ES2901409T3 - Plasticizer composition and resin composition and method of preparing the same - Google Patents

Abstract

A plasticizer composition comprising: a type of terephthalate-based material; epoxidized oil; and a trimellitate-based material, where the terephthalate-based material and the epoxidized oil may have a weight ratio of 99:1 to 1:99. wherein the epoxidized oil is included in 10% by weight or more with respect to the total amount of the plasticizer composition, wherein the trimellitate-based material comprises one or more selected from the group consisting of tri(2-ethylhexyl) trimellitate ), tributyl trimellitate and triisononyl trimellitate. wherein the trimelate-based material is included in between 1 part by weight and 100 parts by weight with respect to 100 parts by total weight of the plasticizer composition.

Description

DESCRIPTION

Plasticizer composition and resin composition and method of preparing the same

field of invention

The present invention relates to a plasticizer composition, a resin composition, and methods of preparing the same.

Description of Related Art

In common plasticizers, alcohols are reacted with polycarboxylic acids such as phthalic acid and adipic acid, to prepare corresponding esters thereof. In addition, studies have been continued on plasticizer compositions capable of replacing phthalate-based plasticizers, such as terephthalate-based, adipate-based and other polymer-based plasticizers, considering domestic and foreign restrictions on phthalate-based plasticizers harmful to the environment. the human body.

Meanwhile, for the manufacture of materials for flooring, wallpaper, products in plate industries and the like, it is necessary to use suitable plasticizers in view of discoloration, migration property, processability, and the like. A plasticizer, a filler, a stabilizer, a viscosity depressant, a dispersant, an antifoaming agent, a foaming agent and the like are mixed with a PVC resin depending on tensile strength, elongation rate, strength in light, a migration property, a gelling property, processability, or the like, properties required for each industry in various applications of this type.

As an example, when using dioctyl terephthalate which is relatively inexpensive among the plasticizer compositions that can be used in PVC, the viscosity has been high, the absorption rate of the plasticizer has relatively decreased, and the migration property has also been unfavorable.

Consequently, continuous studies have been required on technologies capable of being used optimally as a plasticizer for vinyl chloride-based resins, which are achieved through the development of products superior to existing dioctyl terephthalate, or products of new compositions comprising terephthalate. dioctyl.

CN 102964723 A describes PVC material comprising the components based on parts by weight: 100 parts of PVC resin type SG3, 25-30 parts of plasticizer 1, 3-5 parts of plasticizer 2, 10-12 parts of calcium carbonate , 8-12 parts stabilizer, 0.8-1.2 parts polyethylene wax, 2-4 parts ACR impact modifier, 0.1-0.5 parts antioxidant, 2-3 parts nanobarium sulfate and 0.3-0.8 parts of silicone powder, where the plasticizer 1 comprises one or two selected from trioctyl trimelate or dioctyl ester of purified terephthalic acid; plasticizer 2 comprises one or two selected from epoxidized soybean oil and terephthalic acid dioctyl ester; and the silicone powder is silicone-treated silica powder.

US 2013/317152 A1 describes a composition comprising at least one polymer selected from the group consisting of polyvinyl chloride, polyvinylidene chloride, polyvinyl butyrate, polyalkyl (meth)acrylate and copolymers of these, and polyvinyl terephthalate. diisononyl (DINT) as a plasticizer, where the average degree of branching of the isononyl groups of the ester is in the range between 1.15 and 2.5, and at least one additional plasticizer that reduces the processing temperature.

DESCRIPTION OF THE INVENTION

TECHNICAL PROBLEM

In view of the above, while researches on plasticizers are continuously conducted, the inventors of the present invention have identified a plasticizer composition capable of improving poor physical properties caused by structural limitations, and completed the present invention.

In other words, an object of the present invention is to provide a plasticizer capable of improving physical properties such as plasticizing efficiency, migration property and gelation property required in the formulation of sheets and the like when used as a plasticizer of a plasticizer. resin composition, a process for preparing the same and a resin composition comprising comprising the same.

TECHNICAL SOLUTION

The above problems are solved according to the independent claims. Additional embodiments result from the subclaims.

An embodiment of the present invention provides a plasticizer composition comprising:

a type of terephthalate-based material;

epoxidized oil; Y

a trimellitate-based material,

where the terephthalate-based material and the epoxidized oil may have a weight ratio of 99:1 to 1:99. wherein the epoxidized oil is included in 10% by weight or more with respect to the total amount of the plasticizer composition, wherein the trimellitate-based material comprises one or more selected from the group consisting of tri(2-ethylhexyl) trimellitate ), tributyl trimellitate and triisononyl trimellitate.

wherein the trimelate-based material is included in between 1 part by weight and 100 parts by weight with respect to 100 parts by total weight of the plasticizer composition.

The weight ratio of the terephthalate-based material and the epoxidized oil can be from 95:5 to 50:50.

The weight ratio of the terephthalate-based material and the epoxidized oil can be from 90:10 to 50:50.

The terephthalate-based material may be any one selected from the group consisting of di(2-ethylhexyl) terephthalate (DEHTP or DOTP), diisononyl terephthalate (DINTP), dibutyl terephthalate (DBTP), butylisononyl terephthalate ( BINTP), (2-ethylhexyl) butyl terephthalate (BEHTP or BOTP), and (2-ethylhexyl) isonyl terephthalate (EHINTP or OINTP).

The terephthalate-based material may be di(2-ethylhexyl) terephthalate or diisononyl terephthalate.

The epoxidized oil may comprise at least one selected from the group consisting of epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearate, epoxidized oleate, epoxidized pine oil, and epoxidized linoleate.

Another embodiment of the present invention provides a process for preparing a plasticizer composition comprising:

provide a type of material based on terephthalate and epoxidized oil;

mixing the terephthalate-based material and the epoxidized oil in a weight ratio of 99:1 to 1:99 to prepare a plasticizer composition; Y

mixing a trimelate-based material with the plasticizer composition, and

wherein the epoxidized oil is included in 10% by weight or more with respect to the total amount of the plasticizer composition,

wherein the trimellitate-based material comprises one or more selected from the group consisting of tri(2-ethylhexyl) trimellitate and triisononyl trimellitate, and

wherein the trimellitate-based material is included in 1 part by weight to 100 parts by weight with respect to 100 parts by total weight of the terephthalate-based material and the epoxidized oil. Still another embodiment of the present invention provides a resin composition comprising 100 parts by weight of a resin; and 5 parts by weight to 150 parts by weight of the plasticizer composition of claim 1.

The resin can be at least one selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyketone, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomers.

The resin composition may be a material for at least one selected from the group consisting of cables, flooring materials, automotive interior materials, films, sheets, wallpaper, and tubes.

ADVANTAGEOUS EFFECTS

A plasticizer composition according to an embodiment of the present invention can provide excellent properties, such as resistance to migration and resistance to volatility, as well as excellent plasticizing efficiency, tensile strength and elongation rate when used in a resin composition. .

BEST MODE FOR CARRYING OUT THE INVENTION

Example

Hereinafter in this invention, the present invention will be described in detail with reference to examples.

Preparation Example 1: Preparation of DOTP

In a 3-liter 4-neck reactor equipped with a cooler, a condenser, a decanter, a reflux pump, a temperature controller, a stirrer and the like, 498.0 g of purified terephthalic acid (TPA), 1170 g of 2-ethylhexyl alcohol (2-EH) (the molar ratio of TPA:2-EH was (1.0):(3.0)), and 1.54 g of a titanium-based catalyst (TIPT, tetraisopropyl titanate) as catalyst (0.31 pbw based on 100 pbw TPA), and the temperature was slowly raised to about 170°C. Water began to generate near about 170 °C, and esterification was carried out for about 4.5 hours while continuously adding nitrogen gas at a reaction temperature of about 220 °C and under atmospheric pressure, and the reaction was complete when reached an acidity index of 0.01.

After the completion of the reaction, extractive distillation was carried out for 0.5 hour to 4 hours under reduced pressure to remove unreacted raw materials. Steam distillation was carried out for 0.5 hours to 3 hours under reduced pressure using steam to remove unreacted raw materials to a specific content level or less, and neutralization treatment was carried out using an alkaline solution. after cooling the reaction solution to about 90 °C. Washing with water may be further carried out, and then moisture was removed by dehydrating the reaction solution. A filter medium was added to the reaction solution without moisture, and the result was stirred for a certain period of time and then filtered to finally prepare 1326.7 g of di-2-ethylhexyl terephthalate (yield: 99.0 %).

Preparation Example 2: Preparation of DINTP

DINTP was prepared in the same manner as in Preparation Example 1, except that isonyl alcohol was used instead of 2-ethylhexyl alcohol in the esterification reaction.

Preparation example 3: Preparation of TOTM

384.2 g of trimellitic acid and 1171 g of octanol were used as reaction raw materials to finally prepare 1071 g of trioctyl trimellitate (yield: 98%).

Preparation Example 4: Preparation of TINTM

384.2 g of trimellitic acid and 1230 g of isononyl alcohol were used as reaction raw materials to finally prepare 1154 g of triisononyl trimellitate (yield: 98%).

Preparation Example 5: Preparation of TBTM

576.3 g of trimellitic acid and 1000 g of butanol were used as reaction raw materials to finally prepare 1124 g of tributyl trimellitate (yield: 99%).

Preparation Example 6: Preparation of ATOC

384 g of citric acid and 1014 g of 2-ethylhexyl alcohol were used as reaction materials to prepare 1029 g of trioctyl citrate (trioctyl(2-ethylhexyl) citrate) (yield: 98%). Finally, 1119 g of acetyltrioctyl citrate (yield: 98%) was prepared using 214 g of acetic anhydride for the trioctyl citrate prepared above.

Preparation Example 7: Preparation of ATBC

384 g of citric acid and 1000 g of butanol were used as reaction raw materials to prepare 706 g of tributyl citrate (yield: 98%). Finally, 789 g of acetyl tributyl citrate (yield: 98%) was prepared by using 214 g of acetic anhydride for the tributyl citrate prepared above.

The plasticizer compositions of Examples 1 to 4 were prepared using the materials prepared in Preparation Examples 1 to 7 and epoxidized oil, and the preparations are summarized in the following Tables 1 to 4. Physical property evaluations of the plasticizer compositions were performed according to the following test items.

Tl 1

T l 2

Tl 1

Tl 41

<Test Items>

The measurement conditions for the following test items may be for illustrative purposes to describe measurement procedures, and specific measurement and evaluation conditions may be referenced in each of the test examples for the test examples using other conditions. .

Hardness measurement

Shore hardness was measured at 25 °C, 3T 10 s, according to ASTM D2240.

Measurement of tensile strength

After pulling a crosshead speed of 200 mm/min (1T) using U.T.M (manufacturer; Instron, model name; 4466), a test fixture, according to ASTM D638 procedure, the point where shear was measured the sample. The tensile strength was calculated as follows:

Tensile strength {kgf/mirr) = load value

(kgf) /thickness (miti) x width (iran)

Elongation rate measurement

After dragging at a crosshead speed of 200 mm/min (1T) using the UTM according to the procedure of ASTM D638, the point where the sample was cut was measured and then the rate of drag was calculated. elongation as follows:

Elongation rate (%) = [length after elongation(initial length) x 100

Measurement of tensile retention and elongation

The tensile retention and elongation measurement measures the tensile and elongation rate properties remaining in the sample after applying heat for a certain period of time at a specific temperature, and the measurement procedures are the same as procedures that measure tensile strength and rate of elongation.

Measurement of migration loss

A sample having a thickness of 2 mm or more was prepared according to the KSM-3156 standard, and a load of 1 kgf/cm 2 was applied after bonding PS plates on both surfaces of the sample. The sample was left unattended for 72 hours in a forced convection oven (80°C) and then removed and cooled for 4 hours at room temperature. After that, the PS plates attached on both surfaces of the sample were removed, the weights before and after the sample was left unattended in the oven were measured, and the amount of migration loss was calculated through the equation below: sample below.

Migration loss amount (%) = [(initial sample weight at room temperature-sample weight after being left unattended in the oven)/initial sample weight at room temperature] x 100 volatile

After working on the prepared sample for 72 hours at 80°C, the weight of the sample was measured.

Loss of volatiles (%) = [(initial sample weight-sample weight after work)/initial sample weight]x100.

Absorption rate measurement

An absorption rate was evaluated so that the resin and the ester compound were mixed with each other under a condition of 77 and 60 rpm using a Planatary mixer (Brabender, P600), and the time it took for the torque of the mixer to stabilize.

stress test

As for the stress test, the sample was left unattended for a certain period of time while bending, and the degree of migration (the degree of exudation) was observed and expressed as a number. The number closest to 0 represents excellent properties.

Light fastness measurement

The sample was kept in QUV and UV irradiated for 200 hours according to the procedure of ASTM 4329-13, and then a change in color was calculated using a reflectometer.

Thermal resistance measurement

The degree of discoloration in the initial sample and the sample after the loss of volatiles test was measured using the loss of volatiles measurement procedure. The measurement value was determined by the values changed by an E value with respect to the L, a and b values using a colorimeter.

Cold resistance measurement

5 prepared samples were left unattended for 3 minutes at a specific temperature and then pounded, and a temperature at which 3 of the 5 samples were destroyed was measured.

Test Example 1: DOTP-Based Plasticizer Composition

Mixed plasticizer compositions were prepared by mixing DOTP and ESO or ELO in the mixing ratios of Examples 1-1 to 1-5 listed in Table 1, and these were used as samples for testing.

Regarding the preparation of the samples, the samples were prepared, referring to the ASTM D638 standard, by mixing 50 parts by weight of the mixed plasticizer composition and 3 parts by weight of a stabilizer (BZ153T) to 100 parts by weight of PVC in a 3L supermixer at 98°C and 700rpm, then making a 5mm sheet by working on the result for 4 minutes at 160°C using a roller mill, then making a 1mm to 3mm sheet after pressing the result for 2.5 minutes at low pressure and 2 minutes at high pressure at 180 °C. Physical properties were evaluated according to each of the evaluation items described above using each sample, and the results are summarized in the following Table 5.

___ As shown in Table 5, it was identified that the plasticizer composition of Examples 1-1 to 1-5 prepared by mixing epoxidized oil with DOTP (a terephthalate-based material), exhibited an equal or superior level in physical properties. such as tensile strength, hardness, an elongation rate or volatile loss, and showed equal or superior improved physical property in migration loss, stress resistance property and elongation rate compared to DOTP plasticizer from Comparative Example 1.

As identified above, when a plasticizer composition was prepared by mixing terephthalate-based material and epoxidized oil, the plasticizer composition was able to improve migration loss or stress resistance while having an equal or higher level of physical properties. basics of a plasticizer.

Furthermore, when a plasticizer composition comprises the epoxidized oil in a relatively small amount, the plasticizer composition may not be suitable for the use of the plasticizer composition in terms of an absorption rate, loss of volatiles, or permeation test results. effort, and therefore, in order to distinguish epoxidized oil from epoxidized oil used as an auxiliary stabilizer, comprising 5% by weight or more, preferably 10% by weight or more, and optimally 20% by weight of the epoxidized oil. % by weight or more may be suitable for the actual use of the plasticizer.

Test Example 2: DINTP-Based Plasticizer Composition

Mixed plasticizer compositions were prepared by mixing DINTP with ESO or ELO in the mixing ratios of Examples 2-1 to 2-5 listed in Table 2, and these were used as samples for testing. The preparation of the samples and the conditions of the physical property evaluations were the same as in Test Example 1, and the results are shown in the following Table 6.

As shown in Table 6, it was identified that Examples 2-1 to 2-5 preparing the plasticizer composition by mixing epoxidized oil with DINTP, a terephthalate-based material, showed the same or higher level in the physical properties such as tensile strength, hardness, loss of volatiles, and an elongation rate compared to the existing DOTP plasticizer of Comparative Example 1, and showed equal or superior improved physical property in migration loss, strength property to stress, elongation rate and tensile strength property compared with Comparative Example 1.

As identified above, when a plasticizer composition was prepared by mixing a terephthalate-based material and epoxidized oil, the plasticizer composition was able to improve migration loss or stress resistance while having an equal or superior level of properties. basic physics of a plasticizer.

Furthermore, when a plasticizer composition comprises the epoxidized oil in a relatively small amount, the plasticizer composition may not be suitable for the use of the plasticizer composition in terms of an absorption rate,

results of stress tests or loss of volatiles and, therefore, in order to distinguish epoxidized oil from epoxidized oil used as an auxiliary stabilizer, including oil epoxidized by 5% by weight or more, preferably 10% by weight weight or more and optimally 20% by weight or more may be suitable for the actual use of the plasticizer.

Test example 3: Mixed plasticizer composition of DOTP, ESO and trimellitate-based material

The mixed plasticizer compositions were prepared by mixing each of ESO and DOTP, and each of TOTM, TINTM and TBTM as an additive in the mixing ratios of Examples 3-1 to 3-9 and Comparative Example 3-1 listed. in Table 3, and these were used as samples for testing.

Regarding the preparation of the samples, the samples were prepared, referring to the ASTM D638 standard, by mixing 50 parts by weight of the mixed plasticizer composition, 40 parts by weight of a filler (OMYA1T), 5 parts by weight of a stabilizer (RUP-144) and 0.3 parts by weight of a lubricant (St-A) to 100 parts by weight of PVC in a 3L supermixer at 98 °C and 700 rpm, making a compound by working on the result for 4 minutes at 160°C using a roller mill, followed by pressing the result for 2.5 minutes at low pressure and 2 minutes at high pressure at 180°C. Physical properties were evaluated according to each of the evaluation items described above using each sample, and the results are summarized in the following Table 7.

As shown in Table 7, Examples 3-1 to 3-9 were identified to prepare the plasticizer composition by mixing epoxidized oil with DOTP, a terephthalate-based material, and further adding TOTM, TINTM, and TBTM among the materials to be used. trimellitate base, as the additive showed an equal or superior level in physical properties such as tensile strength, loss of volatiles, migration loss and elongation rate compared to the existing DIDP plasticizer of Comparative Example 1.

Furthermore, considering that physical properties such as hardness or tensile strength were more superior compared to DIDp, an existing plasticizer even when Examples 3-1 to 3-9 are mixed plasticizer compositions including 20% epoxidized oil by weight or more, the effect was indirectly identified to be an additive-induced effect. By comparing Examples 3-1 to 3-9 with Comparative Example 3-1 in which the additive content exceeded 100 parts by weight, it was found that physical properties such as plasticizing efficiency, tensile strength, heat retention tensile, elongation rate and elongation retention may decrease when the additive is included in excess.

Existing DIDP plasticizers have excellent physical properties, but they are a material that has restrictions in use due to environmental concerns, and by additionally adding a trimellitate-based material, it was identified that plasticizer compositions capable of replacing existing DIDP plasticizers can be provided in composite industries and the like.

Test Example 4: DOTP mixed plasticizer composition. ESO and acetyl citrate-based material Mixed plasticizer compositions were prepared by mixing each ESO and DOTP, and each of ATOC and ATBC as an additive in the mixing ratios of Examples 4-1 to 4-8 and Comparative Example 4-1 listed in Table 4, and these were used as samples for testing. Sample preparation and physical property evaluations were the same as in Test Example 1, and the results are shown in the following Table 8.

As shown in Table 8, Examples 4-1 to 4-8 were identified to prepare the plasticizer composition by mixing epoxidized oil with DOTP, a terephthalate-based material, and further adding ATOC and ATBC between the terephthalate-based materials. acetyl citrate, as the additive showed an equal or superior level in physical properties such as tensile strength, loss of volatiles, migration loss, and elongation rate compared to the existing DIDP plasticizer of Comparative Example 1.

Furthermore, considering that physical properties such as hardness or tensile strength are more superior compared to DIDp, an existing plasticizer even when Examples 4-1 to 4-8 are mixed plasticizer compositions including 20% epoxidized oil by weight or more, the effect was indirectly identified to be an additive-induced effect. By comparing Examples 4-1 to 4-8 with Comparative Example 4-1 in which the additive content exceeded 100 parts by weight, it was identified that physical properties such as plasticizing efficiency, an elongation rate and retention of elongation may decrease when the additive is included in excess.

Existing DIDP plasticizers have excellent physical properties, but they are a material that has restrictions in use due to environmental problems, and by additionally adding an acetyl citrate-based material, it was identified that plasticizer compositions capable of replacing existing DIDP plasticizers can be provided in the compounding industries and the like.

However, acetyl tributyl citrate has a rather small molecular weight and may have a problem in improving physical properties such as migration loss or volatile loss, and it was identified that the addition of materials having a high molecular weight as the additive was more preferable in compounding industries in view of the above. Additives having a small molecular weight can have a higher elongation rate, hardness or the like than migration loss and volatile loss compared with the cases of adding other materials as the additive, and it can be seen that the Acetyl tributyl citrate can have advantages in terms of productivity and processability, such as excellent plasticizing efficiency in industries other than cable compound industries, emphasizing physical properties, such as loss of volatiles, such as calendar sheets and packaging materials. soils that have simpler procedural conditions.

In the present invention, preferred examples of the present invention have been described in detail, however, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention. present invention defined in the claims are also included in the scope of the present invention.

MODE OF CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

First of all, the present invention has technological characteristics by providing a plasticizer composition capable of improving poor physical properties caused by structural limitation.

According to one embodiment of the present invention, a plasticizer composition comprising a terephthalate-based material may be provided. Specifically, the terephthalate-based material may be included in an amount selected from a range of 1 wt% to 99 wt%, 20 wt% to 99 wt%, 40 wt% and 99% by weight, between 50% by weight and 95% by weight, between 60% by weight and 90% by weight, or the like, based on the total weight of the composition.

As an example, the terephthalate-based material may have a terminal group independently selected from the group consisting of C-C12 alkyl groups, C3-C11 alkyl groups, C4-C10 alkyl groups, C8-C10 alkyl groups, C8-C9 alkyl groups or C8 alkyl group.

The terephthalate-based material may be any one selected from the group consisting of di(2-ethylhexyl) terephthalate (DEHTP or DOTP), diisononyl terephthalate (DINTP), dibutyl terephthalate (DBTP), butylisononyl terephthalate ( BINTP), (2-ethylhexyl) butyl terephthalate (BEHTP or BOTP), and (2-ethylhexyl) isonyl terephthalate (EHINTP or OINTP).

More preferably, the terephthalate-based material may be di(2-ethylhexyl) terephthalate or diisononyl terephthalate.

Furthermore, according to one embodiment, the plasticizer composition may further comprise epoxidized oil and, for example, the epoxidized oil may comprise epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearate, epoxidized oleate, epoxidized pine oil, epoxidized linoleate, or mixtures thereof.

In this invention, in the plasticizer composition, the weight ratio of the terephthalate-based material and the epoxidized oil may be from 99:1 to 1:99. The weight ratio of the terephthalate-based material and the epoxidized oil can be from 99:1 to 20:80, from 99:1 to 40:60, from 99:1 to 50:50, or from 99:1 to 60: 40. And preferably, the weight ratio of the terephthalate-based material and the epoxidized oil can be 95:5 to 50:50, 90:10 to 50:50, or 90:10 to 60:40.

When the amount of epoxidized oil added is increased, the migration resistance property for stress and an absorption rate can become excellent. Physical properties, such as tensile strength or elongation rate, may be somewhat decreased, but may be included in the required physical property range. Therefore, the required physical properties can be freely controlled by adjusting the content of the epoxidized oil, and the epoxidized oil can be suitably used depending on the use of a vinyl chloride-based resin composition.

Further, the epoxidized oil may preferably be included in about 10% by weight or more, and more preferably included in 20% by weight or more based on the total amount of the plasticizer composition.

Generally, epoxidized oil is sometimes included as a stabilizing agent when preparing a plasticizer, however, it can be distinguished from the aforementioned epoxidized oil used as a second plasticizer. The use of terephthalate-based material as the first plasticizer is more environmentally friendly compared to phthalate-based materials, such as diisodecyl phthalate, which has been used in the art as a plasticizer; however, reaching a level suitable for commercialization may be difficult in terms of economic feasibility or existing physical properties, and the addition of epoxidized oil to a level of stabilizing agent may be difficult to approach the physical properties achieved by existing plasticizers.

However, when epoxidized oil is used in 20% by weight or more, migration resistance or absorption property can become excellent, absorption speed can be particularly excellent, and physical properties such as resistance to tensile or elongation rate can be equal to or better compared to existing phthalate-based plasticizers.

The plasticizer composition comprises a terephthalate-based material and epoxidized oil, and comprises an additive that is a trimellitate-based material, comprising at least one selected from the group consisting of tri(2-ethylhexyl) trimellitate ( TEHTM), tributyl trimellitate (TBTM) and triisononyl trimellitate (TINTM) included in 1 part by weight to 100 parts by weight and preferably in 1 part by weight to 80 parts by weight based on 100 parts by weight of the composition of plasticizer

The additive can be mixed with the terephthalate-based compound alone and improve the strength property and the like of a resin composition, however, even when such a small amount of the additive is mixed and included in the plasticizer composition, a compound and the like, having excellent physical properties, can be prepared. When a larger amount of the additive is included, the physical properties of the plasticizer composition may be out of control to control the physical properties suitable for the application, and problems such as excessively enhancing undesired physical properties or lowering physical properties may arise. unwished.

Specifically, in the mixed plasticizer composition of the terephthalate-based material and the epoxidized oil, if the epoxidized oil is included in excess, the content of the terephthalate-based material is relatively low. In such cases, physical properties such as plasticizing efficiency related to processability may not be relatively superior among various physical properties. And such property can be complemented by adding the additive.

As a means for preparing the plasticizer composition in the present invention, a mixing process can be used, and an example of the mixing preparation process is as follows.

The plasticizer composition can be prepared by providing a terephthalate-based material and epoxidized oil, and mixing the terephthalate-based material and epoxidized oil in a weight ratio of 1:99 to 99:1.

As for the terephthalate-based material, the terephthalate-based compound can be prepared by direct esterification with terephthalic acid and alcohol. The alcohol is at least one selected from the group consisting of 2-ethylhexyl alcohol, isonyl alcohol, butyl alcohol, and isobutyl alcohol.

Furthermore, the method may further comprise mixing 1 part by weight to 100 parts by weight of an additive based on 100 parts by weight of the plasticizer composition after mixing to prepare a plasticizer composition and the descriptions therein are as follows: previously described.

The additive comprises a trimellitate-based material as described above.

Direct esterification can be done by adding terephthalic acid to an alcohol, then adding a catalyst, and reacting the result under a nitrogen atmosphere; removing unreacted alcohol, and neutralizing unreacted acid; and dehydrating and filtering by vacuum distillation.

The alcohol used in the mixture preparation process can be used in an amount of 150 mol% to 500 mol%, 200 mol% to 400 mol%, 200 mol% to 350 mol%, of the 250 mol% to 400 mol% or 270 mol% to 330 mol% based on 100 mol% terephthalic acid.

Meanwhile, for example, the catalyst used in the mixture preparation process may comprise at least one selected from the group consisting of acid catalysts such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, paratoluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid. acid, propanesulfonic acid, butanesulfonic acid and alkylsulfuric acid, metal salts such as aluminum sulfate, lithium fluoride, potassium chloride, cesium chloride, calcium chloride, iron chloride and aluminum phosphate, metal oxides such as heteropolyacid, zeolite natural/synthetic, cation and anion exchange resins, and organic metals such as tetraalkyl titanate and polymers thereof. As specific examples thereof, tetraalkyl titanate can be used as the catalyst.

The amount of the catalyst used may be different depending on the types, and as an example, a homogeneous catalyst may be used in an amount of 0.01 wt% to 5 wt%, 0.01 wt% by weight and 3% by weight, between 1% by weight and 5% by weight or between 2% by weight and 4% by weight based on 100% by weight of the total reactants, and can be use a heterogeneous catalyst in an amount of between 5% by weight and 200% by weight, between 5% by weight and 100% by weight, between 20% by weight and 200% by weight or between 20 % by weight and 150% by weight based on the total weight of the reagents.

In this invention, the reaction temperature may be 180°C to 280°C, 200°C to 250°C, or 210°C to 230°C.

Direct esterification and a transesterification to be described later can also be used to prepare the zwitterionic or non-hybrid acetyl citrate-based material or trimellitate-based material described above. In this case, the acetyl citrate-based material can also be prepared as a mixed composition having a certain ratio, and a composition ratio of the produced mixture can be controlled depending on the setting of the alcohol content as a raw material of reaction.

Also, when the trimellitate-based material is prepared by direct esterification or transesterification, the descriptions used to prepare the terephthalate-based material can be used in the same manner.

The "transesterification" used in the present invention means a reaction in which an alcohol and an ester react to exchange R'' of the ester with R' of the alcohol as shown in Reaction Formula 1 below:

According to one embodiment, when the transesterification progresses, 3 kinds of ester compositions can be produced in three cases such as carbon alkoxide attacking the alcohol of two ester groups (RCOOR'') present in the ester-based compound; carbon alkoxide which attacks the alcohol of an ester group (RCOOR'') present in the ester-based compound; and without having reacted with any reaction.

In addition, transesterification has the advantage of not causing a wastewater problem compared to an acid-alcohol esterification reaction, and can proceed without a catalyst, and therefore is able to solve a problem caused by the use of an acid catalyst. Also, the mixture prepared by transesterification can control a composition ratio of the mixture depending on the amount of alcohol added.

The amount of alcohol added may be from 0.1 part by weight to 89.9 parts by weight, specifically from 3 parts by weight to 50 parts by weight, and more specifically from 5 parts by weight to 40 parts by weight based on 100 parts by weight of the ester.

As for the ester, a molar fraction of the ester participating in the transesterification increases as the amount of alcohol added increases, and therefore the content of the two esters, a product, can increase in the mixture and consequently , the content of the unreacted ester present corresponding thereto tends to decrease.

According to an embodiment of the present invention, a molar ratio of the ester and the alcohol, which are reactive, may be, for example, from 1:0.005 to 5.0, from 1:0.05 to 2.5, or from 1:0.1 to 1.0, and in these intervals, the effect is obtained to prepare an ester-based plasticizer composition with high process efficiency and excellent processability-improving effect.

According to an embodiment of the present invention, the transesterification can be carried out at a reaction temperature of from 120 °C to 190 °C, preferably from 135 °C to 180 °C and more preferably from 141 °C to 179 °C for 10 minutes. to 10 hours, preferably from 30 minutes to 8 hours, and more preferably from 1 hour to 6 hours. The mixture which is an ester having an objective composition can be efficiently prepared within the above-mentioned time and temperature ranges. In this invention, the reaction time can be calculated from the time the reaction temperature is reached after raising the temperature of the reactants.

The transesterification can be carried out in the presence of an acid catalyst or a metal catalyst, and in this case an effect of shorter reaction time is obtained.

Examples of the acid catalyst may comprise sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid or the like, and examples of the metal catalyst may comprise organic metal catalysts, metal oxide catalysts, metal salt catalysts or the metals themselves.

Examples of the metal component may be at least one selected from the group consisting of tin, titanium, and zirconium.

Furthermore, after the transesterification reaction, the transesterification may further comprise distilling off unreacted alcohol and reaction by-products such as an ester-based compound represented by Chemical Formula 3 to remove unreacted alcohol and reaction by-products.

An example of the distillation may comprise two-stage distillation which performs separation of alcohol and reaction by-products using a difference in boiling point.

As another example, the distillation may be a mixed distillation. In this case, the effect of relatively stable securing of the ester-based plasticizer composition in an objective composition is achieved. Mixed distillation means distilling the butanol and the reaction by-product at the same time.

A resin composition may comprise 5 parts by weight to 150 parts by weight, 40 parts by weight to 100 parts by weight, or 40 parts by weight to 50 parts by weight of the plasticizer composition based on 100 parts by weight of a resin. The resin is selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyketone, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomers. The resin composition is effective for all compound formulations, sheet formulations, and plastisol formulations.

As an example, the plasticizer composition can be used in the manufacture of cables, flooring materials, automotive interior materials, films, sheets, wallpaper or tubes.

Claims (12)

1. A plasticizer composition comprising: a type of terephthalate-based material; epoxidized oil; Y a trimellitate-based material, where the terephthalate-based material and the epoxidized oil may have a weight ratio of 99:1 to 1:99. wherein the epoxidized oil is included in 10% by weight or more with respect to the total amount of the plasticizer composition, wherein the trimellitate-based material comprises one or more selected from the group consisting of tri(2-ethylhexyl) trimellitate, tributyl trimellitate and triisononyl trimellitate. wherein the trimelate-based material is included in between 1 part by weight and 100 parts by weight with respect to 100 parts by total weight of the plasticizer composition. 2. The plasticizer composition of claim 1, wherein the terephthalate-based material and the epoxidized oil have a weight ratio of 95:5 to 50:50, and the epoxidized oil is included in 20% by weight or more relative to the total amount of the plasticizer composition. 3. The plasticizer composition of claim 1, wherein the terephthalate-based material and the epoxidized oil have a weight ratio of 90:10 to 50:50. 4. The plasticizer composition of claim 1, wherein the terephthalate-based material is a single compound or a mixture of two or more compounds selected from the group consisting of di(2-ethylhexyl) terephthalate (DEHTP or DOTP) , diisononyl terephthalate (DINTP), dibutyl terephthalate (DBTP), butylisononyl terephthalate (BINTP), butyl (2-ethylhexyl) terephthalate (BEHTP or b Ot P), and isonyl (2-ethylhexyl) terephthalate (EHINTP or OINTP) . 5. The plasticizer composition of claim 4, wherein the individual compound is di(2-ethylhexyl) terephthalate or diisononyl terephthalate. 6. The plasticizer composition of claim 1, wherein the epoxidized oil includes one or more selected from the group consisting of epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearic acid, epoxidized oleic acid, epoxidized pine oil and epoxidized linoleic acid. 7. A process for preparing a plasticizer composition comprising: provide a type of material based on terephthalate and epoxidized oil; mixing the terephthalate-based material and the epoxidized oil in a weight ratio of 99:1 to 1:99 to prepare a plasticizer composition; Y mixing a trimelate-based material with the plasticizer composition, and wherein the epoxidized oil is included in 10% by weight or more with respect to the total amount of the plasticizer composition, wherein the trimellitate-based material comprises one or more selected from the group consisting of tri(2-ethylhexyl) trimellitate and triisononyl trimellitate, and wherein the trimelate-based material is included in between 1 part by weight and 100 parts by weight with respect to 100 parts by total weight of the terephthalate-based material and the epoxidized oil. 8. The process for preparing a plasticizer composition of claim 7, wherein the terephthalate-based material is prepared by a direct esterification reaction reacting an alcohol selected from the group consisting of 2-ethylhexyl alcohol, isonyl alcohol , butyl alcohol and isobutyl alcohol and terephthalic acid. 9. The process for preparing a plasticizer composition of claim 8, further comprising, after obtaining a plasticizer composition by blending, blending a trimellitate-based material at 1 part by weight per 100 parts by weight relative to 100 parts by weight of the plasticizer composition. 10. A resin composition comprising: 100 parts by weight of a resin; Y 5 parts by weight to 150 parts by weight of the plasticizer composition of claim 1. 11. The resin composition of claim 10, wherein the resin is one or more of the types selected from the group consisting of ethylene vinyl acetate, polyethylene, polyketone, polypropylene, chloride of polyvinyl, polystyrene, polyurethane and thermoplastic elastomers. 12. The resin composition of claim 10, wherein the resin composition is a material of one or more product types selected from the group consisting of cables, flooring materials, automotive interior materials, films, sheets, wallpapers and tubes.