KR101650528B1

KR101650528B1 - Preparing method of glycidyl esters of alpha-branched aliphatic monocarboxylic acids

Info

Publication number: KR101650528B1
Application number: KR1020150057825A
Authority: KR
Inventors: 이해민; 권가희
Original assignee: 대달산업주식회사
Priority date: 2015-04-24
Filing date: 2015-04-24
Publication date: 2016-08-23

Abstract

The present invention relates to a method for producing glycidyl ester for alpha-branched aliphatic monocarboxylic acid. According to the present invention, production of glycidyl ester of high-purity branched monocarboxylic acid is possible in a high yield. To this end, the method includes the following steps: (a) forming an intermediate including halohydrin ester; and (b) forming glycidyl ester of alpha-branched aliphatic monocarboxylic acid.

Description

PREPARING METHOD OF GLYCIDYL ESTERS OF ALPHA-BRANCHED ALIPHATIC MONOCARBOXYLIC ACIDS < RTI ID = 0.0 >

The present invention relates to a process for preparing glycidyl esters of alpha-branched aliphatic monocarboxylic acids.

The carboxylic acid glycidyl ester represented by the following formula (1) reacts with acrylic acid to form an intermediate, and the intermediate is used for producing a urethane-modified resin, a polyester-modified resin, and the like. Also, as a reactive diluent, a bisphenol-type epoxy resin or the like is also used for diluting to give an appropriate viscosity.

[Chemical Formula 1]

In Formula 1, the total number of carbon atoms of R ₁ + R ₂ + R ₃ is 8 to 12, for example, a reaction product of neodecanoic acid and epihalohydrin.

A method of reacting a carboxylic acid and an epoxyalkyl halide to prepare a glycidyl ester has been conventionally known. The method of preparing glycidyl esters by reacting an alkali metal salt of carboxylic acid and epihalohydrin is carried out under anhydrous conditions in order to increase the reactivity and to solve difficulties such as product separation resulting from saponification reaction.

U.S. Patent No. 2,448,602 discloses the use of an alkaline salt of a carboxylic acid by drying at a high temperature in a vacuum state and U.S. Patent No. 3,142,686 discloses that an aqueous alkali solution of a carboxylic acid is first prepared and then an appropriate organic solvent such as 2-pentanone The reaction conditions were made anhydrous by removing water by azeotropic distillation. Further, Japanese Patent Laid-Open No. 50-76,012 removes water while adding an aqueous alkaline solution of carboxylic acid under the condition that excessive epichlorohydrin can be azeotropically distilled with water. However, these processes have low yields, require complex processes to separate the product from the reactants, and have the disadvantage that 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 ° C to 93 ° C in the presence of a catalyst such as a trivalent amine or tetravalent amine salt to produce an intermediate chlorohydrin ester A method for producing glycidyl esters by ring closure reaction has been disclosed. However, the use of excess epichlorohydrin lowers productivity and consumes a lot of energy to completely remove it.

Japanese Patent Application Laid-Open No. 57-203,077 discloses a process wherein epichlorohydrin is reacted with 1.1 to 1.9 equivalents of carboxylic acid in the presence of a catalyst and an appropriate amount of alkali is added to dichloropropanol obtained as a reaction byproduct after completion of the reaction to obtain epichlorohydrin To reduce the amount of epichlorohydrin. However, the method of recovering epichlorohydrin through the above-mentioned additional steps is difficult to apply industrially.

China Patent No. 10,1245,053 discloses that a catalyst such as epichlorohydrin and quaternary ammonium salt in an excess amount of 10% by mol relative to carboxylic acid is added and the temperature is raised to 90 캜, followed by addition of carboxylic acid to obtain chlorohydrin as an intermediate, Is stirred at the same temperature until the acid value becomes 0.1 or less, and then an aqueous solution of sodium hydroxide is added to effect a ring-closing reaction to obtain a glycidyl ester. However, the yield of the process is low at 86% and the epichlorohydrin, which is a toxic substance, is heated to 90 ° C and is likely to adversely affect the environment. Epichlorohydrin, which is relatively small in volume compared to carboxylic acid, And adding a bulky carboxylic acid to adjust the temperature is difficult to industrially apply.

Korean Patent No. 2012-0016313 discloses a method for preparing a polyurethane obtained by adding a quaternary ammonium salt as a catalyst to a carboxylic acid and adding epichlorohydrin at a temperature lower than 80 캜 for 5 hours at the same temperature so that the acid content of the reaction becomes 0.3 wt% A chlorohydrin reaction mixture is disclosed in which a ring closure reaction is performed to obtain glycidyl esters. However, it takes a long time of 5 to 6 hours to terminate the reaction, 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 tetravalent ammonium salt used as the catalyst is not removed, the remaining epichlorohydrin is concentrated and removed to remove all of the impurities, and 1,3-dichloro-2- It is said that epichlorohydrin may remain in the product by changing to chlorohydrin. If epichlorohydrin remains in the product, health problems of the workers due to the toxicity of epichlorohydrin and corrosion of 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, in the production of chlorohydrin ester, Since a large amount of an alkanol (for example, isopropanol) is used to occupy a large volume of the reactor, the production efficiency is extremely low and a process for recovering an alkanol which is miscible with water is required. When epichlorohydrin is used in an amount of 200% To 2,000% molar ratio should be used and recovered.

PCT Patent CN2011-079677 discloses that epichlorohydrin, which is relatively small in volume compared to carboxylic acid, is first added to the reactor using an organic solvent and an alkali metal hydroxide is added to the reactor containing epichlorohydrin as carboxylic acid and catalyst And it is difficult to industrially apply a large amount of a carboxylic acid and a catalyst to adjust the temperature.

PCT Patent CN2012-087553 discloses a process for recovering isopropanol by using isopropanol which is miscible with water in a ring closure reaction in which a catalyst of the same type is used but excessive epichlorohydrin is used, A device is needed.

Accordingly, the present invention provides a process for preparing glycidyl esters of alpha-branched aliphatic monocarboxylic acids.

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

(A) an aliphatic carboxylic 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 alkyl group having from 1 to 20 carbon atoms ) To 50% by weight to 95% by weight of the total amount of epoxyalkyl halide and an excess of epoxyalkyl halide, followed by the addition of a catalyst to form an intermediate comprising a halohydrin ester; (b) adding an alkali solution to form a glycidyl ester of an alpha-branched aliphatic monocarboxylic acid by a ring closure reaction of the intermediate containing the halohydrin ester to form a glycidyl ester of an alpha-branched aliphatic monocarboxylic acid Wherein the catalyst is an aqueous solution of an alkali metal salt obtained by reacting an aliphatic carboxylic acid and an alkali metal hydroxide in an amount of 5 wt% to 50 wt% of the total amount of the catalyst, and the molar ratio of the aliphatic carboxylic acid to the epoxyalkyl halide is 1 to 1 to 1.2, with the proviso that an organic solvent is not used in the above steps. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view of a glycidyl ester of an alpha-branched aliphatic monocarboxylic acid.

According to any one of the above-mentioned means for solving the problems, in the production of the glycidyl ester of the branched monocarboxylic acid with an aliphatic carboxylic acid and an epoxy alkyl halide, an organic solvent is not used and the epoxyalkyl halide is used in a ratio of 1: An excess of 1.2 is used to recover the epoxy alkyl halide after completion of the reaction, and when a process for recovering the epoxy alkyl halide is required, a high yield is obtained by using a simple device for recovering a small amount, A glycidyl ester of a high-purity branched monocarboxylic acid can be produced.

According to any one of the above-mentioned means for solving the problems, an alkali metal hydroxide aqueous solution is firstly reacted with a part of the aliphatic carboxylic acid to be used for the reaction to prepare an alkali metal salt aqueous solution of a weakly basic aliphatic carboxylic acid and added as a catalyst to the reactor to decompose the epoxyalkyl halide And the problem of the cyclization reaction of the resulting intermediate chlorohydrin ester can be avoided.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows a gas chromatograph for tracking the glycidyl ester reaction of carboxylic acid in one embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. It should be understood, however, that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In the drawings, the same reference numbers are used throughout the specification to refer to the same or like parts.

Throughout this specification, when a part is referred to as being "connected" to another part, it is not limited to a case where it is "directly connected" but also includes the case where it is "electrically connected" do.

Throughout this specification, when a member is "on " another member, it includes not only when the member is in contact with the other member, but also when there is another member between the two members.

Throughout this specification, when an element is referred to as "comprising ", it means that it can include other elements as well, without departing from the other elements unless specifically stated otherwise.

The terms "about "," substantially ", etc. used to the extent that they are used throughout the specification are intended to be taken to mean the approximation of the manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure.

The word " step (or step) "or" step "used to the extent that it is used throughout the specification does not mean" step for.

Throughout this specification, the term "combination (s) thereof " included in the expression of the machine form 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 marker, Quot; means at least one selected from the group consisting of the above-mentioned elements.

Throughout this specification, the description of "A and / or B" means "A or B, or A and B".

Throughout the specification, the term "alkyl (group)" refers to an 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, Linear or branched alkyl group having 1 to 10 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, CC1 ₃ or CF ₃ ), alkoxy, alkylthio, (-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 (-SH) . 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.

Hereinafter, embodiments of the present invention are described in detail, but the present invention is not limited thereto.

In one embodiment herein, in step (a), the glycidyl ester of the alpha-branched aliphatic monocarboxylic acid is reacted with an aliphatic carboxylic acid in which the alpha position is branched, in the presence of a catalyst, An aliphatic carboxylic acid, and an epoxy alkyl halide are added to the reactor to form the halohydrin ester intermediate, and the alkali metal salt of the monocarboxylic acid is slowly added at less than 50 < 0 > C to 80 & And the reaction is carried out. Then, the glycidyl ester of the alpha-branched aliphatic monocarboxylic acid can be prepared by adding an alkali solution to the intermediate to effect a ring-closing reaction.

In one embodiment herein, the aliphatic carboxylic acid is a secondary or tertiary monocarboxylic acid (or a mixture thereof) containing one or two alkyl groups bonded to a carbon atom in the alpha position to a carboxy carbon atom. For example, the aliphatic carboxylic acid may include neodecanoic acid, pivalic acid, 2-methylbutanoic acid, isobutyric acid, isovaleric acid, 2-methylpentanoic acid, 2,4-dimethylvaleric acid, or diethylacetic acid However, the present invention is not limited thereto.

In one embodiment of the invention, the alpha-branched aliphatic monocarboxylic acid is a carboxylic acid in which the alpha position is tertiary branched, specifically a mixture of neodecanoic acids (R ₁ , R ₂ , and Total carbon number of R < ₃ > = 8)

(2)

.

In one embodiment herein, the epoxy alkyl halide is an unsubstituted 1-halo-2,3-epoxyalkane of 3 to 13 carbon atoms. For example, the epoxy alkyl halide may include, but is not limited to, an epihalohydrin or 2-methylhexyl halohydrin. The halogen atom of the epoxy alkyl halide is preferably chlorine or bromine. More preferably, the epoxyalkyl halide may be, but is not limited to, epichlorohydrin.

In one embodiment herein, in step (a), the alkali metal hydroxide is present in an aqueous solution at a concentration of from about 15% to about 60% by weight, more preferably at a concentration of from about 20% to about 50% Can be used. The alkali metal hydroxide may be, for example, a hydroxide of Na, K, or Li, but may not be limited thereto.

In one embodiment of the invention, after the final washing step, a drying step may be performed if necessary, but it is not limited thereto.

In one embodiment of the invention, the glycidyl ester of a very pure branched monocarboxylic acid, i.e., the glycidyl ester having an impurity content of less than 6 wt%, preferably less than 5 wt%, more preferably less than 4 wt% Dilute ester, which is a preferred improved purity, which does not require tailing such as, for example, distillation for purification, and may have a very high conversion rate, but may not be limited thereto.

In one embodiment of the invention, the epoxyalkyl halide is used in stoichiometric excess (1: 1 to 1.2 molar ratio) than the aliphatic carboxylic acid. When the epoxyalkyl halide is added in an amount less than the aliphatic carboxylic acid, the aliphatic carboxylic acid remaining unreacted may form a by-product in the ring closure reaction. In addition, a part of the aliphatic carboxylic acid is not reacted, and the yield is also reduced. The use of excess epoxyalkyl halide may require a process to remove residual epoxyalkyl halide after the reaction before the ring closure reaction.

In one embodiment of the present invention, the total carbon number of R ₁ , R ₂ , and R ₃ may be 8 to 10, but may not be limited thereto. Preferably, the total carbon number of R ₁ , R ₂ , and R ₃ may be 8, but is not limited thereto.

In one embodiment of the present invention, R ₁ , R ₂ , and R ₃ may each independently be a linear or branched saturated alkyl group, but may not be limited thereto.

In one embodiment herein, the reaction temperature of step (a) may be from about 50 < 0 > C to less than about 80 < 0 > C, but is not limited thereto.

In one embodiment herein, the unreacted epoxyalkyl halide of step (a) may be removed prior to the ring closure reaction, but may not be limited thereto. If the epoxy alkyl halide is not removed prior to the ring closure reaction, it is preferred that 1,3-dichloro-2-propanol is produced by an epoxy exchange reaction with the resulting intermediate or the hydrolysis product of the epoxy alkyl halide can be produced as a by-product, .

In one embodiment of the present application, in the step (a), the aliphatic carboxylic acid represented by the formula R ₁ R ₂ R ₃ CCOOH and the epichlorohydrin as the epoxy alkyl halide are reacted in the presence of the catalyst to obtain the chloroauric acid (Step 1) of Step (a).

[Reaction Scheme 1]

In one embodiment of the invention, in step (b), the chlorohydrin ester of the carboxylic acid as the intermediate may be treated with a ring closure reaction to produce the glycidyl ester of the alpha-branched carboxylic acid, (Scheme 2 of step (b)).

[Reaction Scheme 2]

In one embodiment herein, the reaction time of step (a) is less than about 3 hours, such as from about 0.5 hours to about 3 hours, from about 1 hour to about 3 hours, from about 1.5 hours to about 3 hours, About 2 hours to about 3 hours, about 2.5 hours to about 3 hours, about 0.5 hours to about 2.5 hours, about 0.5 hours to about 2 hours, about 0.5 hours to about 1.5 hours, or about 0.5 hours to about 1 hour But may not be limited thereto.

In one embodiment of the present invention, in the step (a), the catalyst may contain, for example, an alkali metal salt of neodecanoic acid (total number of carbon atoms of R ₁ , R ₂ , and R ₃ = 8) But are not limited to:

(3)

The M may be, but is not limited to, Na, K, or Li.

In one embodiment of the present invention, the alkali metal salt of neodecanoic acid may be a mixture of neodecanoic acid and an alkali metal hydroxide aqueous solution.

In one embodiment herein, about 50% to about 95% by weight of the total amount of aliphatic carboxylic acid is used in step (a) and the remainder may be used for catalyst preparation. For example, from about 50 wt% to about 95 wt% of the total amount of the aliphatic carboxylic acid in step (a), from about 5 wt% to about 50 wt% for the catalyst preparation; From about 50 wt% to about 90 wt% in step (a), from about 10 wt% to about 50 wt% for catalyst preparation; From about 60 wt% to about 95 wt% in step (a), from about 5 wt% to about 40 wt% for catalyst preparation; Or from about 60% to about 90% by weight in step (a), and from about 10% to about 40% by weight for preparing the catalyst, but is not limited thereto.

In one embodiment herein, the reaction temperature of step (b) may be from about 40 ° C to about 60 ° C, but is not limited thereto.

In one embodiment herein, the alkali solution of step (b) may include, but is not limited to, NaOH, KOH, or LiOH.

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

68.9 g of neodecanoic acid (80 wt.% Of total amount) and 53 g of epichlorohydrin were added to a 500 mL reactor and heated to 70 占 폚. Thereafter, an aqueous sodium neodecanoate solution prepared in advance by mixing 40 g of a 10% sodium hydroxide aqueous solution with 17.2 g of neodecanoic acid (20% by weight of total amount) was added over 1 hour. After further stirring at the same temperature for 2 hours, a sample was collected and analyzed by gas chromatography. 0.6% of neodecanoic acid remained. After the reaction solution was allowed to stand to remove the water layer, an aqueous solution of sodium hydroxide was added thereto, followed by a ring closure reaction at 45 ° C, followed by washing and concentration to obtain neodecanoic acid glycidyl ester (yield: 96.0%, EEW 248). The unit of the EEW (epoxy equivalent weight) is g / mole, and the smaller the EEW value, the more the epoxy group is.

Wherein the step (a) comprises reacting neodecanoic acid (total carbon number of R ₁ , R ₂ , and R ₃ ) represented by the formula R ₁ R ₂ R ₃ CCOOH with epichlorohydrin as an epoxy alkyl halide in the presence of a catalyst May be reacted to prepare the chlorohydrin ester of carboxylic acid as an intermediate, but may not be limited thereto (Scheme 1 of step (a)).

[Reaction Scheme 1]

The total carbon number of R ₁ , R ₂ , and R ₃ in Reaction Scheme 1 is 8.

The step (b) can be, but is not limited to, the treatment of the chlorohydrin ester of the carboxylic acid, the intermediate, with a ring closure reaction, to produce the glycidyl ester of the alpha-branched carboxylic acid (Scheme (b) 2).

[Reaction Scheme 2]

The total carbon number of R ₁ , R ₂ , and R _{3 in} the above Reaction Formula 2 is 8.

Example 2

68.9 g of neodecanoic acid (80% by weight of total amount), 53 g of epichlorohydrin and 36 mL of water were added to a 500 mL reactor and heated to 60 占 폚. Thereafter, an aqueous sodium neodecanoate solution prepared in advance by mixing 40 g of a 10% sodium hydroxide aqueous solution with 17.2 g of neodecanoic acid (20 wt% of the total amount) was added over 1 hour. After further stirring at the same temperature for 2 hours, a sample was collected and analyzed by gas chromatography. 0.3% of neodecanoic acid remained. After the reaction solution was allowed to stand to remove the water layer, an aqueous solution of sodium hydroxide was added thereto, followed by ring closure reaction at 45 ° C, followed by washing and concentration to obtain neodecanoic acid glycidyl ester (yield 98.5%, EEW 245).

Example 3

51.7 g of neodecanoic acid (60 wt.% Of total amount) and 53 g of epichlorohydrin were added to a 500 mL reactor and heated to 60 占 폚. Thereafter, 40 g of a 10% aqueous solution of sodium hydroxide was mixed with 34.5 g of neodecanoic acid (40% by weight of total amount), and an aqueous sodium neodecanoate solution prepared in advance was added over 1 hour. After further stirring at the same temperature for 2 hours, a sample was collected and analyzed by gas chromatography. 0.6% of neodecanoic acid remained. After the reaction solution was allowed to stand to remove the water layer, an aqueous solution of sodium hydroxide was added thereto, followed by a ring closure reaction at 45 ° C, followed by washing and concentration to obtain neodecanoic acid glycidyl ester (yield 97.2%, EEW 248).

Example 4

68.9 g of neodecanoic acid (80 wt.% Of the total amount used) and 53 g of epichlorohydrin were added to a 500 mL reactor and heated to 60 占 폚. Thereafter, 56 g of a 10% aqueous solution of potassium hydroxide was mixed with 17.2 g of neodecanoic acid (20% by weight of the total amount used), and a previously prepared aqueous solution of potassium neodecanoate was added over 1 hour. After further stirring at the same temperature for 2 hours, a sample was collected and analyzed by gas chromatography. 0.5% of neodecanoic acid remained. After the reaction solution was allowed to stand to remove the water layer, an aqueous solution of sodium hydroxide was added thereto, followed by a ring closure reaction at 45 ° C, followed by washing and concentration to obtain neodecanoic acid glycidyl ester (yield: 96.0%, EEW 251).

Comparative Example One

86.1 g of neodecanoic acid and 53 g of epichlorohydrin were added to a 500 mL reactor and heated to 70 占 폚. Thereafter, 40 g of a 10% sodium hydroxide aqueous solution as a catalyst was added over 1 hour. After further stirring at the same temperature for 2 hours, a sample was collected and analyzed by gas chromatography. 0.5% of neodecanoic acid remained. After the reaction solution was allowed to stand to remove the water layer, an aqueous solution of sodium hydroxide was added and the mixture was subjected to ring closure reaction at 45 ° C, followed by washing and concentration to obtain neodecanoic acid glycidyl ester (yield 95.2%, EEW 268).

Comparative Example 2

86.1 g of neodecanoic acid and 53 g of epichlorohydrin were added to a 500 mL reactor and heated to 70 占 폚. Then, 56 g of a 10% aqueous solution of potassium hydroxide was added over 1 hour. After further stirring at the same temperature for 2 hours, a sample was collected and analyzed by gas chromatography. 0.2% of neodecanoic acid remained. After the reaction solution was allowed to stand to remove the water layer, an aqueous solution of sodium hydroxide was added and the reaction solution was subjected to ring closure reaction at 45 ° C, followed by washing and concentration to obtain neodecanoic acid glycidyl ester (yield 94.1%, EEW 275).

Comparative Example 3

A 500-mL reactor was charged with 86.1 g of neodecanoic acid and 40 g of a 10% aqueous sodium hydroxide solution and heated to 70 ° C. Then, 53 g of epichlorohydrin was added over 1 hour. After further stirring at the same temperature for 2 hours, a sample was collected and analyzed by gas chromatography. 0.3% of neodecanoic acid remained. After the reaction solution was allowed to stand to remove the water layer, an aqueous solution of sodium hydroxide was added thereto, followed by ring closure reaction at 45 ° C, followed by washing and concentration to obtain neodecanoic acid glycidyl ester (yield 88.6%, EEW 272).

The contents of the above Examples and Comparative Examples are shown in Table 1 below. The unit of the EEW (epoxy equivalent weight) is g / mole, and the smaller the EEW value, the more the epoxy group is. In step (a), when the glycidyl ester as the ring-closing reaction product (B) is produced, it is important to minimize the amount of the ring-closing reaction product by reacting with neodecanoic acid to form a byproduct. In Examples 1 to 4 of Table 1 below, the numerical values of the neodecanoic acid glycidyl ester as the ring-closing reagent (B) were lower than those of Comparative Examples 1 to 3 after the step (a). The EEW in Table 1 below is the value of the glycidyl ester of neodecanoic acid obtained after proceeding all the way up to step (b).

The reaction was analyzed using gas chromatography to confirm the reaction of this example. For gas chromatography, an HP-5, 30 m capillary column was used. After the step (a), the analysis results of the gas chromatography are 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, and the peak group indicated by C is the chlorohydrin ester of the intermediate neodecanoic acid. The area percentage in Figure 1 is the residual amount of neodecanoic acid remaining after step (a) and the amount of neodecanoic acid glycidyl ester.

A basic catalyst was used for the reaction of carboxylic acid and epoxy. The alkali metal hydroxide itself is strong in alkalinity, and besides hydrolyzing epichlorohydrin, it is confirmed that it partially proceeds from the catalytic reaction to the subsequent closure reaction to catalyze the production of chlorohydrin ester Respectively. When the reaction progresses to the ring closure reaction, the neodecanoic acid reacts again with the epoxy group of the glycidyl ester of the resulting neodecanoic acid to form an impurity having a high boiling point. On the other hand, in the examples of the present invention, the alkali metal salt was used to minimize the ring closure reaction in the chlorohydrin ester reaction step (a). In order to minimize the ring closure reaction in the chlorohydrin ester reaction, the basic catalyst should be added little by little to the reactor, and a weak basic catalyst such as an alkali metal salt of neodecanoic acid is more advantageous than a strong basic catalyst such as alkali metal hydroxide I could.

It will be understood by those of ordinary skill in the art that the foregoing description of the embodiments is for illustrative purposes and that those skilled in the art can easily modify the invention without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. 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 detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be interpreted as being included in the scope of the present invention .

Claims

(a) an aliphatic carboxylic 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 alkyl group having 1 to 20 carbon atoms, % To 95% by weight of an excess of an epoxyalkyl halide, followed by the addition of a catalyst to form an intermediate comprising the halohydrin ester;
(b) adding an alkali solution to form a glycidyl ester of an alpha-branched aliphatic monocarboxylic acid by ring closure reaction of the intermediate containing the halohydrin ester
A process for preparing a glycidyl ester of an alpha-branched aliphatic monocarboxylic acid,
The catalyst is an aqueous solution of an alkali metal salt obtained by reacting an aliphatic carboxylic acid and an alkali metal hydroxide in an amount of 5 wt% to 50 wt%
Wherein the molar ratio of aliphatic carboxylic acid to epoxyalkyl halide is from 1: 1 to 1.2,
With the proviso that no organic solvent is used in said steps,
Process for the preparation of glycidyl esters of alpha-branched aliphatic monocarboxylic acids.

The method according to claim 1,
Wherein the total number of carbon atoms of R ₁ , R ₂ , and R ₃ is from 8 to 10. The present invention also provides a method for producing glycidyl esters of alpha-branched aliphatic monocarboxylic acids.

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 (a) is less than 50 < 0 > C to less than 80 < 0 > C.

The method according to claim 1,
Wherein the reaction temperature of step (b) is between 40 ° C. and 60 ° C. 3. The process according to claim 1, wherein the glycidyl ester of the α-branched aliphatic monocarboxylic acid is obtained.

The method according to claim 1,
Wherein the epoxy alkyl halide comprises an unsubstituted 1-halo-2,3-epoxyalkane having from 3 to 13 carbon atoms.