Polyester resins for high-strength articles
View Patent ↗The present invention relates to slow-crystallizing, titanium-catalyzed polyethylene terephthalate resins that are useful for making high-strength, high-clarity bottles that possess improved resistance to stress cracking and thermal creep. The polyethylene terephthalate resins possess improved reheating profiles and are especially useful for making polyester articles that have exceptional clarity, dimensional stability, and thermal stability.
1. A polyethylene terephthalate resin, comprising:
polyethylene terephthalate polymers including between about 2 and 6 mole percent comonomer substitution;
between about 2 and 50 ppm of elemental titanium;
less than about 100 ppm of elemental antimony, if any;
more than about 20 ppm of elemental phosphorus;
a branching agent; and
a heat-up rate additive that is present in the resin in an amount sufficient to improve the resin's reheating profile; and
a nucleating agent, if any, in an amount that is insufficient to significantly decrease heating crystallization exotherm peak temperature (T CH );
wherein the polyethylene terephthalate resin has an L* value of more than about 65 as classified in the CIE L*a*b* color space, and an absorbance of at least about 0.18 cm −1 at a wavelength of 1100 nm or at a wavelength of 1280 nm.
2. A polyethylene terephthalate resin according to claim 1 , comprising nucleating agent, if any, in an amount that is insufficient to decrease heating crystallization exotherm peak temperature (T CH ) below about 140° C. at a heating rate of 10° C. per minute as measured by differential scanning calorimetry.
3. A polyethylene terephthalate resin according to claim 1 , comprising less than about 20 ppm of elemental titanium.
4. A polyethylene terephthalate resin according to claim 1 , further comprising between about 15 and 40 ppm of elemental cobalt.
5. A polyethylene terephthalate resin according to claim 1 , comprising branching agent in an amount greater than zero and less than about 0.4 percent mole-equivalent branches per mole of standardized polymer, the standardized polymer being unmodified polyethylene terephthalate.
6. A polyethylene terephthalate resin according to claim 1 , comprising branching agent in an amount between about 0.02 and 0.2 percent mole-equivalent branches per mole of standardized polymer, the standardized polymer being unmodified polyethylene terephthalate.
7. A polyethylene terephthalate resin according to claim 1 , comprising branching agent in an amount between about 0.04 and 0.075 percent mole-equivalent branches per mole of standardized polymer, the standardized polymer being unmodified polyethylene terephthalate.
8. A polyethylene terephthalate resin according to claim 1 , 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.
9. A polyethylene terephthalate resin according to claim 1 , wherein the polyethylene terephthalate resin has an L* 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 has an intrinsic viscosity greater than about 0.68 dL/g.
11. An article according to claim 1 , wherein the article comprises a film, a sheet, a preform, or a container.
12. A polyethylene terephthalate resin, comprising:
polyethylene terephthalate polymers including less than about 6 mole percent comonomer substitution;
between about 2 and 25 ppm of elemental titanium;
less than about 75 ppm of elemental antimony, if any;
more than about 15 ppm of elemental phosphorus;
a branching agent that is present in the resin in an amount greater than 0 and less than 0.1 mole percent; and
a heat-up rate additive that is present in the resin in an amount greater than 0 ppm and less than about 300 ppm; and
a nucleating agent, if any, in an amount that is insufficient to decrease heating crystallization exotherm peak temperature (T CH ) below 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 L* value of more than about 70 as classified in the CIE L*a*b* color space, and an absorbance of at least about 0.18 cm −1 at a wavelength of 1100 nm or at a wavelength of 1280 nm.
13. A polyethylene terephthalate resin according to claim 12 , wherein the polyethylene terephthalate polymers include between about 2 and 5 mole percent comonomer substitution.
14. A polyethylene terephthalate resin according to claim 12 , comprising:
less than about 50 ppm of elemental antimony, if any; and
less than about 20 ppm of elemental germanium, if any.
15. A polyethylene terephthalate resin according to claim 12 , 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.
16. A polyethylene terephthalate resin, comprising:
polyethylene terephthalate polymers including between about 2 and 6 mole percent comonomer substitution;
between about 2 and 20 ppm of elemental titanium;
less than about 25 ppm of elemental antimony, if any;
more than about 5 ppm of elemental phosphorus;
a branching agent; and
a heat-up rate additive comprising (i) a metal-containing heat-up rate additive that is present in the resin in an amount between about 10 and 300 ppm, optionally, (ii) 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; and
a nucleating agent, if any, in an amount that is insufficient to decrease heating crystallization exotherm peak temperature (T CH ) below 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 L* value of more than about 65 as classified in the CIE L*a*b* color space, and an absorbance of at least about 0.18 cm −1 at a wavelength of 1100 nm or at a wavelength of 1280 nm.
17. A polyethylene terephthalate resin according to claim 16 , comprising branching agent in an amount between about 0.01 and 0.1 percent mole-equivalent branches per mole of standardized polymer, the standardized polymer being unmodified polyethylene terephthalate.
18. A polyethylene terephthalate resin according to claim 16 , wherein the polyethylene terephthalate resin has an L* value of more than about 70 as classified in the CIE L*a*b* color space.
19. A polyethylene terephthalate resin according to claim 16 , wherein the polyethylene terephthalate resin possesses a b* color value of between −3 and 2 as classified by the CIE L*a*b* color space.
20. The polyethylene terephthalate resin according to claim 1 , wherein the heat-up rate additive is a chromite-spinel.
21. The polyethylene terephthalate resin according to claim 12 , wherein the heat-up rate additive is a chromite-spinel.
22. The polyethylene terephthalate resin according to claim 16 , wherein the heat-up rate additive is a chromite-spinel.
23. The polyethylene terephthalate resin according to claim 1 , wherein the absorbance (A) is at least about 0.30 cm −1 at a wavelength of 1100 nm or at a wavelength of 1280 nm.
24. The polyethylene terephthalate resin according to claim 12 , wherein the absorbance (A) is at least about 0.30 cm −1 at a wavelength of 1100 nm or at a wavelength of 1280 nm.
25. The polyethylene terephthalate resin according to claim 16 , wherein the absorbance (A) is at least about 0.30 cm −1 at a wavelength of 1100 nm or at a wavelength of 1280 nm.