Slow-crystallizing polyester resins
View Patent ↗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.
1. A polyethylene terephthalate resin, comprising:
less than about 25 ppm of elemental antimony, if any; and
more than about 5 ppm of elemental phosphorus; 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 0.18 cm −1 at a wavelength of 1100 nm or at a wavelength of 1280 nm; and
wherein the polyethylene terephthalate resin has an L* luminosity 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 an L* luminosity 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 an L* luminosity 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 additive 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, and combinations thereof.
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 less than about 60 ppm of elemental phosphorus.
37. A polyethylene terephthalate resin according to claim 1 , wherein the polyethylene terephthalate resin comprises less than about 40 ppm of elemental phosphorus.
38. A polyethylene terephthalate resin according to claim 1 , wherein the polyethylene terephthalate resin comprises less than about 10 ppm of elemental germanium, if any.
39. A polyethylene terephthalate resin according to claim 1 , wherein the polyethylene terephthalate resin comprises less than about 10 ppm of elemental antimony.
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 an 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 25 ppm of elemental antimony, if any;
more than about 5 ppm of elemental phosphorus; and
less than about 6 mole percent comonomer 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 −1 at a wavelength of 1100 nm or at a wavelength of 1280 nm; and
wherein the polyethylene terephthalate resin has an L* luminosity 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 an L* luminosity 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 , wherein the polyethylene terephthalate resin comprises between about 2 and 20 ppm of elemental titanium, between about 15 and 40 ppm of elemental cobalt, and less than about 60 ppm of elemental phosphorus.
60. A polyethylene terephthalate resin according to claim 45 , wherein the polyethylene terephthalate resin comprises less than about 10 ppm of elemental antimony and less than about 5 ppm of elemental germanium, if any.
61. A polyethylene terephthalate resin, comprising:
between about 2 and 50 ppm of elemental titanium;
less than about 25 ppm of elemental antimony, if any; and
at least about 5 ppm of elemental phosphorus; and
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;
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 an L* luminosity 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 , wherein the polyethylene terephthalate resin comprises less than about 40 ppm of elemental phosphorus.
74. A polyethylene terephthalate resin according to claim 61 , wherein the polyethylene terephthalate resin comprises between 15 and 40 ppm of elemental cobalt and less than about 60 ppm of elemental phosphorus.
75. A polyethylene terephthalate resin according to claim 61 , wherein the polyethylene terephthalate resin comprises less than about 10 ppm of elemental antimony and 20 ppm of elemental germanium, if any.
76. A polyethylene terephthalate resin, comprising:
between about 2 and 20 ppm of elemental titanium;
between about 15 and 40 ppm of elemental cobalt;
less than about 25 ppm of elemental antimony, if any;
at least about S ppm ofelemental phosphorus; 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 −1 at a wavelength of 1100 nm or at a wavelength of 1280 nm; and
wherein the polyethylene terephthalate resin has an L* luminosity 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 an L* luminosity 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 , wherein the polyethylene terephthalate resin comprises less than about 60 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, comprising:
less than about 25 ppm of elemental antimony, if any; and
at least about 5 ppm of elemental phosphorus; 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 0.20 cm −1 at a wavelength of 1100 nm and at a wavelength of 1280 nm; and
wherein 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 an L* luminosity 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 less than about 60 ppm of elemental phosphorus.
104. A polyethylene terephthalate resin according to claim 93 , wherein the polyethylene terephthalate resin comprises less than about 5 ppm of elemental germanium, if any.