Plasticizer composition including cyclohexane 1,4-diester-based compound and resin composition including the same

Abstract

The present invention relates to a plasticizer composition in which three types of cyclohexane 1,4-diester-based compounds prepared through trans-esterification and hydrogenation are mixed, wherein alkyl substituents of the dicarboxylate are a 2-ethylhexyl group and a butyl group or an isobutyl group, which has fewer carbon atoms than the 2-ethylhexyl group, so that the plasticizer composition may exhibit excellent properties in terms of stress resistance, migration resistance, plasticization efficiency, and the like while maintaining an excellent level of tensile strength and elongation rate, when used for a resin composition.

Claims

1. A plasticizer composition comprising: a cyclohexane 1,4-diester-based compound represented by Chemical Formula 1; a cyclohexane 1,4-diester-based compound represented by Chemical Formula 2; and a cyclohexane 1,4-diester-based compound represented by Chemical Formula 3, wherein the cyclohexane 1,4-diester-based compound represented by Chemical Formula 1, the cyclohexane 1,4-diester-based compound represented by Chemical Formula 2, and the cyclohexane 1,4-diester-based compound represented by Chemical Formula 3 are included at 0.5 to 70 wt %, 0.5 to 50 wt %, and 0.5 to 85 wt %, respectively, with respect to a total weight of the plasticizer composition, and wherein a weight average carbon number of R.sub.1 and R.sub.2 is in a range of 5.7 to 7.9: ##STR00005## wherein R.sub.1 is independently a butyl group or an isobutyl group, and R.sub.2 is a 2-ethylhexyl group.

2. The plasticizer composition of claim 1, wherein the cyclohexane 1,4-diester-based compound represented by Chemical Formula 1, the cyclohexane 1,4-diester-based compound represented by Chemical Formula 2, and the cyclohexane 1,4-diester-based compound represented by Chemical Formula 3 are included at 10 to 50 wt %, 0.5 to 50 wt %, and 35 to 80 wt %, respectively, with respect to a total weight of the plasticizer composition.

3. The plasticizer composition of claim 1, wherein a weight ratio between a sum of the cyclohexane 1,4-diester-based compound represented by Chemical Formula 2 and the cyclohexane 1,4-diester-based compound represented by Chemical Formula 3, and the cyclohexane 1,4-diester-based compound represented by Chemical Formula 1 is 95:5 to 30:70.

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

5. The resin composition of claim 4, wherein the resin includes one or more selected from the group consisting of ethylene vinyl acetate, polyethylene, polyketone, polypropylene, polyvinyl chloride, polystyrene, polyurethane, and a thermoplastic elastomer.

6. A material for producing an article comprising the resin composition of claim 4, wherein the article is one or more selected from the group consisting of electric wires, flooring materials, interior materials for automobiles, films, sheets, wallpaper sheets, and tubes.

Description

EXAMPLES

(1) Hereinafter, the present invention will be described in detail with reference to embodiments. However, the 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.

Example 1

(2) 1) Esterification

(3) 2,000 g of di(2-ethylhexyl) terephthalate (DEHTP) and 340 g (17 parts by weight with respect to 100 parts by weight of DEHTP) of n-butanol were added to a reaction vessel equipped with a stirrer, a condenser, and a decanter, and then trans-esterification was performed at a reaction temperature of 160° C. under a nitrogen atmosphere for 2 hours, thereby obtaining an ester-based plasticizer composition including dibutyl terephthalate (DBTP), butyl(2-ethylhexyl) terephthalate (BEHTP), and di(2-ethylhexyl) terephthalate (DEHTP) at 4 wt %, 35 wt %, and 61 wt %, respectively.

(4) The ester-based plasticizer composition was subjected to mixed distillation to remove butanol and 2-ethylhexyl alcohol, thereby finally preparing a mixed composition.

(5) 2) Hydrogenation

(6) 1,000 g of the composition produced through the esterification and 20 g of a ruthenium catalyst (N.E CHEMCAT) were added as raw materials to a 1.5 L high-pressure reaction vessel, and hydrogen was added under a pressure of 8 MPa to perform hydrogenation at 150° C. for 3 hours, and then the reaction was completed. After the reaction was completed, the catalyst was filtered, and a conventional purification process was performed, thereby preparing a hydrogenated mixed composition with a yield of 99%.

Example 2

(7) 1) Esterification

(8) 498.0 g of purified terephthalic acid (PTA), 585 g of 2-ethylhexyl alcohol (2-EH) (a molar ratio of PTA:2-EH=1.0:1.5), and 333 g of butyl alcohol (BA) (a molar ratio of PTA:BA=1.0:1.5) were added to a 3 L four-neck reaction vessel equipped with a cooler, a condenser, a decanter, a reflux pump, a temperature controller, a stirrer, and the like. 10 g (2.0 parts by weight with respect to 100 parts by weight of PTA) of a sulfonic acid-based catalyst (methane sulfonic acid (MSA)) was added thereto, and then the temperature of the reaction vessel was slowly raised up to about 150° C. The generation of produced water started at about 130° C., and esterification was performed at a final reaction temperature of about 220° C. under an atmospheric pressure condition for about 4.5 hours while continuously introducing nitrogen gas and was terminated when an acid value reached 6.0.

(9) After the reaction was completed, distillation extraction was performed under reduced pressure for 0.5 to 4 hours to remove unreacted raw materials. To reduce the level of the unreacted raw materials to a predetermined content level or less by removing the same, steam extraction was performed under reduced pressure using steam for 0.5 to 3 hours. A temperature of a reaction solution was cooled to about 90° C., and neutralization treatment was performed using an alkaline solution. In this case, washing may be optionally performed. Thereafter, the reaction solution was dehydrated to remove water. A filtering material was introduced into the dehydrated reaction solution, stirred for a predetermined period of time, and then filtered, thereby finally obtaining a mixed composition.

(10) 2) Hydrogenation

(11) A hydrogenated mixed composition was prepared by performing hydrogenation of the mixed composition in the same manner as in Example 1.

Example 3

(12) 516.0 g of 1,4-cyclohexanedicarboxylic acid (CHDA), 897 g of 2-ethylhexyl alcohol (2-EH) (a molar ratio of CHDA:2-EH=1.0:2.3), and 155 g of butyl alcohol (BA) (a molar ratio of CHDA:BA=1.0:0.7) were added to a 3 L four-neck reaction vessel equipped with a cooler, a condenser, a decanter, a reflux pump, a temperature controller, a stirrer, and the like. 10 g (2.0 parts by weight with respect to 100 parts by weight of CHDA) of a sulfonic acid-based catalyst (MSA) was added thereto, and then the temperature of the reaction vessel was slowly raised up to about 150° C. The generation of produced water started at about 130° C., and esterification was performed at a final reaction temperature of about 220° C. under an atmospheric pressure condition for about 4.5 hours while continuously introducing nitrogen gas and was terminated when an acid value reached 6.0.

(13) After the reaction was completed, distillation extraction was performed under reduced pressure for 0.5 to 4 hours to remove unreacted raw materials. To reduce the level of the unreacted raw materials to a predetermined content level or less by removing the same, steam extraction was performed under reduced pressure using steam for 0.5 to 3 hours. A temperature of a reaction solution was cooled to about 90° C., and neutralization treatment was performed using an alkaline solution. In this case, washing may be optionally performed. Thereafter, the reaction solution was dehydrated to remove water. A filtering material was introduced into the dehydrated reaction solution, stirred for a predetermined period of time, and then filtered, thereby finally obtaining a mixed composition.

Comparative Example 1

(14) A mixed composition of dibutyl cyclohexane 1,4-diester, butylbenzyl cyclohexane 1,4-diester, and dibenzyl cyclohexane 1,4-diester was prepared in the same manner as in Example 1 except that benzyl alcohol was used instead of n-butanol.

Comparative Example 2

(15) A mixed composition of diisononyl cyclohexane 1,4-diester, isononyl(2-ethylhexyl) cyclohexane 1,4-diester, and di(2-ethylhexyl) cyclohexane 1,4-diester was prepared in the same manner as in Example 1 except that isononanol was used instead of butanol.

Comparative Example 3

(16) A composition was prepared by using di(2-ethylhexyl) cyclehexane 1,4-diester (LG Chem) alone.

Comparative Example 4

(17) A composition was prepared by using dibutyl cyclohexane 1,4-diester (LG Chem) alone.

Comparative Example 5

(18) A mixed composition of dibutyl cyclohexane 1,2-diester, butyl(2-ethylhexyl) cyclohexane 1,2-diester, and di(2-ethylhexyl) cyclohexane 1,2-diester was prepared in the same manner as in Example 1 except that phthalic anhydride was used instead of terephthalic acid.

(19) Composition ratios of the compositions according to Examples 1 to 3 and Comparative Examples 1 to 5 are shown in Table 1 below.

(20) TABLE-US-00001 TABLE 1 Compound Compound Compound represented represented represented by Chemical by Chemical by Chemical Formula 2 Formula 1 Formula 3 Example 1  4 (1,4-DBCH) 35 (1,4-BEHCH)  61 (1,4-DEHCH) Example 2  16 (1,4-DBCH) 48 (1,4-BEHCH)  36 (1,4-DEHCH) Example 3  2 (1,4-DBCH) 25 (1,4-BEHCH)  73 (1,4-DEHCH) Comparative  3 (1,4-DBCH) 31 (1,4-BBeCH)  66 (1,4-DBeCH) Example 1 Comparative  6 (1,4-DINCH) 38 (1,4-INEHCH)  56 (1,4-DEHCH) Example 2 Comparative — — 100 (1,4-DEHCH) Example 3 Comparative 100 (1,4-DBCH) — — Example 4 Comparative  3 (1,2-DBCH) 34 (1,2-BEHCH)  63 (1,2-DEHCH) Example 5

Experimental Example 1

Specimen Preparation and Performance Evaluation

(21) The plasticizers according to Examples 1 to 3 and Comparative Examples 1 to 5 were used as experimental specimens. For specimen preparation, referring to ASTM D638, 40 parts by weight of each of the plasticizers and 3 parts by weight of a stabilizer (LOX 912 NP) were mixed with 100 parts by weight of PVC in a mixer, and the resulting mixture was then subjected to roll-milling at 170° C. for 4 minutes and pressed for 2.5 minutes (low pressure) and 2 minutes (high pressure) at 180° C. using a press, thereby manufacturing 1 T and 3 T sheets. Each specimen was subjected to tests for the following properties, the results of which are shown in Table 2 below.

(22) <Test Items>

(23) Measurement of Hardness

(24) According to ASTM D2240, Shore hardness (Shore “A”) was measured at 25° C.

(25) Measurement of Tensile Strength

(26) According to ASTM D638, each specimen was pulled at a cross head speed of 200 mm/min using a universal testing machine (UTM) (Manufacturer; Instron, Model No.; 4466), and a point at which the specimen was broken was then determined. The tensile strength was calculated as follows:
Tensile strength(kgf/cm.sup.2)=Load value(kgf)/Thickness(cm)×Width(cm)

(27) Measurement of Elongation Rate

(28) According to ASTM D638, each specimen was pulled at a cross head speed of 200 mm/min using a universal testing machine (UTM), and a point at which the specimen was broken was then determined. The elongation rate was calculated as follows:
Elongation rate (%)=Length after elongation/Initial length×100

(29) Measurement of Migration Loss

(30) A specimen having a thickness of 2 mm or more was obtained according to KSM-3156, ABS (natural color) was attached to both sides of the specimen, and a load of 1 kgf/cm.sup.2 was then applied thereto. The specimen was placed in a hot-air convection oven (80° C.) for 72 hours, then taken out of the oven, and cooled at room temperature for 4 hours. Thereafter, the ABS attached to both sides of the specimen were removed, weights of the specimen before and after being placed in the oven were measured, and thus a migration loss was calculated by the equation as follows.
Migration loss(%)={(Initial weight of specimen at room temperature−Weight of specimen after being placed in oven)/Initial weight of specimen at room temperature}×100

(31) Measurement of Volatile Loss

(32) The prepared specimen was processed at 100° C. for 72 hours, and then a weight of the specimen was measured.
Volatile loss(%)=Initial weight of specimen−(Weight of specimen after being processed at 100° C. for 72 hours)/Initial weight of specimen×100

(33) Stress Test

(34) A stress test was performed by maintaining a specimen in a bent state at room temperature for 24 hours, 72 hours, and 168 hours, and a degree of migration (degree of leakage) was then observed and expressed as a numerical value. In the test, values closer to 0 indicate excellent characteristics.

(35) TABLE-US-00002 TABLE 2 Tensile Migration Volatile Hardness strength Elongation rate loss loss (Shore “A”) (kgf/cm.sup.2) (%) (%) (%) Stress test Example 1 82.4 248.0 276.1 1.24 1.74 0.5 Example 2 81.9 243.3 277.1 0.50 2.84 0 Example 3 82.9 251.2 280.6 1.35 1.45 0.5 Comparative 85.2 245.0 270.5 1.77 1.54 1.5 Example 1 Comparative 86.0 229.4 275.2 1.53 0.90 2.0 Example 2 Comparative 85.7 228.6 273.3 1.73 1.70 2.0 Example 3 Comparative 75.6 188.6 256.3 5.60 12.50 1.0 Example 4 Comparative 80.8 223.0 254.9 1.15 2.28 0.5 Example 5

(36) Referring to Table 2, it can be confirmed that all of Examples 1 to 3 exhibited excellent properties compared to Comparative Examples 1 to 5 and had uniformly excellent properties.

(37) Specifically, it can be confirmed that Comparative Example 2 to which an alkyl group having a large carbon number was applied and Comparative Example 1 to which an aromatic ring was applied exhibited high hardness, and thus lower plasticization efficiency than those of Examples 1 to 3. Also, it can be confirmed that Comparative Examples 1 and 2 exhibited a significantly high degree of migration upon stress and relatively poor mechanical properties in terms of elongation rate and tensile strength.

(38) In addition, it can be confirmed that a few properties of Comparative Examples 3 and 4 to which a single compound was applied were particularly poor. In particular, Comparative Example 3 exhibited poor plasticization efficiency (high hardness) and a high degree of migration upon stress, and Comparative Example 4 exhibited significantly poor mechanical properties in terms of tensile strength and elongation rate and exhibited high migration loss and high volatile loss. However, it can be confirmed that Examples 1 to 3, in which weaknesses of Comparative Examples 3 and 4 have been complemented, exhibited an improvement in all of the above-mentioned properties, especially in tensile strength, elongation rate, and migration upon stress, compared to those of Comparative Examples 3 and 4.

(39) Additionally, it can be confirmed that Comparative Example 5, in which a hydrogenated substance derived from a terephthalate-based compound was used, exhibited relatively poor properties compared to Examples 1 to 3, not to mention the inability to avoid causing environmental problems in the preparation process.

(40) Accordingly, it was confirmed that, when a hydrogenated substance to which each of C4 and C8 alkyl groups was applied is used as a plasticizer, particularly, in consideration of a weight average carbon number thereof as in the case of Examples 1 to 3 according to the present invention, migration ability and plasticization efficiency can be improved while excellent mechanical properties in terms of tensile strength and elongation rate are being maintained, and, particularly, migration upon stress can be significantly improved.