Polyester Compositions Containing Cyclobutanediol Having High Glass Transition Temperature and Articles Made Therefrom

Abstract

Described are polyester compositions comprising at least one polyester which comprises terephthalic acid residues, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and cyclohexanedimethanol, wherein the inherent viscosity and the Tg of the polyester provides for certain polyester properties. The polyesters may be manufactured into articles such as fibers, films, bottles or sheets.

1 . A polyester composition comprising:
 (I) at least one polyester which comprises:
 a) a dicarboxylic acid component comprising:
 i) 80 to 100 mole % of terephthalic acid residues; 
 ii) 0 to 20 mole % of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and 
 iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and 
 
 (b) a glycol component comprising:
 i) 30 to 40 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and 
 ii) 60 to 70 mole % of cyclohexanedimethanol residues, and 
 
   (II) at least one thermal stabilizer chosen from at least one of alkyl phosphate esters, aryl phosphate esters, mixed alkyl aryl phosphate esters, reaction products thereof, and mixtures thereof;
 wherein the weight ratio of total tin atoms to total phosphorus atoms in the final polyester is 2-10:1; 
   
       wherein the total mole % of the dicarboxylic acid component is 100 mole %, and the total mole % of the glycol component is 100 mole %; and 
       wherein the inherent viscosity of said polyester is from 0.55 to 0.68 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at 25° C.; and wherein said polyester has a Tg from 110 to 150° C. 
     
     
         2 . (canceled) 
     
     
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         10 . The composition of  claim 1 , wherein the inherent viscosity of said polyester is from 0.60 to 0.68 dL/g. 
     
     
         11 . The composition of  claim 1 , wherein said polyester has a Tg of 110 to 130° C. 
     
     
         12 . The composition of  claim 1 , wherein said polyester has a Tg of 110 to 125° C. 
     
     
         13 . (canceled) 
     
     
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         17 . The composition of  claim 1 , wherein the dicarboxylic acid component comprises 90 to 100 mole % of terephthalic acid residues. 
     
     
         18 . (canceled) 
     
     
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         21 . The polyester composition of  claim 1 , wherein the polyester comprises from 0.01 to 10 mole % of ethylene glycol. 
     
     
         22 . (canceled) 
     
     
         23 . The composition of  claim 1 , wherein said 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues is a mixture comprising from 40 to 60 mole % of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and from 40 to 60 mole % of trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol residues. 
     
     
         24 . The composition of  claim 1 , wherein said polyester composition comprises at least one polymer chosen from at least one of the following: nylons; polyesters other than those of  claim 1 ; polyamides; polystyrene; polystyrene copolymers; styrene acrylonitrile copolymers; acrylonitrile butadiene styrene copolymers; poly(methylmethacrylate); acrylic copolymers; poly(ether-imides); polyphenylene oxides; or poly(phenylene oxide)/polystyrene blends; polyphenylene sulfides; polyphenylene sulfide/sulfones; poly(ester-carbonates); polycarbonates; polysulfones; polysulfone ethers; and poly(ether-ketones) of aromatic dihydroxy compounds; or mixtures thereof. 
     
     
         25 . The composition of  claim 1 , wherein said polyester composition contains no polycarbonate including bisphenol A polycarbonate. 
     
     
         26 . The composition of  claim 1 , wherein said polyester comprises residues of at least one branching agent for the polyester. 
     
     
         27 . (canceled) 
     
     
         28 . The composition of  claim 1 , wherein said polyester comprises residues of at least one branching agent in an amount of 0.01 to 5 weight % based on the total mole percentage of the acid or glycol residues. 
     
     
         29 . (canceled) 
     
     
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         38 . The composition of  claim 1 , wherein said polyester composition comprises at least one thermal stabilizer, reaction products thereof, and/or mixtures thereof chosen from at least one of alkyl phosphate esters, aryl phosphate esters, mixed alkyl aryl phosphate esters, reaction products, thereof, and mixtures thereof. 
     
     
         39 . The composition of  claim 1 , wherein said polyester composition comprises at least one thermal stabilizer, reaction products thereof, and/or mixtures thereof chosen from at least one one aryl phosphate ester. 
     
     
         40 . The composition of  claim 1 , wherein said polyester composition comprises at least one thermal stabilizer, reaction products thereof, and/or mixtures thereof chosen from at least one triaryl phosphate ester. 
     
     
         41 . The composition of  claim 1 , wherein said polyester composition of the invention may comprise at least one alkyl phosphate ester. 
     
     
         42 . The composition of  claim 1 , wherein said polyester composition comprises at least one thermal stabilizer, reaction products thereof, and/or mixtures thereof comprising triphenyl phosphate. 
     
     
         43 . (canceled) 
     
     
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         71 . The composition of  claim 1 , wherein said polyester composition comprises at least one thermal stabilizer, reaction products thereof, and/or mixtures thereof chosen from at least one of alkyl phosphate esters, aryl phosphate esters, mixed alkyl aryl phosphate esters, reaction products, thereof, and mixtures thereof. 
     
     
         72 . The composition of  claim 1 , wherein said polyester composition comprises at least one thermal stabilizer, reaction products thereof, and/or mixtures thereof chosen from at least one one aryl phosphate ester. 
     
     
         73 . The composition of  claim 1 , wherein said polyester composition comprises at least one thermal stabilizer, reaction products thereof, and/or mixtures thereof chosen from at least one one triaryl phosphate ester. 
     
     
         74 . (canceled) 
     
     
         75 . (canceled) 
     
     
         76 . The composition of  claim 1 , wherein said polyester comprises at least one thermal stabilizer, reaction products thereof, and/or mixtures thereof comprising phosphorus atoms. 
     
     
         77 . (canceled) 
     
     
         78 . An article of manufacture comprising the polyester composition of  claim 1 . 
     
     
         79 . A film or sheet comprising a polyester composition according to  claim 1 . 
     
     
         80 . The article of  claim 78  wherein the article of manufacture is formed by extrusion blow molding. 
     
     
         81 . (canceled) 
     
     
         82 . The article of  claim 78  wherein the article of manufacture is formed by injection molding. 
     
     
         83 . The article of  claim 78  wherein the article of manufacture is formed by injection stretch blow molding. 
     
     
         84 . A film or sheet according to  claim 79  wherein said film or sheet was produced by extrusion or calendering. 
     
     
         85 . (canceled) 
     
     
         86 . A blend comprising:
 (a) at least one polyester of  claim 1  in an amount from 5 to 95 weight %; and   (b) at least one polymeric component in an amount from 5 to 95 weight %.   
     
     
         87 . A blend of  claim 86 , wherein the at least one polymeric component is chosen from at least one of the following: nylons; polyesters other than the polyester of  claim 1 ; polyamides; polystyrene; polystyrene copolymers; styrene acrylonitrile copolymers; acrylonitrile butadiene styrene copolymers; poly(methylmethacrylate); acrylic copolymers; poly(ether-imides); polyphenylene oxides, such as poly(2,6-dimethylphenylene oxide); or poly(phenylene oxide)/polystyrene blends; polyphenylene sulfides; polyphenylene sulfide/sulfones; poly(ester-carbonates); polycarbonates; polysulfones; polysulfone ethers; and poly(ether-ketones) of aromatic dihydroxy compounds. 
     
     
         88 . A process for making the polyester of  claim 1  comprising the following steps:
 1. (I) heating a mixture at least one temperature chosen from 150° C. to 250° C., under at least one pressure chosen from the range of 0 psig to 75 psig wherein said mixture comprises:
 (a) a dicarboxylic acid component comprising:
 2. (i) 80 to 100 mole % of terephthalic acid residues; 
 3. (ii) 0 to 20 mole % of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and 
 (iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and 
 
 (b) a glycol component comprising:
 (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and 
 (ii) cyclohexanedimethanol residues; 
 
 wherein the molar ratio of glycol component/dicarboxylic acid component added in Step (I) is 1.0-1.5/1.0; 
 wherein the mixture in Step (I) is heated in the presence of: 
   (i) at least one catalyst comprising at least one tin compound, and, optionally, at least one catalyst chosen from titanium, gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium, aluminum compounds and an aluminum compound with lithium hydroxide or sodium hydroxide; and (ii) at least one thermal stabilizer chosen from at least one thermal stabilizer chosen from at least one of alkyl phosphate esters, aryl phosphate esters, mixed alkyl aryl phosphate esters, reaction products thereof, and mixtures thereof;
 wherein the weight ratio of total tin atoms to total phosphorus atoms in the final polyester is 2-10:1; 
   (II) heating the product of Step (I) at a temperature of 230° C. to 320° C. for 1 to 6 hours, under at least one pressure chosen from the range of the final pressure of Step (I) to 0.02 torr absolute, to form the final polyester;   
       wherein the total mole % of the dicarboxylic acid component of the final polyester is 100 mole %; wherein the total mole % of the glycol component of the final polyester is 100 mole %. 
     
     
         89 . The process of  claim 88  wherein the weight ratio of total tin atoms to total phosphorus atoms in the final polyester is 5-9:1. 
     
     
         90 . The process of  claim 88  wherein the thermal stabilizer is added in Steps (I) and (II). 
     
     
         91 . (canceled)