WO2017018741A1 - Plasticizer composition, resin composition, and preparation methods therefor - Google Patents

Abstract

Provided are a plasticizer composition, a method for preparing the same, and a resin composition including the plasticizer composition, the plasticizer composition comprising: an isophthalate-based material; and an epoxy-based alkyl ester compound represented by chemical formula 1, wherein the weight ratio of the isophthalate-based material to the epoxy-based alkyl ester compound is 99:1 to 1:99, and the epoxy-based alkyl ester compound comprises a single compound or a mixture including at least two kinds of compounds. (In chemical formula 1, R1 is an alkyl group having eight to 20 carbon atoms or an alkyl group containing at least one epoxy group, and R2 is an alkyl group having four or eight carbon atoms.) The present invention can provide: a plasticizer capable of improving physical properties required when used as a plasticizer for a resin composition, such as tensile strength, migration resistance, and heating loss, by ameliorating inferior physical properties caused by structural limitations; and a resin composition including the plasticizer.

Description

Plasticizer composition, resin composition, and preparation method thereof

Citation with Related Applications

This application claims the benefit of priority based on Korean Patent Application No. 10-2015-0105324 dated July 24, 2015 and Korean Patent Application No. 10-2016-0092874 dated July 21, 2016. All content disclosed in the literature is included as part of this specification.

Technical Field

The present invention relates to a plasticizer composition, a resin composition and a method for producing the same.

Typically, plasticizers react with alcohols to polycarboxylic acids such as phthalic acid and adipic acid to form the corresponding esters. In addition, in consideration of domestic and international regulations on phthalate-based plasticizers that are harmful to humans, research on plasticizer compositions that can replace phthalate-based plasticizers such as terephthalate-based, adipate-based, and other polymer-based plastics is being continued.

Meanwhile, in order to manufacture products such as flooring, wallpaper, sheets, interior and exterior materials of automobiles, films, and wires, appropriate plasticizers should be used in consideration of transferability, heating loss, tensile strength, elongation, and plasticization efficiency. Plasticizers, fillers, stabilizers, viscosity-reducing agents, dispersants, antifoaming agents, foaming agents, etc. may be blended with PVC resins according to the tensile strength, elongation, light resistance, transferability, gelling properties, etc., which are required for various types of industries.

For example, among the plasticizer compositions applicable to PVC, when inexpensive diethylhexyl terephthalate is applied, the plasticizer efficiency is low, the plasticizer absorption rate is relatively slow, and the light resistance and the transferability are not good.

Accordingly, by developing products of new compositions such as products superior to the diethylhexyl terephthalate, studies on technologies that can be optimally applied as plasticizers for vinyl chloride resins are still needed.

Accordingly, the inventors have identified a plasticizer composition that can improve the poor physical properties caused by structural limitations while continuing to study the plasticizer, and have completed the present invention.

That is, an object of the present invention is to provide a plasticizer capable of improving the physical properties such as plasticization efficiency, transferability, gelling property, light resistance, etc. required in the prescription of a sheet, etc., when used as a plasticizer of the resin composition, a method for producing the same, and a resin composition comprising the same I'm trying to provide.

According to an embodiment of the present invention to solve the above problems, isophthalate-based material; And an epoxy-based alkyl ester compound represented by Formula 1; wherein the weight ratio of the isophthalate-based material to the epoxy-based alkyl ester compound is 99: 1 to 1:99, and the epoxy-based alkyl ester compound is a single compound or A plasticizer composition is provided that is a mixture containing two or more species.

[Formula 1]

In Formula 1, R1 is an alkyl group having 8 to 20 carbon atoms or an alkyl group containing at least one epoxy group, and R2 is an alkyl group having 4 or 8 carbon atoms.

The weight ratio of the isophthalate-based material to the epoxy-based alkyl ester compound may be 95: 5 to 5:95.

The isophthalate-based material may be di (2-ethylhexyl) isophthalate (DEHIP), diisononylisophthalate (DINIP), or a mixture thereof.

The epoxy alkyl ester compounds may be iodine value of less than 4 g I _2/100 g.

The epoxidation alkyl ester compound may have an epoxidation index (E.I.) of 1.5 or more.

The plasticizer composition may further comprise an epoxidized oil.

The epoxidized oil may include 1 to 100 parts by weight based on 100 parts by weight of the mixed weight of the isophthalate-based material and the epoxy-based alkyl ester compound.

The epoxidized oil is epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearic acid acid), epoxidized oleic acid, epoxidized tall oil, and epoxidized linoleic acid.

According to an embodiment of the present invention to solve the above problem, obtaining an isophthalate-based material; Esterifying a epoxidized oil with a primary alkyl alcohol having 4 or 8 carbon atoms to obtain an epoxy-based alkyl ester compound represented by Formula 1 below; And mixing the isophthalate-based material and the epoxy-based alkyl ester compound in a weight ratio of 99: 1 to 1:99, wherein the epoxy-based alkyl ester compound is a single compound or a mixture of two or more thereof. Provided is a method for preparing.

[Formula 1]

In Formula 1, R1 is an alkyl group containing 8 to 20 carbon atoms or an alkyl group containing at least one epoxy group, and R2 is an alkyl group having 4 or 8 carbon atoms.

The primary alkyl alcohol may be one or more selected from the group consisting of butyl alcohol, isobutyl alcohol, 2-ethylhexyl alcohol and octyl alcohol.

The isophthalate-based material may be prepared through a direct esterification reaction of isophthalic acid and at least one alcohol selected from primary alkyl alcohols having 4 to 12 carbon atoms.

The primary alkyl alcohol having 4 to 12 carbon atoms may be one or more selected from the group consisting of 2-ethylhexyl alcohol, octyl alcohol and isononyl alcohol.

The epoxidized oil is epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearic acid acid), epoxidized oleic acid, epoxidized tall oil, and epoxidized linoleic acid.

According to an embodiment of the present invention to solve the above problems, 100 parts by weight of resin; And 5 to 150 parts by weight of the above-described plasticizer composition is provided.

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

When used in a resin composition, the plasticizer composition according to an embodiment of the present invention can provide excellent physical properties such as migration resistance and volatility, as well as excellent plasticization efficiency and tensile strength and elongation. It can be suitably used for resin products that have excellent absorption rate and require eco-friendly plasticizers using vegetable raw materials.

Figure 1 is an image of the results of the thermal stability test for the samples of the Examples and Comparative Examples.

2 is an image photographing the results of the thermal stability test for the samples of Examples and Comparative Examples.

Example

Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, the scope of the present invention should not be construed as limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

Preparation Example 1 Preparation of DEHIP

498.0 g of purified isophthalic acid (IPA), 1170 g of 2-ethylhexyl alcohol (2-EH) in a four-necked three-liter reactor with chiller, condenser, decanter, reflux pump, temperature controller, stirrer, etc. (IPA: The molar ratio of 2-EH (1.0): (3.0)), 1.54 g (0.31 parts by weight based on 100 parts by weight of TPA) of a titanium catalyst (TIPT, tetra isopropyl titanate) was added as a catalyst, and the temperature was gradually raised to about 170 ° C. I was. The production of water was started at about 170 ° C., and the reaction was carried out for about 4.5 hours while nitrogen gas was continuously added at a reaction temperature of about 220 ° C. and atmospheric pressure. The reaction was terminated when the acid value reached 0.01.

After the reaction is completed, distillation is performed under reduced pressure for 0.5 to 4 hours to remove unreacted raw materials. In order to remove unreacted raw materials below a certain content level, steam extraction is performed under reduced pressure using steam for 0.5 to 3 hours, the reaction solution temperature is cooled to about 90 ° C., and neutralization is performed using an alkaline solution. . In addition, washing with water may be performed, and then the reaction solution is dehydrated to remove moisture. The filtrate was added to the reaction solution from which the water had been removed, followed by stirring for some time, and then filtered to obtain 1326.7 g (yield: 99.0%) of di (2-ethylhexyl) isophthalate.

Preparation Example 2 Preparation of Epoxidized Fatty Acid Butyl Ester (eFABE)

The transesterification reaction was carried out using 500 g of epoxidized soybean oil and 490 g of butanol as a reaction raw material, and finally 510 g (yield: 95%) of epoxidized butyl soyate was obtained.

Preparation Example 3 Preparation of Epoxidized Fatty Acid 2-Ethylhexyl Ester (eFAEHE)

Except for using 490 g of 2-ethylhexyl alcohol instead of 490 g of butanol, 584 g (yield: 95%) of epoxidized 2-ethylhexyl soyate was obtained in the same manner as in Preparation Example 2.

By using the materials prepared in Preparation Examples 1 to 3, Examples and Comparative Examples were configured as shown in Tables 1 to 3 below.

IP material eFAAE substance Mixing weight ratio Example 1-1 DEHIP eFABE 7: 3 Example 1-2 DEHIP eFABE 5: 5 Example 1-3 DEHIP eFABE 3: 7 Example 1-4 DEHIP eFAEHE + eFABE (5: 5) 7: 3 Example 1-5 DEHIP eFAEHE 7: 3 Example 1-6 DEHIP eFAEHE 5: 5 Example 1-7 DEHIP eFAEHE 3: 7

IP material eFAAE substance Mixing weight ratio Article 3 Example 2-1 DEHIP eFAEHE 7: 3 ESO (70 parts by weight) Example 2-2 DEHIP eFAEHE 7: 3 ESO (30 parts by weight)

Article 1 Article 2 Mixing weight ratio Comparative Example 1 DEHP - - Comparative Example 2 DEHTP - - Comparative Example 3 DEHIP - - Comparative Example 4 DEHIP eFAME 9: 1 Comparative Example 5 DEHIP eFAME 7: 3 Comparative Example 6 DEHIP eFAME 5: 5 Comparative Example 7 DEHIP eFAME 3: 7 Comparative Example 8 DEHIP eFAME 1: 9

Experimental Example 1: Test Piece Fabrication and Performance Evaluation

Experimental specimens were prepared using the plasticizer compositions of Examples and Comparative Examples above. The specimen is prepared by referring to ASTM D638, 40 parts by weight of plasticizer and 3 parts by weight of plasticizer (BZ-153T) in 100 parts of PVC, blended at 700 rpm at 98 ° C. in a mixer, followed by a roll mill at 160 ° C. for 4 minutes. After working and working at 180 ° C. for 2.5 minutes at low pressure and 2 minutes at high pressure, 1-3 sheets were produced. Using each specimen, the following physical properties were tested.

<Test item>

Hardness Measurement

Shore (shore "A") hardness at 25 ° C. was measured using ASTM D2240.

Tensile strength measurement

By the ASTM D638 method, the cross head speed was pulled to 200 mm / min (1T) using a test instrument, UTM (manufacturer; Instron, model name; 4466), and the point where the specimen was cut was measured. . Tensile strength was calculated as follows:

Tensile Strength (kgf / cm ² ) = Load Value (kgf) / Thickness (cm) x Width (cm)

Elongation Rate Measurement

By using the ASTM D638 method, the crosshead speed was pulled to 200 mm / min (1T) using the U.T.M, and then measured at the point where the specimen was cut, the elongation was calculated as follows:

Elongation (%) = calculated after elongation / initial length x 100.

Migration loss measurement

Test specimens having a thickness of 2 mm or more were obtained according to KSM-3156, and a PS plate was attached to both sides of the specimens, and a load of 1 kgf / cm ² was applied thereto. The test piece was left in a hot air circulation oven (80 ° C.) for 72 hours and then taken out and cooled at room temperature for 4 hours. Then, after removing the PS attached to both sides of the test piece, the weight before and after leaving in the oven was measured and the transfer loss was calculated by the following equation.

% Of transfer loss = {(initial weight of test piece at room temperature-weight of test piece after leaving the oven) / initial weight of test piece at room temperature} x 100

Measurement of volatile loss

After working the prepared specimen at 100 ℃ for 72 hours, the weight of the specimen was measured.

Loss of heating (% by weight) = initial specimen weight-(100 ° C., specimen weight after 72 hours of operation) / initial specimen weight × 100.

Absorption Rate Measurement

Absorption rate was evaluated by measuring the time required for the resin and the ester compound to be mixed to stabilize the torque of the mixer by using a Planatary mixer (Brabender, P600) under the conditions of 77 ℃, 60rpm.

Thermal stability measurement

The prepared specimen was heated to 230 ° C. in a Mathis oven to check the burned degree of the specimen.

The results of evaluating the performance of the specimens based on the above items are shown in Tables 4 to 6 below, and the results of the heat resistance evaluation are shown in FIG. 1.

Shore "A" Tensile Strength (kg / cm ² ) % Elongation Performance loss (%) Heating loss (%) Absorption rate (sec) Example 1-1 84.1 237.2 326.6 4.02 3.32 4:35 Example 1-2 83.0 233.4 334.5 3.88 3.70 3:52 Example 1-3 81.5 229.7 324.9 3.76 4.31 3:27 Example 1-4 84.7 240.8 321.5 3.88 3.25 4:40 Example 1-5 85.2 245.0 317.1 3.68 3.23 4:55 Example 1-6 84.9 244.1 323.7 3.94 3.30 4:53 Example 1-7 84.3 246.1 320.2 4.16 3.05 4:28

Shore "A" Tensile Strength (kg / cm ² ) % Elongation Performance loss (%) Heating loss (%) Absorption rate (sec) Example 2-1 84.0 256.7 324.0 1.21 1.52 5:08 Example 2-2 84.5 250.4 321.6 1.45 1.88 4:50

Shore "A" Tensile Strength (kg / cm ² ) % Elongation Performance loss (%) Heating loss (%) Absorption rate (sec) Comparative Example 1 86.0 224.6 287.1 1.75 5.61 4:50 Comparative Example 2 88.0 240.3 306.4 4.12 2.34 6:31 Comparative Example 3 87.1 231.9 305.9 3.86 3.32 5:50 Comparative Example 4 83.7 226.3 304.5 4.23  4.09 5:05 Comparative Example 5 82.3 228.0 305.1 6.56 5.71 3:20 Comparative Example 6 80.8 230.1 305.7 7.98 7.90 2:35 Comparative Example 7 79.2 230.9 308.9 9.34 9.13 2:03 Comparative Example 8 78.0 231.7 309.1 11.87 12.90 1:43

Referring to Tables 4 to 6, Comparative Examples 1 to 3, in which the epoxy-based alkyl ester compound is not added, are materials that have been conventionally used as general-purpose products, which have excellent basic physical properties but are competitive in price, limited use, or environment. It is a material having a problem such as a problem, and compared with the examples, the specimens of the examples have almost the same mechanical properties (tensile strength and elongation) of these, and in terms of absorption rate or plasticization efficiency Significant improvements have been made and improvements have been found in the case of transition losses and heating losses.

In addition, in the case of Comparative Examples 4 to 8 using an epoxidized methyl ester compound having no carbon number of 4 or 8 in the epoxy-based alkyl ester compound, the plasticization efficiency and elongation may be improved, but the transition characteristics and heating loss In the case of showing a significant difference depending on the content, it can be seen that the poor level so difficult to use, but in the case of using the carbon number 4 or 8 of Examples 1-1 to 1-7 basic tensile strength or elongation Of course, it can be seen that a significant improvement is achieved, particularly in the loss of heating or in the loss of transition.

Through this, when the isophthalate-based material and the epoxy-based alkyl ester compound are used in combination, when the carbon number of alkyl is 4 or 8 in the epoxy-based alkyl ester compound, not only the mechanical properties but also the transition characteristics and heating It can be seen that there is a significant level of improvement in the weight loss characteristics.

In addition, in Examples 2-1 and 2-2, as well as tensile strength and elongation, the transfer loss and heating loss are of course superior to the comparative examples, and are improved from Examples 1-1 to 1-7. It can be confirmed that this is done.

Through this, it can be seen that when the additional epoxidized oil is applied together, the physical property supplement is made more.

Further, referring to FIGS. 1 and 2, it can be seen that the thermal stability can be improved in the case of the specimens using the examples compared to the plasticizers of the comparative examples. In the case of Comparative Examples 1 to 3, the specimens It can be confirmed that all burned and burned black, and in Examples 1-1 to 1-3 and Examples 1-5, 1-6, and 2-2, the degree of combustion is considerably smaller than that of the comparative example. have.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best explain their invention in the best way possible. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.

As used herein, the term "butyl" refers to an alkyl group having 4 carbon atoms, and may be used as a term including both straight and branched chains, and may be, for example, n-butyl, isobutyl, or t-butyl. But preferably n-butyl or isobutyl.

As used herein, the terms "octyl" and "2-ethylhexyl" are alkyl groups having 8 carbon atoms, and may be mixed with octyl as an abbreviation of 2-ethylhexyl, and in some cases, may mean octyl which is a linear alkyl group. However, it can be interpreted to mean 2-ethylhexyl, which is a branched alkyl group.

Plasticizer composition

According to an embodiment of the present invention isophthalate-based material; And an epoxy-based alkyl ester compound, wherein the weight ratio of the isophthalate-based material to the epoxy-based alkyl ester compound is 99: 1 to 1:99, and the epoxy-based alkyl ester compound includes a single compound or two or more kinds thereof. A plasticizer composition is provided that is a mixture.

It is possible to provide a plasticizer composition containing the isophthalate-based material. Specifically, the isophthalate-based material has a content selected from the range of 1 to 99% by weight, 20 to 99% by weight, 40 to 99% by weight, 50 to 95% by weight or 60 to 90% by weight, based on the total weight of the composition. Can be applied.

The isophthalate-based material may be di (2-ethylhexyl) isophthalate (DEHIP), diisononylisophthalate (DINIP) or a mixture thereof, preferably di (2-ethylhexyl) isophthalate. .

The composition ratio may be a mixture composition ratio produced by the esterification reaction, and may be an intended composition ratio by additionally mixing a specific compound, and the mixture composition ratio may be appropriately adjusted to suit desired physical properties.

The plasticizer composition includes an isophthalate-based material and includes an epoxy-based alkyl ester compound. The epoxy alkyl ester compound may be represented by the following general formula (1), the iodine value may be less than (Iodine Value, IV) a 4 g I _2/100 g.

[Formula 1]

In Formula 1, R1 is an alkyl group having 8 to 20 carbon atoms or an alkyl group having at least one epoxy group, and R2 is an alkyl group having 4 or 8 carbon atoms.

The epoxy-based alkyl ester compound may have an oxirane value (Oxirane Value, O.V.) of 6.0% or more, 6.3% or more, and preferably 6.5% or more. In addition, the oxirane can be changed according to the number of epoxy groups contained in the substituent represented by R1 in the formula (1), can be measured by a titration method, the method of ASTM D1562-04 using a sample and an acid solution It may be measured by.

Further, the epoxy alkyl ester compound, but the iodine can be less than 4 g I _2/100 g, can be not more than preferably 3.8 I _2/100 g. The iodine number represents the content of the double bond present in the molecule, and may be derived from a value measured by a titration method through iodization of the double bond.

The epoxy-based alkyl ester compound may be an important element when the measured iodine and oxirane are applied to the plasticizer composition. In particular, the iodine value is 4 g I _2/100 g, if more than this out, the compatibility with the resin is significantly reduced, and can not be used in the plasticizer purpose, incidentally it is iodine value is 4 g I ₂ When less than / 100 g, the mechanical and physical properties such as tensile strength, elongation and absorption rate may also be improved. In addition, oxiraga can also have similar technical significance and similar effects as iodine number.

The iodine number may represent the content of the double bond, and the content of the double bond may be the content of the double bond remaining after the epoxidation reaction such as epoxidation of vegetable oil or epoxidation of fatty acid alkyl ester is performed. That is, the oxirags and iodines may be indicative of how much epoxidation has been performed, and thus may be partially related to each other, and in theory, may be inversely related to each other.

However, in practice, the double bonds of vegetable oils or fatty acid alkyl esters may vary from material to material, so the two parameters do not form an exact inverse relationship or trade off relationship, and a higher iodine value between the two materials. The material may be higher in oxirane at the same time. Therefore, it may be preferable to apply to the plasticizer composition that the iodine number and the oxirane value of an epoxy-type alkyl ester compound satisfy the above-mentioned range.

Meanwhile, the epoxidation index (E.I.) of the epoxy-based alkyl ester compound may be 1.5 or more.

As mentioned above, although the relationship between the iodine number and the oxirane value is as described above, it may be desirable to satisfy that the epoxidation index is at least 1.5. The 'epoxidation index' is a ratio of oxirane to iodine number of the epoxy-based alkyl ester compound, and may be a ratio of remaining double bonds that do not react with the double bonds epoxidized by the epoxidation reaction.

As described above, when the oxirane content is small, the iodine value is large, and the epoxidation index is smaller than 1.5, or when the epoxidation itself is not performed, the hardness may increase and the plasticization efficiency may be greatly deteriorated. And heat loss characteristics may be greatly deteriorated.

Specifically, the epoxidation index may be 1.5 or more as the ratio of oxiraga to iodine number (oxiraga / iodine number). That is, when the oxirane value of the epoxy-based alkyl ester divided by iodine number is 1.5 or more, a more optimized plasticizer composition can be obtained, and in particular, the compatibility with the resin may be improved.

The epoxy-based alkyl ester compound may be an epoxidized Fatty Acid Alkyl Ester (eFAAE), specifically, may be represented by Formula 1, 'alkyl' of the epoxy-based alkyl ester compound has 4 carbon atoms Or eight.

However, in the present invention, in Formula 1, R 2 may have 4 to 8 carbon atoms, and preferably, a butyl group or a 2-ethylhexyl group. In addition, the epoxy-based alkyl ester compound represented by the formula (1) may include two or more kinds to form a mixed composition, when two or more kinds are included is a mixture of 4 and 8 carbon atoms It may be preferable, when the carbon number of R2 of Formula 1 is 4 or 8, the absorption characteristics are excellent to reduce the gelling phenomenon, the processability can be improved, and the mechanical properties such as basic tensile strength and elongation is also excellent In particular, excellent performance can be exhibited in transitional performance and heat loss characteristics.

Here, the isophthalate-based material and the epoxy-based alkyl ester compound in the plasticizer composition may be included in a weight ratio of 99: 1 to 1:99, 99: 1 to 20:80, or 99: 1 to 40:60 days It may be, preferably contained in a ratio of 95: 5 to 50:50, or 90:10 to 60:40.

As described above, in the case of applying the plasticizer composition mixed with the isophthalate-based material and the epoxy-based alkyl ester compound, the tensile strength and elongation may be excellent, and an improved effect may be observed in the transition and heating loss, and the absorption rate It can be controlled so that the workability can be improved together.

Method of Preparation of Plasticizer Composition

According to an embodiment of the present invention, obtaining an isophthalate-based material; Esterifying a epoxidized oil with a primary alkyl alcohol having 4 or 8 carbon atoms to obtain an epoxy-based alkyl ester compound represented by Formula 1 below; And mixing the isophthalate-based material and the epoxy-based alkyl ester compound in a weight ratio of 99: 1 to 1:99, wherein the epoxy-based alkyl ester compound is a single compound or a mixture of two or more thereof. Provided is a method for preparing.

Obtaining the isophthalate-based material and the epoxy-based alkyl ester compound may be carried out respectively, and the materials may be prepared through direct esterification reaction and / or trans esterification reaction.

The isophthalate-based material may be prepared through a direct esterification reaction in which isophthalic acid and an alcohol selected from primary alkyl alcohols having 8 to 10 carbon atoms react. In addition, the epoxy-based alkyl ester compound may be prepared by the trans esterification reaction of the epoxidized oil and the primary alkyl alcohol having 4 or 8 carbon atoms.

The primary alkyl alcohol having 8 to 10 carbon atoms may be selected from the group consisting of 2-ethylhexyl alcohol, octyl alcohol and isononyl alcohol.

In addition, the primary alkyl alcohol having 4 or 8 carbon atoms used as a raw material for producing the epoxy-based alkyl ester compound may be one or more selected from the group consisting of butyl alcohol, isobutyl alcohol, 2-ethylhexyl alcohol and octyl alcohol. have. In this case, the alkyl group of the alcohol may correspond to R2 of Formula 1 in the epoxy-based alkyl ester compound represented by Formula 1 after the reaction is completed.

The epoxidized oil, for example, epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized palm oil, epoxidized palm oil Stearic acid (epoxidized stearic acid), epoxidized oleic acid, epoxidized tall oil, epoxidized linoleic acid, or mixtures thereof. Through this, the compound may be introduced into a certain amount of epoxy group.

For example, the epoxidized oil may be represented by the following Chemical Formula 2, and may include three ester groups in one molecule, and may contain a certain amount of epoxy groups.

[Formula 2]

The epoxidized oil represented by Formula 2 corresponds to one example.

Further, the epoxidized oil can be a iodine value is 4 g I _2/100 g is less than can there, iodine value and substantially the same level of iodine transesterification reaction varied potential is lowered product of epoxy alkyl esters for compound The characteristics thereof are the same as those of the iodine number of the above-mentioned epoxy-based alkyl ester compound.

When the epoxidized oil is transesterified with an alkyl alcohol having 4 or 8 carbon atoms, all three ester groups may be separated, thereby forming three or more epoxy-based ester compounds in which the alkyl groups of the alcohol are newly bonded. Can be.

As used herein, the "trans-esterification reaction" refers to a reaction in which an alcohol reacts with an ester as shown in Scheme 1, where R " of the ester is interchanged with R ′ of the alcohol as shown in Scheme 1 below:

Scheme 1

According to an embodiment of the present invention, when the trans esterification reaction is carried out, the alkoxide of the alcohol is substituted with an ester (RCOOR ″) group present in the ester compound to generate R ″ alcohol. In the case of a general vegetable oil, glycerol is generated by separation with alcohol and substitution reaction, and an fatty acid alkyl chain may generate an ester composition having a chain of R ′ alcohol. In addition, the trans esterification reaction has an advantage that the reaction rate is faster than the acid and alcohol esterification reaction without causing a waste water problem.

In general, the trans esterification reaction for preparing an epoxy-based alkyl ester compound may be performed, for example, under the following conditions.

The trans esterification reaction is 10 minutes to 10 hours, preferably 30 minutes to 8 hours, more preferably 1 to 4 under a reaction temperature of 40 to 230, preferably 50 to 200, more preferably 70 to 200. May be performed in time. It is possible to effectively obtain the desired epoxy-based alkyl ester compound within the above temperature and time range. In this case, the reaction time may be calculated from the time point at which the reaction temperature is reached after the reaction temperature is raised.

In addition, the polyhydric alcohol and the reaction by-products and the unreacted alcohol produced after the trans-esterification reaction may further comprise the step of separating, washing and distilling the reaction by-products.

Specifically, the purification process may be performed after the trans esterification reaction for a certain period of time to cool and settle at a temperature of 80 to 100 ℃, in which case layer separation occurs, the upper layer includes an epoxy-based alkyl ester and alcohol The lower layer may contain glycerin and other byproducts. Next, neutralization and water washing can be induced by adding a catalyst neutralization aqueous solution to neutralize the catalyst.

The neutralization and washing process may be performed after first separating the lower layer containing mainly by-products, and may be discharged by dissolving the by-products of the lower layer in water during the neutralization and washing process, and then unreacted after the repeated washing process Alcohol and water can be recovered and removed.

However, it may be necessary to vary the neutralization and washing process according to the carbon number of the alcohol used in the trans esterification reaction.

For example, when using butanol having 4 carbon atoms, if the neutralization and washing process are performed immediately, it may be desirable to distill the butanol first to remove the waste water due to the problem of waste water generation. However, in this case, since the activity of the catalyst remains, there may be a double problem that the byproduct glycerol and the product epoxy-based alkyl ester may react back to produce epoxidized oil-like substances such as diglyceride or triglyceride. Therefore, it is necessary to pay attention to the design of the process.

As another example, when 2-ethylhexyl alcohol having 8 carbon atoms is used, 2-ethylhexyl alcohol has low solubility in water, and there is no problem of waste water generation. Therefore, in this case, the alcohol is removed after neutralization and washing with water. In the case of the removal, the neutralization and washing with water after removing the byproduct layer of the lower layer may be advantageous without proceeding with a fatal problem.

In addition, when preparing the epoxy-based alkyl ester compound, the physical properties of the epoxy-based alkyl ester compound to be produced may vary depending on the type and content of the catalyst to be used, the reaction time or 1 to react with the epoxidized oil Depending on the content of the primary alkyl alcohol, the physical properties, yield or quality of the product may also be modified.

Specifically, NaOMe is preferably used as a catalyst in the process of preparing the epoxy-based alkyl ester compound, and the color of the prepared epoxy-based alkyl ester compound does not meet the standard compared to a catalyst such as sodium hydroxide or potassium hydroxide. The epoxidation index, oxirane content, etc. of an epoxy-type alkyl ester compound may not produce the target numerical value.

In addition, the catalyst may be the most effective in terms of reaction rate of 0.1 to 2.0% by weight, preferably 0.1 to 1.0% by weight relative to the total weight of the epoxidized oil as a reaction raw material, the content of the catalyst when out of this range Failure to control may not meet the quality standards of epoxy-based alkyl ester compounds such as epoxidation indexes.

In the preparation of the epoxy-based alkyl ester compound, the addition amount of the epoxidized oil and the primary alkyl alcohol may also be an important factor. In the case of the primary alkyl alcohol, it is preferable to add 30 to 100 parts by weight relative to the epoxidized oil, and 30 parts by weight. In case of less than, efficient reaction does not proceed, so impurities such as residual epoxidized oil or dimerized material of epoxidized oil may remain excessively. There are many concerns about energy and process efficiency issues during the process.

As described above, after preparing the isophthalate-based material and the epoxy-based alkyl ester compound, mixing may be performed. The mixing ratio may be suitably selected within the range of 99: 1 to 1:99, and may be mixed by applying the above-described mixing weight ratio.

In addition, the plasticizer composition according to the present invention may further include an epoxidized oil in addition to the isophthalate-based material and the epoxy-based alkyl ester compound.

In the case of the mixed plasticizer composition of the isophthalate-based material and the epoxy-based alkyl ester compound, among the various physical properties, the heat resistance may not be excellent, and the heat resistance may be compensated by further including the epoxidized oil.

The epoxidized oil is, for example, epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized palm oil, epoxidized stearic acid (epoxidized stearic acid), epoxidized oleic acid, epoxidized tall oil, epoxidized linoleic acid, or mixtures thereof. Preferably, epoxidized soybean oil (ESO), or epoxidized linseed oil (ELO) may be applied, but is not limited thereto.

In addition, the epoxidized oil may include 1 to 100 parts by weight, preferably 10 to 100 parts by weight, preferably 20 to 100 parts by weight of the mixed weight of the isophthalate-based material and the epoxy-based alkyl ester compound. To 100 parts by weight may be included. When included within the above range, a plasticizer composition having suitably superior physical properties between mechanical properties and heat resistance properties can be obtained.

Furthermore, when the isophthalate-based product and the epoxidized oil are used in combination, the overall freezing point of the plasticizer composition can be further lowered, and thus the freezing point is lower than that of the epoxy-based plasticizer composition. A composition can be provided.

Resin composition

According to an embodiment of the present invention, 100 parts by weight of the resin; And 5 to 150 parts by weight of the above-described plasticizer composition.

The resin may be at least one resin selected from ethylene vinyl acetate, polyethylene, polypropylene, polyketone, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomer, wherein the plasticizer composition is based on 100 parts by weight of the resin, 5 It may be included in the range of from 150 to 150 parts by weight, 40 to 100 parts by weight, or 40 to 50 parts by weight to provide a resin composition effective for all of the compound formulation, sheet formulation and plastisol formulation.

The resin composition includes the plasticizer composition as described above, and can be applied to various applications such as flooring, wallpaper, automobile interior, sheet, film, hose, or electric wire, and has tensile strength and elongation, plasticization efficiency and heating loss. The same basic mechanical properties may also exhibit physical properties equivalent to those of conventional plasticizers.

According to an embodiment of the present invention, the resin composition may further include a filler.

The filler may be 0 to 300 parts by weight, preferably 50 to 200 parts by weight, more preferably 100 to 200 parts by weight based on 100 parts by weight of the resin.

The filler may be a filler known in the art, it is not particularly limited. For example, it may be at least one mixture selected from silica, magnesium carbonate, calcium carbonate, hard coal, talc, magnesium hydroxide, titanium dioxide, magnesium oxide, calcium hydroxide, aluminum hydroxide, aluminum silicate, magnesium silicate and barium sulfate.

The resin composition may further include other additives such as stabilizers as necessary.

Other additives such as the stabilizer may be, for example, 0 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the resin.

Stabilizers that can be used can be used, for example, calcium-zinc-based (Ca-Zn-based) stabilizers, such as calcium-zinc complex stearic acid salt, but is not particularly limited thereto.

Claims (15)

Isophthalate-based materials; And an epoxy-based alkyl ester compound represented by Formula 1; The weight ratio of the isophthalate-based material to the epoxy-based alkyl ester compound is 99: 1 to 1:99, wherein the epoxy-based alkyl ester compound is a single compound or a mixture containing two or more. [Formula 1]

In Chemical Formula 1, R 1 is an alkyl group containing 8 to 20 carbon atoms or an epoxy group or more, and R 2 is an alkyl group having 4 or 8 carbon atoms. The method of claim 1, Plasticizer composition wherein the weight ratio of the isophthalate-based material to the epoxy-based alkyl ester compound is 95: 5 to 20:80. The method of claim 1, The isophthalate-based material is a plasticizer composition is di (2-ethylhexyl) isophthalate (DEHIP), diisononyl isophthalate (DINIP), or a mixture thereof. The method of claim 1, The epoxy compound is an alkyl ester plasticizer composition of the iodine 4 g I _2/100 g of less than. The method of claim 1, Plasticizer composition wherein the epoxidation alkyl ester compound has an epoxidation Index (E.I.) of 1.5 or more. The method of claim 1, A plasticizer composition further comprising an epoxidized oil. The method of claim 6, The epoxidized oil is a plasticizer composition comprising 1 to 100 parts by weight based on the mixed weight of the isophthalate-based material and the epoxy-based alkyl ester compound. The method of claim 6, The epoxidized oil is epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearic acid plasticizer composition comprising at least one selected from the group consisting of acid), epoxidized oleic acid, epoxidized tall oil and epoxidized linoleic acid. Obtaining an isophthalate-based material; Esterifying a epoxidized oil with a primary alkyl alcohol having 4 or 8 carbon atoms to obtain an epoxy-based alkyl ester compound represented by Formula 1 below; And And mixing the isophthalate-based material and the epoxy-based alkyl ester compound in a weight ratio of 99: 1 to 1:99. The epoxy-based alkyl ester compound is a method for producing a plasticizer composition is a single compound or a mixture of two or more. [Formula 1]

In Formula 1, R1 is an alkyl group containing 8 to 20 carbon atoms or an alkyl group containing at least one epoxy group, and R2 is an alkyl group having 4 or 8 carbon atoms. The method of claim 9, The primary alkyl alcohol having 4 or 8 carbon atoms is at least one selected from the group consisting of butyl alcohol, isobutyl alcohol, 2-ethylhexyl alcohol and octyl alcohol. The method of claim 9, The isophthalate-based material is a method of producing a plasticizer composition is prepared through the direct esterification of isophthalic acid and alcohol selected from primary alkyl alcohol having 8 to 10 carbon atoms. The method of claim 11, The primary alkyl alcohol having 8 to 10 carbon atoms is selected from the group consisting of 2-ethylhexyl alcohol, octyl alcohol and isononyl alcohol. The method of claim 9, The epoxidized oil is epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearic acid acid), an epoxidized oleic acid, an epoxidized tall oil, and an epoxidized linoleic acid. 100 parts by weight of resin; And 5 to 150 parts by weight of the plasticizer composition of claim 1. The method of claim 14, The resin composition is one or more selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyketone, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomer.

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