KR101570386B1 - Composite plasticizer composition comprising epoxy ester compound and polymer resin composition using the same - Google Patents

Abstract

The present invention relates to a composite plasticizer composition containing an epoxy-based ester compound and a polymeric resin composition using the same. More particularly, the present invention relates to a composite plasticizer composition obtained by mixing an epoxy ester compound with a compound conventionally used as a plasticizer for a polymer resin such as a vinyl chloride resin It is possible to realize the same physical properties as the amount of the plasticizer to be used and also to increase the production rate and production amount during processing This reduces work time and reduces utility costs.

Description

[0001] The present invention relates to a composite plasticizer composition containing an epoxy ester compound and a polymeric resin composition using the same,

The present invention relates to a composite plasticizer composition containing an epoxy ester compound and a polymeric resin composition using the same. More particularly, the present invention relates to a composite plasticizer composition containing an epoxy ester compound usable as a novel plasticizer material together with a plasticizer compound used in the past, And a polymeric resin composition.

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.

Korean Patent No. 0957134 (Patent Document 1) discloses a plasticizer composition for heat-resistant wires. It is required to develop 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 conventionally because of the tendency of improvement of physical properties such as aging resistance of plasticizers along with industrial development in recent years It is a fact that is demanded.

Korean Patent No. 0957134

In order to solve the problems of the prior art as described above, the present invention provides a novel plasticizer composition containing an epoxy ester compound as a novel plasticizer capable of improving the physical properties of a compound using a conventional polymer resin, and a polymer resin composition using the same .

It is another object of the present invention to provide a new composite plasticizer composition having excellent resistance to aging, compatibility, and particularly, an elongation percentage as compared with conventional plasticizers, and a polymer composition using the same.

In order to accomplish the above object, the present invention provides an epoxy resin composition comprising 5 to 95% by weight of an epoxy ester compound represented by the following formula (2); And 5 to 95% by weight of at least one ester compound selected from the group consisting of phthalate ester compounds, terephthalate ester compounds, phthalate-based and terephthalate-based ester compounds and trimellitate-based ester compounds .

(2)

이며, 상기 R_x 및 R_y는 각각 독립적으로 수소, (C1-C5)알킬 또는

이며, 상기 알킬은 (C1-C5)알킬 또는

이 더 치환될 수 있고, 상기 R₄₁ 및 R₄₂는 각각 독립적으로 (C8-C20)에폭시알킬이며, 상기 n은 1 내지 5에서 선택되는 정수이다.)Wherein R ₄ is (C 8 -C 20) epoxyalkyl and R ₅ is (C 1 -C 10) alkyl or

, R _x and R _y are each independently hydrogen, (C 1 -C 5) alkyl or

(C1-C5) alkyl or < RTI ID = 0.0 >

And R ₄₁ and R ₄₂ are each independently (C 8 -C 20) epoxyalkyl, and n is an integer selected from 1 to 5.)

According to one embodiment of the present invention, there is provided an epoxy resin composition comprising 5 to 30% by weight of an epoxy ester compound represented by the following formula (2); And 70 to 95% by weight of one or more ester compounds selected from the group consisting of a phthalate ester compound, a terephthalate ester compound, a phthalate-based and terephthalate-based ester mixture, and a trimellitate-based ester compound.

(2)

이며, 상기 R_x 및 R_y는 각각 독립적으로 수소, (C1-C5)알킬 또는

이며, 상기 알킬은 (C1-C5)알킬 또는

이 더 치환될 수 있고, 상기 R₄₁ 및 R₄₂는 각각 독립적으로 (C8-C20)에폭시알킬이며, 상기 n은 1 내지 5에서 선택되는 정수이다.)Wherein R ₄ is (C 8 -C 20) epoxyalkyl and R ₅ is (C 1 -C 10) alkyl or

, R _x and R _y are each independently hydrogen, (C 1 -C 5) alkyl or

(C1-C5) alkyl or < RTI ID = 0.0 >

And R ₄₁ and R ₄₂ are each independently (C 8 -C 20) epoxyalkyl, and n is an integer selected from 1 to 5.)

The epoxy-based ester compound may be prepared by reacting an epoxidized vegetable oil represented by the following formula (1) with an alcohol.

[Chemical Formula 1]

(Wherein R ₁ , R ₂ and R ₃ are each independently (C 8 -C 20) epoxyalkyl).

The epoxy-based ester compound is prepared by mixing an epoxidized vegetable oil, an alcohol and a catalyst, and then reacting at a temperature of 70 to 230 ° C for 4 to 12 hours under a gas atmosphere; Removing the excessively charged alcohol and glycerol generated as a by-product after completion of the reaction; And a step of washing the reaction product with distilled water, dehydrating and then filtering to prepare an epoxy ester compound represented by the general formula (2).

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, Oil, sunflower oil and perilla seed oil.

In order to accomplish the above object, the present invention relates to a polymer resin composition comprising 30 to 120 parts by weight of the composite plasticizer composition described above relative to 100 parts by weight of the polymer resin.

The polymer resin may be selected from the group consisting of a polyvinyl chloride resin, an olefin resin, an ABS resin, an acrylic resin, and a polyester resin.

The polymer resin composition may be used in various applications such as a compound, a wire compound, a wallpaper, a sheet, a film, a tarpaulin, a hose, a shoe, a sealant, an office supplies, a glove, a bottle cap, a mat, a gasket, a food packaging material, Electrical < / RTI > mechanical parts, and the like.

According to another embodiment of the present invention, the composite plasticizer composition includes a composite plasticizer composition having a glycerol content of 5,000 ppm or less, and a polymeric resin composition including the composite plasticizer composition.

According to another aspect of the present invention, there is provided a process for producing a polyurethane foam, comprising the steps of: mixing an epoxidized vegetable oil, an alcohol and a catalyst, Vacuum distilling the reaction product; Separating the vacuum distillation residue to remove glycerol; And a step of washing and dehydrating the glycerol-free residue. The present invention also relates to a method for producing an epoxy-based ester compound having a glycerol content of 5000 ppm or less.

The temperature during the reaction may be from 70 to 230 ° C, and the dehydration may be performed with water-adsorbing inorganic particles or vacuum distillation.

The manufacturing method may further include a step of adding deodorization and dehydratable inorganic particles after the water washing and dehydration step, and then filtering the water.

INDUSTRIAL APPLICABILITY According to the present invention, by using a composite plasticizer composition in which an epoxy ester compound is mixed with a compound conventionally used as a plasticizer for a polymer resin such as a vinyl chloride resin or the like, the thermal stability is superior to that of the conventional plasticizer compound, The defective rate is remarkably reduced.

In addition, since the plasticization efficiency is excellent, the same physical properties can be realized even with a small amount of plasticizer used. In addition, the production speed and production amount during processing can be increased, thereby reducing work time and utility.

Furthermore, it has been surprisingly found that when the content of glycerol as a byproduct in the complex plasticizer of the present invention is maintained at 5000 ppm or less, a remarkably excellent effect such as a remarkably increased elongation percentage can be achieved.

1 is a graph showing the results of GC analysis according to Example 1 of the present invention.
FIG. 2 is a digital photograph showing a result of comparing the thermal stability of a specimen according to Example 1 of the present invention with a specimen according to Comparative Example 1. FIG.

Hereinafter, the present invention will be described in more detail.

As a result of efforts to improve the thermal stability and plasticizing efficiency of plasticizers such as phthalate ester compounds and terephthalate ester compounds which have been conventionally used, the present inventors have found that a composite plasticizer composition comprising an epoxy ester compound together with a conventional plasticizer It is possible to improve heat stability, plasticization efficiency and economical efficiency, thereby completing the present invention.

In addition, the present invention is not limited to the case where the content of glycerol generated as a by-product in the production of the epoxy plasticizer of Formula 2, which is one of the components of the composite plasticizer in the polymer composition, is controlled to be 5000 ppm or less, And the present invention has been completed.

That is, the present invention relates to an epoxy ester compound (A) represented by the general formula (2);

(2)

이며, 상기 R_x 및 R_y는 각각 독립적으로 수소, (C1-C5)알킬 또는

이며, 상기 알킬은 (C1-C5)알킬 또는

이 더 치환될 수 있고, 상기 R₄₁ 및 R₄₂는 각각 독립적으로 (C8-C20)에폭시알킬이며, 상기 n은 1 내지 5에서 선택되는 정수이다.)Wherein R ₄ is (C 8 -C 20) epoxyalkyl and R ₅ is (C 1 -C 10) alkyl or

, R _x and R _y are each independently hydrogen, (C 1 -C 5) alkyl or

(C1-C5) alkyl or < RTI ID = 0.0 >

And R ₄₁ and R ₄₂ are each independently (C 8 -C 20) epoxyalkyl, and n is an integer selected from 1 to 5.)

Phthalate ester compounds such as DOP (di-2-ethylhexyl phthalate), DINP (diisonoyl phthalate) and DIDP (diisodecyl phthalate), terephthalate compounds such as Di-2-ethylhexyl terephthalate and NEO-T3 Phthalate-based and terephthalate-based ester compositions such as ester compounds, Mixed Di-2-propylheptyl phthalate and terephalate (PYRO-C), and trimellitic esters such as Tri-2-ethylhexyl trimellitate (TOTM) and TINTM (Triisononyl trimellitate) (B group) selected from the group consisting of an ester compound and an ester compound.

Further, the present invention provides a composite plasticizer composition wherein the content of glycerol present in the epoxy ester plasticizer of Formula 2 in the composite plasticizer composition is kept at 5000 ppm or less.

The composite plasticizer composition comprises 5 to 95% by weight of an epoxy ester compound (A) and 5 to 95% by weight of a conventional plasticizer compound (B), preferably 5 to 30% by weight of an epoxy ester compound (A) By weight, and 70 to 95% by weight of a conventional plasticizer compound (group B). At this time, excellent effects such as thermal stability, plasticizing efficiency and the like of the plasticizer within the above content range can be achieved.

Examples of the epoxy ester compounds include epoxidized methyl palmitoleate, epoxidized methyl oleate, epoxidized methyl linoleate, epoxidized methyl guar oleate Epoxidized methyl gadoleate, Epoxidized n-butyl palmitoleate, Epoxidized n-butyl oleate, Epoxidized n-butyl linoleate, epoxidized n-butyl gadoleate, epoxidized 2-ethylhexyl palmitoleate, epoxidized 2-ethylhexyl oleate, oleate, epoxidized 2-ethylhexyl linoleate, epoxidized 2-ethylhexyl gadoleate, but are not limited thereto. It is not.

"(C8-C20) epoxyalkyl" represented by "epoxidation" in the present invention means that at least one epoxy ring structure is contained in the main chain having 8 to 20 carbon atoms.

For example, it can be represented by the following general formula (3), but is not limited thereto.

(3)

Also, the composite plasticizer composition according to the present invention can be applied to a polymer resin, and is not limited to 100 parts by weight of the polymer resin, but it is preferable to include, for example, 30 to 120 parts by weight of the composite plasticizer composition. The polymer resin may include, but is not limited to, a polyvinyl chloride resin, an olefin resin, an ABS resin, an acrylic resin, a polyester resin, and the like.

 In addition, the polymer resin composition may further include one or more additives selected from the group consisting of a secondary plasticizer, a stabilizer, a filler, a lubricant, a flame retardant, a viscosity regulator, a foaming agent, an enhancer and a pigment.

The polymer resin composition according to the present invention can be applied to a variety of applications such as a compound, a wire compound, a wallpaper, a sheet, a film, a tarpaulin, a hose, a shoe, a sealant, an office product (eraser), a glove, a bottle cap, Toys, baby products, flooring, electromechanical parts and so on.

In the present invention, the production method of the epoxy ester compound is as follows.

Mixing the epoxidized vegetable oil, the alcohol and the catalyst, and heating and reacting in an atmosphere of gas; Removing the excessively charged alcohol and glycerol generated as a by-product after completion of the reaction; And a step of washing the reaction product with distilled water, dehydrating and then filtering to prepare an epoxy ester compound represented by the general formula (2).

[Chemical Formula 1]

(Wherein R ₁ , R ₂ and R ₃ are each independently (C 8 -C 20) epoxyalkyl).

That is, mixing the epoxidized vegetable oil, the alcohol and the catalyst, and heating and reacting the mixture, decompressing the reaction product, separating the reduced-pressure distillation residue to remove glycerol, And a step of washing and dehydrating the glycerol-free residue, wherein the glycerol-containing residue has a glycerol content of 5000 ppm or less.

The temperature for raising the temperature during the reaction is not limited, but is, for example, from 70 to 230 占 폚, and the dehydration may be performed, for example, by water-adsorbing inorganic particles or vacuum distillation. It is preferable that the manufacturing method further comprises a step of adding deodorization and dehydratable inorganic particles after the washing and dehydrating step and then filtering.

Specifically,

Mixing the epoxidized vegetable oil, the alcohol and the catalyst, and then reacting at a temperature of 70 to 230 캜 for 4 to 12 hours under a gas atmosphere;

Removing excessively charged alcohol through the vacuum distillation after completion of the reaction, and removing glycerol generated as a by-product by layer separation by specific gravity difference; And

The reaction product may be washed with distilled water to remove residual alcohol and glycerol, followed by dehydration and filtration to produce an epoxy ester compound represented by formula (2).

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 an alcohol having 1 to 10 carbon atoms, particularly preferably an alcohol having 1 to 4 carbon atoms. In this case, 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 lower than the above range, the reaction rate is low and the reaction time is prolonged, Problems can arise, and high costs are not economically viable.

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; Or the like can be used, and an alkali metal compound can be preferably used.

At this time, although the content of the catalyst can be selected as needed, for example, when 0.01 to 0.1 parts by weight is added to 100 parts by weight of the epoxidized vegetable oil, the reaction can be appropriately controlled and a sufficient yield can be obtained, which is effective .

The method for preparing the epoxy ester compound is preferably an ester exchange reaction in which the reaction is carried out in a nitrogen or argon gas atmosphere in order to block the reaction from the outside air, particularly oxygen, during the reaction. For example, when nitrogen is bubbled into the reaction solution ), Thereby shortening the reaction time.

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.

Hereinafter, the method for obtaining the plasticizer of the present invention and the method for removing the side reaction product according to the transesterification reaction of the present invention will be described in detail.

In the present invention, after completion of the reaction, removing excessively charged alcohol through reduced pressure distillation, removing glycerol produced as a by-product by layer separation by specific gravity difference, and washing the reaction product with excess distilled water, Removing the alcohol and glycerol and dehydrating them to prepare an epoxy ester compound represented by the general formula (2). The dehydration and filtration may be further performed to further increase the purity.

The dehydration process may be performed by dewatering inorganic dehydrated particles, but in the present invention, a process for removing water by distillation under reduced pressure is more preferred in the process. At this time, the dehydration temperature can be reduced by depressurizing at 100 to 150 ° C, but can be carried out by suitably selecting the depressurization condition and the temperature condition.

As the filtration method, inorganic particles such as talc, activated carbon or inorganic oxide, inorganic carbide, inorganic sulfide (such as mark sodium sulfate) which have deodorization and dehydration function at the same time and have an adsorption function are added and stirred sufficiently, It is preferable to adopt a means to

Particularly, in order to control the glycerol content to 5000 ppm or less in the present invention, the compounded plasticizer having excellent physical properties can be prepared by adjusting the residual amount of the glycerol to be the object of the present invention by carrying out the above vacuum distillation, layer separation, washing and dehydration steps can do.

That is, when the transesterification reaction is completed, the excess alcohol and the glycerol generated as a by-product are removed, and then the glycerol and the catalyst are washed with distilled water and then dehydrated. In the above, the decomposition distillation only results in a high loss of the compound of the formula (2) as a product, and the productivity is not good. Therefore, the by-product is separated by adding a water washing and a dehydrating step to obtain a product having a glycerol content of 5000 ppm or less A plasticizer of formula (2) can be prepared.

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.

Synthesis Example 1 Synthesis of epoxy 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 solution (30 wt% in methanol) were added and mixed. Then, the mixture was reacted for 4 hours while elevating the temperature to 70 ° C under nitrogen atmosphere (atmospheric pressure). After the reaction, the excess unreacted alcohol was removed under reduced pressure at 100-150 ° C., and the glycerol was separated into the lower part of the reactor after stagnating for 1 to 6 hours in order to remove by-product Glycerol by layer separation by specific gravity difference. To remove some residual glycerol, it was rinsed twice with distilled water (10 to 50 wt% of the amount of epoxidized soybean oil), stagnated, removed with water to the bottom of the reactor, and dehydrated at 100 to 150 ° C under reduced pressure.

Active carbon and diatomaceous earth were mixed and filtered through a filter to remove color and odor of the product. The product was analyzed by GC to obtain 984 g of an epoxidized soybean oil methyl ester as an end product And the content of glycerol was 450 ppm.

Synthesis Example 2 Synthesis of epoxy 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 solution (30 wt% in methanol) were added and mixed. Then, the mixture was reacted for 4 hours while elevating the temperature to 70 ° C under nitrogen atmosphere (atmospheric pressure). After the reaction, the excess unreacted alcohol was removed under reduced pressure at 100-150 ° C., and the glycerol was separated into the lower part of the reactor after stagnating for 1 to 6 hours in order to remove by-product Glycerol by layer separation by specific gravity difference.

In order to remove the color and off-odor of the product immediately after the separation of the separated product without any dehydration step, the activated carbon and the diatomaceous earth were mixed and filtered using a filter, and analyzed by GC. As a result, the final product, epoxidized soybean oil methyl ester (Epoxidized soybean oil methyl ester) was obtained, and the content of glycerol was 6010 ppm.

Example 1 Production of Polymeric Resin Composition Containing Composite Plasticizer

A complex plasticizer was prepared by mixing 15 wt% of the waxy ester compound of Synthesis Example 1 synthesized above and 85 wt% of DOTP (Di-2-ethylhexyl terephthalate).

Subsequently, 70 parts by weight of the composite plasticizer and 2.5 parts by weight of CZ-400 (Complex of Ca-Zn organics, Songwon Industry) were added to 100 parts by weight of a polyvinyl chloride resin (PVC, polymerization degree 1000) At 175 占 폚 for 5 minutes, 15 MPa was added at 175 占 폚 for 3 minutes in a heating press, and after cooling to 90 占 폚 or less, a specimen was prepared.

The tensile strength and the elongation of the specimens were measured at room temperature for 168 hours in a Geer oven at 100 ° C. The tensile strength and elongation were measured, The residual rate and the residual rate were calculated. In addition, 100% modulus is the tensile strength when the material is stretched 100% by tensile, which means the plasticizing efficiency, and the lower the modulus of 100%, the better the plasticizing efficiency of the material.

The tensile test after heating is conducted by measuring the mechanical properties of the material after a certain aging condition (heat treatment), for example, the tensile residual rate and the residual rate, and measuring the rate of change before and after aging. The rate of change of tensile strength is referred to as a tensile residual rate, The rate of change is expressed as the percentage of elongation. The closer to 100%, the similar mechanical properties as before aging. This property means the durability of how long the wire compound can be maintained and used.

As a result, as shown in Table 1, all the polymeric resin compositions showed tensile strength and elongation satisfying UL 90 Grade. On the other hand, the 100% modulus showing the plasticization efficiency was superior to the comparative examples including Comparative Example 1. In addition, the tensile test results after heating were also superior to the comparative examples in the examples.

As a result of measuring the degree of aging of the test piece at intervals of 10 minutes in a Geer Oven fixed at 180 캜 with respect to thermal stability (heat resistance), it was found that the test piece according to Example 1 was superior to the test piece according to Comparative Example 1 Stability.

The plasticizer absorption rate was measured in accordance with DIN 54802-1. The test conditions were as follows: 400 g of polyvinyl chloride resin and 200 g of plasticizer were put into a bowl driven at 80 DEG C and 100 rpm.

As a result, as shown in the following Table 2, it can be seen that the plasticizer of the composition to which the epoxy ester compound is added has a higher absorption rate than the plasticizer to which the epoxy ester compound is not added. For example, in Example 1 and Comparative Example 1, Comparative Example 1 was used as a DOTP plasticizer alone, but Example 1 is a mixture of DOTP and an epoxy ester compound.

≪ Comparative Example 1 > Production of a polymer resin composition containing a conventional plasticizer

Except that DOTP ester plasticizer was used alone and 70 parts by weight of a plasticizer (DOTP) and 2.5 parts by weight of CZ-400 were added to 100 parts by weight of a polyvinyl chloride resin (PVC, degree of polymerization: 1000) Specimens were prepared.

Example 2 Preparation of Polymeric Resin Composition Containing Composite Plasticizer

A specimen was prepared in the same manner as in Example 1, except that DIDP (Di-isodecyl phthalate) was used instead of DOTP as a conventional plasticizer.

As a result, as shown in Table 1, all the polymeric resin compositions showed tensile strength and elongation satisfying UL 90 Grade. On the other hand, the 100% modulus showing the plasticizing efficiency was superior to the comparative examples in the examples. In addition, the tensile test results after heating were also superior to the comparative examples in the examples.

≪ Comparative Example 2 > Production of a polymer resin composition containing a conventional plasticizer

A specimen was prepared in the same manner as in Example 1 except that 70 parts by weight of a plasticizer and 2.5 parts by weight of CZ-400 were added to 100 parts by weight of a polyvinyl chloride resin (PVC, polymerization degree 1000) using a DIDP ester plasticizer alone Respectively.

Example 3 Preparation of Polymeric Resin Composition Containing a Composite Plasticizer

A specimen was prepared in the same manner as in Example 1, except that PYRO-C (Mixed Di-2-propylheptyl phthalate and terephthalate) was used instead of DOTP as a conventional plasticizer.

As a result, as shown in Table 1, all the polymeric resin compositions showed tensile strength and elongation satisfying UL 90 Grade. On the other hand, the 100% modulus showing the plasticizing efficiency was superior to the comparative examples in the examples. In addition, the tensile test results after heating were also superior to the comparative examples in the examples.

Comparative Example 3 Production of polymeric resin composition containing conventional plasticizer

Except that PYRO-C ester plasticizer was used alone and 70 parts by weight of a plasticizer and 2.5 parts by weight of CZ-400 were added to 100 parts by weight of a polyvinyl chloride resin (PVC, degree of polymerization: 1000) Respectively.

Example 4 Preparation of Polymeric Resin Composition Containing a Composite Plasticizer

A specimen was prepared in the same manner as in Example 1, except that a composite plasticizer prepared by mixing 15 wt% of the waxy ester compound of Synthesis Example 2 synthesized above and 85 wt% of DOTP (Di-2-ethylhexyl terephthalate) was used .

As a result, when compared with Comparative Example 1 in which the mixed plasticizer was not used, the absorption rate of the plasticizer was fast, and the results of the 100% modulus showing the plasticization efficiency and the tensile test after heating were also excellent. However, it was found that the physical properties were inferior to Example 1 in which glycerol as a by-product was maintained at 5000 ppm or less as a whole, but it was found to be superior to Comparative Examples not containing the plasticizer of Chemical Formula 2 of the present invention .

[Table 1] Comparison of physical properties according to Examples and Comparative Examples

[Table 2] Comparison of plasticizer absorption rates according to Examples and Comparative Examples

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 (14)

5 to 95% by weight of an epoxy ester compound represented by the following formula (2); And
And 5 to 95% by weight of at least one ester compound selected from the group consisting of a phthalate ester compound, a terephthalate ester compound, a phthalate compound and a terephthalate compound, and a trimellitate compound,
The epoxy-based ester compound is prepared by mixing an epoxidized vegetable oil, an alcohol and a catalyst, and then reacting at a temperature of 70 to 230 ° C for 4 to 12 hours under a gas atmosphere; Removing the excessively charged alcohol and glycerol generated as a by-product after completion of the reaction; And a step of washing the reaction product with distilled water, dehydrating and then filtering to prepare an epoxy ester compound represented by the general formula (2).
(2)

Wherein R ₄ is (C 8 -C 20) epoxyalkyl and R ₅ is (C 1 -C 10) alkyl or

, R _x and R _y are each independently hydrogen, (C 1 -C 5) alkyl or

(C1-C5) alkyl or < RTI ID = 0.0 >

And R ₄₁ and R ₄₂ are each independently (C 8 -C 20) epoxyalkyl, and n is an integer selected from 1 to 5.)
The method according to claim 1,
5 to 30% by weight of an epoxy ester compound represented by the following formula (2); And
70 to 95% by weight of at least one ester compound selected from the group consisting of phthalate ester compounds, terephthalate ester compounds, phthalate-based and terephthalate-based ester compounds, and trimellitate-based ester compounds.
(2)

Wherein R ₄ is (C 8 -C 20) epoxyalkyl and R ₅ is (C 1 -C 10) alkyl or

, R _x and R _y are each independently hydrogen, (C 1 -C 5) alkyl or

(C1-C5) alkyl or < RTI ID = 0.0 >

And R ₄₁ and R ₄₂ are each independently (C 8 -C 20) epoxyalkyl, and n is an integer selected from 1 to 5.)
3. The method of claim 2,
Wherein the epoxy-based ester compound is prepared by reacting an epoxidized vegetable oil represented by the following formula (1) with an alcohol:
[Chemical Formula 1]

(Wherein R ₁ , R ₂ and R ₃ are each independently (C 8 -C 20) epoxyalkyl).
delete The method of claim 3,
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, Wherein the composition is selected from the group consisting of oil, sunflower oil and perilla seed oil.
A polymer resin composition comprising 30 to 120 parts by weight of a composite plasticizer composition according to any one of claims 1 to 3 and 100 parts by weight of a polymer resin.
The method according to claim 6,
Wherein the polymer resin is selected from the group consisting of a polyvinyl chloride resin, an olefin resin, an ABS resin, an acrylic resin, and a polyester resin.
The method according to claim 6,
The polymer resin composition may be used in various applications such as a compound, a wire compound, a wallpaper, a sheet, a film, a tarpaulin, a hose, a shoe, a sealant, an office supplies, a glove, a bottle cap, a mat, a gasket, a food packaging material, Wherein the polymeric resin composition is a material of a product selected from the group consisting of an electromechanical component and an electromechanical component.
6. The method according to any one of claims 1 to 5,
Wherein the composite plasticizer composition has a glycerol content of 5000 ppm or less.
A polymeric resin composition comprising the composite plasticizer composition of claim 9.
An epoxidized vegetable oil, an alcohol and a catalyst;
Vacuum distilling the reaction product;
Separating the vacuum distillation residue to remove glycerol; And
And washing and dehydrating the glycerol-free residue. The method for producing an epoxy-based ester compound according to claim 1, wherein the glycerol-containing residue is glycerol.
12. The method of claim 11,
Wherein the reaction temperature during the reaction is 70 to 230 占 폚, and the content of glycerol is 5,000 ppm or less.
12. The method of claim 11,
The method for producing an epoxy-based ester compound as described above, wherein the dehydration has a content of water-absorbing inorganic particles or glycerol of not more than 5000 ppm which is subjected to vacuum distillation.
12. The method of claim 11,
The method for producing an epoxy-based ester compound according to any one of claims 1 to 5, wherein the production method further comprises a step of adding deodorizing and dehydrating inorganic particles after the water washing and dehydrating step and then filtering the water.

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