Thermoplastic polyether ester elastomer comprising anhydrosugar alcohol derivative and method for preparing same

Abstract

The present invention relates to a thermoplastic polyether ester elastomer (TPEE) having a hard segment and a soft segment and a method for preparing the same and, more specifically, to a thermoplastic polyether ester elastomer and a method for preparing the same, wherein a unit derived from an anhydrosugar alcohol derivative with improved reactivity derived from biomass is contained in the soft segment, and thus through the adjustment of the content of the anhydrosugar alcohol derivative, elastic characteristics and physical characteristics (for example, hardness, etc.), which are important characteristics of an elastomer, can be favorably maintained, the melting point variously required in the molding process of a final product can be easily controlled, a problem of depletion of, especially, petroleum resources as finite resources, can be solved, and environmental friendliness can be improved.

Claims

1. A thermoplastic polyether ester elastomer consisting of a hard segment and a soft segment, wherein the hard segment comprises an aromatic dicarboxylic compound and an aliphatic diol component as polymerized units, the soft segment comprises an aromatic dicarboxylic compound and a glycol component as polymerized units, the glycol component comprises an anhydrosugar alcohol-alkylene glycol, the anhydrosugar alcohol-alkylene glycol is an adduct obtained by reacting an alkylene oxide with a hydroxyl group(s) at both terminals or one terminal of anhydrosugar alcohol, and the content of anhydrosugar alcohol-alkylene glycol in 100% by weight of the thermoplastic polyether ester elastomer is 3.3% by weight to 29% by weight.

2. The thermoplastic polyether ester elastomer according to claim 1, wherein the aromatic dicarboxylic compound is selected from the group consisting of terephthalic acid, isophthalic acid, 1,5-dinaphthalene dicarboxylic acid, 2,6-dinaphthalene dicarboxylic acid, dimethyl terephthalate, dimethyl isophthalate and combinations thereof.

3. The thermoplastic polyether ester elastomer according to claim 1, wherein the aliphatic diol component is a linear aliphatic diol having 2 to 8 carbon atoms or a cyclic aliphatic diol having 3 to 8 carbon atoms.

4. The thermoplastic polyether ester elastomer according to claim 1, wherein the aliphatic diol component is selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol and combinations thereof.

5. The thermoplastic polyether ester elastomer according to claim 1, wherein the anhydrosugar alcohol is selected from the group consisting of isosorbide, isomannide, isoidide and combinations thereof.

6. The thermoplastic polyether ester elastomer according to claim 1, wherein the alkylene oxide is a linear alkylene oxide having 2 to 8 carbon atoms and a branched alkylene oxide having 3 to 8 carbon atoms.

7. The thermoplastic polyether ester elastomer according to claim 1, wherein the anhydrosugar alcohol is isosorbide and the alkylene oxide is ethylene oxide, propylene oxide or a combination thereof.

8. The thermoplastic polyether ester elastomer according to claim 1, wherein the anhydrosugar alcohol-alkylene glycol is a compound represented by the following Formula 1: ##STR00004## In Formula 1, each of R.sup.1 and R.sup.2 independently represents a linear alkylene group having 2 to 8 carbon atoms or a branched alkylene group having 3 to 8 carbon atoms, each of m and n independently represents an integer of 0 to 15, and m+n represents an integer of 1 to 30.

9. The thermoplastic polyether ester elastomer according to claim 8, wherein each of R.sup.1 and R.sup.2 independently represents an ethylene group, a propylene group or an isopropylene group, each of m and n independently represents an integer of 1 to 14, and m+n represents an integer of 2 to 15.

10. The thermoplastic polyether ester elastomer according to claim 1, wherein the glycol component comprised as the polymerized unit in the soft segment further comprises a polyalkylene ether glycol.

11. The thermoplastic polyether ester elastomer according to claim 10, wherein the polyalkylene ether glycol is selected from the group consisting of polyethylene ether glycol, polypropylene ether glycol, polytetramethylene ether glycol and combinations thereof.

12. The thermoplastic polyether ester elastomer according to claim 1, wherein the content of the soft segment in 100% by weight of the thermoplastic polyether ester elastomer is 5% by weight to 75% by weight.

13. A molded article comprising the thermoplastic polyether ester elastomer according to claim 1.

14. A method for preparing a thermoplastic polyether ester elastomer comprising a polycondensation reaction of an aromatic dicarboxylic compound with a polyol, wherein the polyol comprises an aliphatic diol component and a glycol component, and the glycol component comprises an anhydrosugar alcohol-alkylene glycol, the anhydrosugar alcohol-alkylene glycol is an adduct obtained by reacting an alkylene oxide with a hydroxyl group(s) at both terminals or one terminal of anhydrosugar alcohol, and the content of anhydrosugar alcohol-alkylene glycol in 100% by weight of the thermoplastic polyether ester elastomer is 3.3% by weight to 29% by weight.

Description

EXAMPLES

Preparation of an Anhydrosugar Alcohol-Alkylene Glycol

Preparation Example A1: Preparation of Isosorbide-Ethylene Glycol (5-Mole Ethylene Oxide Adduct of Isosorbide)

(1) 73.1 g (0.5 mol) of isosorbide, 110 g (2.5 mol) of ethylene oxide and 0.2 g of sodium hydroxide as a catalyst were placed in a pressurizable reactor equipped with a column having nitrogen gas pipes and a cooling device, a stirrer, a thermometer and a heater, and were gradually warmed up. The mixture was reacted while maintaining the temperature at 120 to 160° C. for 2 to 4 hours to obtain isosorbide-ethylene glycol (5-mole ethylene oxide adduct of isosorbide)—which is a form in which the hydrogen of the hydroxyl groups at both terminals of the isosorbide are substituted with hydroxyethyl groups.

Preparation Example A2: Preparation of Isosorbide-Ethylene Glycol (10-Mole Ethylene Oxide Adduct of Isosorbide)

(2) 73.1 g (0.5 mol) of isosorbide, 220 g (5 mol) of ethylene oxide and 0.2 g of sodium hydroxide as a catalyst were placed in a pressurizable reactor equipped with a column having nitrogen gas pipes and a cooling device, a stirrer, a thermometer and a heater, and were gradually warmed up. The mixture was reacted while maintaining the temperature at 120 to 160° C. for 2 to 4 hours to obtain isosorbide-ethylene glycol (10-mole ethylene oxide adduct of isosorbide)—which is a form in which the hydrogen of the hydroxyl groups at both terminals of the isosorbide are substituted with hydroxyethyl groups.

Preparation Example B1: Preparation of Isosorbide-Propylene Glycol (5-Mole Propylene Oxide Adduct of Isosorbide)

(3) 73.1 g (0.5 mol) of isosorbide, 145 g (2.5 mol) of propylene oxide and 0.2 g of sodium hydroxide as a catalyst were placed in a pressurizable reactor equipped with a column having nitrogen gas pipes and a cooling device, a stirrer, a thermometer and a heater, and were gradually warmed up. The mixture was reacted while maintaining the temperature at 120 to 160° C. for 2 to 4 hours to obtain isosorbide-propylene glycol (5-mole propylene oxide adduct of isosorbide)—which is a form in which the hydrogen of the hydroxyl groups at both terminals of the isosorbide are substituted with hydroxypropyl groups.

Preparation Example B2: Preparation of Isosorbide-Propylene Glycol (8-Mole Propylene Oxide Adduct of Isosorbide)

(4) 73.1 g (0.5 mol) of isosorbide, 232 g (4 mol) of propylene oxide and 0.2 g of sodium hydroxide as a catalyst were placed in a pressurizable reactor equipped with a column having nitrogen gas pipes and a cooling device, a stirrer, a thermometer and a heater, and were gradually warmed up. The mixture was reacted while maintaining the temperature at 120 to 160° C. for 2 to 4 hours to obtain isosorbide-propylene glycol (8-mole propylene oxide adduct of isosorbide)—which is a form in which the hydrogen of the hydroxyl groups at both terminals of the isosorbide are substituted with hydroxypropyl groups.

Preparation of a Thermoplastic Polyether Ester Elastomer

Examples 1 to 10

(5) The reactants having the composition shown in the following Table 1 were placed in a 15 L melt condensation reactor, and 700 ppm of a titanium-based catalyst based on the acid component (dimethyl terephthalate, DMT) was added thereto. Then, the alcohol produced as a by-product was removed while raising the temperature to 210° C., 300 ppm of a titanium-based catalyst was added, and the pressure of the reaction system was gradually reduced to 1 mmHg while raising the temperature to 245° C. to prepare thermoplastic polyether ester elastomers according to Examples 1 to 10.

(6) TABLE-US-00001 TABLE 1 Example 1 2 3 4 5 Aromatic dicarboxylic compound 35.3 35.8 37.2 32.3 37.2 (DMT, wt %) Polyol HS BDO (wt %) 16.8 19.2 20.7 16.9 20.7 SS PTMEG Molecular 2,000 2,000 2,000 2,000 2,000 weight Content 36.1 37.5 38.8 37.9 38.8 (wt %) ISB-EO Molecular 365.47 365.47 5 mole weight Content 11.8 7.5 (wt %) ISB-EO Molecular 578.05 10 weight mole Content 3.3 (wt %) ISB-PO Molecular 5 mole weight Content (wt %) ISB-PO Molecular 618.52 618.52 8 mole weight Content 12.9 3.3 (wt %) Properties of eco- 4.6 2.9 0.8 3.1 0.8 elastomer friendly monomer (wt %) Intrinsic 1.157 1.178 1.152 1.259 1.264 viscosity (IV) Melting 162.69 183.54 185.95 172.53 191.98 point (° C.) Hardness 36 38 37 36 40 Example 6 7 8 9 10 Aromatic dicarboxylic compound 39.0 36.0 37.0 35.4 36.3 (DMT, wt %) Polyol HS BDO (wt %) 16.3 19.0 18.0 19.2 18.6 SS PTMEG Molecular 2,000 2,000 2,000 2,000 2,000 weight Content 16.0 32.0 16.0 39.1 31.8 (wt %) ISB-EO Molecular 365.47 5 mole weight Content 28.7 (wt %) ISB-EO Molecular 578.05 578.05 10 weight mole Content 13.0 29.0 (wt %) ISB-PO Molecular 432.37 432.37 5 mole weight Content 6.3 13.3 (wt %) ISB-PO Molecular 8 mole weight Content (wt %) Properties of eco- 13.8 4.0 8.7 2.7 5.3 elastomer friendly monomer (wt %) Intrinsic 1.191 1.365 1.161 1.052 1.170 viscosity (IV) Melting 132 175 151 177 183 point (° C.) Hardness 35 41 36 40 37 HS: hard segment SS: soft segment BDO: 1,4-butanediol PTMEG: polytetramethylene ether glycol ISB-EO 5 mole: isosorbide-ethylene glycol (5-mole ethylene oxide adduct of isosorbide) ISB-EO 10 mole: isosorbide-ethylene glycol (10-mole ethylene oxide adduct of isosorbide) ISB-PO 5 mole: isosorbide-propylene glycol (5-mole propylene oxide adduct of isosorbide) ISB-PO 8 mole: isosorbide-propylene glycol (8-mole propylene oxide adduct of isosorbide)

Comparative Examples 1 to 4

(7) The reactants having the composition shown in the following Table 2 were placed in a 15 L melt condensation reactor, and 700 ppm of a titanium-based catalyst based on the acid component (dimethyl terephthalate, DMT) was added thereto. Then, the alcohol produced as a by-product was removed while raising the temperature to 210° C., 300 ppm of a titanium-based catalyst was added, and the pressure of the reaction system was gradually reduced to 1 mmHg while raising the temperature to 245° C. to prepare thermoplastic polyether ester elastomers according to Comparative Examples 1 to 4.

(8) TABLE-US-00002 TABLE 2 Comparative Example 1 2 3 4 Aromatic dicarboxylic compound 34.5 29.8 27.6 38.0 (DMT, wt %) Polyol HS BDO (wt %) 19.3 20.7 16.4 17.3 SS PTMEG Molecular 2,000 2,000 2,000 2,000 weight Content (wt %) 46.2 49.5 56.0 0 ISB-EO Molecular 5 mole weight Content (wt %) ISB-EO Molecular 10 mole weight Content (wt %) ISB-PO Molecular 5 mole weight Content (wt %) ISB-PO Molecular 618.52 8 mole weight Content (wt %) 44.7 Properties of elastomer eco-friendly 0 0 0 18.3 monomer (wt %) Intrinsic 1.322 1.289 1.255 0.425 viscosity (IV) Melting point 198.21 190 178 126 (° C.) Hardness 40 35 30 35 HS: hard segment SS: soft segment BDO: 1,4-butanediol PTMEG: polytetramethylene ether glycol ISB-EO 5 mole: isosorbide-ethylene glycol (5-mole ethylene oxide adduct of isosorbide) ISB-EO 10 mole: isosorbide-ethylene glycol (10-mole ethylene oxide adduct of isosorbide) ISB-PO 5 mole: isosorbide-propylene glycol (5-mole propylene oxide adduct of isosorbide) ISB-PO 8 mole: isosorbide-propylene glycol (8-mole propylene oxide adduct of isosorbide)

(9) As can be seen from the results of Tables 1 and 2 above, the thermoplastic polyether ester elastomers of Examples 1 to 10 according to the present invention (TPEE containing an anhydrosugar alcohol-alkylene glycol within the range of 1 to 30 wt %) show that as the content of the anhydrosugar alcohol-alkylene glycol (isosorbide-alkylene glycol) increases, physical properties such as hardness remain at the same level, while improving the environmental friendliness and easily controlling the melting point of the elastomer.

(10) That is, in the case of Examples 1 to 10 according to the present invention, the viscosity, elastic properties and physical properties (for example, hardness, etc.), which are important properties of the elastomer, were maintained at the same level, the environmental friendliness was improved, and melting points variously required in the molding process of the final product were easily controlled. However, in the case of Comparative Examples 1 to 3 (TPEE which does not comprise an anhydrosugar alcohol-alkylene glycol) not according to the present invention, the physical properties such as hardness, etc. were remarkably deteriorated by variously controlling the melting point of the elastomer. And in the case of Comparative Example 4 not according to the present invention (TPEE comprising an anhydrosugar alcohol-alkylene glycol in a range exceeding 30 wt %), it can be seen that the intrinsic viscosity was remarkably poor (that is, the degree of polymerization of TPEE was significantly reduced) by controlling the melting point of the elastomer.

(11) The properties of the thermoplastic elastomers prepared in the above Examples and Comparative Examples were measured as follows.

(12) (1) Environmental (eco-) friendliness (wt %): The weight % of an anhydrosugar alcohol (isosorbide) as an environmentally friendly monomer was measured based on the total weight of the polyether ester elastomer.

(13) (2) Intrinsic viscosity (IV): A polyether ester elastomer was dissolved in phenol/tetrachloroethane (weight ratio 50/50) to prepare a 0.5 wt % solution, and then intrinsic viscosity was measured at 35° C. with a Ubbelohde viscometer.

(14) (3) Melting point: Using a thermal differential scanning calorimeter (DSC), the temperature was raised at a heating rate of 10° C. per minute and cooled down. Then, the temperature was raised again, and the melting point was measured.

(15) (4) Hardness: Hardness was measured with Handpi's Showa D durometer.