US2007059465A1PendingUtilityA1

Polyester Resins for High-Strength Articles

43
Individually held — no corporate assignee on recordPriority: May 20, 2004Filed: Aug 21, 2006Published: Mar 15, 2007
Est. expiryMay 20, 2024(expired)· nominal 20-yr term from priority
Inventors:David ThompsonCarl Steven NicholsTony Clifford MooreSharon Sue GriffithBilly Mack HumelsineRobert Joseph Schiavone
Y10T428/1352Y10T428/1355C08K 3/08C08G 63/672C08G 63/183C08G 63/80C08G 63/20
43
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Claims

Abstract

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.

Claims

exact text as granted — not AI-modified
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;    branching agent; and    heat-up rate additive that is present in the resin in an amount sufficient to improve the resin's reheating profile; and    wherein the polyethylene terephthalate resin has an L* value of more than about 65 as classified in the CIE L*a*b* color space.    
   
   
       2 . A polyethylene terephthalate resin according to  claim 1 , comprising less than about 20 ppm of elemental titanium.  
   
   
       3 . A polyethylene terephthalate resin according to  claim 1 , further comprising between about 15 and 40 ppm of elemental cobalt.  
   
   
       4 . 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.  
   
   
       5 . 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.  
   
   
       6 . A polyethylene terephthalate resin according to  claim 1 , comprising branching agent in an amount between about 0.03 and 0.14 percent mole-equivalent branches per mole of standardized polymer, the standardized polymer being unmodified polyethylene terephthalate.  
   
   
       7 . A polyethylene terephthalate resin according to  claim 6 , wherein the branching agent is selected from the group consisting of trimesic acid (C 6 H 3 (COOH) 3 ), pyromellitic acid (C 6 H 2 (COOH) 4 ), pyromellitic dianhydride, trimellitic acid, trimellitic anhydride, trimethylol propane (C 2 H 5 C(CH 2 OH) 3 ), ditrimethylol propane (C 2 H 5 C(CH 2 OH) 2 C 2 H 4 OC(CH 2 OH) 2 C 2 H 5 ), dipentaerythritol (CH 2 OHC(CH 2 OH) 2 C 2 H 4 OC(CH 2 OH) 2 CH 2 OH), pentaerythritol (C(CH 2 OH) 4 ), butanetetracarboxylic acid, ethoxylated glycerol, ethoxylated pentaerythritol, ethoxylated trimethylol propane, benzophenone tetracarboxylic acid, benzophenone tetracarboxylic dianhydride, naphthalene tetracarboxylic acid, naphthalene tetracarboxylic dianhydride, mixtures thereof, and derivatives thereof.  
   
   
       8 . 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.  
   
   
       9 . A polyethylene terephthalate resin according to  claim 1 , wherein the branching agent comprises dendrimers.  
   
   
       10 . A polyethylene terephthalate resin according to  claim 1 , wherein the branching agent comprises one or more aliphatic branching agents.  
   
   
       11 . A polyethylene terephthalate resin according to  claim 1 , wherein the branching agent comprises one or more aromatic branching agents.  
   
   
       12 . A polyethylene terephthalate resin according to  claim 1 , wherein the heat-up rate additive comprises one or more metal-containing heat-up rate additives.  
   
   
       13 . A polyethylene terephthalate resin according to  claim 1 , 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.  
   
   
       14 . A polyethylene terephthalate resin according to  claim 1 , 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.  
   
   
       15 . 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.  
   
   
       16 . 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.  
   
   
       17 . A polyethylene terephthalate resin according to  claim 1 , wherein the polyethylene terephthalate resin has a b* color value of less than 4 as classified by the CIE L*a*b* color space.  
   
   
       18 . A polyethylene terephthalate resin according to  claim 1 , wherein the polyethylene terephthalate resin has an intrinsic viscosity greater than about 0.50 dL/g.  
   
   
       19 . A polyethylene terephthalate resin according to  claim 1 , wherein the polyethylene terephthalate resin has an intrinsic viscosity greater than about 0.68 dL/g.  
   
   
       20 . An article formed from the polyethylene terephthalate resin according to  claim 1 .  
   
   
       21 . An article according to  claim 20 , wherein the article comprises a film, a sheet, a preform, or a container.  
   
   
       22 . 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;    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    wherein the polyethylene terephthalate resin has an L* value of more than about 70 as classified in the CIE L*a*b* color space.    
   
   
       23 . A polyethylene terephthalate resin according to  claim 22 , wherein the polyethylene terephthalate polymers include between about 2 and 5 mole percent comonomer substitution.  
   
   
       24 . A polyethylene terephthalate resin according to  claim 22 , comprising between about 5 and 15 ppm of elemental titanium.  
   
   
       25 . A polyethylene terephthalate resin according to  claim 22 , comprising: 
 less than about 50 ppm of elemental antimony, if any; and    less than about 20 ppm of elemental germanium, if any.    
   
   
       26 . A polyethylene terephthalate resin according to  claim 22 , comprising branching agent in an amount between about 0.03 and 0.08 percent mole-equivalent branches per mole of standardized polymer, the standardized polymer being unmodified polyethylene terephthalate.  
   
   
       27 . A polyethylene terephthalate resin according to  claim 26 , wherein the branching agent comprises (i) pentaerythritol or its derivatives, and/or (ii) trimellitic anhydride or its derivatives.  
   
   
       28 . A polyethylene terephthalate resin according to  claim 22 , wherein the heat-up rate additive is selected from the group consisting of spinels, carbon black, activated carbon, and graphite, and combinations thereof.  
   
   
       29 . A polyethylene terephthalate resin according to  claim 22 , 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.  
   
   
       30 . A polyethylene terephthalate resin according to  claim 22 , wherein the polyethylene terephthalate resin has an absorbance (A) of at least about 0.28 cm −1  at a wavelength of 1100 nm or at a wavelength of 1280 nm.  
   
   
       31 . A polyethylene terephthalate resin according to  claim 22 , wherein the polyethylene terephthalate resin has an intrinsic viscosity greater than about 0.6 dL/g.  
   
   
       32 . A polyethylene terephthalate resin according to  claim 22 , wherein the polyethylene terephthalate resin possesses less than 10 percent haze at a thickness of between 4.5 and 6.0 mm as measured in a step parison.  
   
   
       33 . A preform or container formed from the polyethylene terephthalate resin according to  claim 22 .  
   
   
       34 . 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;    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, and/or (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    wherein the polyethylene terephthalate resin has an L* value of more than about 65 as classified in the CIE L*a*b* color space.    
   
   
       35 . A polyethylene terephthalate resin according to  claim 34 , comprising less than about 10 ppm of elemental antimony, if any.  
   
   
       36 . A polyethylene terephthalate resin according to  claim 34 , comprising less than about 60 ppm of elemental phosphorus.  
   
   
       37 . A polyethylene terephthalate resin according to  claim 34 , further comprising between about 10 and 50 ppm of elemental cobalt.  
   
   
       38 . A polyethylene terephthalate resin according to  claim 34 , comprising branching agent in an amount greater than 0 and less than 0.1 mole percent.  
   
   
       39 . A polyethylene terephthalate resin according to  claim 38 , wherein the branching agent comprises pentaerythritol.  
   
   
       40 . A polyethylene terephthalate resin according to  claim 38 , wherein the branching agent comprises trimellitic anhydride and/or its corresponding acid.  
   
   
       41 . A polyethylene terephthalate resin according to  claim 34 , 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.  
   
   
       42 . A polyethylene terephthalate resin according to  claim 34 , comprising branching agent in an amount between about 0.025 and 0.075 percent mole-equivalent branches per mole of standardized polymer, the standardized polymer being unmodified polyethylene terephthalate.  
   
   
       43 . A polyethylene terephthalate resin according to  claim 34 , wherein the heat-up rate additive comprises a spinel that is present in the resin in an amount between about 10 and 100 ppm.  
   
   
       44 . A polyethylene terephthalate resin according to  claim 34 , wherein the heat-up rate additive comprises carbon black, activated carbon, or graphite, or combinations thereof.  
   
   
       45 . A polyethylene terephthalate resin according to  claim 34 , 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.  
   
   
       46 . A polyethylene terephthalate resin according to  claim 34 , wherein the polyethylene terephthalate resin has an L* value of more than about 70 as classified in the CIE L*a*b* color space.  
   
   
       47 . A polyethylene terephthalate resin according to  claim 34 , wherein the polyethylene terephthalate resin has an L* value of more than about 80 as classified in the CIE L*a*b* color space.  
   
   
       48 . A polyethylene terephthalate resin according to  claim 34 , 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.  
   
   
       49 . A polyethylene terephthalate resin according to  claim 34 , wherein the polyethylene terephthalate resin has an intrinsic viscosity between about 0.50 and 0.70 dL/g.  
   
   
       50 . A polyethylene terephthalate resin according to  claim 34 , wherein the polyethylene terephthalate resin has an intrinsic viscosity greater than about 0.68 dL/g.  
   
   
       51 . A polyethylene terephthalate resin according to  claim 34 , wherein the polyethylene terephthalate resin possesses less than 15 percent haze at a thickness of more than about 6 mm as measured in a step parison.  
   
   
       52 . An article formed from the polyethylene terephthalate resin according to  claim 34 .  
   
   
       53 . An article according to  claim 34 , wherein the article comprises a polyester bottle having sidewall haze of less than 10 percent.  
   
   
       54 . A polyethylene terephthalate resin, comprising: 
 polyethylene terephthalate polymers including less than about 6 mole percent comonomer substitution;    between about 10 and 25 ppm of elemental titanium;    less than about 100 ppm of elemental antimony, if any;    branching agent; and    heat-up rate additive that is present in the resin in an amount sufficient to improve resin reheating; and    wherein the polyethylene terephthalate resin has an L* value of more than about 65 as classified in the CIE L*a*b* color space.    
   
   
       55 . A polyethylene terephthalate resin according to  claim 54 , comprising: 
 less than about 75 ppm of elemental antimony, if any; and    more than about 15 ppm of elemental phosphorus.    
   
   
       56 . A polyethylene terephthalate resin according to  claim 54 , comprising: 
 less than about 50 ppm of elemental antimony, if any; and    more than about 10 ppm of elemental phosphorus.    
   
   
       57 . A polyethylene terephthalate resin according to  claim 54 , comprising: 
 less than about 25 ppm of elemental antimony, if any; and    more than about 5 ppm of elemental phosphorus.    
   
   
       58 . A polyethylene terephthalate resin according to  claim 54 , comprising branching agent in an amount greater than 0 and less than 0.1 mole percent.  
   
   
       59 . A polyethylene terephthalate resin according to  claim 58 , wherein the branching agent is selected from the group consisting of trifunctional, tetrafunctional, pentafunctional, and hexafunctional alcohols or acids, and mixtures and derivatives thereof, that will copolymerize with polyethylene terephthalate.  
   
   
       60 . A polyethylene terephthalate resin according to  claim 54 , comprising branching agent in an amount between about 0.025 and 0.1 percent mole-equivalent branches per mole of standardized polymer, the standardized polymer being unmodified polyethylene terephthalate.  
   
   
       61 . A polyethylene terephthalate resin according to  claim 54 , wherein the heat-up rate additive comprises (i) a metal-containing heat-up rate additive that is present in the resin in an amount between about 10 and 300 ppm, and/or (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.  
   
   
       62 . A polyethylene terephthalate resin according to  claim 54 , wherein the polyethylene terephthalate resin has an absorbance (A) of at least about 0.20 cm −1  at a wavelength of 1100 nm or at a wavelength of 1280 nm.  
   
   
       63 . A polyethylene terephthalate resin according to  claim 54 , wherein the polyethylene terephthalate resin has an L* value of more than about 70 as classified in the CIE L*a*b* color space.  
   
   
       64 . A polyethylene terephthalate resin according to  claim 54 , wherein the polyethylene terephthalate resin has an L* value of more than about 80 and a b* color value of less than 2 as classified by the CIE L*a*b* color space.  
   
   
       65 . A polyethylene terephthalate resin according to  claim 54 , wherein the polyethylene terephthalate resin has an intrinsic viscosity greater than about 0.6 dL/g.  
   
   
       66 . An article formed from the polyethylene terephthalate resin according to  claim 54.

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