KR101469725B1 - Preparation method of epoxy ester compound and plasticizer composition using the same - Google Patents

Abstract

The present invention relates to a process for producing an epoxy ester compound, and more particularly, to an epoxy ester compound which can be usefully used as a plasticizer for vinyl chloride resin by shortening the reaction time by omitting the neutralization process unlike the conventional method for synthesizing an ester compound Thereby minimizing the reaction process and recycling the glycerin generated as a by-product.

Description

The present invention relates to a method for preparing an epoxy ester compound and a plasticizer composition using the epoxy ester compound,

The present invention relates to a process for producing an epoxy-based ester compound which can be used as a novel plasticizer material for vinyl chloride resin.

Polymer resins have been used in various fields such as life and home appliances, clothing, automobiles, construction materials, and packaging materials to suit their characteristics. Up to now, plastic resins such as polyethylene (PE), polypropylene (PP), polystyrene (PP), polyurethane (PU) and polyvinyl chloride (PVC) have been widely used. In particular, PVC resin is applicable to a variety of applications ranging from household goods to industrial materials because of its hardness, softness and various molding properties and excellent price competitiveness.

PVC resin can not be used alone and plasticizer is added for various properties. Plasticizers provide flexibility of PVC resin and improve the processability and applicability. However, as the industry has developed, the role of plasticizer has diversified and various characteristics have been diversified according to the application fields such as resistance to aging, resistance to cold, oil resistance, water resistance, heat resistance and heat resistance.

In general, the plasticizer has an excellent resistance to aging properties as the molecular weight is larger, but compatibility with vinyl chloride resin tends to be lowered. Thus, plasticizers suitable for aging resistance and compatibility are selected according to application fields.

However, the development of new plasticizers that can satisfy both aging resistance and compatibility in order to improve the aging resistance and compatibility of plasticizers that have been used in the past is in need of improvement in physical properties such as aging resistance of plasticizers along with industrial development. It was desperate situation.

Korean Patent No. 0957134 discloses a plasticizer composition for heat-resistant wires comprising di- (2-propylheptyl phthalate) and di- (2-propylheptyl terephthalate).

It is an object of the present invention to develop a process for producing an epoxy ester compound as a novel plasticizer capable of improving physical properties of a compound using a conventional vinyl chloride resin.

In order to accomplish the above object, the present invention provides an epoxy-based ester compound preparation method comprising reacting an epoxidized vegetable oil represented by the following formula 1 with an alcohol to produce an epoxy-based ester compound represented by the following formula 2 do:

[Chemical Formula 1]

Wherein R ¹ , R ² and R ³ are each independently C 8 to C 20 epoxyalkyl,

(2)

R ⁴ is C 1 to C 10 alkyl, and R ⁵ is C 8 to C 20 epoxy alkyl corresponding to R ¹ , R ² and R ³ .

More particularly, the present invention relates to a process for producing a polyurethane foam, which comprises mixing an epoxidized vegetable oil represented by the following general formula (1), an alcohol and a catalyst, followed by reaction at a temperature of 70 to 230 캜 for 4 to 12 hours under a gas atmosphere; Removing the excess amount of the alcohol and the glycerin generated as a byproduct after the completion of the reaction; And a step of washing the reaction product with distilled water, dehydration and filtration to prepare an epoxy ester compound represented by the general formula (2).

At this time, if the reaction conditions are exceeded, problems such as prolongation of reaction time and residual by-products may be caused.

The vegetable oil may be selected from the group consisting of soybean oil, palm oil, linseed oil, sesame oil, safflower oil, corn oil, palm oil, sesame oil, castor oil, coconut oil, olive oil, barbara milk, cottonseed oil, oiticica oil, But are not limited to, oils, sunflower oil and perilla seed oil.

The alcohol may be a C1 to C10 alcohol, preferably a C1 to C4 alcohol.

The alcohol may be added in an amount of 100 to 500 parts by weight based on 100 parts by weight of the epoxidized vegetable oil. If the content of the alcohol is out of the above range, the reaction rate is low and the reaction time is prolonged or the efficiency of the reaction is poor. .

The catalyst may be selected from the group consisting of an alkali metal compound, a metal alkoxide compound, paratoluene sulfonic acid, and an acid catalyst. Examples of the alkali metal compound include NaOCH ₃ , NaOH, KOH, NaBH ₄ and the like. The metal alkoxide compound includes tetranormal butyl titanate, tetraisopropyl titanate, etc. The acid catalyst includes sulfuric acid, Nitric acid, and the like can be used, and an alkali metal compound can be preferably used.

The catalyst may be added in an amount of 0.01 to 0.1 part by weight based on 100 parts by weight of the epoxidized vegetable oil. If the content of the catalyst is out of the above range, the reaction may not proceed or the reaction rate may be slowed down.

In addition, the present invention provides a plasticizer composition comprising an epoxy-based ester compound produced according to the above production method.

According to the present invention, an epoxy ester compound which can be usefully used as a plasticizer for vinyl chloride resin can be produced by omitting the neutralization process unlike the conventional ester compound synthesis method, thereby shortening the reaction time and minimizing the reaction process, Glycerin can be recycled.

Fig. 1 shows the results of GC analysis according to Example 1. Fig.

Hereinafter, a method for producing an epoxy ester compound using an epoxidized vegetable oil represented by the following formula (3) will be described in more detail.

(3)

Herein, R 1, R 2, and R 3 are each an epoxy alkyl compound having 8 to 20 carbon atoms, particularly preferably an epoxy alkyl compound having 16, 18, or 20 carbon atoms.

The alcohol may be an alcohol having 1 to 10 carbon atoms, particularly preferably an alcohol having 1 to 4 carbon atoms. At this time, the alcohol may be added in an amount of 100 to 500 parts by weight based on 100 parts by weight of the epoxidized vegetable oil. If the content of the alcohol is out of the above range, the reaction rate is low and the reaction time is prolonged or the efficiency of the reaction is inferior Lt; / RTI >

The catalyst is an alkali metal including _{NaOCH 3, NaOH, KOH, NaBH} 4 compound; Metal alkoxide compounds including tetra n-butyl titanate, tetraisopropyl titanate and the like; Sulfuric acid, hydrochloric acid, nitric acid and the like can be used, and an alkali metal compound can be preferably used. At this time, the catalyst may be added in an amount of 0.01 to 0.1 part by weight based on 100 parts by weight of the epoxidized vegetable oil. If the content of the alcohol is out of the above range, the reaction may not proceed or the reaction rate may be slowed have.

In the method for producing an epoxy ester according to the present invention, as an ester exchange reaction, the reaction is carried out in a nitrogen or argon gas atmosphere in order to block from outside air, particularly oxygen, during the reaction. For example, nitrogen is bubbled into the reaction solution, .

In addition, although the reaction temperature varies depending on the type of alcohol, the reaction can be generally carried out at a temperature of 70 to 230 ° C for 4 to 12 hours.

After the ester exchange reaction is completed, excess alcohol is distilled off to remove glycerin generated as a by-product, and glycerin and catalyst remaining in a small amount can be removed by washing with distilled water and dehydration can proceed. When the dehydration is completed, an epoxy ester compound as a product can be obtained through filtration.

The epoxy-based ester compound synthesized according to the present invention can be produced by reacting epoxidized methyl palmitoleate, epoxidized methyl oleate, epoxidized methyl linoleate, epoxidized methyl oleate, Epoxidized methyl gadoleate, Epoxidized n-butyl palmitoleate, Epoxidized n-butyl oleate, Epoxidized n-butyl oleate ( Epoxidized n-butyl linoleate, Epoxidized n-butyl gadoleate, Epoxidized 2-ethylhexyl palmitoleate, Epoxidized 2-ethylhexyl oleate Epoxidized 2-ethylhexyl oleate, epoxidized 2-ethylhexyl linoleate, and epoxidized 2-ethylhexyl gadoleate. However, But is not limited thereto.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

≪ Example 1 > Preparation of epoxy-based ester compound

995.98 g of Epoxidized Soybean Oil (ESO), 480 g of methyl alcohol (ESO) were added to a 4-neck round flask equipped with a thermometer, a stirrer, a decanter, a condenser and an inert gas- ) And 2.99 g of sodium methoxide as a catalyst were added and mixed, and the mixture was reacted for 4 hours while elevating the temperature to 70 ° C in a nitrogen atmosphere (normal pressure). After the reaction, the unreacted product in the reactor was removed under reduced pressure at 100 to 150 ° C, and glycerin, which is a by-product, was separated. The product was washed with distilled water and dehydrated. The activated carbon and diatomaceous earth were mixed and filtered using a filter. The product was analyzed by GC. As a result, 984 g of the epoxidized soybean oil methyl ester as the final product . At this time, glycerol was also obtained as a by-product (see FIG. 1).

≪ Example 2 > Preparation of epoxy-based ester compound

Epoxidized Palm Oil (995.98 g) and Methyl alcohol (430.80 g) were added to a 4-neck round flask equipped with a thermometer, a stirrer, a decanter, a condenser and an inert gas injection device. and 2.99 g of sodium methoxide as a catalyst, 977 g of an epoxidized palm oil methyl ester as an epoxy ester compound was obtained in the same manner as in Example 1. At this time, glycerol was obtained as a byproduct.

≪ Example 3 > Preparation of epoxy ester compound

995.98 g of Epoxidized Linseed Oil (Arkema, ^Vikoflex® 7190) was added to a 4-neck round flask equipped with a thermometer, a stirrer, a decanter, a condenser and an inert gas injector, 430.80 g of methyl alcohol and 2.99 g of sodium methoxide as a catalyst were added to obtain an epoxidized linseed oil methyl ester as an epoxy ester compound in the same manner as in Example 1, 972 g was obtained. At this time, glycerol was obtained as a byproduct.

<Example 4> Preparation of epoxy-based ester compound

884.74 g of Epoxidized Soybean Oil (ESO), n-butanol (n-hexane) were added to a 4-neck round flask equipped with a thermometer, a stirrer, a decanter, a condenser and an inert gas- Butyl alcohol (885.29 g) as a catalyst and 2.65 g of sodium methoxide as a catalyst were added and mixed. Then, the mixture was reacted for 6 hours while elevating the temperature to 118 ° C under atmospheric pressure (atmospheric pressure). After the reaction, the unreacted product in the reactor was removed under reduced pressure at 180 ° C and glycerin, which is a by-product, was separated. After the product was washed with distilled water and dehydrated, activated carbon and diatomaceous earth were mixed and filtered using a filter to obtain 950 g of an epoxidized soybean oil n-butyl ester as an end product . At this time, glycerol was obtained as a byproduct.

&Lt; Example 5 > Preparation of epoxy-based ester compound

770.05 g of Epoxidized Soybean Oil (ESO) was added to a 4-neck round flask equipped with a thermometer, a stirrer, a decanter, a condenser and an inert gas injector, and 2-ethylhexyl alcohol 1,353.84 g of 2-ethylhexyl alcohol and 2.31 g of sodium methoxide as a catalyst were added and mixed, and the mixture was reacted for 9 hours while heating to 180 ° C in a nitrogen atmosphere (atmospheric pressure). After the reaction, the unreacted product in the reactor was removed under reduced pressure at 180 ° C and glycerin, which is a by-product, was separated. The product was washed with distilled water and dehydrated. The activated carbon and the diatomaceous earth were mixed and filtered using a filter. Thereafter, 938 g of an epoxidized soybean oil 2-ethylhexyl ester (epoxidized soybean oil 2-ethylhexyl ester) . At this time, glycerol was obtained as a byproduct.

&Lt; Example 6 > Preparation of epoxy-based ester compound

995.98 g of Epoxidized Soybean Oil (ESO), 470 g of methyl alcohol (NMP) were added to a 4-neck round flask equipped with a thermometer, a stirrer, a decanter, a condenser and an inert gas- ) And 18.64 g of tetra-n-butyl titanate as a catalyst were added thereto to obtain an epoxidized soybean oil methyl ester (epoxidized ester compound) in the same manner as in Example 1, 932 g was obtained. At this time, glycerol was obtained as a byproduct.

&Lt; Example 7 > Preparation of epoxy-based ester compound

995.98 g of Epoxidized Soybean Oil (ESO), 470 g of methyl alcohol (NMP) were added to a 4-neck round flask equipped with a thermometer, a stirrer, a decanter, a condenser and an inert gas- ) And 9.43 g of p-toluenesulfonic acid as a catalyst were added to obtain 910 g of an epoxidized soybean oil methyl ester as an epoxy ester compound in the same manner as in Example 1 . At this time, glycerol was obtained as a byproduct.

<Experimental Example 1> Characterization of epoxy ester compounds

The acid value, hue, specific gravity and refractive index of the epoxy-based ester compounds prepared in the preceding Examples were respectively analyzed, and the results are shown in Table 1 below.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Inspection / Test Method Reference
(Outside analysis method) Acid value (mg) 0.06 0.11 0.11 0.12 0.07 0.13 0.16 BP6-PD04 JIS K 6751 Color (APHA) 94 102 110 121 142 155 152 B06-PD01 JIS K 6751 Specific gravity (20/20 ℃) 0.961 0.957 0.950 0.943 0.961 0.961 0.961 B06-PD02 JIS K 6751 Refractive index (n.25 / D) 1.454 1.453 1.452 1.452 1.454 1.454 1.454 B06-PD03 JIS K 6751

While the invention has been described with reference to a limited number of embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims.

Claims (8)

delete An epoxy vegetable oil selected from epoxidized palm oil, epoxidized soybean oil or epoxidized linseed oil, a C1 to C4 alcohol and sodium methoxide, tetranormal butyl titanate or paratoluenesulfonic acid, Lt; RTI ID = 0.0 &gt; 230 C &lt; / RTI &gt; for 4 to 12 hours;
Removing the excess amount of the alcohol and the glycerin generated as a byproduct after the completion of the reaction; And
The reaction product is washed with distilled water, dehydrated and then filtered to prepare an epoxy ester compound represented by the general formula (2)
Wherein the epoxy ester compound is selected from the group consisting of:
(2)

Wherein R &lt; ⁴ &gt; is C1 to C4 alkyl and R &lt; ⁵ &gt; is an epoxyalkyl of C16, C18 or C20. delete delete [Claim 3] The method according to claim 2, wherein the alcohol is added in an amount of 100 to 500 parts by weight based on 100 parts by weight of the epoxy vegetable oil. delete [Claim 3] The method according to claim 2, wherein the catalyst is added in an amount of 0.01 to 0.1 part by weight based on 100 parts by weight of the epoxy vegetable oil. delete

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