POLYESTER COPOLYMER COMPRISING RECYCLED MONOMERS

Abstract

The present disclosure relates to polyester copolymer comprising recycled monomers, a method for preparation thereof, and an article comprising the same, and can provide polyester copolymer having excellent properties while using recycled monomers.

Claims

1. Polyester copolymer copolymerized from recycled bis-2-hydroxyethylterephthalate, dicarboxylic acid or a derivative thereof, and diol comprising ethylene glycol and comonomers, having a structure in which a part derived from the bis-2-hydroxyethylterephthalate, an acid part derived from the dicarboxylic acid or derivative thereof, and a diol part derived from the diol are repeated, wherein the polyester copolymer comprises 10 to 80 wt % of the part derived from recycled bis-2-hydroxyethylterephthalate, and the mole ratio of the diol and the dicarboxylic acid or derivative thereof is 0.2:1 to 1.35:1.

2. The polyester copolymer according to claim 1, wherein the comonomer is cyclohexanedimethanol or isosorbide.

3. The polyester copolymer according to claim 1, wherein the mole ratio of the comonomers and ethyleneglycol is 0.1:1 to 20:1.

4. The polyester copolymer according to claim 1, wherein the mole ratio of the diol and the dicarboxylic acid or derivative thereof is 0.2:1 to 1.35:1.

5. The polyester copolymer according to claim 1, wherein the intrinsic viscosity of the polyester copolymer is 0.50 to 1.0 dl/g.

6. The polyester copolymer according to claim 1, wherein by-products of the polyester copolymer is 2.0 wt % or less.

7. The polyester copolymer according to claim 1, wherein the Haze of the polyester copolymer is 4 or less.

8. The polyester copolymer according to claim 1, wherein (Hunter L color value)-(Hunter b color value) of the polyester copolymer to a specimen with a thickness of 6 mm is 85 or more.

9. A method for preparing the polyester copolymer according to claim 1, comprising steps of: subjecting recycled bis-2-hydroxyethylterephthalate, dicarboxylic acid or a derivative thereof, and diol comprising ethylene glycol and comonomers to an esterification reaction (step 1); and subjecting the product of step 1 to a polycondensation reaction (step 2).

10. The method according to claim 9, wherein the esterification reaction is conducted in the presence of an esterification catalyst comprising zinc acetate, zinc acetate dihydrate, zinc chloride, zinc sulfate, zinc sulfide, zinc carbonate, zinc citrate, zinc gluconate, or a mixture thereof.

11. The method according to claim 9, wherein the polycondensation reaction is conducted in the presence of a polycondensation catalyst comprising a titanium-based compound, a germanium-based compound, an antimony-based compound, an aluminum-based compound, a tin-based compound, or a mixture thereof.

12. An article comprising the polyester copolymer according to claim 1.

13. A method for preparing the polyester copolymer according to claim 2, comprising steps of: subjecting recycled bis-2-hydroxyethylterephthalate, dicarboxylic acid or a derivative thereof, and diol comprising ethylene glycol and comonomers to an esterification reaction (step 1); and subjecting the product of step 1 to a polycondensation reaction (step 2).

14. A method for preparing the polyester copolymer according to claim 3, comprising steps of: subjecting recycled bis-2-hydroxyethylterephthalate, dicarboxylic acid or a derivative thereof, and diol comprising ethylene glycol and comonomers to an esterification reaction (step 1); and subjecting the product of step 1 to a polycondensation reaction (step 2).

15. A method for preparing the polyester copolymer according to claim 4, comprising steps of: subjecting recycled bis-2-hydroxyethylterephthalate, dicarboxylic acid or a derivative thereof, and diol comprising ethylene glycol and comonomers to an esterification reaction (step 1); and subjecting the product of step 1 to a polycondensation reaction (step 2).

16. A method for preparing the polyester copolymer according to claim 5, comprising steps of: subjecting recycled bis-2-hydroxyethylterephthalate, dicarboxylic acid or a derivative thereof, and diol comprising ethylene glycol and comonomers to an esterification reaction (step 1); and subjecting the product of step 1 to a polycondensation reaction (step 2).

17. An article comprising the polyester copolymer according to claim 5.

18. An article comprising the polyester copolymer according to claim 6.

19. An article comprising the polyester copolymer according to claim 7.

20. An article comprising the polyester copolymer according to claim 8.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0042] Hereinafter, preferable examples will be presented to assist in understanding of the invention. However, these examples are only presented for better understanding of the invention, and the scope of the invention is not limited thereby.

Example 1

[0043] Into a reactor with a capacity of 10 L to which a column, and a condenser that can be cooled by water are connected, recycled bis-2-hydroxyethylterephthalate (1269.7 g; hereinafter, referred to as ‘r-BHET’), TPA (terephthalic acid; 2361.8 g), EG (ethylene glycol; 673.5 g), CHDM (1,4-cyclohexanedimethanol; 221.5 g), and ISB(isosorbide; 98.2 g) were introduced, and GeO.sub.2 (1.0 g) was introduced as a catalyst, phosphoric acid (1.46 g) as a stabilizer, and cobalt acetate (0.7 g) as a coloring agent.

[0044] Subsequently, nitrogen was introduced into the reactor to pressurize the reactor such that the pressure of the reactor is higher than atmospheric pressure by 1.0 kgf/cm.sup.2 (absolute pressure: 1495.6 mmHg). And, the temperature of the reactor was raised to 220° C. for 90 minutes, maintained at 220° C. for 2 hours, and then, raised to 260° C. for 2 hours. And then, the mixture in the reactor was observed with unaided eyes, and until the mixture became transparent, while maintaining the temperature of the reactor at 260° C., an esterification reaction was progressed. During this process, by-products were discharged through the column and condenser. After the esterification reaction was completed, nitrogen in the pressurized reactor was discharged outside to lower the pressure of the reactor to atmospheric pressure, and then, the mixture in the reactor was transferred to a reactor with a capacity of 7 L in which a vacuum reaction can be progressed.

[0045] And, the pressure of the reactor was lowered from atmospheric pressure to 5 Torr (absolute pressure: 5 mmHg) for 30 minutes, and simultaneously, the temperature of the reactor was raised to 280° C. for 1 hour, and while maintaining the pressure of the reactor at 1 Torr (absolute pressure: 1 mmHg) or less, a polycondensation reaction was conducted. At the beginning of the polycondensation reaction, a stirring speed is set rapid, but as the polycondensation reaction progressed, in case stirring force decreases due to increase in the viscosity of the reactant or the temperature of the reactant increases beyond the established temperature, the stirring speed can be appropriately controlled. The polycondensation reaction was progressed until the intrinsic viscosity (IV) of the mixture (molten material) in the reactor became 0.55 dl/g. If the intrinsic viscosity of the mixture in the reactor reached a desired level, the mixture was discharged outside the reactor to make strand, which was solidified with a coolant, and then, granulated such that the average weight became 12 to 14 mg.

[0046] The particles were left at 150° C. for 1 hour to crystallize, and then, introduced into a solid phase polymerization reactor with a capacity of 20 L. And then, into the reactor, nitrogen was flowed at a speed of 50 L/min. Wherein, the temperature of the reactor was raised from room temperature to 140° C. at a speed of 40° C./hour, maintained at 140° C. for 3 hours, and then, raised to 200° C. at a speed of 40° C./hour, and maintained at 200° C. The solid phase polymerization reaction was progressed until the intrinsic viscosity of the particles in the reactor became 0.70 dl/g, thus preparing polyester copolymer.

Example 2

[0047] Into a reactor with a capacity of 10 L to which a column, and a condenser that can be cooled by water are connected, r-BHET (3461.1 g), TPA (969.4 g), EG (12.1 g), CHDM (140.2 g), ISB (113.7 g) were introduced, and GeO.sub.2 (1.0 g) was introduced as a catalyst, phosphoric acid (1.46 g) as a stabilizer, and cobalt acetate (0.7 g) as a coloring agent.

[0048] Subsequently, nitrogen was introduced into the reactor to pressurize the reactor such that the pressure of the reactor is higher than atmospheric pressure by 1.0 kgf/cm.sup.2 (absolute pressure: 1495.6 mmHg). And, the temperature of the reactor was raised to 220° C. for 90 minutes, maintained at 220° C. for 2 hours, and then, raised to 260° C. for 2 hours. And then, the mixture in the reactor was observed with unaided eyes, and until the mixture became transparent, while maintaining the temperature of the reactor at 260° C., an esterification reaction was progressed. During this process, by-products were discharged through the column and condenser. After the esterification reaction was completed, nitrogen in the pressurized reactor was discharged outside to lower the pressure of the reactor to atmospheric pressure, and then, the mixture in the reactor was transferred to a reactor with a capacity of 7 L in which a vacuum reaction can be conducted.

[0049] And, the pressure of the reactor was lowered from atmospheric pressure to 5 Torr (absolute pressure: 5 mmHg) for 30 minutes, and simultaneously, the temperature of the reactor was raised to 280° C. for 1 hour, and while maintaining the pressure of the reactor at 1 Torr (absolute pressure: 1 mmHg) or less, a polycondensation reaction was conducted. At the beginning of the polycondensation reaction, a stirring speed is set rapid, but as the polycondensation reaction progressed, in case stirring force decreases due to increase in the viscosity of the reactant or the temperature of the reactant increases beyond the established temperature, the stirring speed can be appropriately controlled. The polycondensation reaction was progressed until the intrinsic viscosity (IV) of the mixture (molten material) in the reactor became 0.60 dl/g. If the intrinsic viscosity of the mixture in the reactor reached a desired level, the mixture was discharged outside the reactor to make strand, which was solidified with a coolant, and then, granulated such that the average weight became 12 to 14 mg.

[0050] The particles were left at 150° C. for 1 hour to crystallize, and then, introduced into a solid phase polymerization reactor with a capacity of 20 L. And then, into the reactor, nitrogen was flowed at a speed of 50 L/min. Wherein, the temperature of the reactor was raised from room temperature to 140° C. at a speed of 40° C./hour, maintained at 140° C. for 3 hours, and then, raised to 200° C. at a speed of 40° C./hour, and maintained at 200° C. The solid phase polymerization reaction was progressed until the intrinsic viscosity of the particles in the reactor became 0.95 dl/g, thus preparing polyester copolymer.

Example 3

[0051] Into a reactor with a capacity of 10 L to which a column, and a condenser that can be cooled by water are connected, r-BHET (4019.2 g), TPA (875.6 g), EG (39.2 g), CHDM (121.5 g) were introduced, and TiO.sub.2 (0.5 g) was introduced as a catalyst, phosphoric acid (1.46 g) as a stabilizer, Polysynthren Blue RLS(Clarient corporation, 0.016 g) as blue toner, and Solvaperm Red BB (Clarient corporation, 0.004 g) as red toner.

[0052] Subsequently, nitrogen was introduced into the reactor to pressurize the reactor such that the pressure of the reactor is higher than atmospheric pressure by 0.5 kgf/cm.sup.2 (absolute pressure: 1127.8 mmHg). And, the temperature of the reactor was raised to 220° C. for 90 minutes, maintained at 220° C. for 2 hours, and then, raised to 260° C. for 2 hours. And then, the mixture in the reactor was observed with unaided eyes, and until the mixture became transparent, while maintaining the temperature of the reactor at 260° C., an esterification reaction was progressed. During this process, by-products were discharged through the column and condenser. After the esterification reaction was completed, nitrogen in the pressurized reactor was discharged outside to lower the pressure of the reactor to atmospheric pressure, and then, the mixture in the reactor was transferred to a reactor with a capacity of 7 L in which a vacuum reaction can be progressed.

[0053] And, the pressure of the reactor was lowered from atmospheric pressure to 5 Torr (absolute pressure: 5 mmHg) for 30 minutes, and simultaneously, the temperature of the reactor was raised to 275° C. for 1 hour, and while maintaining the pressure of the reactor at 1 Torr (absolute pressure: 1 mmHg) or less, a polycondensation reaction was conducted. At the beginning of the polycondensation reaction, a stirring speed is set rapid, but as the polycondensation reaction progressed, in case stirring force decreases due to increase in the viscosity of the reactant or the temperature of the reactant increases beyond the established temperature, the stirring speed can be appropriately controlled. The polycondensation reaction was progressed until the intrinsic viscosity (IV) of the mixture (molten material) in the reactor became 0.60 dl/g. If the intrinsic viscosity of the mixture in the reactor reached a desired level, the mixture was discharged outside the reactor to make strand, which was solidified with a coolant, and then, granulated such that the average weight became 12 to 14 mg.

[0054] The particles were left at 150° C. for 1 hour to crystallize, and then, introduced into a solid phase polymerization reactor with a capacity of 20 L. And then, into the reactor, nitrogen was flowed at a speed of 50 L/min. Wherein, the temperature of the reactor was raised from room temperature to 140° C. at a speed of 40° C./hour, maintained at 140° C. for 3 hours, and then, raised to 210° C. at a speed of 40° C./hour, and maintained at 210° C. The solid phase polymerization reaction was progressed until the intrinsic viscosity (IV) of the particles in the reactor became 0.80 dl/g, thus preparing polyester copolymer.

Example 4

[0055] Into a reactor with a capacity of 10 L to which a column, and a condenser that can be cooled by water are connected, r-BHET (795.8 g), TPA (3814.0 g), EG (1554.0 g), CHDM (188.0 g) were introduced, and TiO.sub.2 (0.5 g) was introduced as a catalyst, phosphoric acid (1.46 g) as a stabilizer, and cobalt acetate (1.1 g) as a coloring agent.

[0056] Subsequently, nitrogen was introduced into the reactor to pressurize the reactor such that the pressure of the reactor is higher than atmospheric pressure by 1.0 kgf/cm.sup.2 (absolute pressure: 1495.6 mmHg). And, the temperature of the reactor was raised to 220° C. for 90 minutes, maintained at 220° C. for 2 hours, and then, raised to 250° C. for 2 hours. And then, the mixture in the reactor was observed with unaided eyes, and until the mixture became transparent, while maintaining the temperature of the reactor at 250° C., an esterification reaction was progressed. During this process, by-products were discharged through the column and condenser. After the esterification reaction was completed, nitrogen in the pressurized reactor was discharged outside to lower the pressure of the reactor to atmospheric pressure, and then, the mixture in the reactor was transferred to a reactor with a capacity of 7 L in which a vacuum reaction can be progressed.

[0057] And, the pressure of the reactor was lowered from atmospheric pressure to 5 Torr (absolute pressure: 5 mmHg) for 30 minutes, and simultaneously, the temperature of the reactor was raised to 265° C. for 1 hour, and while maintaining the pressure of the reactor at 1 Torr (absolute pressure: 1 mmHg) or less, a polycondensation reaction was conducted. At the beginning of the polycondensation reaction, a stirring speed is set rapid, but as the polycondensation reaction progressed, in case stirring force decreases due to increase in the viscosity of the reactant or the temperature of the reactant increases beyond the established temperature, the stirring speed can be appropriately controlled. The polycondensation reaction was progressed until the intrinsic viscosity (IV) of the mixture (molten material) in the reactor became 0.55 dl/g. If the intrinsic viscosity of the mixture in the reactor reached a desired level, the mixture was discharged outside the reactor to make strand, which was solidified with a coolant, and then, granulated such that the average weight became 12 to 14 mg.

[0058] The particles were left at 150° C. for 1 hour to crystallize, and then, introduced into a solid phase polymerization reactor with a capacity of 20 L. And then, into the reactor, nitrogen was flowed at a speed of 50 L/min. Wherein, the temperature of the reactor was raised from room temperature to 140° C. at a speed of 40° C./hour, maintained at 140° C. for 3 hours, and then, raised to 220° C. at a speed of 40° C./hour, and maintained at 220° C. The solid phase polymerization reaction was progressed until the intrinsic viscosity (IV) of the particles in the reactor became 0.85 dl/g, thus preparing polyester copolymer.

Example 5

[0059] Into a reactor with a capacity of 10 L to which a column, and a condenser that can be cooled by water are connected, r-BHET (2439.2 g), TPA (1471.5 g), EG (68.7 g), CHDM (797.8 g) were introduced, and TiO.sub.2 (1.0 g) was introduced as a catalyst, phosphoric acid (1.46 g) as a stabilizer, and cobalt acetate (0.8 g) as a coloring agent.

[0060] Subsequently, nitrogen was introduced into the reactor to pressurize the reactor such that the pressure of the reactor is higher than atmospheric pressure by 2.0 kgf/cm.sup.2 (absolute pressure: 2231.1 mmHg). And, the temperature of the reactor was raised to 220° C. for 90 minutes, maintained at 220° C. for 2 hours, and then, raised to 255° C. for 2 hours. And then, the mixture in the reactor was observed with unaided eyes, and until the mixture became transparent, while maintaining the temperature of the reactor at 255° C., an esterification reaction was progressed. During this process, by-products were discharged through the column and condenser. After the esterification reaction was completed, nitrogen in the pressurized reactor was discharged outside to lower the pressure of the reactor to atmospheric pressure, and then, the mixture in the reactor was transferred to a reactor with a capacity of 7 L in which a vacuum reaction can be progressed.

[0061] And, the pressure of the reactor was lowered from atmospheric pressure to 5 Torr (absolute pressure: 5 mmHg) for 30 minutes, and simultaneously, the temperature of the reactor was raised to 285° C. for 1 hour, and while maintaining the pressure of the reactor at 1 Torr (absolute pressure: 1 mmHg) or less, a polycondensation reaction was conducted. At the beginning of the polycondensation reaction, a stirring speed is set rapid, but as the polycondensation reaction progressed, in case stirring force decreases due to increase in the viscosity of the reactant or the temperature of the reactant increases beyond the established temperature, the stirring speed can be appropriately controlled. The polycondensation reaction was progressed until the intrinsic viscosity (IV) of the mixture (molten material) in the reactor became 0.70 dl/g. If the intrinsic viscosity of the mixture in the reactor reached a desired level, the mixture was discharged outside the reactor to make strand, which was solidified with a coolant, and then, granulated such that the average weight became 12 to 14 mg, thus preparing polyester copolymer.

Example 6

[0062] Into a reactor with a capacity of 10 L to which a column, and a condenser that can be cooled by water are connected, r-BHET (1320.0 g), TPA (2164.2 g), EG (599.2 g), CHDM (525.1 g) were introduced, and TiO.sub.2 (1.0 g) was introduced as a catalyst, phosphoric acid (1.46 g) as a stabilizer, and cobalt acetate (1.0 g) as a coloring agent.

[0063] Subsequently, nitrogen was introduced into the reactor to pressurize the reactor such that the pressure of the reactor is higher than atmospheric pressure by 1.5 kgf/cm.sup.2 (absolute pressure: 1715.5 mmHg). And, the temperature of the reactor was raised to 220° C. for 90 minutes, maintained at 220° C. for 2 hours, and then, raised to 250° C. for 2 hours. And then, the mixture in the reactor was observed with unaided eyes, and until the mixture became transparent, while maintaining the temperature of the reactor at 250° C., an esterification reaction was progressed. During this process, by-products were discharged through the column and condenser. After the esterification reaction was completed, nitrogen in the pressurized reactor was discharged outside to lower the pressure of the reactor to atmospheric pressure, and then, the mixture in the reactor was transferred to a reactor with a capacity of 7 L in which a vacuum reaction can be progressed.

[0064] And, the pressure of the reactor was lowered from atmospheric pressure to 5 Torr (absolute pressure: 5 mmHg) for 30 minutes, and simultaneously, the temperature of the reactor was raised to 270° C. for 1 hour, and while maintaining the pressure of the reactor at 1 Torr (absolute pressure: 1 mmHg) or less, a polycondensation reaction was conducted. At the beginning of the polycondensation reaction, a stirring speed is set rapid, but as the polycondensation reaction progressed, in case stirring force decreases due to increase in the viscosity of the reactant or the temperature of the reactant increases beyond the established temperature, the stirring speed can be appropriately controlled. The polycondensation reaction was progressed until the intrinsic viscosity (IV) of the mixture (molten material) in the reactor became 0.80 dl/g. If the intrinsic viscosity of the mixture in the reactor reached a desired level, the mixture was discharged outside the reactor to make strand, which was solidified with a coolant, and then, granulated such that the average weight became 12 to 14 mg, thus preparing polyester copolymer.

Example 7

[0065] Into a reactor with a capacity of 10 L to which a column, and a condenser that can be cooled by water are connected, r-BHET (1132.4 g), TPA (2220.2 g), EG (265.4 g), CHDM (1284.0 g), ISB (156.2 g) were introduced, and GeO.sub.2 (1.0 g) was introduced as a catalyst, phosphoric acid (1.46 g) as a stabilizer, Polysynthren Blue RLS(Clarient corporation, 0.013 g) as blue toner, and Solvaperm Red BB (Clarient corporation, 0.004 g) as red toner

[0066] Subsequently, nitrogen was introduced into the reactor to pressurize the reactor such that the pressure of the reactor is higher than atmospheric pressure by 1.0 kgf/cm.sup.2 (absolute pressure: 1495.6 mmHg). And, the temperature of the reactor was raised to 220° C. for 90 minutes, maintained at 220° C. for 2 hours, and then, raised to 265° C. for 2 hours. And then, the mixture in the reactor was observed with unaided eyes, and until the mixture became transparent, while maintaining the temperature of the reactor at 265° C., an esterification reaction was progressed. During this process, by-products were discharged through the column and condenser. After the esterification reaction was completed, nitrogen in the pressurized reactor was discharged outside to lower the pressure of the reactor to atmospheric pressure, and then, the mixture in the reactor was transferred to a reactor with a capacity of 7 L in which a vacuum reaction can be progressed.

[0067] And, the pressure of the reactor was lowered from atmospheric pressure to 5 Torr (absolute pressure: 5 mmHg) for 30 minutes, and simultaneously, the temperature of the reactor was raised to 275° C. for 1 hour, and while maintaining the pressure of the reactor at 1 Torr (absolute pressure: 1 mmHg) or less, a polycondensation reaction was conducted. At the beginning of the polycondensation reaction, a stirring speed is set rapid, but as the polycondensation reaction progressed, in case stirring force decreases due to increase in the viscosity of the reactant or the temperature of the reactant increases beyond the established temperature, the stirring speed can be appropriately controlled. The polycondensation reaction was progressed until the intrinsic viscosity (IV) of the mixture (molten material) in the reactor became 0.65 dl/g. If the intrinsic viscosity of the mixture in the reactor reached a desired level, the mixture was discharged outside the reactor to make strand, which was solidified with a coolant, and then, granulated such that the average weight became 12 to 14 mg, thus preparing polyester copolymer.

Example 8

[0068] Into a reactor with a capacity of 10 L to which a column, and a condenser that can be cooled by water are connected, r-BHET (612.8 g), TPA (2269.3 g), EG (49.9 g), CHDM (1158.0 g), ISB (587.0 g) were introduced, and GeO.sub.2 (1.0 g) was introduced as a catalyst, phosphoric acid (1.46 g) as a stabilizer, Polysynthren Blue RLS(Clarient corporation, 0.020 g) as blue toner, and Solvaperm Red BB (Clarient corporation, 0.008 g) as red toner

[0069] Subsequently, nitrogen was introduced into the reactor to pressurize the reactor such that the pressure of the reactor is higher than atmospheric pressure by 0.5 kgf/cm.sup.2 (absolute pressure: 1127.8 mmHg). And, the temperature of the reactor was raised to 220° C. for 90 minutes, maintained at 220° C. for 2 hours, and then, raised to 260° C. for 2 hours. And then, the mixture in the reactor was observed with unaided eyes, and until the mixture became transparent, while maintaining the temperature of the reactor at 260° C., an esterification reaction was progressed. During this process, by-products were discharged through the column and condenser. After the esterification reaction was completed, nitrogen in the pressurized reactor was discharged outside to lower the pressure of the reactor to atmospheric pressure, and then, the mixture in the reactor was transferred to a reactor with a capacity of 7 L in which a vacuum reaction can be progressed.

[0070] And, the pressure of the reactor was lowered from atmospheric pressure to 5 Torr (absolute pressure: 5 mmHg) for 30 minutes, and simultaneously, the temperature of the reactor was raised to 275° C. for 1 hour, and while maintaining the pressure of the reactor at 1 Torr (absolute pressure: 1 mmHg) or less, a polycondensation reaction was conducted. At the beginning of the polycondensation reaction, a stirring speed is set rapid, but as the polycondensation reaction progressed, in case stirring force decreases due to increase in the viscosity of the reactant or the temperature of the reactant increases beyond the established temperature, the stirring speed can be appropriately controlled. The polycondensation reaction was progressed until the intrinsic viscosity (IV) of the mixture (molten material) in the reactor became 0.80 dl/g. If the intrinsic viscosity of the mixture in the reactor reached a desired level, the mixture was discharged outside the reactor to make strand, which was solidified with a coolant, and then, granulated such that the average weight became 12 to 14 mg, thus preparing polyester copolymer.

Example 9

[0071] Into a reactor with a capacity of 10 L to which a column, and a condenser that can be cooled by water are connected, r-BHET (3418.5 g), TPA (957.5 g), DMT (dimethyl terephthalate; 1119.0 g), EG (346 g), CHDM (221.5 g), ISB (84.2 g) were introduced, and acetate tetrahydrate (1.5 g) and Sb.sub.2O.sub.3 (1.8 g) were introduced as catalysts, and cobalt acetate (0.7 g) as a coloring agent.

[0072] Subsequently, nitrogen was introduced into the reactor such that the pressure of the reactor became atmospheric pressure. And, the temperature of the reactor was raised to 220° C. for 90 minutes, maintained at 220° C. for 2 hours, and then, raised to 240° C. for 2 hours. And then, the mixture in the reactor was observed with unaided eyes, and until the mixture became transparent, while maintaining the temperature of the reactor at 240° C., an esterification reaction was progressed. During this process, by-products were discharged through the column and condenser. After the esterification reaction was completed, nitrogen in the pressurized reactor was discharged outside to lower the pressure of the reactor to atmospheric pressure, and then, the mixture in the reactor was transferred to a reactor with a capacity of 7 L in which a vacuum reaction can be progressed.

[0073] And, the pressure of the reactor was lowered from atmospheric pressure to 5 Torr (absolute pressure: 5 mmHg) for 30 minutes, and simultaneously, the temperature of the reactor was raised to 265° C. for 1 hour, and while maintaining the pressure of the reactor at 1 Torr (absolute pressure: 1 mmHg) or less, a polycondensation reaction was conducted. At the beginning of the polycondensation reaction, a stirring speed is set rapid, but as the polycondensation reaction progressed, in case stirring force decreases due to increase in the viscosity of the reactant or the temperature of the reactant increases beyond the established temperature, the stirring speed can be appropriately controlled. The polycondensation reaction was progressed until the intrinsic viscosity (IV) of the mixture (molten material) in the reactor became 0.60 dl/g. If the intrinsic viscosity of the mixture in the reactor reached a desired level, the mixture was discharged outside the reactor to make strand, which was solidified with a coolant, and then, granulated such that the average weight became 12 to 14 mg.

[0074] The particles were left at 150° C. for 1 hour to crystallize, and then, introduced into a solid phase polymerization reactor with a capacity of 20 L. And then, into the reactor, nitrogen was flowed at a speed of 50 L/min. Wherein, the temperature of the reactor was raised from room temperature to 140° C. at a speed of 40° C./hour, maintained at 140° C. for 3 hours, and then, raised to 200° C. at a speed of 40° C./hour, and maintained at 200° C. The solid phase polymerization reaction was progressed until the intrinsic viscosity (IV) of the particles in the reactor became 0.95 dl/g, thus preparing polyester copolymer.

Example 10

[0075] Into a reactor with a capacity of 10 L to which a column, and a condenser that can be cooled by water are connected, r-BHET (3461.1 g), TPA (969.4 g), IPA (isopropyl alcohol; 2262.0 g), EG (12.1 g), CHDM (140.2 g), ISB (113.7 g) were introduced, and GeO.sub.2 (1.0 g) was introduced as catalysts, and cobalt acetate (0.7 g) as a coloring agent.

[0076] Subsequently, nitrogen was introduced into the reactor to pressurize the reactor such that the pressure of the reactor is higher than atmospheric pressure by 1.0 kgf/cm.sup.2 (absolute pressure: 1495.6 mmHg). And, the temperature of the reactor was raised to 220° C. for 90 minutes, maintained at 220° C. for 2 hours, and then, raised to 260° C. for 2 hours. And then, the mixture in the reactor was observed with unaided eyes, and until the mixture became transparent, while maintaining the temperature of the reactor at 260° C., an esterification reaction was progressed. During this process, by-products were discharged through the column and condenser. After the esterification reaction was completed, nitrogen in the pressurized reactor was discharged outside to lower the pressure of the reactor to atmospheric pressure, and then, the mixture in the reactor was transferred to a reactor with a capacity of 7 L in which a vacuum reaction can be progressed.

[0077] And, the pressure of the reactor was lowered from atmospheric pressure to 5 Torr (absolute pressure: 5 mmHg) for 30 minutes, and simultaneously, the temperature of the reactor was raised to 280° C. for 1 hour, and while maintaining the pressure of the reactor at 1 Torr (absolute pressure: 1 mmHg) or less, a polycondensation reaction was conducted. At the beginning of the polycondensation reaction, a stirring speed is set rapid, but as the polycondensation reaction progressed, in case stirring force decreases due to increase in the viscosity of the reactant or the temperature of the reactant increases beyond the established temperature, the stirring speed can be appropriately controlled. The polycondensation reaction was progressed until the intrinsic viscosity (IV) of the mixture (molten material) in the reactor became 0.60 dl/g. If the intrinsic viscosity of the mixture in the reactor reached a desired level, the mixture was discharged outside the reactor to make strand, which was solidified with a coolant, and then, granulated such that the average weight became 12 to 14 mg.

[0078] The particles were left at 150° C. for 1 hour to crystallize, and then, introduced into a solid phase polymerization reactor with a capacity of 20 L. And then, into the reactor, nitrogen was flowed at a speed of 50 L/min. Wherein, the temperature of the reactor was raised from room temperature to 140° C. at a speed of 40° C./hour, maintained at 140° C. for 3 hours, and then, raised to 190° C. at a speed of 40° C./hour, and maintained at 190° C. The solid phase polymerization reaction was progressed until the intrinsic viscosity (IV) of the particles in the reactor became 1.0 dl/g, thus preparing polyester copolymer.

Comparative Example 1

[0079] Into a reactor with a capacity of 10 L to which a column, and a condenser that can be cooled by water are connected, r-BHET (390.7 g), TPA (2936.3 g), EG (1400.7 g), CHDM (221.5 g), ISB (98.2 g) were introduced, and GeO.sub.2 (1.0 g) was introduced as catalysts, and phosphoric acid (1.46 g) as a stabilizer.

[0080] Subsequently, nitrogen was introduced into the reactor to pressurize the reactor such that the pressure of the reactor is higher than atmospheric pressure by 0.5 kgf/cm.sup.2 (absolute pressure: 1127.8 mmHg). And, the temperature of the reactor was raised to 220° C. for 90 minutes, maintained at 220° C. for 2 hours, and then, raised to 260° C. for 2 hours. And then, the mixture in the reactor was observed with unaided eyes, and until the mixture became transparent, while maintaining the temperature of the reactor at 260° C., an esterification reaction was progressed. During this process, by-products were discharged through the column and condenser. After the esterification reaction was completed, nitrogen in the pressurized reactor was discharged outside to lower the pressure of the reactor to atmospheric pressure, and then, the mixture in the reactor was transferred to a reactor with a capacity of 7 L in which a vacuum reaction can be progressed.

[0081] And, the pressure of the reactor was lowered from atmospheric pressure to 5 Torr (absolute pressure: 5 mmHg) for 30 minutes, and simultaneously, the temperature of the reactor was raised to 280° C. for 1 hour, and while maintaining the pressure of the reactor at 1 Torr (absolute pressure: 1 mmHg) or less, a polycondensation reaction was conducted. At the beginning of the polycondensation reaction, a stirring speed is set rapid, but as the polycondensation reaction progressed, in case stirring force decreases due to increase in the viscosity of the reactant or the temperature of the reactant increases beyond the established temperature, the stirring speed can be appropriately controlled. The polycondensation reaction was progressed until the intrinsic viscosity (IV) of the mixture (molten material) in the reactor became 0.60 dl/g. If the intrinsic viscosity of the mixture in the reactor reached a desired level, the mixture was discharged outside the reactor to make strand, which was solidified with a coolant, and then, granulated such that the average weight became 12 to 14 mg.

[0082] The particles were left at 150° C. for 1 hour to crystallize, and then, introduced into a solid phase polymerization reactor with a capacity of 20 L. After maintaining at 100 mmHg for 1 hour, nitrogen was flowed into the reactor at a speed of 50 L/min. Wherein, the temperature of the reactor was raised from room temperature to 140° C. at a speed of 40° C./hour, maintained at 140° C. for 3 hours, and then, raised to 200° C. at a speed of 40° C./hour, and maintained at 200° C. The solid phase polymerization reaction was progressed until the intrinsic viscosity (IV) of the particles in the reactor became 0.7 dl/g, thus preparing polyester copolymer.

Comparative Example 2

[0083] Into a reactor with a capacity of 10 L to which a column, and a condenser that can be cooled by water are connected, r-BHET (2645.6 g), TPA (1729.0 g), EG (6.5 g), CHDM (150.0 g), ISB (106.4 g) were introduced, and GeO.sub.2 (1.0 g) was introduced as catalysts, phosphoric acid (1.46 g) as a stabilizer, and cobalt acetate (0.7 g) as a coloring agent.

[0084] Subsequently, nitrogen was introduced into the reactor to pressurize the reactor such that the pressure of the reactor is higher than atmospheric pressure by 1.0 kgf/cm.sup.2 (absolute pressure: 1495.6 mmHg). And, the temperature of the reactor was raised to 220° C. for 90 minutes, maintained at 220° C. for 2 hours, and then, raised to 260° C. for 2 hours. And then, the mixture in the reactor was observed with unaided eyes, and until the mixture became transparent, while maintaining the temperature of the reactor at 260° C., an esterification reaction was progressed. During this process, by-products were discharged through the column and condenser. After the esterification reaction was completed, nitrogen in the pressurized reactor was discharged outside to lower the pressure of the reactor to atmospheric pressure, and then, the mixture in the reactor was transferred to a reactor with a capacity of 7 L in which a vacuum reaction can be progressed.

[0085] And, the pressure of the reactor was lowered from atmospheric pressure to 5 Torr (absolute pressure: 5 mmHg) for 30 minutes, and simultaneously, the temperature of the reactor was raised to 280° C. for 1 hour, and while maintaining the pressure of the reactor at 1 Torr (absolute pressure: 1 mmHg) or less, a polycondensation reaction was conducted. At the beginning of the polycondensation reaction, a stirring speed is set rapid, but as the polycondensation reaction progressed, in case stirring force decreases due to increase in the viscosity of the reactant or the temperature of the reactant increases beyond the established temperature, the stirring speed can be appropriately controlled. The polycondensation reaction was progressed until the intrinsic viscosity (IV) of the mixture (molten material) in the reactor became 0.60 dl/g. If the intrinsic viscosity of the mixture in the reactor reached a desired level, the mixture was discharged outside the reactor to make strand, which was solidified with a coolant, and then, granulated such that the average weight became 12 to 14 mg.

[0086] The particles were left at 150° C. for 1 hour to crystallize, and then, introduced into a solid phase polymerization reactor with a capacity of 20 L. And then, nitrogen was flowed into the reactor at a speed of 50 L/min. Wherein, the temperature of the reactor was raised from room temperature to 140° C. at a speed of 40° C./hour, maintained at 140° C. for 3 hours, and then, raised to 200° C. at a speed of 40° C./hour, and maintained at 200° C. The solid phase polymerization reaction was progressed until the intrinsic viscosity (IV) of the particles in the reactor became 0.95 dl/g, thus preparing polyester copolymer.

Comparative Example 3

[0087] Into a reactor with a capacity of 10 L to which a column, and a condenser that can be cooled by water are connected, r-BHET (364.2 g), TPA (3162.2 g), EG (1295.4 g), CHDM (118.0 g) were introduced, and GeO.sub.2 (1.0 g) was introduced as catalysts, phosphoric acid (1.46 g) as a stabilizer, Polysynthren Blue RLS(Clarient corporation, 0.012 g) as blue toner, and Solvaperm Red BB (Clarient corporation, 0.004 g) as red toner.

[0088] Subsequently, nitrogen was introduced into the reactor to pressurize the reactor such that the pressure of the reactor is higher than atmospheric pressure by 0.5 kgf/cm.sup.2 (absolute pressure: 1127.8 mmHg). And, the temperature of the reactor was raised to 220° C. for 90 minutes, maintained at 220° C. for 2 hours, and then, raised to 255° C. for 2 hours. And then, the mixture in the reactor was observed with unaided eyes, and until the mixture became transparent, while maintaining the temperature of the reactor at 255° C., an esterification reaction was progressed. During this process, by-products were discharged through the column and condenser. After the esterification reaction was completed, nitrogen in the pressurized reactor was discharged outside to lower the pressure of the reactor to atmospheric pressure, and then, the mixture in the reactor was transferred to a reactor with a capacity of 7 L in which a vacuum reaction can be progressed.

[0089] And, the pressure of the reactor was lowered from atmospheric pressure to 5 Torr (absolute pressure: 5 mmHg) for 30 minutes, and simultaneously, the temperature of the reactor was raised to 280° C. for 1 hour, and while maintaining the pressure of the reactor at 1 Torr (absolute pressure: 1 mmHg) or less, a polycondensation reaction was conducted. At the beginning of the polycondensation reaction, a stirring speed is set rapid, but as the polycondensation reaction progressed, in case stirring force decreases due to increase in the viscosity of the reactant or the temperature of the reactant increases beyond the established temperature, the stirring speed can be appropriately controlled. The polycondensation reaction was progressed until the intrinsic viscosity (IV) of the mixture (molten material) in the reactor became 0.75 dl/g. If the intrinsic viscosity of the mixture in the reactor reached a desired level, the mixture was discharged outside the reactor to make strand, which was solidified with a coolant, and then, granulated such that the average weight became 12 to 14 mg.

[0090] The particles were left at 150° C. for 1 hour to crystallize, and then, introduced into a solid phase polymerization reactor with a capacity of 20 L. And then, nitrogen was flowed into the reactor at a speed of 50 L/min. Wherein, the temperature of the reactor was raised from room temperature to 140° C. at a speed of 40° C./hour, maintained at 140° C. for 3 hours, and then, raised to 210° C. at a speed of 40° C./hour, and maintained at 210° C. The solid phase polymerization reaction was progressed until the intrinsic viscosity (IV) of the particles in the reactor became 0.80 dl/g, thus preparing polyester copolymer.

Comparative Example 4

[0091] Into a reactor with a capacity of 10 L to which a column, and a condenser that can be cooled by water are connected, r-BHET (3194.9 g), TPA (623.7 g), CHDM (94.1 g) were introduced, and GeO.sub.2 (1.0 g) was introduced as catalysts, phosphoric acid (1.46 g) as a stabilizer, Polysynthren Blue RLS(Clarient corporation, 0.010 g) as blue toner, and Solvaperm Red BB (Clarient corporation, 0.003 g) as red toner.

[0092] Subsequently, nitrogen was introduced into the reactor to pressurize the reactor such that the pressure of the reactor is higher than atmospheric pressure by 1.5 kgf/cm.sup.2 (absolute pressure: 1715.5 mmHg). And, the temperature of the reactor was raised to 220° C. for 90 minutes, maintained at 220° C. for 2 hours, and then, raised to 260° C. for 2 hours. And then, the mixture in the reactor was observed with unaided eyes, and until the mixture became transparent, while maintaining the temperature of the reactor at 260° C., an esterification reaction was progressed. During this process, by-products were discharged through the column and condenser. After the esterification reaction was completed, nitrogen in the pressurized reactor was discharged outside to lower the pressure of the reactor to atmospheric pressure, and then, the mixture in the reactor was transferred to a reactor with a capacity of 7 L in which a vacuum reaction can be progressed.

[0093] And, the pressure of the reactor was lowered from atmospheric pressure to 5 Torr (absolute pressure: 5 mmHg) for 30 minutes, and simultaneously, the temperature of the reactor was raised to 270° C. for 1 hour, and while maintaining the pressure of the reactor at 1 Torr (absolute pressure: 1 mmHg) or less, a polycondensation reaction was conducted. At the beginning of the polycondensation reaction, a stirring speed is set rapid, but as the polycondensation reaction progressed, in case stirring force decreases due to increase in the viscosity of the reactant or the temperature of the reactant increases beyond the established temperature, the stirring speed can be appropriately controlled. The polycondensation reaction was progressed until the intrinsic viscosity (IV) of the mixture (molten material) in the reactor became 0.65 dl/g. If the intrinsic viscosity of the mixture in the reactor reached a desired level, the mixture was discharged outside the reactor to make strand, which was solidified with a coolant, and then, granulated such that the average weight became 12 to 14 mg.

[0094] The particles were left at 150° C. for 1 hour to crystallize, and then, introduced into a solid phase polymerization reactor with a capacity of 20 L. And then, nitrogen was flowed into the reactor at a speed of 50 L/min. Wherein, the temperature of the reactor was raised from room temperature to 140° C. at a speed of 40° C./hour, maintained at 140° C. for 3 hours, and then, raised to 220° C. at a speed of 40° C./hour, and maintained at 220° C. The solid phase polymerization reaction was progressed until the intrinsic viscosity (IV) of the particles in the reactor became 0.85 dl/g, thus preparing polyester copolymer.

Comparative Example 5

[0095] Into a reactor with a capacity of 10 L to which a column, and a condenser that can be cooled by water are connected, r-BHET (320.1 g), TPA (3009.6 g), EG (1166.1 g), CHDM (837.7 g) were introduced, and GeO.sub.2 (1.0 g) was introduced as catalysts, phosphoric acid (1.5 g) as a stabilizer, and cobalt acetate (0.7 g) as a coloring agent.

[0096] Subsequently, nitrogen was introduced into the reactor to pressurize the reactor such that the pressure of the reactor is higher than atmospheric pressure by 2.0 kgf/cm.sup.2 (absolute pressure: 2231.1 mmHg). And, the temperature of the reactor was raised to 220° C. for 90 minutes, maintained at 220° C. for 2 hours, and then, raised to 265° C. for 2 hours. And then, the mixture in the reactor was observed with unaided eyes, and until the mixture became transparent, while maintaining the temperature of the reactor at 265° C., an esterification reaction was progressed. During this process, by-products were discharged through the column and condenser. After the esterification reaction was completed, nitrogen in the pressurized reactor was discharged outside to lower the pressure of the reactor to atmospheric pressure, and then, the mixture in the reactor was transferred to a reactor with a capacity of 7 L in which a vacuum reaction can be progressed.

[0097] And, the pressure of the reactor was lowered from atmospheric pressure to 5 Torr (absolute pressure: 5 mmHg) for 30 minutes, and simultaneously, the temperature of the reactor was raised to 270° C. for 1 hour, and while maintaining the pressure of the reactor at 1 Torr (absolute pressure: 1 mmHg) or less, a polycondensation reaction was conducted. At the beginning of the polycondensation reaction, a stirring speed is set rapid, but as the polycondensation reaction progressed, in case stirring force decreases due to increase in the viscosity of the reactant or the temperature of the reactant increases beyond the established temperature, the stirring speed can be appropriately controlled. The polycondensation reaction was progressed until the intrinsic viscosity (IV) of the mixture (molten material) in the reactor became 0.60 dl/g. If the intrinsic viscosity of the mixture in the reactor reached a desired level, the mixture was discharged outside the reactor to make strand, which was solidified with a coolant, and then, granulated such that the average weight became 12 to 14 mg, thus preparing polyester copolymer.

Comparative Example 6

[0098] Into a reactor with a capacity of 10 L to which a column, and a condenser that can be cooled by water are connected, r-BHET (4278.0 g), TPA (310.7 g), CHDM (539.0 g) were introduced, and GeO.sub.2 (1.0 g) was introduced as catalysts, phosphoric acid (1.46 g) as a stabilizer, and cobalt acetate (0.8 g) as a coloring agent.

[0099] Subsequently, nitrogen was introduced into the reactor to pressurize the reactor such that the pressure of the reactor is higher than atmospheric pressure by 1.5 kgf/cm.sup.2 (absolute pressure: 1715.5 mmHg). And, the temperature of the reactor was raised to 220° C. for 90 minutes, maintained at 220° C. for 2 hours, and then, raised to 270° C. for 2 hours. And then, the mixture in the reactor was observed with unaided eyes, and until the mixture became transparent, while maintaining the temperature of the reactor at 270° C., an esterification reaction was progressed. During this process, by-products were discharged through the column and condenser. After the esterification reaction was completed, nitrogen in the pressurized reactor was discharged outside to lower the pressure of the reactor to atmospheric pressure, and then, the mixture in the reactor was transferred to a reactor with a capacity of 7 L in which a vacuum reaction can be progressed.

[0100] And, the pressure of the reactor was lowered from atmospheric pressure to 5 Torr (absolute pressure: 5 mmHg) for 30 minutes, and simultaneously, the temperature of the reactor was raised to 275° C. for 1 hour, and while maintaining the pressure of the reactor at 1 Torr (absolute pressure: 1 mmHg) or less, a polycondensation reaction was conducted. At the beginning of the polycondensation reaction, a stirring speed is set rapid, but as the polycondensation reaction progressed, in case stirring force decreases due to increase in the viscosity of the reactant or the temperature of the reactant increases beyond the established temperature, the stirring speed can be appropriately controlled. The polycondensation reaction was progressed until the intrinsic viscosity (IV) of the mixture (molten material) in the reactor became 0.65 dl/g. If the intrinsic viscosity of the mixture in the reactor reached a desired level, the mixture was discharged outside the reactor to make strand, which was solidified with a coolant, and then, granulated such that the average weight became 12 to 14 mg, thus preparing polyester copolymer.

Comparative Example 7

[0101] Into a reactor with a capacity of 10 L to which a column, and a condenser that can be cooled by water are connected, r-BHET (420.6 g), TPA (2473.9 g), EG (657.1 g), CHDM (1192.3 g), ISB (145.1 g) were introduced, and GeO.sub.2 (1.0 g) was introduced as catalysts, phosphoric acid (1.46 g) as a stabilizer, and cobalt acetate (0.8 g) as a coloring agent.

[0102] Subsequently, nitrogen was introduced into the reactor to pressurize the reactor such that the pressure of the reactor is higher than atmospheric pressure by 1.5 kgf/cm.sup.2 (absolute pressure: 1715.5 mmHg). And, the temperature of the reactor was raised to 220° C. for 90 minutes, maintained at 220° C. for 2 hours, and then, raised to 270° C. for 2 hours. And then, the mixture in the reactor was observed with unaided eyes, and until the mixture became transparent, while maintaining the temperature of the reactor at 270° C., an esterification reaction was progressed. During this process, by-products were discharged through the column and condenser. After the esterification reaction was completed, nitrogen in the pressurized reactor was discharged outside to lower the pressure of the reactor to atmospheric pressure, and then, the mixture in the reactor was transferred to a reactor with a capacity of 7 L in which a vacuum reaction can be progressed.

[0103] And, the pressure of the reactor was lowered from atmospheric pressure to 5 Torr (absolute pressure: 5 mmHg) for 30 minutes, and simultaneously, the temperature of the reactor was raised to 275° C. for 1 hour, and while maintaining the pressure of the reactor at 1 Torr (absolute pressure: 1 mmHg) or less, a polycondensation reaction was conducted. At the beginning of the polycondensation reaction, a stirring speed is set rapid, but as the polycondensation reaction progressed, in case stirring force decreases due to increase in the viscosity of the reactant or the temperature of the reactant increases beyond the established temperature, the stirring speed can be appropriately controlled. The polycondensation reaction was progressed until the intrinsic viscosity (IV) of the mixture (molten material) in the reactor became 0.70 dl/g. If the intrinsic viscosity of the mixture in the reactor reached a desired level, the mixture was discharged outside the reactor to make strand, which was solidified with a coolant, and then, granulated such that the average weight became 12 to 14 mg, thus preparing polyester copolymer.

[0104] The contents of ingredients introduced for preparation of polyester copolymers in the Examples and Comparative Examples were shown in the following Table 1.

TABLE-US-00001 TABLE 1 (EG + CHDM + EG/(CHDM + r-BHET TPA EG CHDM ISB ISB)/TPA ISB) unit mol mol mol mol mol — — Example 1 5.0 14.2 10.9 1.5 0.7 0.92 4.91 Example 2 13.6 5.38 0.2 1.0 0.8 0.33 0.11 Example 3 15.8 5.3 0.6 0.8 — 0.28 0.75 Example 4 3.1 23.0 25.1 1.3 — 1.15 19.20 Example 5 9.6 8.9 1.1 5.5 — 0.75 0.20 Example 6 5.2 13.0 9.7 3.6 — 1.02 2.65 Example 7 4.5 13.4 4.3 8.9 1.1 1.07 0.43 Example 8 2.4 13.7 0.8 8.0 4.0 0.94 0.07 Example 9 13.5 5.8 5.6 1.5 0.6 1.33 2.64 Example 10 13.6 5.8 0.2 1.0 0.8 0.33 0.11 Comparative 1.5 17.7 22.6 1.5 0.7 1.40 10.22 Example 1 Comparative 10.4 10.4 0.1 1.0 0.7 0.18 0.06 Example 2 Comparative 1.4 19.0 20.9 0.8 — 1.14 25.50 Example 3 Comparative 12.6 3.8 — 0.7 — 0.17 — Example 4 Comparative 1.3 18.1 18.8 5.8 — 1.36 3.23 Example 5 Comparative 16.8 1.9 — 3.7 — 2.00 — Example 6 Comparative 1.7 14.9 10.6 8.3 1.0 1.33 1.14 Example 7

Experimental Example

[0105] For the copolymers prepared in the Examples and Comparative Examples, properties were evaluated as follows.

[0106] (1) Composition of Residues

[0107] The compositions (mol %) of residues derived from acid and diol in polyester resin were confirmed through 1H-NMR obtained using nuclear magnetic resonance device (JEOL, 600 MHz FT-NMR) at 25° C., after dissolving a sample in a CDCl.sub.3 solvent at the concentration of 3 mg/m L. And, TMA residues were confirmed by quantitatively analyzing the content of benzene-1,2,4-triethylcarboxylate produced by the reaction of ethanol with TMA through ethanolysis, through the spectrum measured using gas chromatography (Agilent Technologies, 7890B) at 250° C., and contents (wt %) based on the total weight of polyester resin were confirmed.

[0108] (2) Intrinsic Viscosity

[0109] The polyester copolymer was dissolved in 150° C. orthochlorophenol (OCP) at the concentration of 0.12%, and then, the intrinsic viscosity was measured using Ubbelohde viscometer in a constant-temperature bath of 35° C. Specifically, the temperature of the viscometer was maintained at 35° C., and an efflux time (t0) required for the solvent to pass between specific internal sections of the viscometer, and a time (t) required for the solution to pass through were calculated. And then, the t0 value and the t value were substituted in the following Formula 1 to calculate specific viscosity, and the calculated specific viscosity value was substituted in the following Formula 2 to calculate intrinsic viscosity.

[00001]$\begin{array}{cc}{\eta }_{\mathrm{sp}}=\frac{t-t_0}{t_0}& \left[\mathrm{Formula}1\right]\end{array}$$\begin{array}{cc}\left[\eta \right]=\frac{\sqrt{1+4A{\eta }_{\mathrm{sp}}-1}}{2\mathrm{Ac}}& \left[\mathrm{Formula}2\right]\end{array}$

[0110] (3) Haze

[0111] A polyester resin specimen with a thickness of 6 mm was prepared, and the Haze of the specimen was measured using CM-3600A measuring device of Minolta Inc. by ASTM D1003-97 measurement method.

[0112] (4) Plaque Color L-b

[0113] The chromaticity and brightness of the sample were measured using Varian Cary 5 UV/Vis/NIR spectrophotometer equipped with a diffused reflection component. A polyester resin specimen with a thickness of 6 mm was prepared, and transmission date was obtained at the observer angle of 2° with Illuminant D65, it was processed using color analysis device in Grams/32 software to calculate Hunter L*a*b*, and in the following Table, L-b was described.

[0114] (5) By-Products

[0115] By-products were measured by GC quantitative analysis of polyester resin, and specifically, measured under the following conditions.

[0116] a. pretreatment of sample: 0.1 g of a sample was dissolved in 5 mL of MeOH.

[0117] b. GC conditions

[0118] i. Model: Agilent 7890

[0119] ii. Column: DB-WAX (30 m*0.25 mm*0.25 μm)

[0120] iii. Oven Temperature: 50° C. (2 min)-10° C./min-250° C. (5 min)

[0121] iv. Injector Temp.: 250° C.

[0122] v. Detector Temp.: 250° C.

[0123] vi. Flow: 1.5 mL/min (N.sub.2), Split ratio: 1/30

[0124] Quantitative analysis of diol other than EG (ethylene glycol) was progressed to measure the sum of by-products.

[0125] The results were shown in the following Table 2.

TABLE-US-00002 TABLE 2 Intrinsic Plaque By- r-BHET CHDM ISB viscosity Haze Color L-b products Unit wt % mol % mol % dg/l — — wt % Example 1 30 8 2 0.70 0.8 93 0.5 Example 2 75 5 2 0.95 2.0 90 2.0 Example 3 80 4 — 0.80 4.0 85 1.5 Example 4 14 5 — 0.85 2.0 91 1.5 Example 5 50 30 — 0.70 1.0 90 1.2 Example 6 30 20 — 0.80 1.0 92 1.0 Example 7 22 50 3 0.65 1.5 90 1.0 Example 8 15 50 15  0.80 0.8 88 0.7 Example 9 69 8 2 0.95 4.0 85 2.0 Example 10 75 5 2 1.00 4.0 85 1.0 Comparative 9 8 2 0.70 3.0 83 2.5 Example 1 Comparative 61 5 2 0.95 30.0 85 0.5 Example 2 Comparative 8 4 — 0.80 2.0 80 2.5 Example 3 Comparative 82 4 — 0.85 15.0 85 0.5 Example 4 Comparative 6 30 — 0.60 10.0 75 2.1 Example 5 Comparative 80 20 — 0.65 8.0 65 4.0 Example 6 Comparative 8 50 3 0.70 5.0 70 2.3 Example 7