Plasticizer composition, resin composition and methods of preparing the same

Abstract

The present disclosure relates to an environmentally friendly plasticizer composition suitable for use in applications such as a resin for a food wrapping material, comprising an epoxidized alkyl ester composition including one or more compounds represented by the following Chemical Formula 1 and having an iodine value (I.V.) of less than 3.5 g I.sub.2/100 g, and a resin composition including the same, and methods of preparing the same: ##STR00001##

Claims

1. A plasticizer composition comprising an epoxidized alkyl ester composition including one or more compounds represented by the following Chemical Formula 1 and having an iodine value (I.V.) of less than 3.5 g I.sub.2/100 g, as measured in accordance with ASTM D5768: ##STR00009## wherein R.sub.1 is an alkyl group having 8 to 20 carbon atoms and including one or more epoxy groups and R.sub.2 is an alkyl group having 4 to 10 carbon atoms; and an alkyl ester composition including one or more compounds represented by the following Chemical Formula 2: ##STR00010## 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.

2. The plasticizer composition according to 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.

3. The plasticizer composition according to claim 1, wherein R.sub.2 in Chemical Formula 1 is selected from the group consisting of a butyl group, an isobutyl group, a 2-ethylhexyl group, an isononyl group, a 6-methyloctyl group and a 2-propylheptyl group.

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

5. The plasticizer composition according to claim 1, wherein the epoxidized alkyl ester composition has an oxirane content (O.C.) of 3.5% or more, as measured in accordance with ASTM D1652.

6. The plasticizer composition according to claim 1, wherein the epoxidized alkyl ester composition has an oxirane index (O.I.) of 1.0 or more, wherein O.I. is a ratio of an oxirane content of the epoxidized alkyl ester compound to an iodine value thereof, as measured in accordance with ASTM D1652 and ASTM D5768 respectively.

7. A resin composition comprising: 100 parts by weight of a resin; and 5 to 150 parts by weight of the plasticizer composition according to claim 1.

8. The resin composition according to claim 7, wherein the resin is one or more selected from the group consisting of ethylene vinyl acetate, polyethylene, polyketone, polypropylene, polyvinyl chloride, polystyrene, polyurethane and a thermoplastic elastomer.

9. The resin composition according to claim 7, wherein the resin composition is applied in preparation of one or more selected from the group consisting of electric wires, flooring materials, interior materials for automobiles, films, sheets, wallpaper and tubes.

10. The resin composition according to claim 7, wherein the resin composition is applied in preparation of one or more selected from the group consisting of a blood bag, intravenous bag, saline bag, syringe, intravenous tube, nasogastric tube, catheter, drainage tube, medical glove, oxygen mask, retainer, artificial skin and food wrapping material.

Description

EXAMPLE

(1) Hereinafter, embodiments will be described in detail for promoting an understanding of the present invention. However, embodiments of the present invention may be modified in several different forms, and the scope of the present invention is not limited to the embodiments to be described below. The embodiments of the present invention are provided so that this disclosure will be thorough and complete, and will fully convey the concept of embodiments to those skilled in the art.

BEST MODE

Example 1

(2) 1,000 g of epoxidized soybean oil (ESO) having an oxirane content of 6.97% and an iodine value of 1.93 (g I.sub.2/100 g), 500 g of 2-ethylhexyl alcohol (2-EH) and 5.5 g of a metallic salt catalyst as a catalyst were input to a 3 L 4-neck reaction vessel equipped with a cooler, a condenser, a decanter, a reflux pump, a temperature controller, an stirrer and the like, and a temperature was slowly increased to about 180 C.

(3) After it was confirmed through gas chromatography that ESO as a raw material was completely reacted and thus consumed, the reaction was terminated. After the reaction was completed, glycerine as a by-product and an unreacted raw material were removed, and a product was purified to finally obtain 1,210 g of an epoxidized 2-ethylhexyl ester composition having an oxirane content of 5.21% and an iodine value of 1.70 g I.sub.2/100 g.

Example 2

(4) An epoxidized butyl ester composition was prepared in the same manner as in Example 1 except that butanol was used instead of 2-ethylhexanol, and used as a plasticizer. In this case, the oxirane content and iodine value of an epoxidized oil and the prepared epoxidized alkyl ester composition were measured, results of which are shown in the following Table 1.

Example 3

(5) An epoxidized isononyl ester composition was prepared in the same manner as in Example 1 except that isononanol was used instead of 2-ethylhexanol, and used as a plasticizer. In this case, the oxirane content and iodine value of an epoxidized oil and the prepared epoxidized alkyl ester composition were measured, results of which are shown in the following Table 1.

Example 4

(6) An epoxidized butyl ester and epoxidized 2-ethylhexyl ester composition was prepared in the same manner as in Example 1 except that butanol and 2-ethylhexanol were used in a weight ratio of 5:5 instead of 2-ethylhexanol, and used as a plasticizer. In this case, the oxirane content and iodine value of an epoxidized oil and the prepared epoxidized alkyl ester composition were measured, results of which are shown in the following Table 1.

Example 5

(7) An epoxidized pentyl ester and epoxidized isononyl ester composition was prepared in the same manner as in Example 1 except that pentanol and isononanol were used in a weight ratio of 5:5 instead of 2-ethylhexanol, and used as a plasticizer. In this case, the oxirane content and iodine value of an epoxidized oil and the prepared epoxidized alkyl ester composition were measured, results of which are shown in the following Table 1.

Example 6

(8) An epoxidized 2-ethylhexyl ester composition was prepared in the same manner as in Example 1 except that ESO having an oxirane content of 4.73% and an iodine value of 3.80 (g I.sub.2/100 g) was used, and used as a plasticizer. In this case, the oxirane content and iodine value of an epoxidized oil and the prepared epoxidized alkyl ester composition were measured, results of which are shown in the following Table 1.

Example 7

(9) An epoxidized 2-ethylhexyl ester composition was prepared in the same manner as in Example 1 except that ESO having an oxirane content of 4.98% and an iodine value of 2.32 (g I.sub.2/100 g) was used, and used as a plasticizer. In this case, the oxirane content and iodine value of an epoxidized oil and the prepared epoxidized alkyl ester composition were measured, results of which are shown in the following Table 1.

Comparative Example 1

(10) An epoxidized methyl ester composition was prepared in the same manner as in Example 1 except that methanol was used instead of 2-ethylhexanol, and used as a plasticizer. In this case, the oxirane content and iodine value of an epoxidized oil and the prepared epoxidized alkyl ester composition were measured, results of which are shown in the following Table 1.

Comparative Example 2

(11) An epoxidized propyl ester composition was prepared in the same manner as in Example 1 except that propanol was used instead of 2-ethylhexanol, and used as a plasticizer. In this case, the oxirane content and iodine value of an epoxidized oil and the prepared epoxidized alkyl ester composition were measured, results of which are shown in the following Table 1.

Comparative Example 3

(12) An epoxidized dodecyl ester (epoxidized fatty acid dodecyl ester (eFADDE)) composition was prepared in the same manner as in Example 1 except that dodecanol was used instead of 2-ethylhexanol, and used as a plasticizer. In this case, the oxirane content and iodine value of an epoxidized oil and the prepared epoxidized alkyl ester composition were measured, results of which are shown in the following Table 1.

Comparative Example 4

(13) An epoxidized 2-ethylhexyl ester composition was prepared in the same manner as in Example 1 except that ESO having an oxirane content of 4.70% and an iodine value of 4.02 (g I.sub.2/100 g) was used, and used as a plasticizer. In this case, the oxirane content and iodine value of an epoxidized oil and the prepared epoxidized alkyl ester composition were measured, results of which are shown in the following Table 1.

Comparative Example 5

(14) An epoxidized 2-ethylhexyl ester composition was prepared in the same manner as in Example 1 except that ESO having an oxirane content of 2.07% and an iodine value of 8.90 (g I.sub.2/100 g) was used, and used as a plasticizer. In this case, the oxirane content and iodine value of an epoxidized oil and the prepared epoxidized alkyl ester composition were measured, results of which are shown in the following Table 1.

Comparative Example 6 (Comparative Example for Treatment of Wrap Film)

(15) EBN.WG (LG Chem), a commercially available plasticizer for a wrap film, was applied as a plasticizer.

(16) Measurement of Iodine Value and Oxirane Content

(17) For each of the compositions prepared in examples and comparative examples, the oxirane content and iodine value of an epoxidized oil and the epoxidized alkyl ester composition were measured, results of which are shown in the following Table 1. In this case, the oxirane content was measured with reference to ASTM D1652, and the iodine value was measured with reference to ASTM D5768.

(18) TABLE-US-00001 TABLE 1 Epoxidized oil Epoxidized alkyl ester Oxirane Oxirane Iodine content Iodine content Plasticizer value (%) value (%) Example 1 eFAEHE 1.93 6.97 1.70 5.21 Example 2 eFABE 1.93 6.97 1.68 5.18 Example 3 eFAINE 1.93 6.97 1.71 5.22 Example 4 eFABE + 1.93 6.97 1.72 5.26 eFAEHE Example 5 eFAPE + 1.93 6.97 1.68 5.24 eFAINE Example 6 eFAEHE 3.80 4.73 3.46 3.58 Example 7 eFAEHE 2.32 4.98 1.98 3.61 Comparative eFAME 1.93 6.97 1.80 5.13 Example 1 Comparative eFAPE 1.93 6.97 1.82 5.20 Example 2 Comparative eFADDE 1.93 6.97 1.78 5.33 Example 3 Comparative eFAEHE 4.02 4.70 3.95 3.50 Example 4 Comparative eFAEHE 8.90 2.07 7.71 1.55 Example 5

Experimental Example 1: Evaluation of Epoxidized Alkyl Ester Composition (Compatibility with Resin and Discoloration)

(19) Experiments were conducted to identify effects of the iodine values and oxirane contents in examples and comparative examples shown in Table 1 on compatibility with polyvinyl chloride (PVC) and the discoloration degree of a liquid product.

(20) Compatibility with Resin

(21) Each of products according to examples and comparative examples was used as a plasticizer composition. Specifically, 60 parts by weight of each of the plasticizer compositions was mixed with 100 parts by weight of PVC (LS100S) using a 3 L super mixer at 98 C. and 700 rpm, and then a migration (or bleeding) degree of the plasticizer in the resin was observed while the resulting mixture was stored in a convection oven at 80 C. for a long time. In this case, the migration degree, which was expressed as a value of 0 to 5 (compatibility is excellent as the value is close to 0 and compatibility is poor as the value is close to 5), is shown in the following Table 2.

(22) TABLE-US-00002 TABLE 2 Epoxidized alkyl ester Oxirane Compatibility with resin Iodine content (80 C.) Plasticizer value (%) 1 week 2 weeks Example 1 eFAEHE 1.70 5.21 0 1 Example 2 eFABE 1.68 5.18 0 0 Example 3 eFAINE 1.71 5.22 0 1 Example 6 eFAEHE 3.46 3.58 0.5 2 Comparative eFAEHE 3.95 3.50 1.0 3 Example 4 Comparative eFAEHE 7.71 1.55 2 5 Example 5

(23) Referring to Table 2, it can be seen that compatibilities with a resin were significantly different according to the iodine value and oxirane content. That is, it can be seen that the plasticizer compositions according to Comparative Examples 4 and 5 having significantly high iodine values had considerably poor compatibility with a resin when just stored for about 2 weeks. Therefore, it can be seen that it is necessary to appropriately adjust the iodine value and oxirane content of an epoxidized alkyl ester composition.

(24) In addition, it was confirmed that, when an iodine value was increased by about 100% from 1.71 in Example 3 to 3.46 in Example 6, compatibility was increased by 0.5, but even when an iodine value was increased just by about 14% from 3.46 in Example 6 to 3.95 in Comparative Example 4, compatibility was also increased by 0.5. Therefore, it can be seen that it is necessary to appropriately adjust the iodine value.

(25) Liquid Discoloration

(26) A predetermined amount of each of liquid products according to examples and comparative examples was put into a 100 ml glass vessel, and then a discoloration degree of a liquid plasticizer product was observed while the liquid products were stored in a convection oven at 80 C. for a long time. The discoloration degree was measured with a colormeter, results of which are shown in the following Table 3.

(27) TABLE-US-00003 TABLE 3 Epoxidized alkyl ester Discoloration of product Oxirane (80 C.) Iodine content Initial stage 2 weeks Plasticizer value (%) (APHA) (APHA) Example 1 eFAEHE 1.70 5.21 95 110 Example 2 eFABE 1.68 5.18 100 115 Example 3 eFAINE 1.71 5.22 90 105 Example 6 eFAEHE 3.46 3.58 155 230 Comparative eFAEHE 3.95 3.50 160 310 Example 4 Comparative eFAEHE 7.71 1.55 180 365 Example 5

(28) Referring to Table 3, it was confirmed that the discoloration degree of a product was significantly different according to the iodine value and oxirane content. That is, it can be seen that the plasticizer composition according to Comparative Example 5 having a significantly high iodine value exhibited a significantly poor discoloration degree when just stored for about 2 weeks. Therefore, it can be seen that it is necessary to appropriately adjust the iodine value and oxirane content of an epoxidized alkyl ester composition to obtain a product having excellent chromaticity.

Experimental Example 2: Evaluation of Properties 1 (Treatment of Sheet)

(29) Each specimen was prepared, according to ASTM D638, by mixing 30 parts by weight of each of the plasticizer compositions according to Examples 1 to 7 and Comparative Examples 1 to 5 and 3 parts by weight of a stabilizer (BZ-153T) with 100 parts by weight of PVC (LS100S) using a 3 L super mixer at 98 C. and 700 rpm, roll milling the resulting mixture at 160 C. for 4 minutes to prepare a 5-mm sheet, and performing pressing at 180 C. under low pressure for 2.5 minutes, and under high pressure for 2 minutes to prepare 1T and 3T sheets. Properties of each specimen were evaluated by test items listed below, results of which are shown in the following Table 4.

(30) <Test Items>

(31) Evaluation was conducted by test items listed below for examples and comparative examples.

(32) Measurement of Hardness

(33) According to ASTM D2240, Shore (Shore D) hardness was measured at 25 C. under 3T and 10 s conditions.

(34) Measurement of Tensile Strength

(35) According to ASTM D638, each specimen was pulled at a cross head speed of 200 mm/min (1T) using a tester, U.T.M (Manufacturer; Instron, Model No.; 4466), and then a position at which the specimen was broken was detected. A tensile strength was calculated as follows:
Tensile strength (kgf/mm.sup.2)=Load value (kgf)/Thickness (mm)Width (mm)

(36) Measurement of Elongation Rate

(37) According to ASTM D638, each specimen was pulled at a cross head speed of 200 mm/min (1T) using the tester, U.T.M, and then a position at which the specimen was broken was detected. An elongation rate was calculated as follows:
Elongation rate (%)=Length after elongation/Initial length100

(38) Measurement of Migration Loss

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

(40) Measurement of Volatile Loss

(41) The prepared specimen was processed at 80 C. for 72 hours, and then a weight of the specimen was measured as follows:
Volatile loss (wt %)=Initial weight of specimen(Weight of specimen after processed at 80 C. for 72 hours)/Initial weight of specimen100

(42) TABLE-US-00004 TABLE 4 Tensile Elongation Migration Volatile Hardness strength rate loss loss (Shore D) (kg/cm.sup.2) (%) (%) (%) Example 1 54.8 245.4 288.5 2.19 0.74 Example 2 52.5 243.1 280.6 1.56 1.20 Example 3 55.7 250.3 290.5 2.30 0.55 Example 4 53.4 246.5 285.7 0.98 1.02 Example 5 54.3 247.6 286.0 1.90 0.88 Example 6 55.0 234.0 271.3 2.74 1.25 Example 7 54.9 235.7 273.5 2.65 1.15 Comparative 52.1 221.0 250.3 6.71 11.58 Example 1 Comparative 53.0 230.8 258.9 5.04 8.52 Example 2 Comparative 58.4 260.4 275.1 3.56 0.51 Example 3 Comparative 55.3 203.4 270.6 2.80 1.33 Example 4 Comparative 60.2 245.0 232.1 10.5 9.57 Example 5

(43) Referring to Table 4, it was confirmed that the plasticizer compositions according to Examples 1 to 7 were excellent in all properties in balance without any one poor property, whereas the plasticizer compositions according to Comparative Examples 1 to 5 were poor in all properties or particularly poor in any one or two or more properties. Therefore, it can be seen that it is difficult to apply the plasticizer compositions according to Comparative Examples 1 to 5 as plasticizer compositions.

(44) Specifically, it can be seen that, in the case of Comparative Examples 1 and 2, a considerable amount of components was volatilized during a process because the epoxidized alkyl ester compositions had a few number of carbon atoms, that is, 1 and 3, and properties were significantly degraded according thereto, resulting in high migration loss and volatile loss. However, it was confirmed that, in the case of Example 2 in which an epoxidized alkyl ester composition had 4 carbon atoms, hardness (plasticization efficiency) was maintained at a level similar to that in Comparative Examples 1 and 2, but volatile loss and migration loss were significantly low although a difference in the number of carbon atoms is not relatively large, resulting in significantly improved properties.

(45) In addition, it was confirmed that, in the case of Comparative Example 3, high migration loss was exhibited compared to examples because the number of carbon atoms was 12, which is too large, resulting in poor properties. Also, it was confirmed that significantly high hardness (plasticization efficiency) was exhibited compared to Examples 1 and 3 in which each of the number of carbon atoms was 8 and 9, resulting in poor plasticization efficiency.

(46) Additionally, it was confirmed that tensile strength was sharply degraded in the case of Comparative Example 4 in which an iodine value was 3.5 or more, and poor compatibility with a resin was exhibited in the case of Comparative Example 5 in which both an iodine value and an oxirane content were not satisfactory, thereby processing itself is difficult, the mixing with the resin cannot be smoothly performed, and all properties of the resin specimen such as hardness, an elongation rate, migration loss, volatile loss were poor.

Experimental Example 3: Evaluation of Properties 2 (Treatment of Wrap Film)

(47) The plasticizers according to Examples 1 to 3 and Comparative Examples 1 to 3 and 6 were used as test specimens. Each specimen was prepared, according to ASTM D638, by mixing 40.5 parts by weight of each of the plasticizers, 7.2 parts by weight of ESO as an auxiliary stabilizer, 2.16 parts by weight of an anti-fog agent (Almax-9280) and 1.17 parts by weight of a stabilizer (LTX-630P) with 100 parts by weight of PVC in a 3 L super mixer at 98 C. and 700 rpm, roll milling the resulting mixture at 160 C. for 4 minutes, and performing pressing at 180 C. for 2.5 minutes (low pressure) and for 2 minutes (high pressure) to manufacture a wrap film. Properties of each specimen were evaluated by test items listed below, results of which are shown in the following Table 5.

(48) <Additional Test Items>

(49) Measurement of Hardness

(50) According to ASTM D2240, Shore (Shore A) hardness was measured at 25 C. under 3T and 10s conditions.

(51) 100% Modulus

(52) According to ASTM D638, each specimen was pulled at a cross head speed of 200 mm/min (1T) using the tester, U.T.M, and then a force when the specimen was subjected to 100% strain was measured.

(53) Transparency

(54) A haze value was measured with a haze meter. The haze value is an indicator to show a degree of turbidity of a film, and it was evaluated that as a value is low, transparency is excellent.

(55) Evaluation of Adhesiveness

(56) An adhesion degree was evaluated into 5 scales by touching the film by hand, and it was evaluated that 1 was excellent and 5 was poor.

(57) TABLE-US-00005 TABLE 5 Tensile Elongation 100% Migration Volatile Hardness strength rate modulus loss loss Haze (Shore A) (kg/cm.sup.2) (%) (%) (%) (%) (%) Adhesiveness Example 1 69.5 189.7 337.9 74.7 2.08 0.73 3.95 2 Example 2 67.5 196.3 317.7 85.9 1.06 2.39 3.21 1 Example 3 71.0 186.0 312.5 86.9 2.03 0.57 4.67 2 Comparative 65.4 165.4 284.1 88.7 4.50 8.30 3.55 5 Example 1 Comparative 66.8 168.9 290.5 90.1 4.20 6.58 3.87 3 Example 2 Comparative 73.6 190.5 308.7 108.6 2.11 0.50 5.67 5 Example 3 Comparative 70.2 192.6 309.7 95.1 2.45 2.59 4.31 2 Example 6

(58) Referring to Table 5, it can be seen that results were similar to the results in Experimental Example 2. That is, it can be seen that the epoxidized alkyl ester compositions according to Comparative Examples 1 and 2 in which each of the number of carbon atoms was 1 and 3, exhibited significantly poor migration loss and volatile loss, also exhibited poor adhesiveness, and thus are not appropriate to be used as wrapping materials. Also, it can also be seen that an elongation rate and tensile strength also were significantly low.

(59) In addition, it can be seen that, in the case of Comparative Example 3, a high haze value was exhibited because the number of carbon atoms was 12, which is too large, and poor adhesiveness was also exhibited. Also, it can be seen that plasticization efficiency was degraded due to high hardness.

(60) Further, it can be seen that when the plasticizers according to Examples 1 to 3 were applied, an elongation rate and 100% modulus may be improved compared to Comparative Example 6 in which a commercially available plasticizer was used. Also, it can be seen that the plasticizers applied to wrapping materials may be easily stretched and not broken.