KR101669213B1

KR101669213B1 - Method of preparing glycidyl esters of alpha-branched aliphatic monocarboxylic acids

Info

Publication number: KR101669213B1
Application number: KR1020160039105A
Authority: KR
Inventors: 김영훈; 권가희
Original assignee: 대달산업주식회사
Priority date: 2016-03-31
Filing date: 2016-03-31
Publication date: 2016-10-25

Abstract

The present invention relates to a method for producing glycidyl ester of alpha-branched aliphatic monocarboxylic acid in high purity and high yield, showing improved color productivity on finished products. To this end, the method comprises a reaction mixture production step, an intermediate production step, and a glycidyl ester production step.

Description

METHOD OF PREPARING GLYCIDYL ESTERS OF ALPHA-BRANCHED ALIPHATIC MONOCARBOXYLIC ACIDS BACKGROUND OF THE INVENTION [0001]

The present invention relates to a process for preparing an alpha-branched aliphatic monocarboxylic acid glycidyl ester by reacting an unreacted epihalohydrin remaining in the final product, an impurity derived from epihalohydrin, a chlorohydrin ester intermediate and an unreacted The present invention relates to a process for producing glycidyl esters of alpha-branched aliphatic monocarboxylic acids with high purity and high yields, with almost no byproducts derived from aliphatic monocarboxylic acids and having improved color of the product.

The alpha-branched aliphatic monocarboxylic acid glycidyl ester represented by the following formula (1) can be used as a raw material of a synthetic resin by directly reacting with (meth) acrylic acid to form an intermediate, or the addition of an amine, a polyol, For example, in the production of thermoplastic and thermosetting resins such as acrylic, epoxy, polyester and alkyd resins through intermediates such as water, urethane-modified resins, and polyester-modified resins. It is also used for imparting appropriate viscosity to a bisphenol-type epoxy resin or the like as a reactive diluent, and is also used as a modifier or adhesive for paper and fiber, a polymer material, and the like.

[Chemical Formula 1]

In Formula 1,

R ₁ + R ₂ + R ₃ represents an alkyl group having a linear or branched structure having a total of 8 to 12 carbon atoms, preferably, the total carbon atom sum of R ₁ + R ₂ + R ₃ is 8. The alpha-branched aliphatic monocarboxylic acid glycidyl ester is a reaction product of neodecanoic acid and epihalohydrin, more preferably a reaction product of neodecanoic acid and epichlorohydrin.

Methods for preparing glycidyl esters by reacting carboxylic acids with epoxy alkyl halides are well known and well known in the art and common types of glycidyl esters and their preparation are described in U.S. Patent Nos. 3,075,999, 3,178,454, 3,275,583 No. 3,397,176. The method of producing glycidyl ester by reacting an alkali metal salt of carboxylic acid with epihalohydrin increases the reactivity and makes it difficult to separate the product resulting from the saponification reaction The reaction was carried out under anhydrous conditions.

U.S. Patent No. 2,448,602 discloses that an alkali salt of a carboxylic acid is used by drying at a high temperature in a vacuum state and U.S. Patent No. 3,142,686 discloses a method in which an alkali aqueous solution of a carboxylic acid is first prepared and then an appropriate organic solvent Pentanone) was used to remove water by azeotropic distillation to make the reaction anhydrous. Further, Japanese Patent Laid-Open No. 50-76,012 removes water while adding an aqueous alkaline solution of carboxylic acid under the condition that excess epichlorohydrin can be azeotropically distilled with water. However, these methods have the disadvantage that the yield is low, an additional complicated process is required to separate the product from the reactants, and much energy and equipment are used to remove the water.

U.S. Patent No. 3,859,314 discloses that a carboxylic acid and two or more equivalents of epichlorohydrin are reacted at 65 to 93 in the presence of a catalyst such as a trivalent amine or tetravalent amine salt to prepare an intermediate chlorohydrin ester, A method for producing glycidyl esters by ring closure reaction has been disclosed. However, this method is less productive due to the use of excess epichlorohydrin and consumes a lot of energy to completely remove unreacted epihalohydrin.

Japanese Patent Application Laid-Open No. 57-203,077 discloses a method of reacting epichlorohydrin with 1.1 to 1.9 equivalents based on the carboxylic acid in the presence of a catalyst and adding an appropriate amount of alkali to the dichloropropanol obtained as a reaction by- It has been attempted to reduce the amount of epichlorohydrin by converting it into epichlorohydrin. However, the method of recovering epichlorohydrin through the additional process is difficult to be industrially applied.

Chinese Patent No. 101245053 discloses that a catalyst such as epichlorohydrin and quaternary ammonium salt in an excess amount of 10 mol% based on the carboxylic acid is added and the temperature is raised to 90 ° C., followed by addition of carboxylic acid to obtain chlorohydrin as an intermediate, Is stirred at the same temperature until the acid value becomes less than 0.1, and then an aqueous solution of sodium hydroxide is added to effect a ring closure reaction to obtain a glycidyl ester. However, it is industrially applicable to add epichlorohydrin, which is low in yield of 86% and relatively small in volume compared to carboxylic acid, to the reactor and to control the temperature by adding a bulky carboxylic acid There are difficulties in doing so.

Korean Laid-Open Patent Application No. 2012-0016313 discloses a method in which a quaternary ammonium salt is added to a carboxylic acid as a catalyst and epichlorohydrin is added at a temperature of less than 80 ° C to produce a product having an acid content of 5 Clms Page number 2 > reaction mixture obtained by stirring for a period of time to give glycidyl esters. However, in order to complete the reaction, it takes a long time of 5 to 6 hours, so that the production efficiency is lowered in the apparatus, and it is necessary to remove the quaternary ammonium salt used as the catalyst.

Japanese Unexamined Patent Publication (Kokai) No. 63-255273 discloses that if the quaternary ammonium salt used as a catalyst is not removed, even if all of the remaining unreacted epichlorohydrin is removed and concentrated, 1,3-dichloro-2-propanol It is said that epichlorohydrin can be changed into epichlorohydrin and thus epichlorohydrin can remain in the product. If such epichlorohydrin remains in the product, there is a high possibility that the health problem of the workers due to the toxicity of epichlorohydrin and corrosion problems in the electric and electronic fields will occur when these organic chlorine compounds are contained in the product.

A large amount of water is required when the quaternary ammonium salt is removed by washing with water because the quaternary ammonium salt is more organic-friendly than the inorganic metal salt. Japanese Patent Application Laid-Open No. 2003-171371 discloses a method in which an adsorbent such as bentonite, perlite, or kaolin is added in place of washing with water to remove tetravalent ammonium, followed by heating at 60 ° C to 90 ° C followed by filtration. However, .

Korean Patent No. 10-0663575 discloses a method of using a catalyst such as an alkali metal hydroxide instead of a catalyst such as a tetravalent ammonium salt. However, when a chlorohydrin ester is prepared, Since most of the volume of the reactor is occupied by using a large amount of an alkanol (for example, isopropanol), the production efficiency is extremely low and a process for recovering an alkanol which is miscible with water is indispensable, and epichlorohydrin to carboxylic acid Over a 200 to 2,000% molar ratio should be used and recovered.

PCT Patent CN2011-079677 discloses that carboxylic acid and an alkali metal hydroxide as a catalyst are added to a reactor containing epichlorohydrin, but epichlorohydrin, which is relatively small in volume compared to carboxylic acid, It is difficult to apply it industrially since it is first put into a reactor and the temperature is controlled by adding a bulky carboxylic acid and a catalyst.

In the PCT patent CN2012-087553, the same type of catalyst was used, but excessive epichlorohydrin was used to recover the product. Isopropanol, which is miscible with water in the ring closure reaction, is used as a solvent, so isopropanol A process and an apparatus are required.

And U.S. Patent No. 3,075,999 discloses a process for preparing glycidyl esters of fatty acids. The process comprises reacting an excess of an epoxyalkyl halide with an acid while adding an aqueous solution of an alkaline compound at a temperature of from 70 ° C to 117 ° C in the presence of a quaternary ammonium salt catalyst, wherein the quaternary ammonium salt catalyst comprises tetramethylammonium bromide, Used epichlorohydrin and a 10 fold excess of epichlorohydrin on an acid basis, an equimolar amount of potassium hydroxide was added under reflux conditions and excess epihalohydrin and water were separated overhead. Although this method can be produced at a reasonable yield, it has a disadvantage of relatively low purity.

And despite recent developments, there has been no proposal for a method of producing a high purity product with improved color in a high yield in the method of producing glycidyl ester of a branched monocarboxylic acid.

Accordingly, it is an object of the present invention to provide an improved method for producing an alpha-branched aliphatic monocarboxylic acid glycidyl ester at a high yield in a high purity product with reduced reaction time.

However, the problems to be solved by the present invention are not limited to those described above, and other matters not mentioned can be clearly understood by those skilled in the art from the following description.

(A) an aliphatic monocarboxylic acid represented by the formula R ₁ R ₂ R ₃ CCOOH, wherein each of R ₁ , R ₂ , and R ₃ is independently a linear or branched C 1 -C 20, Adding a mixture of an EDTA alkali metal salt and a catalyst to the aliphatic monocarboxylic acid to adjust the pH of the aliphatic monocarboxylic acid to less than 6.0 to less than 7.0 to form a reaction mixture; (b) an epoxyalkyl halide in an amount of 50% by weight to 95% by weight, based on the aliphatic monocarboxylic acid, is added to the reaction mixture and reacted at a temperature ranging from 30 ° C to 95 ° C to obtain an intermediate containing a halohydrin ester ; And (c) adding an alkali solution to the intermediate containing the halohydrin ester to form a glycidyl ester of an alpha-branched aliphatic monocarboxylic acid by ring-closing the intermediate containing the halohydrin ester Wherein the catalyst in step (a) is selected from the group consisting of quaternary ammonium salts, phosphonium salts, alkali metal hydroxides, alkyllithium salts, Wherein the aliphatic monocarboxylic acid is selected from the group consisting of carbonates, alkyllithium metal hydroxides, alkali metal or alkaline earth metal alkanolates, and combinations thereof, wherein said step (a) A mixture of salt and catalyst is added in a molar ratio of 0.01 to 0.5, provided that in the above steps the organic solvent is used Would do not, alpha-minute provides a method for producing branched aliphatic monocarboxylic acid glycidyl ester.

In preparing the glycidyl ester of a branched monocarboxylic acid using an aliphatic monocarboxylic acid and an epoxyalkyl halide in accordance with the production method of one embodiment of the present invention, When an EDTA-nNa mixed solution is prepared by adding a catalyst in a molar ratio of 0.01 to 0.5 and adjusting the pH of the mixture to a range of 6.0 to 7.0 and then adding an excess of 50 to 95 wt% of an epoxyalkyl halide, It is possible to produce a high-purity alpha-branched monocarboxylic acid glycidyl ester having a higher yield and improved product color as compared with the conventional production method without any process or apparatus.

Compared with the prior art, the present invention reduces the reaction time by adjusting the pH of the aliphatic monocarboxylic acid and the reaction temperature with the epoxy alkyl halide, and is characterized by an APHA color index (Platinum-Cobalt Scale, brown , Higher yields and higher purity alpha-branched monocarboxylic acids with improved color yields with increased purity by about 3 to 14 wt% or more and increased by about 1 to 3 wt% Of glycidyl ester can be prepared.

In comparison with the prior art, in the process for preparing alpha-branched aliphatic monocarboxylic acid glycidyl esters according to an embodiment of the present invention, a mixture of an alkali metal salt of EDTA and a catalyst is added to an aliphatic monocarboxylic acid to be used for the production reaction Characterized in that the pH of the aliphatic monocarboxylic acid is adjusted in the range of 6.0 to 7.0, more preferably in the range of 6.0 to 6.5, by adding the aqueous solution first so that no solvent is required, The reaction time is shortened by controlling the reaction temperature to increase the color of the product and the content of the byproduct due to the heating, heating or distillation for a long time, and the product yield is remarkably increased It is possible to prevent the problem of the conventional art from deteriorating.

In addition, in the method of producing the alpha-branched aliphatic monocarboxylic acid glycidyl ester according to one embodiment of the present invention, EDTA is used in combination with a quaternary ammonium salt in comparison with a quaternary ammonium salt conventionally used as a catalyst, And it is possible to stably produce glycidyl esters of alpha-branched aliphatic monocarboxylic acids having a certain range of epoxy equivalents (EEW 233 to 245) without any additional equipment.

FIG. 1 is a graph showing the results of gas chromatography analysis of an intermediate product obtained by adding epichlorohydrin and reacting in a comparative example of the present application. FIG.
FIG. 2 is a graph showing the result of gas chromatography analysis of an intermediate produced by adding epichlorohydrin in one embodiment of the present invention. FIG.
Figure 3 is a graph showing the results of gas chromatography analysis of the final product after the ring closure reaction in one embodiment of the present application.

The method for producing the alpha-branched aliphatic monocarboxylic acid glycidyl ester will now be described in detail with reference to the accompanying drawings by way of examples and embodiments so as to be easily carried out by those skilled in the art. Will be described in detail. The present invention may, however, be embodied and carried out in various forms and is not limited to the embodiments and examples described herein. In the drawings, the same reference numerals are used to denote the same parts throughout the drawings.

In this specification, when a section is referred to as including an element, it is to be understood that the element may include other elements as long as it does not exclude other elements.

As used herein, the terms "about", "approximately", "substantially", and the like are used herein to refer to the manufacturing and material tolerances inherent in the stated sense, To facilitate understanding of the invention, exact numerical values and absolute numerical values are used to prevent unauthorized use of the disclosure by the infringer.

Throughout this specification, the terms 'to (step)' or 'step of ~' do not mean 'step for ~' and do not mean 'step (s)' Means a mixture or combination of one or more elements selected from the group consisting of the constituents described in the expression of the form of a mark, and includes at least one selected from the group consisting of the constituent elements.

Also, in this specification, the description of the term 'A and / or B' means 'A and B, or A or B'.

Throughout this specification, the term "alkyl group" refers to a linear, branched, or cyclic alkyl group having from 1 to 20 carbon atoms, from 1 to 10 carbon atoms, from 1 to 8 carbon atoms, from 1 to 6 carbon atoms, Or a branched alkyl group. When the alkyl group is substituted by an alkyl group, it is also used interchangeably as a 'branched alkyl group'. Substituents which may be substituted by the alkyl group include halo (for example, F, Cl, Br, I), haloalkyl (for example, CC1 ₃ or CF ₃ ), alkoxy, alkylthio, acid (-C (O) -OH), alkyloxycarbonyl (-C (O) -OR), alkylcarbonyloxy (-OC (O) -R), amino (-NH _2), carbamoyl ( At least one selected from the group consisting of -NHC (O) OR- or -OC (O) NHR-), urea (-NH-C (O) -NHR- and thiol But may not be limited. In addition, the alkyl group having 2 or more carbon atoms in the alkyl group described above may include, but not limited to, at least one carbon to carbon double bond or at least one carbon to carbon triple bond. For example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, , Eicosanyl, or any of the possible isomers thereof, but is not limited thereto.

Throughout this specification, the percentages of purity and yield may be, but are not limited to,% by weight, unless otherwise stated. The% by weight of the purity may be determined, but not limited thereto, calculated from the area% standard on GC (gas chromatography). Gas chromatography was used for the measurement of the purity of the product, the glycidyl ester of carboxylic acid, epihalohydrin and the content of carboxylic acid, and the measurement equipment and measuring conditions were carried out in the same manner as in the prior art, However, the present invention is not limited thereto.

In the following, embodiments of the present invention have been described in detail, but the present invention is not limited thereto.

(A) an aliphatic monocarboxylic acid represented by the formula R ₁ R ₂ R ₃ CCOOH, wherein each of R ₁ , R ₂ , and R ₃ is independently a linear or branched C 1 -C 20, Adding a mixture of an EDTA alkali metal salt and a catalyst to the aliphatic monocarboxylic acid to adjust the pH of the aliphatic monocarboxylic acid to less than 6.0 to less than 7.0 to form a reaction mixture; (b) an epoxyalkyl halide in an amount of 50% by weight to 95% by weight, based on the aliphatic monocarboxylic acid, is added to the reaction mixture and reacted at a temperature ranging from 30 ° C to 95 ° C to obtain an intermediate containing a halohydrin ester ; And (c) adding an alkali solution to the intermediate containing the halohydrin ester to form a glycidyl ester of an alpha-branched aliphatic monocarboxylic acid by ring-closing the intermediate containing the halohydrin ester Wherein the catalyst is selected from the group consisting of a quaternary ammonium salt, a phosphonium salt, an alkali metal hydroxide, an alkali metal carbonate, and an alkali metal carbonate. The process according to claim 1, wherein the aliphatic monocarboxylic acid glycidyl ester is an aliphatic monocarboxylic acid glycidyl ester. , An alkaline earth metal hydroxide, an alkali metal or alkaline earth metal alcoholate, and a combination thereof, wherein in the step (a), a mixture of an alkali metal salt of EDTA and a catalyst is added to the aliphatic monocarboxylic acid Is added in a molar ratio of from 0.01 to 0.5, and in the above steps the organic solvent is not used The alpha-minute provides a process for the preparation of a branched monocarboxylic acid glycidyl esters.

In one embodiment of the invention, a mixture of the alkali metal salt of EDTA and the catalyst is added in a molar ratio of from about 0.01 to about 0.5, for example from about 0.05 to about 0.5, from about 0.1 to about 0.5, from about 0.01 to about 0.1, The pH of the aliphatic monocarboxylic acid may be adjusted to a pH of from 6.0 to less than 7.0, for example, from 6.0 to 6.5, by adding at a molar ratio of about 0.01 to about 0.05. When the pH of the aliphatic monocarboxylic acid is adjusted to 6.0 or less in the step (a), the reaction is very slow and the coloring proceeds due to polymerization of epihalohydrin or a high temperature reaction for a long time, resulting in poor color of the final product. On the contrary, when the pH is adjusted to 7.0 or more, the reaction is very fast due to the increase of the alkali salt, but the rate of the reaction is not easily controlled and the conversion of the halohydrin ester into the byproduct is rapidly proceeded, The purity and yield of the final product are significantly lowered.

In one embodiment of the invention, the EDTA alkali metal salt may be used in the form of about 5 to about 50 weight percent diluent solution. For example, the EDTA alkali metal salt may be used in the form of about 5 to about 25% by weight, or about 5 to about 15% by weight of a dilute solution, but may not be limited thereto. The EDTA alkali metal salt is _{EDTA-nNa nH 2 O (n} = 2 to 4) in accordance with the number of n, can be a salt, EDTA sodium represented by _{EDTA-2Na2H 2 O, EDTA-} 3Na3H 2 O, EDTA-4Na4H 2 O. The _{EDTA-nNa nH 2 O (n} = 2 to 4), but can have, to the structure by means ethylenediaminetetraacetic acid and n sodium salt (sodium salt), may not be limited thereto. The sodium salt of EDTA can be appropriately selected depending on the pH, in the present reaction conditions is EDTA-4Na4H ₂ O is most preferred.

In one embodiment of the present invention, in step (b), 50 to 95% by weight of an excess of the epoxyalkyl halide with respect to the aliphatic monocarboxylic acid is added, and in this step the addition rate of the epoxyalkyl halide and the exotherm Unlike conventional known processes in which the reaction is kept at a low temperature of 70 DEG C or lower to inhibit the production of byproducts due to the reaction, the temperature ranges from about 30 DEG C to 95 DEG C, for example, from about 75 DEG C to about 90 DEG C , Or from about 80 ° C to about 85 ° C, to form an intermediate comprising a halohydrin ester, thereby effectively converting a portion of the intermediate halohydrin ester to a by-product It can be avoided.

The ring opening reaction at this stage may be carried out for example, from about 0.5 to about 1% by weight, or from about 0.1 to about 0.3% by weight, until the residual amount of the aliphatic monocarboxylic acid is less than about 1% The reaction proceeds until it is reduced to the residual level in the range of% by weight. In the present invention, as a function of the reaction temperature, the reactant ratio, and the reaction time, the ring opening reaction is performed by adjusting the pH of the reaction product before the reaction using EDTA-nNa (n = 2 to 4) It is possible to significantly avoid the conversion of a part of the intermediate halohydrin ester to a by-product even at a temperature of 80 ° C to about 85 ° C, thereby remarkably shortening the reaction time, and the residual level of the carboxylic acid is 0.3 to 0.1 weight % Range level, a high yield of 95 wt% or more based on the acid is achieved relatively stably. The value of less than 1 wt%, which is the residual criterion of the acid, may be based on the% area based on GC (gas chromatography), but is not limited thereto. Gas chromatography was used for the measurement of the purity of the product, the glycidyl ester of carboxylic acid, epihalohydrin and the content of carboxylic acid, and the measurement equipment and measuring conditions were carried out in the same manner as in the prior art, Respectively.

In one embodiment of the present invention, the glycidyl ester of the alpha-branched aliphatic monocarboxylic acid may be prepared by the following steps, but is not limited thereto. Addition of an aliphatic monocarboxylic acid in the step (a) into the reactor and _{EDTA-nNa nH 2 O (n} = 2 to 4) and adjusting the pH of an aliphatic monocarboxylic acid of a mixture of diluent from about 6.0 to less than 7.0 of a catalyst The mixture is stirred and heated to a temperature of about 80 캜 to about 85 캜. In said step (b), the alpha position in the under EDTA in the presence of sodium salt and the catalyst mixture is represented by about 80 ℃ to the _{EDTA-nNa nH 2 O (n} = 2 to 4) while maintaining a temperature of about 85 ℃ reactor Is reacted by adding an epoxy alkyl halide to the branched aliphatic carboxylic acid to form an intermediate containing a halohydrin ester. In step (c), an alkali solution is added to the halohydrin ester intermediate to carry out a ring closure reaction, thereby producing a glycidyl ester of an alpha-branched aliphatic monocarboxylic acid having improved color of the product in high purity and high yield can do.

In the aliphatic monocarboxylic acid represented by the formula R ₁ R ₂ R ₃ CCOOH, each of R ₁ , R ₂ , and R ₃ is independently selected from the group consisting of 1 to 20 carbon atoms, 1 to 10 carbon atoms, Refers to a linear or branched alkyl group having from 8 to 8 carbon atoms, from 1 to 6 carbon atoms, or from 1 to 3 carbon atoms. When the alkyl group is substituted by an alkyl group, it is also used interchangeably as a 'branched alkyl group'. Substituents which may be substituted by the alkyl group include halo (for example, F, Cl, Br, I), haloalkyl (for example, CCl ₃ or CF ₃ ), alkoxy, alkylthio, acid (-C (O) -OH), alkyloxycarbonyl (-C (O) -OR), alkylcarbonyloxy (-OC (O) -R), amino (-NH _2), carbamoyl ( At least one selected from the group consisting of -NHC (O) OR- or -OC (O) NHR-), urea (-NH-C (O) -NHR- and thiol But may not be limited. In addition, the alkyl group having 2 or more carbon atoms in the alkyl group described above may include, but not limited to, at least one carbon to carbon double bond or at least one carbon to carbon triple bond. For example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, , Eicosanyl, or any of the possible isomers thereof, but is not limited thereto.

The aliphatic monocarboxylic acid represented by the formula R ₁ R ₂ R ₃ CCOOH may be an alpha-branched aliphatic monocarboxylic acid, for example having less than 20 total carbon atoms and having an alpha position relative to the carbon atom of the carboxyl group Secondary or tertiary monocarboxylic acids containing one or two alkyl groups bonded to the carbon atoms to which they are attached, or combinations thereof. For example, neodecanoic acid, pivalic acid, 2-methylbutanoic acid, isobutylic acid, isovaleric acid, 2-methylpentanoic acid, 2,4-dimethylvaleric acid, or diethylacetic acid, But may not be limited thereto.

More specifically, the alpha-branched aliphatic monocarboxylic acid may be a neodecanoic acid represented by the following formula (2) as a carboxylic acid in which the alpha position is branched into tertiary alcohols, but it is not limited thereto.

(2)

In Formula 2,

R ₁ + R ₂ + R ₃ represents a linear or branched alkyl group having a total of 8 to 12 carbon atoms.

In Formula 2, the total carbon number of R ₁ , R ₂ , and R ₃ is 8 to 10, and the total carbon number of R ₁ and R ₂ may be 7, but may not be limited thereto.

In one embodiment of the present invention, the epoxyalkyl halide may be an unsubstituted 1-halo-2,3-epoxyalkane having 3 to 13 carbon atoms. For example, the epoxy alkyl halide may include, but is not limited to, an epihalohydrin or 2-methylhexyl halohydrin. Specifically, the halogen atom of the epoxy alkyl halide may be chlorine or bromine, and among them, epichlorohydrin is most preferable.

In one embodiment of the present invention, glycidyl esters of alpha-branched aliphatic monocarboxylic acids of very high purity can be obtained by the process of the present invention, for example, when the content of impurities is about 5 Glycidyl esters can be prepared that are less than about 10 weight percent, preferably less than about 4 weight percent, and more preferably less than about 2 weight percent. For example, it is possible to provide glycidyl esters of alpha-branched aliphatic monocarboxylic acids of high purity of at least about 95% by weight or at least about 98% by weight, which, unlike conventional methods, It is possible to provide an improved high-purity product as compared with the conventional method. In addition, the glycidyl ester of an alpha-branched aliphatic monocarboxylic acid can be prepared by the process of the present invention with a high yield of about 95% by weight or more.

In the present invention, it is most preferred that the epoxyalkyl halide be used in close proximity to stoichiometrically stoichiometric amounts, but it is generally preferred to use a molar ratio of 1: 1.0 to 1: 2.0 relative to the aliphatic carboxylic acid Overdose is used. When the epoxyalkyl halide is added in an amount less than the aliphatic carboxylic acid, the aliphatic carboxylic acid remaining unreacted causes a by-product and an impurity in the subsequent ring closure reaction, and since some of the aliphatic carboxylic acid remains in the unreacted state, (Hereinafter referred to as " EEW ") is increased and the yield is decreased. On the contrary, if the epoxyalkyl halide is excessively used excessively, the fraction of the reaction after the reaction is increased and the remaining epoxyalkyl halide must be completely removed before the ring closure reaction. However, by appropriately using the epoxy alkyl halide in an excessive amount, The epoxy alkyl halide can be removed entirely by conventional distillation or similar methods to obtain glycidyl esters of the desired improved color and high purity and yield. For example, the epoxyalkyl halide may be used in an amount of about 1.0 to about 2.0 moles, preferably about 1.5 to about 1.85 moles, more preferably about 1.5 to about 1.65 moles, relative to the amount of the aliphatic carboxylic acid used, But may not be limited.

If the remaining unreacted epoxyalkyl halide in step (b) is not removed prior to the ring closure reaction, the epoxide exchange reaction with the resulting halohydrin ester intermediate results in the formation of 1,3-dichloro-2-propanol or the conversion of the epoxy alkyl halide Since the decomposition products may be produced as by-products, it is preferable to remove them by a conventionally known method, for example, vacuum decompression.

In one embodiment of the present invention, in step (b), the aliphatic monocarboxylic acid represented by the formula R ₁ R ₂ R ₃ CCOOH and the epichlorohydrin as the epoxy alkyl halide are reacted with the EDTA alkali metal salt and the presence of the catalyst mixture (Scheme 1 of step (b)). &Lt; / RTI >

[Reaction Scheme 1]

In one embodiment of the present invention, in step (c), an aqueous alkaline solution is added to the chlorohydrin ester of the carboxylic acid as an intermediate, and the glycidyl ester of the alpha-branched carboxylic acid is prepared by a ring- But may not be limited thereto (Scheme 2 of step (c)).

[Reaction Scheme 2]

In one embodiment of the present invention, the addition of the epoxyalkyl halide of step (b) may vary depending on the cooling efficiency or scale of the reaction, but generally takes from about 0.5 to about 5 hours, for example, within 2 hours And is preferably added within 1 to 2 hours. The reaction time is within about 10 hours, for example from about 0.5 to about 10 hours, from about 0.5 to about 9 hours, from about 0.5 to about 8 hours, from about 0.5 to about 7 hours, from about 0.5 to about 6 hours, 5 hours, about 0.5 to about 4 hours, about 0.5 to about 3 hours, about 0.5 to about 2 hours, or about 0.5 to about 1 hour, preferably 0.5 to 5 hours, more preferably 0.5 to 3 hours But may not be limited thereto.

In one embodiment of the present invention, the EDTA in the catalyst mixture used in step (a) has six pairs of electrons and each electron pair couples one coordination bond to form a stable chelate complex of metal and ring structure And ionized in solution in 6 steps as follows.

H ₄ X = H ⁺ + H ₃ X ^- (pK ₁ = 0.0)

H ₃ X ^- = H ⁺ + H ₂ X ² ^- (pK ₂ = 1.5)

H ₂ X ² ^- = H ⁺ + HX ^3- (pK ₃ = 2.0)

HX ^3- = H ⁺ + X ^4- (pK ₄ = 2.26)

H ₅ X ⁺ = H ⁺ + H ₄ X (pK ₅ = 6.16)

H ₆ X ² ⁺ = H ⁺ + H ₅ X ⁺ (pK ₆ = 10.24)

The total concentration of EDTA in the EDTA solution is expressed as the sum of the concentrations of the following seven compounds.

_{^{EDTA Concentration = [H 6 X 2}} +] + [H 5 X +] + [H 4 X] + [H 3 X -] + [H 2 X 2 -] + [HX 3-] + [X 4-]

The first four values are for carboxyl protons, the last two for ammonium protons, and the neutral acid formula is H ₄ X.

The concentration of the above five compounds in the EDTA solution is determined by the pH of the solution. At pH 10, HX ^3- and X ^4- occupy 64.5% and 35.5%, respectively, and the remaining compounds are almost negligible. EDTA ions (H _n X ^{(4-n) -} ) may react with almost all metal ions (M ^{n +} ) except for alkali metal at a molar ratio of 1: 1 to form a stable complex, but may not be limited thereto. The catalyst may be selected from the group consisting of quaternary ammonium salts, phosphonium salts and alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, alkali metal or alkaline earth metal alcoholates, and combinations thereof, depending on the type and concentration of the EDTA alkali metal salt , But may not be limited thereto. The catalyst may be, for example, a quaternary ammonium salt represented by the following general formula (R ₄ R ₅ R ₆ R ₇ N ⁺ Y ^- ) and may be used alone or in combination with other catalysts, have.

(3)

Wherein R ₄ , R ₅ and R ₆ independently represent an alkyl group of 1 to 18 carbon atoms, R ₇ represents an alkyl group of 1 to 18 carbon atoms, a phenyl group or a benzyl group, and Y represents a hydroxyl group or a halogen .

For example, the catalyst may be selected from the group consisting of tetramethylammonium chloride (TMAC), triethyl benzyl ammonium chloride (TEBAC), diallyldimethylammonium chloride (DADMAC), NaOH, and combinations thereof.

In one embodiment of the present invention, the quaternary ammonium salt may be added to and mixed with the EDTA alkali metal salt aqueous solution.

In one embodiment of the present invention, in step (a), the catalyst is in an aqueous solution or an undiluted state of from about 5 to about 95 wt%, for example, from about 5 to about 50 wt% But may not be limited thereto, in an amount of 5 to 50% by weight in a mixture of a sodium salt and a catalyst.

For example, in step (a), one catalyst selected from the above quaternary ammonium salts is diluted to about 5 to about 95 wt% according to the kind and concentration of EDTA-nNaH ₂ O (n = 2 to 4) , Or about 5 to about 20% by weight, such as about 5 to about 15% by weight, or about 10 to about 15% by weight, based on the amount of EDTA-nNa, is used as a mixed solution without dilution. The EDTA-nNa may be diluted with about 5 to about 50 weight percent solution, for example, about 5 to about 25 weight percent, or about 5 to about 15 weight percent solution, prior to step (b) for preparing the catalyst mixture, State, but may not be limited thereto. Likewise, the catalyst may be used in an amount of from about 5 to about 40% by weight, from about 10 to about 50% by weight, from about 60 to about 95% by weight, or without dilution, have.

In one embodiment of the present invention, the reaction temperature of step (c) is in the range of about 40 캜 to about 70 캜, such as about 50 캜 to about 65 캜, or about 50 캜 to 60 캜, .

In one embodiment of the present invention, the alkali solution of step (c) may be NaOH, KOH or LiOH, and preferably it is not necessarily limited to NaOH.

In this embodiment of the invention, the alpha-branched aliphatic monocarboxylic acid glycidyl ester can be prepared in a yield of about 95% by weight or more, for example, about 95% by weight or more, or about 98% Or more. The alpha-branched aliphatic monocarboxylic acid glycidyl ester may have a purity of at least about 95%, for example, at least about 98%.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are given for the purpose of helping understanding of the present invention, but the present invention is not limited to the following examples.

[ Example ]

Example One

To a 1000 mL four-necked glass flask reactor equipped with a stirrer, a heating mantle, a reflux condenser and a thermometer, 100.0 g of neodecanoic acid was first added, followed by 10 g of 15% EDTA-4Na diluted solution and 50% of tetramethylammonium chloride ), And the mixture was stirred for 10 minutes. Then, the pH was measured using a portable pH meter while the pH of the mixed reaction was adjusted to 6.0 to 6.5 with fine dilution of 15% EDTA-4Na solution and 50% TMAC, followed by heating to 80 ° C with stirring in a heating mantle. When the temperature inside the reactor reached 80 ° C, 85.9 g of epichlorohydrin was added at a constant rate for 2 hours while maintaining the temperature of 82 ± 2 ° C, and after further reaction for 2 hours while maintaining the same temperature, The degree of acid conversion was analyzed by gas chromatography. After confirming that neodecanoic acid remained at 0.28% by area% on the GC analysis, unreacted epichlorohydrin and water which remained at a final gauge pressure of -750 to -760 mmHg for 20 minutes at 80 & Respectively. Thereafter, 90.3 g of 35% sodium hydroxide aqueous solution was added at 50 ° C to complete the ring closure reaction, followed by washing with water, removing water and filtering to obtain 126.70 g of neodecanoic acid glycidyl ester. The yield of the obtained product was 95.6%, the purity was 96.41%, the color of the product was 35 by APHA color, and the epoxy equivalent weight (EEW) was 238.7.

Example 2

100.0 g of neodecanoic acid was first added to a 1000 mL four-neck glass flask reactor equipped with a stirrer, a heating mantle, a reflux condenser and a thermometer, and then 10 g of a 15% EDTA-4Na diluted solution and 50% of TEBAC ammonium chloride) was added and stirred for 10 minutes. Then, while measuring the pH using a portable pH meter, the pH of the reaction mixture was adjusted to be 6.0 to 6.5 with 15% EDTA-4Na dilution and 50% TEBAC, followed by heating to 80 ° C with stirring using a heating mantle . When the temperature inside the reactor reached 80 ° C, 85.9 g of epichlorohydrin was added at a constant rate for 2 hours while maintaining the temperature of 82 ± 2 ° C, and after further reaction for 2 hours while maintaining the same temperature, And analyzed by gas chromatography. At this time, it was confirmed that 0.23% of the neodecanoic acid in the GC analysis remained in the area, and then the unreacted epichlorohydrin remaining at 20 ° C in a final vacuum gauge pressure of -750 to -760 mmHg at 80 ° C for 20 minutes, . Thereafter, 90.3 g of 35% sodium hydroxide aqueous solution was added at 50 DEG C to complete the ring closure reaction, followed by washing with water, removing water and filtering to obtain 127.56 g of neodecanoic acid glycidyl ester. The yield of the obtained product was 96.2%, the purity was 97.11%, the color of the product was 25 by APHA color, and the epoxy equivalent weight (EEW) was 237.4.

Example 3

100.0 g of neodecanoic acid was first added to a 1000 mL four-necked glass flask reactor equipped with a stirrer, a heating mantle, a reflux condenser and a thermometer, and then 10 g of 15% EDTA-4Na diluted solution and 1.8 g of 35% NaOH And the mixture was stirred for 10 minutes. Then, the pH of the reaction mixture was adjusted by using a portable pH meter. The mixture was finely adjusted with 15% EDTA-4Na diluted solution or 35% NaOH to adjust the pH of the mixed reaction solution to 6.0 to 6.5, and then heated to 80 ° C with stirring with stirring. When the temperature inside the reactor reached 80 ° C, 85.9 g of epichlorohydrin was added at a constant rate for 2 hours while maintaining the temperature of 82 ± 2 ° C, and after further reaction for 2 hours while maintaining the same temperature, And analyzed by gas chromatography. At this time, it was confirmed that the area percentage of neodecanoic acid in the GC analysis remained at 0.09%, and then unreacted epichlorohydrin remaining at 20 ° C in a range of -750 to -760 mmHg of final gauge pressure at 80 ° C . Thereafter, 90.3 g of a 35% sodium hydroxide aqueous solution was added at 50 캜 to complete the ring closure reaction, followed by washing with water, removing water and filtering to obtain 125.5 g of neodecanoic acid glycidyl ester. The yield of the obtained product was 94.7%, the purity was 95.82%, the color of the product was 40 by APHA color, and the epoxy equivalent weight (EEW) was 240.3.

Example 4

100.0 g of neodecanoic acid was first added to a 1000 mL four-necked glass flask reactor equipped with a stirrer, a heating mantle, a reflux condenser and a thermometer. 10 g of 15% EDTA-4Na diluted solution and 65% of DADMAC (diallyldimethylammonium chloride ) Was added and stirred for 10 minutes. Subsequently, pH was measured using a portable pH meter. The mixture was finely adjusted with a 15% EDTA-4Na dilution and 65% DADMAC to adjust the pH of the mixed reaction solution to 6.0 to 6.5, followed by heating to 80 ° C with stirring. When the temperature inside the reactor reached 80 ° C, 85.9 g of epichlorohydrin was added at a constant rate for 2 hours while maintaining the temperature of 82 ± 2 ° C, and after further reaction for 2 hours while maintaining the same temperature, And analyzed by gas chromatography. At this time, it was confirmed that 0.16% of the neodecanoic acid in the GC analysis remained in the area of 0.16%. Thereafter, unreacted epichlorohydrin remaining at 20 ° C in a final gauge pressure of -750 to -760 mmHg . Thereafter, 90.3 g of a 35% sodium hydroxide aqueous solution was added at 50 캜 to complete the ring closure reaction, followed by washing with water, removing moisture and filtering to obtain 130.3 g of neodecanoic acid glycidyl ester. The yield of the obtained product was 98.4%, the purity was 98.07%, the color of the product was 20 by APHA color, and the epoxy equivalent weight (EEW) was 234.6.

Comparative Example 1

100.0 g of neodecanoic acid was first added to a 1000 mL four-necked glass flask reactor equipped with a stirrer, a heating mantle, a reflux condenser and a thermometer. 1.5 g of a 50% TMAC dilution was added as a catalyst and stirred for 10 minutes. The pH of the reaction mixture was 4.85. The temperature inside the reactor was heated to 80 ° C with heating mantle without adjusting the pH of the reactant. 80.6 g of epichlorohydrin was kept at a constant rate of 2 hours And then reacted for 2 hours while maintaining the same temperature. Then, the sample was sampled and analyzed by gas chromatography. At this time, it was confirmed that the area% of neodecanoic acid on the GC analysis was 0%, and that a substantial amount of the chlorohydrin ester was converted into the glycidyl ester and the by-product, and the final gauge pressure- Unreacted epichlorohydrin and water remaining in the range of 760 mmHg for 20 minutes were removed. Thereafter, 90.3 g of 35% sodium hydroxide aqueous solution was added at 50 캜 to complete the ring closure reaction, followed by washing with water, removing water and filtering to obtain 123.4 g of neodecanoic acid glycidyl ester. The yield of the obtained product was 93.9%, the purity was 82.76%, the color of the product was 45 in terms of APHA color, and the epoxy equivalent weight (EEW) was 283.3.

Comparative Example 2

100.0 g of neodecanoic acid was first added to a 1000 mL four-necked glass flask reactor equipped with a stirrer, a heating mantle, a reflux condenser and a thermometer. 1.5 g of 50% TEBAC diluent was added as a catalyst and stirred for 10 minutes. The pH of the reaction mixture was 3.24. The temperature inside the reactor was heated to 80 ° C by a heating mantle without adjusting the pH separately. 80.6 g of epichlorohydrin was maintained at a constant rate of 2 hours And then reacted for 2 hours while maintaining the same temperature. Then, the sample was sampled and analyzed by gas chromatography. At this time, it was confirmed that the area% of neodecanoic acid in the GC analysis was 0.67%, and unreacted epichlorohydrin and water were removed at a final vacuum gauge pressure of -750 to -760 mmHg at 80 DEG C for 20 minutes Respectively. Thereafter, 90.3 g of 35% sodium hydroxide aqueous solution was added at 50 DEG C to complete the ring closure reaction, followed by washing with water, removing moisture and filtering to obtain 124.7 g of neodecanoic acid glycidyl ester. The yield of the obtained product was 94.1%, the purity was 95.84%, the color of the product was 35 in APHA color, and the epoxy equivalent weight (EEW) was 250.5.

Comparative Example 3

100.0 g of neodecanoic acid was first added to a 1000 mL four-necked glass flask reactor equipped with a stirrer, a heating mantle, a reflux condenser and a thermometer, followed by addition of 0.35 g of 35% NaOH aqueous solution as a catalyst and stirring for 10 minutes. The pH of the reaction mixture was 10.22 and the temperature inside the reactor was heated to 80 ° C with the heating mantle without adjusting the pH of the reaction mixture. 80.6 g of epichlorohydrin was maintained at 82 ± 2 ° C for 2 hours The reaction was continued at the same temperature for 2 hours while maintaining the same temperature, and then the sample was sampled and analyzed by gas chromatography. At this time, a considerable amount of neodecanoic acid in the GC analysis remained at 11.79%, so that 18.8 g of epihalohydrin was further added and the reaction was further continued for 3 hours to confirm that the area% of neodecanoic acid was 0.40% Unreacted epichlorohydrin and water were removed at 80 DEG C under vacuum at a final gauge pressure of -750 to -760 mmHg for 20 minutes. Then, 90.3 g of a 35% sodium hydroxide aqueous solution was added at 50 ° C to effect a ring closure reaction. However, the reaction was not completed, and 20.5 g of sodium hydroxide was further added to complete the reaction. The reaction was then washed with water, To obtain 120.8 g of decanoic acid glycidyl ester. The yield of the obtained product was 91.1%, the purity was 82.22%, the color of the product was 55 in APHA color, and the epoxy equivalent weight (EEW) was 263.6.

Comparative Example 4

100.0 g of neodecanoic acid was first added to a 1000 mL four-necked glass flask reactor equipped with a stirrer, a heating mantle, a reflux condenser and a thermometer. 1.5 g of 65% DADMAC solution was added as a catalyst and stirred for 10 minutes. The pH of the reaction mixture was 2.46 and the temperature inside the reactor was heated to 80 ° C with heating mantle without adjusting the pH. 80.6 g of epichlorohydrin was maintained at a constant rate of 2 hours And then reacted for 2 hours while maintaining the same temperature. Then, the sample was sampled and analyzed by gas chromatography. At this time, it was confirmed that the area% of neodecanoic acid in the GC analysis was 0.42%, and the unreacted epichlorohydrin remaining in the range of -750 to -760 mmHg of final gauge pressure at 80 DEG C for 20 minutes was removed by vacuum decompression Respectively. Thereafter, 90.3 g of a 35% aqueous solution of sodium hydroxide was added at 50 캜 to complete the ring closure reaction, followed by washing with water, removing water and filtering to obtain 127.0 g of neodecanoic acid glycidyl ester. The yield of the obtained product was 95.8%, the purity was 95.51%, the color of the product was 35 by APHA color, and the epoxy equivalent weight (EEW) (E / Eq.) Was 251.2.

Comparative Example 5

100.0 g of neodecanoic acid was first added to a 1000 mL four-necked glass flask reactor equipped with a stirrer, a heating mantle, a reflux condenser and a thermometer, and 15% EDTA-4Na diluted solution 13.4 g was added and stirred for 10 minutes. At this time, the pH of the reaction mixture was in the desired pH range of 6.21, and the temperature inside the reactor was heated to 80 DEG C with heating mantle without additional pH adjustment, and then 80.6 g of epichlorohydrin was heated to 82 +/- 2 DEG C The mixture was reacted for 2 hours while maintaining the same temperature, and then the sample was sampled and analyzed by gas chromatography. At this time, it was confirmed that the area% of neodecanoic acid in the GC analysis was 0.51%, and unreacted epichlorohydrin and water were removed at a final vacuum gauge pressure of -750 to -760 mmHg at 80 ° C. for 20 minutes at 80 ° C. Respectively. Thereafter, 90.3 g of 35% sodium hydroxide aqueous solution was added at 50 DEG C to complete the ring closure reaction, followed by washing with water, removing moisture and filtering to obtain 124.0 g of neodecanoic acid glycidyl ester. The yield of the obtained product was 93.5%, the purity was 92.20%, the color of the product was 40 by APHA color, and the epoxy equivalent weight (EEW) was 255.7.

Comparative Example 6

100.0 g of neodecanoic acid was first added to a 1000 mL four-necked glass flask reactor equipped with a stirrer, a heating mantle, a reflux condenser and a thermometer. To adjust the pH of the reaction to 6.0 or less, 5.6 g of 50% EDTA- And the mixture was stirred for 10 minutes. At this time, the pH of the reaction mixture was adjusted to 5.87, and the inside temperature of the reactor was heated to 80 DEG C with a heating mantle without further pH adjustment. 80.6 g of epichlorohydrin was added at a constant rate for 2 hours while maintaining the temperature at 82 +/- 2 DEG C Then, the reaction was continued for 2 hours while maintaining the same temperature, and the sample was collected and analyzed by gas chromatography. At this time, the area% of neodecanoic acid in the GC analysis was 18.96%, and a considerable amount of acid remained. Thus, epihalohydrin 18.8 was further added and the reaction was further continued for 6 hours to confirm that the area% of neodecanoic acid was 0.14% Deg.] C to remove unreacted epichlorohydrin and water remaining in the final gauge pressure range of -750 to -760 mmHg for 20 minutes. Then, 90.3 g of a 35% sodium hydroxide aqueous solution was added at 50 ° C to effect a ring closure reaction. However, the reaction was not completed, and 20.5 g of sodium hydroxide was further added to complete the reaction. The reaction was then washed with water, To obtain 120.0 g of decanoic acid glycidyl ester. The yield of the obtained product was 90.5% and the purity was 83.89%. The product had an APHA color of 80 and an epoxy equivalent weight (EEW) of 271.9.

Comparative Example 7

100.0 g of neodecanoic acid was first added to a 1000 mL four-necked glass flask reactor equipped with a stirrer, a heating mantle, a reflux condenser and a thermometer, and then 10 g of 15% EDTA-4Na diluted solution and 3.7 g of 35% 7.24 and stirred. Subsequently, 80.6 g of epichlorohydrin was added at a constant rate for 2 hours while maintaining the temperature of 82 ± 2 ° C, and then 2 hours further After the reaction, samples were collected and analyzed by gas chromatography. At this time, it was confirmed that the area% of neodecanoic acid in the GC analysis was 0%, and it was confirmed that a substantial amount of iminochloro-hydrin ester was converted into glycidyl ester and byproduct. The final gauge pressure was -750 to -760 The unreacted epichlorohydrin and water remaining for 20 minutes in the range of < RTI ID = 0.0 > mmHg < / RTI > Thereafter, 90.3 g of 35% sodium hydroxide aqueous solution was added at 50 DEG C to complete the ring closure reaction, followed by washing with water, removing moisture and filtering to obtain 122.2 g of neodecanoic acid glycidyl ester. The yield of the obtained product was 89.68%, the purity was 83.89%, the color of the product was 50 in APHA color, and the epoxy equivalent weight (EEW) was 258.4. The analysis results of the above Examples and Comparative Examples are shown in Table 1 below. In the following table, the pH refers to the values arbitrarily adjusted or measured by the addition of EDTA-4Na and / or catalyst, APHA color is measured according to ASTM D1209, the smaller the value, the better the color of the product. Also, the epoxy equivalent and the EEW mean that the smaller the number, the more epoxy groups are present.

In order to confirm the reaction processes and results of the examples and comparative examples of the present invention, gas chromatography was used. The gas chromatograph model was GC-17A manufactured by Shimadzu Corporation, the column was a DB-1 capillary column, The inner diameter was 0.25 mm and the length was 30 m. The temperature condition was maintained at 100 ° C. for 5 minutes, then the temperature was increased to 5 ° C. per minute up to 250 ° C., and the percentage of retention time (%) was determined.

The results of gas chromatography analysis for confirming the residual amount of neodecanoic acid after addition of epichlorohydrin in the comparative example were shown in Fig. The peak group indicated by A in Fig. 1 is neodecanoic acid, the peak group indicated by B is the glycidyl ester of neodecanoic acid, the peak group indicated by C is the chlorohydrin ester of the intermediate neodecanoic acid, and D The indicated peak group represents the adduct of glycidyl ester and its acid.

2 and 3 show results of gas chromatography analysis (FIG. 3) after completion of the ring closure reaction by adding epichlorohydrin in Example 4 (FIG. 2) and aqueous sodium hydroxide solution, respectively .

As can be seen from Fig. 1, in the comparative example in which the pH was not adjusted using EDTA-nNa and the catalyst mixture, neodecanoic acid and glycidyl ester, an intermediate chlorohydrin ester, and impurities were mixed together can confirm. However, FIG. 2 shows the results of analysis after adding epichlorohydrin of Example 4, and as a result of the analysis, it was found that the amount of neodecanoic acid remaining as a starting material (A) and the adducts of glycidyl esters and acids, The generation of impurities at the retention time of 19 minutes is also very small, and it can be seen that the used neodecanoic acid reacts with epichlorohydrin, and the purity of the product is increased by converting into chlorinated adipate and glycidyl ester. 3 is a graph showing the results obtained after the completion of the ring closure reaction by adding the sodium hydroxide aqueous solution of Example 4 as a result of which the impurity such as the product of the chlorohydrin ester intermediate and the unreacted epichlorohydrin and the unreacted neodecanoic acid was so small that 98% Area%) of glycidyl ester end product.

As can be seen from Table 1, it was found from Example 1 and Comparative Example 1, from Example 2 and Comparative Example 2, from Example 3 and Comparative Example 3, and from Example 4 and Comparative Example 4 that quaternary ammonium salts and When the pH of the reactant was adjusted using the mixed solution of EDTA-nNa as the catalyst (Examples 1 to 4) and when the quaternary ammonium salt was used alone as the catalyst (Comparative Example 1-4) 1, since some aliphatic carboxylic acids, i.e., neodecanoic acid remain in an unreacted state, the purity decreases and thus the epoxy equivalent (EEW) increases and the yield decreases. In the case of the embodiment, however, The APHA color is improved stably by 10 to 15 or more, the purity is 3 to 14% or more, and the yield is increased by 1 to 3% by weight or more without increasing the epoxy equivalent without distillation or purification. In Comparative Examples 5 and 6, as a result of pH not more than 6.0 and pH not less than 7.0 according to the present invention, the APHA color of the product became wider as the reaction time became longer, .

Therefore, this example enables a product to be stably manufactured in a relatively short time without any additional process or apparatus, with an APHA color of 20 or less, a purity of 95% or more, and a yield of 95% or more by weight within an appropriate epoxy equivalent (EEW, 233 to 245) .

Thus, the process of the present invention can be used to produce alpha-minus having an increased purity by about 3 to about 14 wt% over conventional methods, an increased yield by about 1 to 3 wt% or more, and an APHA color of about 10 to 15 or more improved A glycidyl ester of a terahydrogentanic monocarboxylic acid can be provided.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. You will understand. It is therefore to be understood that the above-described embodiments are illustrative in all respects, and are not necessarily to be construed as limitations. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims rather than the foregoing description, and all changes or modifications derived from the meaning and scope of the claims and the equivalents thereof are included in the scope of the present invention. .

Claims

(a) an aliphatic monocarboxylic acid represented by the formula R ₁ R ₂ R ₃ CCOOH, wherein the total number of carbon atoms of R ₁ , R ₂ , and R ₃ is 8 to 10, each independently a linear or branched alkyl group; Adding a mixture of an EDTA alkali metal salt and a catalyst to adjust the pH of the aliphatic monocarboxylic acid to a range of 6.0 to less than 7.0 to form a reaction mixture;
(b) an epoxyalkyl halide in an amount of 50% by weight to 95% by weight, based on the aliphatic monocarboxylic acid, is added to the reaction mixture and reacted at a temperature ranging from 30 ° C to 95 ° C to obtain an intermediate containing a halohydrin ester ;
(c) adding an alkali solution to the intermediate containing the halohydrin ester to form a glycidyl ester of an alpha-branched aliphatic monocarboxylic acid by subjecting the intermediate containing the halohydrin ester to a ring closure reaction
A method for preparing an alpha-branched aliphatic monocarboxylic acid glycidyl ester,
Wherein the catalyst in said step (a) is comprised of a quaternary ammonium salt, a phosphonium salt, an alkali metal hydroxide, an alkali metal carbonate, an alkaline earth metal hydroxide, an alkali metal or alkaline earth metal alkanolate and combinations thereof , &Lt; / RTI >
In the step (a), a mixture of the alkali metal salt of EDTA and the catalyst is added to the aliphatic monocarboxylic acid at a molar ratio of 0.01 to 0.5,
With the proviso that no organic solvent is used in said steps,
A process for preparing alpha-branched aliphatic monocarboxylic acid glycidyl esters.

delete

The method according to claim 1,
Wherein R ₁ , R ₂ , and R ₃ are each a linear or branched saturated alkyl group.

The method according to claim 1,
Wherein the reaction temperature of step (b) is from 75 ° C to 95 ° C.

The method according to claim 1,
Wherein the reaction temperature in step (c) is from 40 캜 to 70 캜.

The method according to claim 1,
Wherein the epoxy alkyl halide in step (b) comprises an unsubstituted 1-halo-2,3-epoxyalkane having from 3 to 13 carbon atoms, wherein the alpha-branched aliphatic monocarboxylic acid glycidyl ester Way.

The method according to claim 1,
Wherein the step (b) is carried out until the residual amount of the aliphatic carboxylic acid becomes less than 1% by weight based on the initial amount of the glycidyl ester.

The method according to claim 1,
In the step (a), the catalyst is provided in an aqueous solution of 5 wt% to 50 wt%, and is contained in an amount of 5 wt% to 50 wt% in the mixture containing the EDTA sodium salt and the catalyst , A process for producing an alpha-branched aliphatic monocarboxylic acid glycidyl ester.

The method according to claim 1,
A, alpha said EDTA is an alkali metal salt comprises a sodium EDTA salt represented by the _{EDTA-nNa nH 2 O (n} = 2 to 4) - minute method of producing a branched aliphatic monocarboxylic acid glycidyl ester.

The method according to claim 1,
Wherein the alpha-branched aliphatic monocarboxylic acid glycidyl ester is produced in a yield of at least 95% by weight and has a purity of at least 95% by weight.