Plasticizer composition, resin composition and methods of preparing the same

Abstract

The present invention relates to a plasticizer composition, a resin composition and methods of preparing the same, and provides a plasticizer which is environmentally friendly so as to be suitable for use, exhibits excellent transparency and adhesiveness, and can be improved in basic properties such as tensile strength, an elongation rate, hardness and the like when used as a plasticizer for a resin composition, and a resin composition including the same.

Claims

1. A plasticizer composition for a polyvinyl chloride comprising: a cyclohexane 1,4-diester-based material; and a dibenzoate-based material, wherein the plasticizer composition is comprised in an amount of 40 to 130 parts by weight relative to 100 parts by weight of the polyvinyl chloride, wherein a weight ratio of the cyclohexane 1,4-diester-based material to the dibenzoate-based material included in the plasticizer composition is 90:10 to 50:50, wherein the cyclohexane 1,4-diester-based material is a single compound or a mixture of two or more selected from the group consisting of butyl(2-ethylhexyl) cyclohexane-1,4- diester (1,4-BEHCH), (2-ethylhexyl) isononyl cyclohexane-1,4-diester (1,4-EHINCH), butyl isononyl cyclohexane-1,4-diester (1,4-BINCH), dibutyl cyclohexane-1,4-diester (1,4-DBCH), diisononyl cyclohexane-1,4-diester (1,4-DINCH) and di(2-ethylhexyl) cyclohexane-1,4-diester (1,4-DEHCH), and wherein the dibenzoate-based material is one or more selected from the group consisting of diethylene glycol dibenzoate (DEGDB), dipropylene glycol dibenzoate (DPGDB) and triethylene glycol dibenzoate (TEGDB).

2. A polyvinyl chloride resin composition comprising: the plasticizer composition according to claim 1.

Description

BEST MODE

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.

Preparation Example 1: Preparation of di(2-ethylhexyl) cyclohexane-1,4-diester

(2) 1) Esterification

(3) 498.0 g of purified terephthalic acid (PTA), 1,170 g of 2-ethylhexyl alcohol (2-EH; a molar ratio of PTA:INA is (1.0):(3.0)) and 1.54 g of a titanium-based catalyst (tetra isopropyl titanate (TIPT); 0.31 parts by weight with respect to 100 parts by weight of PTA) as a catalyst were put into a 4-neck 3 L reaction vessel equipped with a cooler, a condenser, a decanter, a reflux pump, a temperature controller, an agitator and the like, and then a temperature was slowly increased to about 170 C. At about 170 C., water was generated, and esterification was performed for about 4.5 hours while a nitrogen gas was continuously added at a reaction temperature of about 220 C. under atmospheric pressure, and then terminated when an acid value reached 0.01.

(4) After the reaction, distillation extraction was performed for 0.5 to 4 hours under reduced pressure to remove unreacted components. To remove unreacted components at a predetermined content or less, steam extraction was performed using steam for 0.5 to 3 hours under reduced pressure, and neutralization was performed using an alkali solution after a reaction solution was cooled to about 90 C. Additionally, washing could be performed, and then the reaction solution was dehydrated to remove moisture. Filter media were put into the dehydrated reaction solution, stirred for a predetermined time and then filtered, thereby finally obtaining 1,326.7 g of di(2-ethylhexyl)terephthalate (DEHTP) (yield: 99.0%).

(5) 2) Hydrogenation

(6) 1,000 g of the composition produced by the esterification and 20 g of a ruthenium catalyst (N.E CHEMCAT) were added as components 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, the catalyst was filtered and subjected to a conventional purification process, thereby preparing a hydrogenated material with a yield of 99%.

Preparation Example 2: Preparation of diisononyl cyclohexane-1,4-diester

(7) A hydrogenated material was obtained through esterification and hydrogenation in the same manner as in Preparation Example 1 except that isononyl alcohol was used instead of 2-ethylhexyl alcohol upon esterification.

Preparation Example 3: Preparation of di(2-propylheptyl) cyclohexane-1,4-diester

(8) A hydrogenated material was obtained through esterification and hydrogenation in the same manner as in Preparation Example 1 except that 2-propylheptyl alcohol was used instead of 2-ethylhexyl alcohol upon esterification.

Preparation Example 4: Preparation of Hydrogenated Mixture of DEHTP/BEHTP/DBTP

(9) 1) Esterification

(10) 2,000 g of dioctyl terephthalate (DOTP; GL300 commercially available from LG Chem) and 340 g of n-butanol (17 parts by weight on the basis of 100 parts by weight of DOTP) were put into a reaction vessel equipped with an agitator, a condenser and a decanter, and subjected to trans-esterification for 2 hours at a reaction temperature of 160 C. under a nitrogen atmosphere, thereby obtaining an ester-based plasticizer composition including dibutyl terephthalate (DBTP), butyl isononyl terephthalate (BINTP) and diisononyl terephthalate (DINTP) at 4.0 wt %, 35.0 wt % and 61.0 wt %, respectively.

(11) The reaction product was mixed and distilled to remove butanol and 2-ethylhexyl alcohol, thereby finally preparing a mixed composition.

(12) 2) Hydrogenation

(13) 1,000 g of the composition produced by the esterification and 20 g of a ruthenium catalyst (N.E CHEMCAT) were added as components 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, the catalyst was filtered and subjected to a conventional purification process, thereby preparing a hydrogenated mixed composition with a yield of 99%.

Preparation Example 5: Preparation of diethylene glycol dibenzoate (DEGDB)

(14) 1,221 g of purified benzoic acid (BA), 530.5 g of diethylene glycol (DEG; a molar ratio of BA:DEG is (2.0):(1.0)), 2.0 g of a titanium-based catalyst (tetra isopropyl titanate (TIPT)) as a catalyst and a small amount of xylene were put into a 4-neck 2 L reaction vessel equipped with a cooler, a condenser, a decanter, a reflux pump, a temperature controller, an agitator and the like, and then a temperature was slowly increased to about 170 C. When water was generated at approximately 170 C., the amount of xylene was adjusted to facilitate the removal of the generated water, and the reaction was terminated when the content of a monobenzoate as an intermediate among the reactants was 5% or less. Afterward, 1,530 g of the final product DEGDB (yield: 98%) was obtained by a purification method similar to that described in Preparation Example 1.

Preparation Example 6: Preparation of dipropylene glycol dibenzoate (DPGDB)

(15) DPGDB was obtained in the same manner as in Preparation Example 5 except that dipropylene glycol was used instead of diethylene glycol.

Preparation Example 7: Preparation of triethylene glycol dibenzoate (TEGDB)

(16) TEGDB was obtained in the same manner as in Preparation Example 5 except that triethylene glycol was used instead of diethylene glycol.

Examples 1 to 8 and Comparative Examples 1 to 7

(17) Examples and Comparative Examples were prepared using the materials prepared in Preparation Examples 1 to 7 as shown in the following Table 1.

(18) TABLE-US-00001 TABLE 1 Hydrogenated TP- Benzoate- Mixing based material based material ratio Example 1 1,4-DEHCH DEGDB 7:3 Example 2 1,4-DEHCH DEGDB 9:1 Example 3 1,4-DINCH DEGDB 8:2 Example 4 1,4-DINCH DPGDB 6:4 Example 5 1,4-DPHCH DEGDB 8:2 Example 6 1,4-DPHCH DEGDB 6:4 Example 7 (Preparation DEGDB 7:3 Example 4) Example 8 (Preparation TEGDB 5:5 Example 4) Comparative Example 1 1,4-DEHCH Comparative Example 2 1,2-DEHCH Comparative Example 3 DEGDB Comparative Example 4 1,4-DEHCH DEGDB 1:9 Comparative Example 5 1,4-DEHCH DEGDB 3:7 Comparative Example 6 1,2-DEHCH DEGDB 7:3 Comparative Example 7 1,3-DEHCH DEGDB 7:3

Experimental Example 1: Preparation of Samples and Performance Evaluation

(19) The plasticizers according to Examples 1 to 8 and Comparative Examples 1 to 7 were used as experimental samples. For sample preparation, referring to ASTM D638, 40 parts by weight of each of the plasticizers and 3 parts by weight of a stabilizer (BZ-153T commercially available from Songwon) were mixed with 100 parts by weight of PVC (LS100S commercially available from LG Chem) in a mixer, and the resulting mixture was 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 sample was subjected to a test for properties, results of which are shown in the following Table 2 below.

(20) <Test Items>

(21) Hardness

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

(23) Tensile Strength

(24) According to ASTM D638, each specimen was pulled at a cross head speed of 200 mm/min (1 T) using a tester, U.T.M, (Manufacturer; Instron, Model No.; 4466), and 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)

(25) Measurement of Elongation Rate

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

(27) Measurement of Migration Loss

(28) An experimental specimen having a thickness of 2 mm or more was obtained according to KSM-3156, glass plates was 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 forced convection oven (80 C.) for 72 hours, then taken out of the oven, and cooled at room temperature for 4 hours. Then, after the glass plates attached to both sides of the specimen were removed, a weight before and after the glass plate and the specimen plate were kept in the oven was measured and thus 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

(29) Measurement of Volatile Loss

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

(31) Measurement of Absorption Rate

(32) An absorption rate was evaluated by measuring the time taken to stabilize the torque of a mixer in which a resin and an ester compound are mixed together using a planetary mixer (Brabender, P600) under conditions of 77 C. and 60 rpm.

(33) TABLE-US-00002 TABLE 2 Hard- Elon- Migra- Absorp- ness Tensile gation tion Volatile tion (Shore strength rate loss loss rate A) (kg/cm.sup.2) (%) (%) (%) (m:s) Example 1 81.5 229.1 286.1 3.23 3.88 3:25 Example 2 81.7 231.0 294.6 2.68 3.36 3:45 Example 3 82.5 234.7 304.5 2.56 3.66 4:10 Example 4 81.0 235.8 310.7 2.14 3.70 4:30 Example 5 83.0 240.5 314.0 2.01 3.40 4:30 Example 6 80.6 236.8 306.1 1.67 3.50 3:35 Example 7 79.3 229.7 314.2 3.40 4.82 3:00 Example 8 79.2 235.6 311.5 2.65 4.50 3:25 Comparative 85.7 210.6 293.3 4.57 5.70 5:40 Example 1 Comparative 85.0 204.0 285.0 4.32 6.55 5:30 Example 2 Comparative 76.5 182.3 260.4 3.51 7.02 0:30 Example 3 Comparative 77.1 208.5 261.2 4.40 6.20 1:40 Example 4 Comparative 78.2 215.9 270.7 4.10 5.88 2:25 Example 5 Comparative 81.3 227.1 296.5 4.59 5.23 4:00 Example 6 Comparative 81.7 215.5 300.4 4.93 5.10 4:10 Example 7

(34) Referring to Table 2, it was confirmed that Comparative Examples 1 to 7 exhibited significantly inferior tensile strength, migration loss and volatile loss to those of Examples 1 to 8.

(35) Specifically, it can be seen that Comparative Examples 1 and 2, in which a dibenzoate-based material was not added, exhibited low tensile strength and high hardness, and thus poor plasticization efficiency and significantly high migration loss and volatile loss were exhibited. In addition, it can be seen that Comparative Example 3, in which a cyclohexane 1,4-diester-based material was not added, exhibited a significant decrease in tensile strength and a significantly low elongation rate, and is difficult to function alone as a plasticizer in consideration of the absorption rate or volatile loss. On the other hand, it can be seen that Examples 1 to 8, in which a dibenzoate-based material and a cyclohexane 1,4-diester-based material were used in combination, exhibited a significant increase in tensile strength and an elongation rate due to in a synergistic effect thereof and also exhibited a significant decrease in properties such as migration loss and volatile loss due to a synergistic effect thereof.

(36) In addition, in consideration of a ratio range of two materials, it can be seen that Comparative Examples 4 and 5, in which a dibenzoate-based material was included at 70 wt % or more, were not improved in tensile strength, volatile loss and migration loss as in the case of not adding a dibenzoate-based material, but Examples 1 to 8, in which a dibenzoate-based material was included at less than 70 wt %, were improved in properties.

(37) Further, as shown in Comparative Examples 6 and 7, when a diester is bound not at 1,4 positions but at 1,2 positions or 1,3 positions, it can be seen that most properties such as an elongation rate, tensile strength, migration loss, volatile loss and the like were not improved. Specifically, in Example 1, it can be confirmed that an elongation rate was improved (increased) by about 5%, migration loss was improved (decreased) by 40% or more, and volatile loss was also significantly improved (decreased) compared to Comparative Examples 6 and 7 in which the same mixing ratio as that in Example 1 was applied.

(38) Through the above results, it can be confirmed that properties of the plasticizer may be significantly improved by applying characteristics of mixing a cyclohexane 1,4-diester-based material and a dibenzoate-based material, a weight ratio upon the mixing of two materials and a binding position of a diester group bound to cyclohexane.