Plasticizer composition and preparation method therefor

Abstract

The present invention relates to a plasticizer composition and a preparation method therefor and, more specifically, to a plasticizer composition, which contains an anhydrosugar alcohol monoester, an anhydrosugar alcohol diester, and a sugar alcohol ester at a specific content ratio and has improved plasticity and excellent storage stability, and to a preparation method therefor.

Claims

1. A method for preparing a plasticizer composition, comprising the steps of: (1) synthesizing sugar alcohol ester and anhydrosugar alcohol ester by esterification reaction of an alcohol mixture comprising sugar alcohol and anhydrosugar alcohol with carboxylic acid; and (2) neutralizing the resulting mixture obtained in said step (1) comprising sugar alcohol ester and anhydrosugar alcohol ester with basic material, wherein the amount of sugar alcohol in the alcohol mixture used in said step (1) is 20 to 90 parts by weight, based on 100 parts by weight of the mixture of sugar alcohol and anhydrosugar alcohol.

2. The method for preparing a plasticizer composition of claim 1, wherein the sugar alcohol is selected from sorbitol, mannitol, iditol or mixtures thereof.

3. The method for preparing a plasticizer composition of claim 1, wherein the anhydrosugar alcohol is selected from isosorbide, isomannide, isoidide or mixtures thereof.

4. The method for preparing a plasticizer composition of claim 1, wherein the carboxylic acid is C.sub.2-C.sub.24 alkyl carboxylic acid, C.sub.3-C.sub.24 cycloalkyl carboxylic acid, C.sub.6-C.sub.24 aryl carboxylic acid, or a mixture thereof.

5. The method for preparing a plasticizer composition of claim 1, wherein the basic material is alkali metal hydroxide, alkaline earth metal hydroxide, or a mixture thereof.

6. A PVC resin composition comprising a plasticizer composition prepared by the method of claim 1; and PVC resin.

7. The PVC resin composition according to claim 6, wherein the plasticizer composition comprises anhydrosugar alcohol monoester, anhydrosugar alcohol diester and sugar alcohol ester, wherein the amount of sugar alcohol ester is 20 to 70 parts by weight, based on 100 parts by weight of the plasticizer composition.

Description

EXAMPLES

(1) <Preparation of Plasticizer Composition>

Example A1: Preparation of Plasticizer Composition by Using a Mixture of Anhydrosugar Alcohol and Sugar Alcohol, and Fatty Acid

(2) 100 g of isosorbide (ISB), 900 g of sorbitol and 1,780 g of caprylic acid were fed into a 3-necked glass reactor and the mixture was agitated at the reactor inside temperature of 110° C. After confirming that the mixture of isosorbide, sorbitol and caprylic acid was dissolved completely, 7 g of para-toluenesulfonic acid as an acid catalyst and 3 g of hypophosphorous acid as a color improving agent were added to the reactor, and then the reactor inside temperature was elevated to 150° C. and the reactor inside pressure was reduced to 120 torr, and the mixture was concentrated for 2 hours, and then the reactor inside temperature was elevated to 180° C. and the reactor inside pressure was increased to 150 torr, and the mixture was concentrated for 4 to 24 hours. When the acid value of the reaction solution became 5 mg/g or less, while maintaining the reactor inside temperature at 75° C., 15 g of potassium hydroxide and 270 g of water were added to the reactor and the mixture was agitated for about 1 hour, and then the organic layer was separated. While maintaining the inside temperature of the separated organic layer at 75° C., the mixture was washed with 300 g of a 10 wt % aqueous solution of sodium sulfate and then concentrated under reduced pressure. The solid product in the concentrate was filtered out to obtain 2,300 g of the plasticizer composition. The obtained plasticizer composition comprised isosorbide monoester, isosorbide diester and sorbitan ester, and the amount of sorbitan ester was 70.0 parts by weight, based on 100 parts by weight of the plasticizer composition.

Example A2: Preparation of Plasticizer Composition by Using a Mixture of Anhydrosugar Alcohol and Sugar Alcohol, and Fatty Acid

(3) 2,400 g of a plasticizer composition was prepared by the same method as in Example A1, excepting that the amount of isosorbide was changed from 100 g to 600 g, the amount of sorbitol was changed from 900 g to 400 g, and the amount of caprylic acid was changed from 1,780 g to 1,870 g. The obtained plasticizer composition comprised isosorbide monoester, isosorbide diester and sorbitan ester, and the amount of sorbitan ester was 26.2 parts by weight, based on 100 parts by weight of the plasticizer composition.

Example A3: Preparation of Plasticizer Composition by Using a Mixture of Anhydrosugar Alcohol and Sugar Alcohol, and Fatty Acid

(4) 2,500 g of a plasticizer composition was prepared by the same method as in Example A1, excepting that the amount of isosorbide was changed from 100 g to 950 g, the amount of sorbitol was changed from 900 g to 50 g, the amount of caprylic acid was changed from 1,780 g to 1,980 g, the amount of potassium hydroxide was changed from 15 g to 14 g, and the amount of water was changed from 270 g to 280 g. The obtained plasticizer composition comprised isosorbide monoester, isosorbide diester and sorbitan ester, and the amount of sorbitan ester was 5.0 parts by weight, based on 100 parts by weight of the plasticizer composition.

Example A4: Preparation of Plasticizer Composition by Using a Mixture of Anhydrosugar Alcohol and Sugar Alcohol, and Fatty Acid Mixture (C8/C10)

(5) 2,500 g of a plasticizer composition was prepared by the same method as in Example A1, excepting that the amount of isosorbide was changed from 100 g to 600 g, the amount of sorbitol was changed from 900 g to 400 g, and 1,920 g of fatty acid mixture (containing caprylic acid (C8) and decanoic acid (C10) with a C8:C10 weight ratio of 6:4) was used instead of 1,780 g of caprylic acid. The obtained plasticizer composition comprised isosorbide monoester, isosorbide diester and sorbitan ester, and the amount of sorbitan ester was 25.4 parts by weight, based on 100 parts by weight of the plasticizer composition.

Example A5: Preparation of Plasticizer Composition by Using a Mixture of Anhydrosugar Alcohol and Sugar Alcohol, and Fatty Acid Mixture (C6/C12)

(6) 2,400 g of a plasticizer composition was prepared by the same method as in Example A1, excepting that the amount of isosorbide was changed from 100 g to 600 g, the amount of sorbitol was changed from 900 g to 400 g, and 1,920 g of fatty acid mixture (containing caproic acid (C6) and lauric acid (C12) with a C6:C12 weight ratio of 6:4) was used instead of 1,780 g of caprylic acid. The obtained plasticizer composition comprised isosorbide monoester, isosorbide diester and sorbitan ester, and the amount of sorbitan ester was 24.7 parts by weight, based on 100 parts by weight of the plasticizer composition.

Comparative Example A1: Preparation of Plasticizer Composition by Using Anhydrosugar Alcohol and Fatty Acid

(7) 2,300 g of a plasticizer composition was prepared by the same method as in Example A1, excepting that the amount of isosorbide was changed from 100 g to 1,000 g, the amount of sorbitol was changed from 900 g to 0 g, the amount of caprylic acid was changed from 1,780 g to 1,920 g, the amount of potassium hydroxide was changed from 15 g to 14 g, and the amount of water was changed from 270 g to 280 g. The obtained plasticizer composition comprised isosorbide monoester and isosorbide diester, but the amount of sorbitan ester was 0 part by weight, based on 100 parts by weight of the plasticizer composition.

Comparative Example A2: Preparation of Plasticizer Composition by Using a Mixture of Anhydrosugar Alcohol and Sugar Alcohol, and Fatty Acid

(8) 2,520 g of a plasticizer composition was prepared by the same method as in Example A1, excepting that the amount of isosorbide was changed from 100 g to 970 g, the amount of sorbitol was changed from 900 g to 30 g, and the amount of caprylic acid was changed from 1,780 g to 2,011 g. The obtained plasticizer composition comprised isosorbide monoester, isosorbide diester and sorbitan ester, and the amount of sorbitan ester was 2.2 parts by weight, based on 100 parts by weight of the plasticizer composition.

Comparative Example A3: Preparation of Plasticizer Composition by Using Sugar Alcohol and Fatty Acid

(9) 2,200 g of a plasticizer composition was prepared by the same method as in Example A1, excepting that the amount of isosorbide was changed from 100 g to 0 g, the amount of sorbitol was changed from 900 g to 1,000 g, and the amount of caprylic acid was changed from 1,780 g to 1,620 g. The obtained plasticizer composition comprised isosorbide monoester, isosorbide diester and sorbitan ester, and the amount of sorbitan ester was 85.8 parts by weight, based on 100 parts by weight of the plasticizer composition. During storage of the plasticizer composition at room temperature for 7 days or longer, white colored precipitate was generated.

(10) <Preparation of Polyvinylchloride (PVC) Paste>

Examples B1 to B5, Comparative Examples B1 to B3 and Reference Example 1

(11) In order to compare the plasticizing efficiencies of the plasticizer compositions prepared in the above Examples and Comparative Examples, 100 parts by weight of PVC resin and 60 parts by weight of each of the plasticizer compositions prepared in the above Examples A1 to A5 and Comparative Examples A1 to A3 were mixed and agitated to prepare PVC pastes of Examples B1 to B5 and Comparative Examples B1 to B3, respectively. In addition, 100 parts by weight of PVC resin and 60 parts by weight of conventional plasticizer, dioctyl phthalate (GL-100, LG Chem) were mixed and agitated to prepare a PVC paste of Reference Example 1.

(12) The properties of the PVC pastes prepared above were measured by the methods explained below, and the results are shown in the following Table 2.

(13) (1) Viscosity: The viscosities of the PVC pastes were measured by using Brookfield viscometer.

(14) (2) Precipitate generation: Whether precipitate was generated or not was confirmed by naked eye after storage of the plasticizer compositions at room temperature for 7 days.

(15) X: No precipitate generated

(16) O: Precipitate generated

(17) TABLE-US-00001 TABLE 1 The amounts of ISB and sorbitol used and the compositional ratio of the resulting plasticizer composition Sorbitan ester ISB diester ISB monoester ISB Sorbitol amount amount amount amount amount (parts by (parts by (parts by (g) (g) Fatty acid weight) weight) weight) Example A1 100 900 Caprylic acid (C8) 70.0 13.0 7.4 Example A2 600 400 Caprylic acid (C8) 26.2 60.3 6.1 Example A3 950 50 Caprylic acid (C8) 5.0 82.2 5.7 Example A4 600 400 C8/C10 25.4 59.6 5.9 Fatty acid mixture Example A5 600 400 C6/C12 24.7 58.3 7.9 Fatty acid mixture Comparative 1,000 0 Caprylic acid (C8) 0 94.7 1.8 Example A1 Comparative 970 30 Caprylic acid (C8) 2.2 89.9 5.0 Example A2 Comparative 0 1,000 Caprylic acid (C8) 85.8 5.1 4.2 Example A3 ISB: Isosorbide In the above Table 1, the amounts of ISB diester, ISB monoester and sorbitan ester represent their weight ratio compared with 100 parts by weight of the plasticizer composition. In 100 parts by weight of the plasticizer composition, as well as the ISB diester, ISB monoester and sorbitan ester, impurities are contained in remainder amount.

(18) TABLE-US-00002 TABLE 2 The results of measuring the properties of the PVC paste Reference Example Comparative Example Example B1 B2 B3 B4 B5 B1 B2 B3 1 PVC resin 100 100 100 100 100 100 100 100 100 (parts by weight) Plasticizer Example Example Example Example Example Comparative Comparative Comparative GL-100 (parts by A1 A2 A3 A4 A5 Example A1 Example A2 Example A3 (60) weight) (60) (60) (60) (60) (60) (60) (60) (60) Sorbitan 70.0 26.2 5.0 25.4 24.7 0 2.2 85.8 — ester amount (parts by weight) Viscosity 1.27 1.32 1.35 1.31 1.32 1.51 1.48 1.25 1.35 (×10.sup.4, Pa .Math. s) Precipitate X X X X X X X ◯ — generation GL-100 (LG Chem): dioctyl phthalate-based plasticizer

(19) As described in the above Table 2, the PVC pastes of Examples B1 to B5 prepared by using the plasticizer compositions according to the present invention exhibited the same or superior plasticity as compared with the conventional plasticizer (GL-100), and even after storage at room temperature for 7 days or longer, they did not cause any problem of non-uniformity of composition due to generation of white colored precipitate.

(20) However, the PVC pastes of Comparative Examples B1 (containing no sorbitan ester) and B2 (containing 2.2 parts by weight of sorbitan ester) prepared by using the plasticizer compositions containing less than 5 parts by weight of sorbitan ester exhibited inferior plasticity as compared with the conventional plasticizer (GL-100), and the PVC paste of Comparative Example B3 (containing 85.8 parts by weight of sorbitan ester) prepared by using the plasticizer composition containing greater than 80 parts by weight of sorbitan ester exhibited the same or superior plasticity as compared with the conventional plasticizer (GL-100), but after storage at room temperature for 7 days or longer, white colored precipitate was generated in the composition and thus it was not suitable for application as a plasticizer.