Plasticizer composition, resin composition and method of preparing the same

Abstract

The present invention relates to a plasticizer composition which includes an epoxidized alkyl ester composition including one or more compounds represented by the following Chemical Formula 1; and a citrate-based material, wherein a weight ratio of the epoxidized alkyl ester composition and the citrate-based material is in a range of 90:10 to 10:90: ##STR00001##

Claims

1. A plasticizer composition comprising: an epoxidized alkyl ester composition comprising one or more compounds represented by the following Chemical Formula 1; and an alkyl ester composition comprising one or more compounds represented by the following Chemical Formula 2, and one or more citrate-based materials, wherein a weight ratio of the epoxidized alkyl ester composition and the citrate-based material is in a range of 90:10 to 10:90: ##STR00010## wherein R.sub.1 is an alkyl group containing one or more epoxy groups and having 8 to 20 carbon atoms, and R.sub.2 is an alkyl group having 4 to 10 carbon atoms, ##STR00011## wherein R.sub.3 is an alkyl group having 8 to 20 carbon atoms, and R.sub.4 is an alkyl group having 4 to 10 carbon atoms, and wherein the citrate-based materials are materials which do not have an acetyl group bound thereto.

2. The plasticizer composition of claim 1, wherein the epoxidized alkyl ester composition has an iodine value of less than 3.5 I.sub.2/100 g.

3. The plasticizer composition of claim 1, wherein the epoxidized alkyl ester composition has an oxirane content (O.C.) of 3.5% or more.

4. The plasticizer composition of claim 1, wherein the epoxidized alkyl ester composition has an oxirane index (O.I.) of 1.0 or more.

5. The plasticizer composition of claim 1, wherein R.sub.2 in Chemical Formula 1 is an alkyl group having 4 to 9 carbon atoms.

6. The plasticizer composition of claim 1, wherein R.sub.2 in Chemical Formula 1 is selected from the group consisting of a butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, an isoheptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a 6-methyloctyl group, a decyl group, an isodecyl group, and a 2-propylheptyl group.

7. The plasticizer composition of claim 1, wherein the epoxidized alkyl ester composition comprises two or more compounds having a different number of carbon atoms in R.sub.2 in Chemical Formula 1.

8. The plasticizer composition of claim 1, wherein the citrate-based materials are selected from the group consisting of a hybrid alkyl-substituted citrate-based material having 4 to 10 carbon atoms, and a non-hybrid alkyl-substituted citrate-based material having 4 to 10 carbon atoms.

9. A resin composition comprising 100 parts by weight of a resin; and 5 to 150 parts by weight of the plasticizer composition defined in claim 1.

10. The resin composition of claim 9, wherein the resin comprises one or more selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyketone, polyvinyl chloride, polystyrene, polyurethane, and a thermoplastic elastomer.

Description

BEST MODE

EXAMPLES

(1) Hereinafter, the present invention will be described in detail with reference to embodiments thereof in order to describe the present invention more clearly. However, it should be understood that the embodiments of the present invention can be implemented in various forms and are not intended to limit the scope of the present invention. The embodiments of the present invention are provided herein to describe the present invention more fully to persons having ordinary skill in the art.

Preparative Example 1: Preparation of eFAEHE

(2) 1,000 g of epoxidized soybean oil (ESO) having an oxirane content of 6.97% and an iodine value of 1.93 (I.sub.2/100 g), 500 g of 2-ethylhexyl alcohol (2-EH), 5.5 g of a metal salt catalyst serving as a catalyst were added to a 3 L 4-neck reactor equipped with a cooler, a condenser, a decanter, a reflux pump, a temperature controller, an agitator, etc., and slowly heated to approximately 180 C.

(3) It was confirmed through gas chromatography analysis that ESO as a raw material was completely consumed in a reaction, and the reaction was stopped. After the reaction was completed, 1,210 g of an epoxidized 2-ethylhexyl ester composition having an oxirane content of 5.21% and an iodine value of 1.70 was finally obtained through processes of removing glycerine as a by-product, removing an unreacted raw material, and purifying a product.

Preparative Example 2: Preparation of eFAINE

(4) An epoxidized isononyl ester composition having the same oxirane content and iodine value as listed in the following Table 1 was prepared in the same manner as in Preparative Example 1, except that isononanol was used instead of the 2-ethylhexanol.

Preparative Example 3: Preparation of eFABE

(5) An epoxidized butyl ester composition having the same oxirane content and iodine value as listed in the following Table 1 was prepared in the same manner as in Preparative Example 1, except that butanol was used instead of the 2-ethylhexanol.

Preparative Example 4: Preparation of tributyl citrate (TBC)

(6) 706 g (yield: 98%) of tributyl citrate was finally obtained using 384 g of citric acid and 580 g of butanol as raw materials for reaction.

Preparative Example 5: Preparation of tri(2-ethylhexyl) citrate (TEHC)

(7) 1,029 g (yield: 98%) of tri(2-ethylhexyl)citrate was finally obtained using 384 g of citric acid and 1,014 g of 2-ethylhexanol as raw materials for reaction.

Preparative Example 6: Preparation of triisononyl citrate (TINC)

(8) 1,111 g (yield: 98%) of triisononyl citrate was finally obtained using 384 g of citric acid and 1,123 g of isononanol as raw materials for reaction.

Preparative Example 7: Preparation of eFAEHE

(9) An epoxidized 2-ethylhexyl ester composition having an oxirane content of 3.37% was prepared in the same manner as in Preparative Example 1, except that the oxirane content of the epoxidized soybean oil was lower than that of Preparative Example 1.

Comparative Preparative Example 1: Preparation of eFAME

(10) An epoxidized methyl ester composition was prepared in the same manner as in Preparative Example 1, except that methanol was used instead of the 2-ethylhexanol.

Comparative Preparative Example 2: Preparation of eFAPE

(11) An epoxidized propyl ester composition was prepared in the same manner as in Preparative Example 1, except that propanol was used instead of the 2-ethylhexanol.

Comparative Preparative Example 3: Preparation of eFADDE

(12) An epoxidized dodecyl ester composition was prepared in the same manner as in Preparative Example 1, except that dodecanol was used instead of the 2-ethylhexanol.

EXAMPLES

(13) The plasticizers of examples and comparative examples were composed using the materials prepared in Preparative Examples 1 to 7 and the materials prepared in Comparative Preparative Examples 1 to 3, as listed in the following Table 1.

(14) TABLE-US-00001 TABLE 1 Citrate- Epoxidized alkyl ester composition based Epoxidized Mixing Number of carbon atoms O.C. I.V. material oil ratio Example 1 8 5.21 1.70 TEHC 9:1 (Preparative Example 1) Example 2 8 5.21 1.70 TEHC 7:3 (Preparative Example 1) Example 3 8 5.21 1.70 TEHC 3:7 (Preparative Example 1) Example 4 8 5.21 1.70 TEHC 1:9 (Preparative Example 1) Example 5 9 5.22 1.71 TBC 5:5 (Preparative Example 2) Example 6 9 5.22 1.71 TBC 4:6 (Preparative Example 2) Example 7 4 5.18 1.68 TINC 3:7 (Preparative Example 3) Example 8 4 5.18 1.68 TINC 2:8 (Preparative Example 3) Example 9 8 3.37 3.40 TEHC 7:3 (Preparative Example 7) Example 10 8 5.21 1.70 TEHC ESO 7:1:2 (Preparative Example 1) Example 11 8 5.21 1.70 TEHC ESO 4:1:5 (Preparative Example 1) Comparative 1 (Comparative 5.13 1.80 TBC 5:5 Example 1 Preparative Example 1) Comparative 3 (Comparative 5.20 1.82 TBC 5:5 Example 2 Preparative Example 2) Comparative 12 (Comparative 5.33 1.78 TEHC 5:5 Example 3 Preparative Example 3) Comparative 8 5.21 1.70 Example 4 (Preparative Example 1) Comparative TEHC Example 5

Experimental Example 1: Preparation and Performance Evaluation of Specimens

(15) The plasticizers of Examples 1 to 11 and Comparative Examples 1 to 5 were used as experimental specimens. The preparation of the specimens was performed with reference to ASTM D638, as follows. 40 parts by weight of a plasticizer and 3 parts by weight of a stabilizer (LOX 912 NP) were blended with 100 parts by weight of PVC in a mixer, and the resulting mixture was then processed at 170 C. for 4 minutes in a roll mill, compressed at 180 C. for 2.5 minutes (at low pressure) and 2 minutes (at high pressure) using a press to prepare 1T and 3T sheets. A physical property test was performed on each of the specimens, as follows. The results are listed in the following Table 2.

(16) <Test Items>

(17) The plasticizers of the examples and the comparative examples were evaluated for the following test items, as follows.

(18) Measurement of Hardness

(19) Shore A hardness at 25 C., 3T 10 s was measured using ASTM D2240.

(20) Measurement of Tensile Strength

(21) By an ASTM D638 method, a specimen was drawn in a cross head speed of 200 mm/min (1T) using a test apparatus, U.T.M (Manufacturer: Instron, Model name: 4466), and a point where the specimen was broken was then measured. The tensile strength was calculated, as follows.
Tensile strength (kgf/mm.sup.2)=Load value (kgf)/Thickness (mm)Width (mm)

(22) Measurement of Elongation Rate

(23) By an ASTM D638 method, a specimen was drawn in a cross head speed of 200 mm/min (1T) using the test apparatus, U.T.M, and a point where the specimen was broken was then measured. The elongation rate was calculated, as follows.
Elongation rate (%)=Length after elongation/Initial length100

(24) Measurement of Migration Loss

(25) A specimen having a thickness of 2 mm or more was obtained according to KSM-3156, PS plates were attached to both sides of the specimen, and a load of 1 kgf/cm.sup.2 was then applied thereto. The specimen was kept in a convection oven (80 C.) for 72 hours, taken out, and then cooled at room temperature for 4 hours. Thereafter, the PS plates attached to both sides of the specimen were removed, and the weights of the specimens before and after being kept in the oven were measured. Then, the migration loss was calculated by the following equation.
Migration loss (%)={(Initial weight of specimen at room temperatureWeight of specimen after being kept in oven)/Initial weight of specimen at room temperature}100

(26) Measurement of Volatile Loss

(27) The specimen thus prepared was processed at 80 C. for 72 hours, and a weight of the specimen was measured.
Volatile loss (%)=Initial weight of specimen(Weight of specimen after being processed at 80 C. for 72 hours/Initial weight of specimen)100

(28) TABLE-US-00002 TABLE 2 Tensile Volatile Hardness strength Elongation Migration loss (Shore A) (kg/cm.sup.2) rate (%) loss (%) (%) Example 1 87.0 216.1 305.9 2.85 1.86 Example 2 87.3 225.7 313.5 2.37 1.62 Example 3 87.5 227.1 311.9 2.14 1.23 Example 4 87.8 230.5 313.5 1.84 0.60 Example 5 85.3 220.7 308.5 1.65 2.87 Example 6 85.0 221.4 305.7 1.40 2.93 Example 7 87.5 235.6 312.2 2.45 1.03 Example 8 87.6 238.7 310.8 2.50 1.00 Example 9 87.5 220.4 303.7 2.50 1.55 Example 10 87.1 237.8 320.5 1.88 1.20 Example 11 87.3 248.7 322.4 1.92 0.75 Comparative 82.4 184.6 284.5 3.51 7.80 Example 1 Comparative 85.3 195.6 283.2 3.30 6.58 Example 2 Comparative 87.8 220.8 308.2 4.60 2.22 Example 3 Comparative 86.8 204.9 308.0 3.36 2.41 Example 4 Comparative 89.0 231.0 295.6 5.60 0.42 Example 5

(29) Referring to Table 2, it can be seen that all the plasticizer compositions of Examples 1 to 11 exhibited excellent physical properties in balance without having inferior physical properties, whereas the plasticizer compositions prepared in Comparative Examples 1 to 5 were difficult to apply to the plasticizer composition because the plasticizer compositions had poor levels in all physical properties or particularly poor levels in one or two or more physical properties.

(30) Specifically, it can be seen that a considerable amount of the epoxidized alkyl ester composition was volatilized during processing because the epoxidized alkyl ester composition had a fewer number of carbon atoms, that is, 1 and 3 carbon atoms, respectively, in the case of Comparative Examples 1 and 2, resulting in a drastic drop in physical properties, for example, a high level of migration loss and volatile loss. However, it was confirmed that the plasticizer compositions of Examples 7 and 8 in which an epoxidized alkyl ester composition having 4 carbon atoms was used had significantly lower volatile loss and migration loss, compared to the plasticizer compositions of Comparative Examples 1 and 2, although the plasticizer compositions of Examples 7 and 8 did not have a relatively significant difference in the number of carbon atoms.

(31) Also, in the case of Comparative Example 3, it was revealed that the plasticizer composition had a rather poor migration loss approximately two-fold higher than the plasticizer compositions of the examples because the epoxidized alkyl ester composition had a very high number of carbon atoms, that is, 12 carbon atoms.

(32) In addition, it can be seen that, when comparing the plasticizer compositions Examples 1 to 4 with the plasticizer compositions of Comparative Examples 4 and 5, in which a mixture of the respective materials was not used, physical properties did not linearly change but there was a synergistic effect on physical properties such as elongation rate, migration loss and volatile loss, indicating that the physical properties were improved to a level higher than the physical properties exhibited by the two materials.

(33) Further, when Example 1 was compared with Examples 10 and 11, the effect exhibited by further addition of the epoxidized oil was able to be confirmed. In this case, it was revealed that the tensile strength and elongation rate, and the migration loss and volatile loss were all improved. From these results, it can be seen that the physical properties of the plasticizer compositions were able to be improved when the epoxidized oil was further added to the epoxidized alkyl ester composition and the citrate-based material.