Slow-crystallizing polyester resins

• US 20040236066A1
• Filed: 05/21/2004
• Published: 11/25/2004
• Est. Priority Date: 05/21/2003
• Status: Active Grant

• Current Assignee: DAK Americas Mississippi, Inc. (Grupo Petrotemex)
• Original Assignee: Wellman Incorporated (Wellman Holdings, Inc.)
• Inventors: Humelsine, Billy Mack, Thompson, David Eugene, Moore, Tony Clifford, Schiavone, Robert Joseph, Griffith, Sharon Sue, Nichols, Carl S.
• Granted Patent: US 7,129,317 B2
• Time in Patent Office: Days
• US Class Current: 528/308.1
• CPC Class Codes: B29C 2035/0822 using IR radiation
• CPC Class Codes: B29C 2949/0715 the preform having one end closed
• CPC Class Codes: B29C 49/06 Injection blow-moulding
• CPC Class Codes: B29C 49/6418 Heating of preforms
• CPC Class Codes: C08G 63/183 Terephthalic acids
• CPC Class Codes: C08G 63/20 Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
• CPC Class Codes: C08G 63/672 Dicarboxylic acids and dihydroxy compounds
• CPC Class Codes: C08G 63/80 Solid-state polycondensation

Abstract

The present invention relates to slow-crystallizing polyethylene terephthalate resins that possess a significantly higher heating crystallization exotherm peak temperature (T_CH) as compared with those of conventional antimony-catalyzed polyethylene terephthalate resins. The polyethylene terephthalate resins of the present invention are especially useful for making hot-fill bottles having exceptional clarity.

Claims

1. A polyethylene terephthalate resin, wherein:

the polyethylene terephthalate resin has a heating crystallization exotherm peak temperature (T_CH) of more than about 140°

C. at a heating rate of 10°

C. per minute as measured by differential scanning calorimetry;

the polyethylene terephthalate resin has an absorbance (A) of at least about 0.18 cm<sup>−

1</sup> at a wavelength of 1100 nm or at a wavelength of 1280 nm; and

the polyethylene terephthalate resin has a L* transmission value of more than about 70 as classified in the CIE L*a*b* color space.

2. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin has an absorbance (A) of at least about 0.20 cm⁻

1 at a wavelength of 1100 nm and at a wavelength of 1280 nm.

3. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin has an absorbance (A) of at least about 0.24 cm⁻

1 at a wavelength of 1100 nm and at a wavelength of 1280 nm.

4. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin has an absorbance (A) of at least about 0.28 cm⁻

1 at a wavelength of 1100 nm and at a wavelength of 1280 nm.

5. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin has an absorbance (A) of at least about 0.30 cm⁻

1 at a wavelength of 1100 nm or at a wavelength of 1280 nm.

6. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin has an absorbance (A) of at least about 0.40 cm⁻

1 at a wavelength of 1100 nm or at a wavelength of 1280 nm.

7. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin has a 1100:

550 absorption ratio of at least about 70 percent and a 1280;

550 absorption ratio of at least about 70 percent.

8. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin has a 1100:

700 absorption ratio of at least about 85 percent and a 1280;

700 absorption ratio of at least about 85 percent.

9. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin possesses a L* transmission value of more than about 75 as classified in the CIE L*a*b* color space.

10. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin possesses a L* transmission value of more than about 80 as classified in the CIE L*a*b* color space.

11. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin possesses a b* color value of less than 2 as classified by the CIE L*a*b* color space.

12. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin possesses a b* color value of less than 0 as classified by the CIE L*a*b* color space.

13. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin has an intrinsic viscosity between about 0.72 dl/g and 0.84 dl/g.

14. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin has a crystalline melting peak temperature (T_M) of at least about 240°

C.

15. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin has a crystalline melting peak temperature (T_M) of at least about 250°

C.

16. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin has a cooling crystallization exotherm peak temperature (T_CC) of less than 190°

C. at a cooling rate of 10°

C. per minute as measured by differential scanning calorimetry.

17. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin has a cooling crystallization exotherm peak temperature (T_CC) of less than 180°

C. at a cooling rate of 10°

C. per minute as measured by differential scanning calorimetry.

18. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin possesses less than about 10 percent haze at a thickness of between 4.5 and 6.0 mm as measured in a step parison.

19. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin possesses less than about 15 percent haze at a thickness of more than about 6 mm as measured in a step parison.

20. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin is composed of about a 1:

1 molar ratio of a diacid component and a diol component, and wherein the diacid component includes at least 94 mole percent terephthalic acid and the diol component includes at least 94 mole percent ethylene glycol.

21. A polyethylene terephthalate resin according to claim 20, wherein the diacid component consists essentially of terephthalic acid and isophthalic acid, and wherein the diol component consists essentially of ethylene glycol and diethylene glycol.

22. A polyethylene terephthalate resin according to claim 20, wherein:

the diacid component comprises terephthalic acid and at least one modifier selected from the group consisting of dimethyl isophthalate, 2,6-naphthalene dicarboxylic acid, dimethyl 2,6-naphthalene dicarboxylate, succinic acid, dimethyl succinate, and succinic anhydride; and

the diol component comprises ethylene glycol and at least one modifier selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexane dimethanol, and isosorbide.

23. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin is composed of about a 1:

1 molar ratio of a diester component and a diol component, wherein the diester component includes at least 94 mole percent dimethyl terephthalate and the diol component includes at least 94 mole percent ethylene glycol.

24. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin comprises between about 2 and 5 mole percent comonomer substitution.

25. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin comprises a metal-containing heat-up rate additive that is present in the resin in an amount between about 10 and 300 ppm.

26. A polyethylene terephthalate resin according to claim 25, wherein the metal-containing heat-up rate additive comprises a spinel that is present in the resin in an amount between about 10 and 100 ppm.

27. A polyethylene terephthalate resin according to claim 25, wherein the metal-containing heat-up rate additive comprises a spinel that is present in the resin in an amount between about 15 and 25 ppm.

28. A polyethylene terephthalate resin according to claim 25, wherein the metal-containing heat-up rate additive comprises a molybdenum-based or a tungsten-containing heat-up rate additive.

29. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin comprises a carbon-based heat-up rate additive that is present in the resin in an amount greater than 0 ppm and less than about 25 ppm.

30. A polyethylene terephthalate resin according to claim 29, wherein the carbon-based heat-up rate is present in the resin in an amount between about 6 and 10 ppm.

31. A polyethylene terephthalate resin according to claim 29, wherein the carbon-based heat-up rate additive is selected from the group consisting of carbon black, activated carbon, and graphite.

32. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin comprises between about 2 and 50 ppm of elemental titanium.

33. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin comprises between about 5 and 15 ppm of elemental titanium.

34. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin comprises between about 10 and 50 ppm of elemental cobalt.

35. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin comprises between about 20 and 30 ppm of elemental cobalt.

36. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin comprises between about 2 and 60 ppm of elemental phosphorus.

37. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin comprises between about 2 and 10 ppm of elemental phosphorus.

38. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin comprises less than about 100 ppm of elemental antimony and less than about 20 ppm of elemental germanium.

39. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin comprises less than about 25 ppm of elemental antimony and less than about 5 ppm of elemental germanium.

40. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin comprises an SSP catalyst that increases the rate of solid state polymerization.

41. A polyethylene terephthalate resin according to claim 1, wherein the SSP catalyst comprises an alkali earth metal.

42. A polyethylene terephthalate resin according to claim 1, wherein the SSP catalyst comprises alkaline earth metal.

43. A polyethylene terephthalate resin according to claim 1, wherein the polyethylene terephthalate resin comprises branching agent that is present in the resin in an amount greater than 0 and less than 0.1 mole percent.

44. A polyester container or film formed from the polyethylene terephthalate resin according to claim 1.

45. A polyethylene terephthalate resin, comprising:

less than about 6 mole percent substitution; and

wherein the polyethylene terephthalate resin has an intrinsic viscosity less than about 0.86 dl/g;

wherein the polyethylene terephthalate resin has a heating crystallization exotherm peak temperature (T_CH) of more than about 143°

C. at a heating rate of 10°

C. per minute as measured by differential scanning calorimetry;

wherein the polyethylene terephthalate resin has an absorbance (A) of at least about 0.25 cm<sup>−

1</sup> at a wavelength of 1100 nm or at a wavelength of 1280 nm; and

wherein the polyethylene terephthalate resin has a L* transmission value of more than about 75 as classified in the CIE L*a*b* color space.

46. A polyethylene terephthalate resin according to claim 45, wherein the polyethylene terephthalate resin has an absorbance (A) of at least about 0.30 cm⁻

1 at a wavelength of 1100 nm or at a wavelength of 1280 nm.

47. A polyethylene terephthalate resin according to claim 45, wherein the polyethylene terephthalate resin has an absorbance (A) of at least about 0.40 cm⁻

1 at a wavelength of 1100 nm or at a wavelength of 1280 nm.

48. A polyethylene terephthalate resin according to claim 45, wherein the polyethylene terephthalate resin has a 1100:

550 absorption ratio of at least about 75 percent, a 1280;

550 absorption ratio of at least about 75 percent, a 1100;

700 absorption ratio of at least about 85 percent, and a 1280;

700 absorption ratio of at least about 85 percent.

49. A polyethylene terephthalate resin according to claim 45, wherein the polyethylene terephthalate resin possesses a L* transmission value of more than about 80 as classified in the CIE L*a*b* color space.

50. A polyethylene terephthalate resin according to claim 45, wherein the polyethylene terephthalate resin possesses a b* color value of between about −

3 and 2 as classified by the CIE L*a*b* color space.

51. A polyethylene terephthalate resin according to claim 45, wherein the polyethylene terephthalate resin has an intrinsic viscosity more than about 0.68 dl/g.

52. A polyethylene terephthalate resin according to claim 45, wherein the polyethylene terephthalate resin has a crystalline melting peak temperature (T_M) of at least about 245°

C.

53. A polyethylene terephthalate resin according to claim 45, wherein the polyethylene terephthalate resin has a cooling crystallization exotherm peak temperature (T_CC) of less than 185°

C. at a cooling rate of 10°

C. per minute as measured by differential scanning calorimetry.

54. A polyethylene terephthalate resin according to claim 45, wherein the polyethylene terephthalate resin possesses less than about 10 percent haze at a thickness of more than about 4.5 mm as measured in a step parison.

55. A polyethylene terephthalate resin according to claim 45, wherein the polyethylene terephthalate resin comprises between about 3 and 4 mole percent comonomer substitution.

56. A polyethylene terephthalate resin according to claim 45, further comprising a heat-up rate additive that is present in the resin in an amount sufficient to improve the resin'"'"'s reheating profile.

57. A polyethylene terephthalate resin according to claim 45, further comprising between 2 and 20 ppm of elemental titanium.

58. A polyethylene terephthalate resin according to claim 45, further comprising between 15 and 40 ppm of elemental cobalt.

59. A polyethylene terephthalate resin according to claim 45, further comprising between about 2 and 20 ppm of elemental titanium, between about 15 and 40 ppm of elemental cobalt, and between about 2 and 15 ppm of elemental phosphorus.

60. A polyethylene terephthalate resin according to claim 45, wherein the polyethylene terephthalate resin comprises less than about 25 ppm of elemental antimony and less than about 5 ppm of elemental germanium.

61. A polyethylene terephthalate resin, comprising:

between about 2 and 50 ppm of elemental titanium; and

wherein the polyethylene terephthalate resin has an absorbance (A) of at least about 0.20 cm<sup>−

1</sup> at a wavelength of 1100 nm and at a wavelength of 1280 nm;

wherein the polyethylene terephthalate resin has a b* color value of less than 2 as classified by the CIE L*a*b* color space; and

wherein the polyethylene terephthalate resin has a L* transmission value of more than about 75 as classified in the CIE L*a*b* color space.

62. A polyethylene terephthalate resin according to claim 61, wherein the polyethylene terephthalate resin has an absorbance (A) of at least about 0.30 cm⁻

1 at a wavelength of 1100 nm or at a wavelength of 1280 nm.

63. A polyethylene terephthalate resin according to claim 61, wherein the polyethylene terephthalate resin has an absorbance (A) of at least about 0.40 cm⁻

1 at a wavelength of 1100 nm or at a wavelength of 1280 nm.

64. A polyethylene terephthalate resin according to claim 61, wherein the polyethylene terephthalate resin has a 1100:

550 absorption ratio of at least about 80 percent, a 1280;

550 absorption ratio of at least about 80 percent, a 1100;

700 absorption ratio of at least about 85 percent, and a 1280;

700 absorption ratio of at least about 85 percent.

65. A polyethylene terephthalate resin according to claim 61, wherein the polyethylene terephthalate resin has an intrinsic viscosity between about 0.72 dl/g and 0.84 dl/g.

66. A polyethylene terephthalate resin according to claim 61, wherein the polyethylene terephthalate resin has a crystalline melting peak temperature (T_M) of at least about 250°

C.

67. A polyethylene terephthalate resin according to claim 61, wherein the polyethylene terephthalate resin has a cooling crystallization exotherm peak temperature (T_CC) of less than 180°

C. at a cooling rate of 10°

C. per minute as measured by differential scanning calorimetry.

68. A polyethylene terephthalate resin according to claim 61, wherein the polyethylene terephthalate resin possesses less than about 10 percent haze at a thickness of between 4.5 and 6.0 mm as measured in a step parison.

69. A polyethylene terephthalate resin according to claim 61, wherein the polyethylene terephthalate resin comprises between about 2 and 5 mole percent comonomer substitution.

70. A polyethylene terephthalate resin according to claim 61, further comprising a heat-up rate additive that is present in the resin in an amount sufficient to improve the resin'"'"'s reheating profile.

71. A polyethylene terephthalate resin according to claim 61, wherein the polyethylene terephthalate resin comprises between about 5 and 15 ppm of elemental titanium.

72. A polyethylene terephthalate resin according to claim 61, further comprising between 15 and 40 ppm of elemental cobalt.

73. A polyethylene terephthalate resin according to claim 61, further comprising between about 2 and 10 ppm of elemental phosphorus.

74. A polyethylene terephthalate resin according to claim 61, further comprising between 15 and 40 ppm of elemental cobalt and between about 2 and 15 ppm of elemental phosphorus.

75. A polyethylene terephthalate resin according to claim 61, wherein the polyethylene terephthalate resin comprises less than about 25 ppm of elemental antimony and less than about 5 ppm of elemental germanium.

76. A polyethylene terephthalate resin, comprising:

between about 2 and 20 ppm of elemental titanium and between about 15 and 40 ppm of elemental cobalt; and

a heat-up rate additive; and

wherein the polyethylene terephthalate resin has a heating crystallization exotherm peak temperature (T_CH) of more than about 140°

C. at a heating rate of 10°

C. per minute as measured by differential scanning calorimetry;

wherein the polyethylene terephthalate resin has an absorbance (A) of at least about 0.25 cm<sup>−

1</sup> at a wavelength of 1100 nm or at a wavelength of 1280 nm; and

wherein the polyethylene terephthalate resin has a L* transmission value of more than about 70 as classified in the CIE L*a*b* color space.

77. A polyethylene terephthalate resin according to claim 76, wherein the polyethylene terephthalate resin has an absorbance (A) of at least about 0.30 cm⁻

1 at a wavelength of 1100 nm or at a wavelength of 1280 nm.

78. A polyethylene terephthalate resin according to claim 76, wherein the polyethylene terephthalate resin has an absorbance (A) of at least about 0.40 cm⁻

1 at a wavelength of 1100 nm or at a wavelength of 1280 nm.

79. A polyethylene terephthalate resin according to claim 76, wherein the polyethylene terephthalate resin has a 1100:

550 absorption ratio of at least about 75 percent, a 1280;

550 absorption ratio of at least about 75 percent, a 1100;

700 absorption ratio of at least about 90 percent, and a 1280;

700 absorption ratio of at least about 90 percent.

80. A polyethylene terephthalate resin according to claim 76, wherein the polyethylene terephthalate resin possesses a L* transmission value of more than about 80 as classified in the CIE L*a*b* color space.

81. A polyethylene terephthalate resin according to claim 76, wherein the polyethylene terephthalate resin possesses a b* color value of between about −

3 and 2 as classified by the CIE L*a*b* color space.

82. A polyethylene terephthalate resin according to claim 76, wherein the polyethylene terephthalate resin has an intrinsic viscosity between about 0.68 dl/g and 0.86 dl/g.

83. A polyethylene terephthalate resin according to claim 76, wherein the polyethylene terephthalate resin has a crystalline melting peak temperature (T_M) of at least about 245°

C.

84. A polyethylene terephthalate resin according to claim 76, wherein the polyethylene terephthalate resin has a cooling crystallization exotherm peak temperature (T_CC) of less than 185°

C. at a cooling rate of 10°

C. per minute as measured by differential scanning calorimetry.

85. A polyethylene terephthalate resin according to claim 76, wherein the polyethylene terephthalate resin possesses less than about 20 percent haze at a thickness of more than about 6 mm as measured in a step parison.

86. A polyethylene terephthalate resin according to claim 76, wherein the polyethylene terephthalate resin is composed of about a 1:

1 molar ratio of a diacid component and a diol component, and wherein the diacid component includes at least 94 mole percent terephthalic acid and the diol component includes at least 94 mole percent ethylene glycol.

87. A polyethylene terephthalate resin according to claim 76, wherein the polyethylene terephthalate resin is composed of about a 1:

1 molar ratio of a diester component and a diol component, wherein the diester component includes at least 94 mole percent dimethyl terephthalate and the diol component includes at least 94 mole percent ethylene glycol.

88. A polyethylene terephthalate resin according to claim 76, wherein the heat-up rate additive comprises a spinel that is present in the resin in an amount between about 15 and 25 ppm.

89. A polyethylene terephthalate resin according to claim 76, wherein the heat-up rate additive comprises a carbon-based heat-up rate additive that is present in the resin in an amount between about 4 and 16 ppm.

90. A polyethylene terephthalate resin according to claim 76, further comprising between about 2 and 10 ppm of elemental phosphorus.

91. A polyethylene terephthalate resin according to claim 76, wherein the polyethylene terephthalate resin is essentially free of antimony.

92. A polyethylene terephthalate resin according to claim 76, wherein the polyethylene terephthalate resin is essentially free of germanium.

93. A polyethylene terephthalate resin, wherein:

the polyethylene terephthalate resin has a heating crystallization exotherm peak temperature (T_CH) of more than about 140°

C. at a heating rate of 10°

C. per minute as measured by differential scanning calorimetry;

the polyethylene terephthalate resin has an absorbance (A) of at least about 0.20 cm<sup>−

1</sup> at a wavelength of 1100 nm and at a wavelength of 1280 nm; and

the polyethylene terephthalate resin has a 1100;

550 absorption ratio of at least about 70 percent, a 1280;

550 absorption ratio of at least about 70 percent, a 1100;

700 absorption ratio of at least about 85 percent, and a 1280;

700 absorption ratio of at least about 85 percent.

94. A polyethylene terephthalate resin according to claim 93, wherein the polyethylene terephthalate resin has an absorbance (A) of at least about 0.30 cm⁻

1 at a wavelength of 1100 nm or at a wavelength of 1280 nm.

95. A polyethylene terephthalate resin according to claim 93, wherein the polyethylene terephthalate resin has an absorbance (A) of at least about 0.40 cm⁻

1 at a wavelength of 1100 nm or at a wavelength of 1280 nm.

96. A polyethylene terephthalate resin according to claim 93, wherein the polyethylene terephthalate resin possesses a L* transmission value of more than about 70 and a b* color value of less than about 2 as classified by the CIE L*a*b* color space.

97. A polyethylene terephthalate resin according to claim 93, wherein the polyethylene terephthalate resin has an intrinsic viscosity between about 0.72 dl/g and 0.84 dl/g.

98. A polyethylene terephthalate resin according to claim 93, wherein the polyethylene terephthalate resin has a crystalline melting peak temperature (T_M) of at least about 240°

C.

99. A polyethylene terephthalate resin according to claim 93, wherein the polyethylene terephthalate resin has a cooling crystallization exotherm peak temperature (T_CC) of less than 190°

C. at a cooling rate of 10°

C. per minute as measured by differential scanning calorimetry.

100. A polyethylene terephthalate resin according to claim 93, wherein the polyethylene terephthalate resin possesses less than about 20 percent haze at a thickness of between 5.5 and 6.5 mm as measured in a step parison.

101. A polyethylene terephthalate resin according to claim 93, wherein the polyethylene terephthalate resin comprises between about 2 and 5 mole percent comonomer substitution.

102. A polyethylene terephthalate resin according to claim 93, wherein the polyethylene terephthalate resin comprises a heat-up rate additive.

103. A polyethylene terephthalate resin according to claim 93, wherein the polyethylene terephthalate resin comprises between about 5 and 15 ppm of elemental titanium, between about 15 and 40 ppm of elemental cobalt, and between about 2 and 10 ppm of elemental phosphorus.

104. A polyethylene terephthalate resin according to claim 93, wherein the polyethylene terephthalate resin comprises less than about 25 ppm of elemental antimony and less than about 5 ppm of elemental germanium.