the methanol produced is distilled out of the system under normal pressure or reduced pressure to complete saponification. The separation of the sodium salt from this aqueous solution is
This can be carried out by a precipitation method using acetone, alcohol or the like, or by dehydration in an azeotropic solvent such as benzene. Note that depending on the molar ratio of diester and alkali metal, the alkali salt produced can be di- and mono- or a mixture thereof.

After the alkali metal salt produced in this way is sufficiently dehydrated,
By reacting with (methyl)epichlorohydrin in the presence of a catalyst, it is converted to the desired glycidyl ester.

Preferred examples of the catalyst include quaternary ammonium salts, tertiary amines, and tertiary amine hydrochlorides.

The amount of catalyst used is preferably 0.1 mole percent or more of the alkali metal salt. The molar ratio of (methyl)epichlorohydrin to the alkali metal salt is usually 2 to 10, and it is also possible to use an inert solvent. It is also preferable to add a small amount of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, or phenothiazine.

The reaction temperature is usually preferably 60 to 120°C.

After the reaction is completed, the undissolved components are separated and distilled as is or after washing with water to obtain the desired product. The compound obtained in this way is a completely new glycidyl ester of unsaturated dicarboxylic acid, and the double bond group in the molecule has the characteristics of high copolymerizability and low homopolymerization. It is a very useful compound that can be used as a copolymer raw material for resin compositions for coating materials such as solvent-based paints and powder paints, or as a modifier, adhesives, and raw materials for molding materials.

Next, the present invention will be described with reference to Examples, but the present invention is not limited thereto.

In the examples, parts indicate parts by weight. Example 1 2 (1) parts of dimethyl α-methylene-δ-methyl adipate, 35
2 (9) parts of aqueous sodium chloride solution and 0.2 part of hydroquinone monomethyl ether were charged, and reaction was carried out at 50 to 95° C. for 5 hours while removing methanol produced.

Then, add excess alcohol and acetone mixture to α
The sodium salt of -methylene-δ-methyladipic acid was separated and thoroughly dried.

Next, 218 parts of dry sodium salt, 925 parts of epichlorohydrin, 5 parts of triethylbenzylammonium chloride
90-10 parts, 1 part of phenothiazine was charged into the reactor.
After reacting at 5° C. for 5 hours, the undissolved matter was separated, and the solution was concentrated. Then, toluene is added to the concentrated liquid to make a toluene solution, which is thoroughly washed with water, dehydrated, and distilled to a boiling point of 165-170℃.
185 parts of α-methylene-δ-methyladipate diglycidyl ester as a pale yellow transparent liquid was obtained as a fraction with a concentration of /1 mHg. The calculated elemental analysis value of this compound (Cl4H2OO6) is C: 59.14, H: 7.09, whereas the measured analysis value is C
: 58.80, H: 7.09 (Wt%), which showed good agreement.

Also double bond value 3.49wLM1y1 epoxy value 6.8
57 nM1f, and the analysis results by infrared spectrum and NMR spectrum also indicate the formation of this compound.
Example 2 In a reactor of the same type as in Example 1, 100 ml of dimethyl α-methylene-δ-methyladipate, 148 parts of glycidol,
15% of benzene was charged and the water in the reaction solution was removed by azeotropic distillation with benzene while heating and stirring.

Then triethylbenzylammonium chloride 5.0
m and reacted at 100°C for 7 hours. After concentrating the reaction solution, unreacted glycidol and dimethyl α-methylene-δ-methyladipate were recovered by distillation under reduced pressure, and then a product 5 having a boiling point of 165 to 170°C/1 cup of Hg was recovered by distillation under reduced pressure.
I got 7 copies. This product was found to be α-
It was found to be methylene-δ-methyladipate glycidyl ester. Example 3 Dimethyl α-methylene-δ-methyladipate 2 (
1) parts, 74 parts of glycidol, and 150 parts of benzene were charged, and water in the reaction solution was removed by azeotropy with benzene while heating and stirring.

Then, 5.0 parts of triethylammonium chloride was added and reacted at 100°C for 8 hours.

Thereafter, 50% of benzene was added, and after thorough washing with saturated brine, the organic layer was concentrated to remove benzene, and unreacted glycidol and α-methylene-δ-methyl dimethyl adipate were distilled off under reduced pressure. , boiling point 113-120
114 parts of α-methylene-δ-methyladipate monomethyl monoglycidyl ester at °C/1 mHg and boiling point 1
α-methylene-δ-methyladipate diglycidyl ester 4 was obtained at 65-170°C/1 mHg.

The calculated elemental analysis value of α-methylene-δ-methyladipate monomethyl monoglycidyl ester (Cl2Hl8O.) is C:59.4λH:7.49, and the measured analysis value of the product of the present invention is C:58. 60, H: 7.61.

Also, the double bond value is 4.10mMIy1 and the epoxy group is 4.
．． 05rn, M1y, and the monoglycidyl compound of this example obtained from the NMR spectrum is 2 shown by the following formula.
It was determined that the compound was a mixture of species.

Example 4 α-methylene-δ was placed in a reactor of the same type as Example 1.
- Prepare 20 parts of dimethyl methyl adipate, 80 parts of 50% caustic soda water, and 0.5 part of hydroquinone,
The reaction was carried out at 5°C for 5 hours.

The reaction product was separated into two layers, so the lower layer was taken out, excess acetone was added to precipitate the sodium salt, the mixture was separated and thoroughly dried.

Next, 104 parts of dry sodium salt, 4 parts of epichlorohydrin
Seal part, 2 parts of triethylbenzylammonium chloride,
Charge 02 parts of phenothiazine into the reactor,
After reacting at °C for 5 hours, the undissolved matter was separated and the residual solution was concentrated.

Add toluene to the concentrated solution to make a toluene solution, wash thoroughly with water, dehydrate and concentrate, and then distill under reduced pressure to obtain α-methylene-δ-
A piece of methyladipate monoglycidyl ester was obtained.

It was also confirmed that α-methylene-δ-methyladipate diglycidyl ester was produced as a by-product. Example 5 The reaction was carried out under the same conditions as in Example 1 except that 1065 parts of methyl Epic mastic rehydrin was used instead of Epic mastic rehydrin.

By distilling and purifying the concentrated treatment liquid, the boiling point is 168-1
Two parts of dimethylglycidyl α-methylene-δ-methyladipate were obtained as a fraction of 78°C/0.7TnxtHg.

The calculated elemental analysis value of this compound is C.

H2. O6 is C: 61.52, H: 7.74, whereas the elemental analysis measurement value of the product of this example is C: 61.4.
YoH: 7.85, in good agreement. Also, the double bond value is 3.2
It has an MI da of 0 and an epoxy group of 3.167 nM da, and analysis results by infrared spectrum and NMR spectrum also indicate the formation of this compound.

Claims (1)

[Claims] 1 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, at least one of X and Y has the structure ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and the rest are An unsaturated dicarboxylic acid glycidyl ester represented by an alkyl group having 1 to 4 carbon atoms, and R represents hydrogen or a methyl group. 2. The unsaturated dicarboxylic acid glycidyl ester according to claim 1, which is α-methylene-δ-methyladipate diglycidyl ester. 3 α-methylene-δ-
The unsaturated dicarboxylic acid glycidyl ester according to claim 1, which is methyladipate dimethylglycidyl ester. 4. The unsaturated dicarboxylic acid glycidyl ester according to claim 1, wherein one of X or Y is a methyl group and the other is a glycidyl group. 5 Compounds represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and compounds represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (where R represents hydrogen or a methyl group, R' and R'' represents an alkyl group having 1 to 4 carbon atoms)
General formula characterized by reacting ▲Mathematical formula, chemical formula,
There are tables, etc. ▼ (In the formula, at least one of Method for producing unsaturated dicarboxylic acid glycidyl ester (same as above). 6 Claim 5 using a quaternary ammonium salt as a catalyst
The method described in section. 7 Compounds represented by general formula▲There are mathematical formulas, chemical formulas, tables, etc.▼Compounds and general formulas▲There are mathematical formulas, chemical formulas, tables, etc.▼
(In the formula, R represents hydrogen or a methyl group, and Z represents sodium or potassium.) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (At least one of ▲There are mathematical formulas, chemical formulas, tables, etc.▼
and the remainder is R' or R''. R, R', R'' are each the same as above) A method for producing an unsaturated dicarboxylic acid glycidyl ester. 8. The method according to claim 7, wherein a quaternary ammonium salt, a tertiary amine or a tertiary amine hydrochloride is used as a catalyst.