EP1940910A2 - Polyester compositions comprising minimal amounts of cyclobutanediol - Google Patents
Polyester compositions comprising minimal amounts of cyclobutanediolInfo
- Publication number
- EP1940910A2 EP1940910A2 EP06827056A EP06827056A EP1940910A2 EP 1940910 A2 EP1940910 A2 EP 1940910A2 EP 06827056 A EP06827056 A EP 06827056A EP 06827056 A EP06827056 A EP 06827056A EP 1940910 A2 EP1940910 A2 EP 1940910A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- mole
- polyester
- ppm
- residues
- dicarboxylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
Definitions
- the present invention generally relates to polyester compositions comprising a polyester composition made from terephthalic acid, or an ester thereof, or mixtures thereof, 2,2,4 ,4-tetramethyM ,3-cyclobutanediol, ethylene glycol, and/or cyclohexanedimethanol, having a certain combination of two or more of good- impact strengths, good glass transition temperature (T 9 ), toughness, certain inherent and/or intrinsic viscosities, good ductile-to-brittle transition temperatures, good color and clarity, low densities, chemical resistance, hydrolytic stability, and long crystallization half-times, which allow them to be easily formed into- articles.
- T 9 good glass transition temperature
- PCT PoIy(1 ,4-cyclohexylenedimethylene) terephthalate
- a polyester based solely on terephthalic acid or an ester thereof and 1 ,4- cyclohexanedimethanol is known in the art and is commercially available.
- This polyester crystallizes rapidly upon cooling from the melt, making it very difficult to form amorphous articles by methods known in the art such as extrusion, injection molding, and the like.
- copolyesters can be prepared containing additional dicarboxylic acids or glycols such as isophthalic acid or ethylene glycol.
- ethylene glycol- or isophthalic acid-modified PCTs are also known in the art and are commercially available.
- One common copolyester used to produce films, sheeting, and molded articles is made from terephthalic acid, 1 ,4-cyclohexanedimethanol, and ethylene glycol. While these copolyesters are useful in many end-use applications, they exhibit deficiencies in properties such as glass transition temperature and impact strength when sufficient modifying ethylene glycol is included in the formulation to provide for long crystallization half-times.
- copolyesters made from terephthalic acid, 1 ,4-cyclohexanedimethanol, and ethylene glycol with sufficiently long crystallization half-times can provide amorphous products that exhibit what is believed to be undesirably higher ductile-to-brittle transition temperatures and lower glass transition temperatures than the compositions revealed herein.
- polyester compositions comprising at least one polymer having a combination of two or more properties, chosen from at least one of the following: toughness, good glass transition temperatures, good impact strength, hydrolytic stability, chemical resistance, good ductile to brittle transition temperatures, good color, and clarity, lower density, and/or thermoformability of polyesters while retaining processability on the standard equipment used in the industry.
- polyester compositions formed from terephthalic acid, an ester thereof, or mixtures thereof, and/or cyclohexanedimethanol and/or ethylene glycol, and 2,2,4,4-tetramethyl-1 ,3- cyclobutanediol are superior to certain polymers known in the art.
- this invention relates to a polyester composition
- a polyester composition comprising at least one polyester which comprises:
- a dicarboxylic acid component comprising: i) 70 to 100 mole % of terephthalic acid residues; ii) 0 to 30 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) 0.01 to less than 5 mole % of 2,2,4,4-tetramethyl-i ,3- cyclobutanediol residues; ii) ethylene glycol residues, and iii) optionally, cyclohexanedimethanol residues 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 intrinsic viscosity of the polyester is from 0.10 to 1.2 dL/g
- a dicarboxylic acid component comprising: i) 70 to 100 mole % of terephthalic acid residues; ii) 0 to 30 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
- this invention relates to a polyester composition
- a polyester composition comprising at least one polyester which comprises:
- a dicarboxylic acid component comprising: i) 70 to 100 mole % of terephthalic acid residues; ii) 0 to 30 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) 0.01 to 5 mole % of 2,2 ,4,4 ⁇ tetramethyl-1 ,3-cyclobutanediol residues; ii) ethylene glycol residues, and iii) 0.01 to 5 mole % cyclohexanedimethanol residues 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 intrinsic viscosity of the polyester is from 0.10 to 1.2 d
- a dicarboxylic acid component comprising: i) 70 to 100 mole % of terephthalic acid residues; ii) 0 to 30 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
- a glycol component comprising: i) 0.01 to 10 mole % or 0.01 to 5 mole % of 2,2,4,4-tetramethyl-
- the Tg can be from 70 to 100 0 C; or 70 to 95°C; or 70 to 90 0 C; or 70 to 100°C; or 70 to 95°C; or 70 to 90°C; 75 to 100°C; or 75 to 95°C; or 75 to 90 0 C; 80 to 105 0 C; or 80 to 100°C; or 80 to 95°C; or 80 to 90 0 C.
- the invention relates to a polyester composition
- a polyester composition comprising at least one polyester which comprises: (a) a tricarboxylic acid component comprising: i) 70 to 100 mole % of terephthalic acid residues; ii) 0 to 30 mole % of aromatic dicarboxylic acid residues having up to 2Q carbon atoms; and iii) 0-to 10 mole % of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and
- this invention relates to a polyester composition
- a polyester composition comprising at least one polyester which comprises:
- a dicarboxylic acid component comprising: i) 70 to 100 mole % of terephthalic acid residues; ii) 0 to 30 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
- the invention comprises a process for making any of the polyesters useful in the invention comprising the following steps:
- Step (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 phosphorus compound, reaction products thereof, and mixtures thereof; (II) heating the product of Step (I) at a temperature of 230 0 C to 320 0 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 a final polyester; wherein the total mole % of the dicarboxylic acid component of the final
- the invention comprises a process for making any of the polyesters of the invention comprising the following steps:
- Step (ii) cyclohexanedimethanol residues; wherein the molar ratio of glycol component/dicarboxylic acid component added in Step (I) is 1.05-1.15/1.0; 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 phosphorus compound, reaction products thereof, and mixtures thereof; (II) heating the product of Step (I) at a temperature of 230 0 C to 320 0 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 a final polyester; wherein the total mole % of the dicarboxylic acid component of the
- the invention comprises a process for making any of the polyesters of the invention comprising the following steps:
- Step (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; (II) heating, the product of Step (I) at a temperature of 230 0 C to 320 0 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, in the presence of at least one thermal stabilizer chosen from at least one phosphorus compound, reaction products thereof, and mixtures thereof; wherein the total mole % of the dicarboxylic acid component of the final polyester is 100 mole %;
- the invention comprises a process for making any of the polyesters of the invention comprising the following steps:
- Step (ii) cyclohexanedimethanol residues; wherein the molar ratio of glycol component/dicarboxylic acid component added in Step (I) is 1.05-1.15/1.0; wherein the mixture in Step (I) is heated in the presence of 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;
- Step (II) heating the product of Step (I) at a temperature of 230 0 C to 320 0 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, in the presence of at least one thermal stabilizer chosen from at least one phosphorus compound, reaction products thereof, and mixtures thereof; wherein the total mole % of the dicarboxylic acid component of the final polyester is 100 mole %; and wherein the total mole % of the glycol component of the final polyester is 100 mole %.
- the invention comprises a process for making any of the polyesters of the invention comprising the following steps:
- Step (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, antimo ⁇ y, 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 phosphorus compound, reaction products thereof, and mixtures thereof;
- Step (II) heating the product of Step (I) at a temperature of 250 0 C to 305 0 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 a final polyester; wherein the total mole % of the dicarboxylic acid component of the final polyester is 100 mole %; and wherein the total mole % of the glycol component of the final polyester is 100 mole %.
- the invention comprises a process for making any of the polyesters of the invention comprising the following steps:
- Step (ii) cyclohexanedimethanol residues; wherein the molar ratio of glycol component/dicarboxylic acid component added in Step (I) is 1.05-1.15/1.0; 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 phosphorus compound, reaction products thereof, and mixtures thereof;
- Step (II) heating the product of Step (I) at a temperature of 250 0 C to 305 0 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 a final polyester; wherein the total mole % of the dicarboxylic acid component of the final polyester is 100 mole %; and wherein the total mole % of the glycol component of the final polyester is 100 mole %.
- the invention comprises a process for making any of the polyesters of the invention comprising the following steps:
- Step (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 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;
- Step (II) heating the product of Step (I) at a temperature of 250 0 C to 305 0 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, in the presence of at least one thermal stabilizer chosen from at least one phosphorus compound, reaction products thereof, and mixtures thereof; wherein the total mole % of the dicarboxylic acid component of the final polyester is 100 mole %; and wherein the total mole % of the glycol component of the final polyester is 100 mole %.
- the invention comprises a process for making any of the polyesters of the invention comprising the following steps:
- Step (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 1.05-1.15/1.0; wherein the mixture in Step (I) is heated in the presence of 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;
- Step (II) heating the product of Step (I) at a temperature of 250 0 C to 305 0 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, in the presence of at least one thermal stabilizer chosen from at least one phosphorus compound, reaction products thereof, and mixtures thereof; wherein the total mole % of the dicarboxylic acid component of the final polyester is 100 mole %; and wherein the total mole % of the glycol component of the final polyester is 100 mole %°C.
- the invention comprises a process for making any of the polyesters of the invention comprising the following steps:
- Step (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 of alkyl phosphate esters, aryl phosphate esters, mixed alkyl aryl phosphate esters, reaction products thereof, and mixtures thereof;
- Step (II) heating the product of Step (I) at a temperature of 230 0 C to 320 0 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 a final polyester; wherein the total mole % of the dicarboxylic acid component of the final polyester is 100 mole %; and wherein the total mole % of the glycol component of the final polyester is 100 mole %°C.
- the invention comprises a process for making any of the polyesters useful in the invention comprising the following steps:
- Step (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 1.05-1.15/1.0; 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 of alkyl phosphate esters, aryl phosphate esters, mixed alkyl aryl phosphate esters, reaction products thereof, and mixtures thereof; to form a polyester; and (II) heating the product of Step (I) at a temperature of 230
- the invention comprises a process for making any of the polyesters useful in the invention comprising the following steps:
- Step (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 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;
- Step (II) heating the product of Step (I) at a temperature of 23O 0 C to 320 0 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, in the presence of 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; to form a polyester; and wherein the total mole % of the dicarboxylic acid component of the final polyester is 100 mole %; and wherein the total mole % of the glycol component of the final polyester is 100 mole %.
- the invention comprises a process for making any of the polyesters useful in the invention comprising the following steps:
- Step (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 1.05-1.15/1.0; wherein the mixture in Step (I) is heated in the presence of 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;
- Step (II) heating the product of Step (I) at a temperature of 230 0 C to 320 0 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, in the presence of 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; to form a 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 %.
- the invention comprises a process for making any of the polyesters useful in the invention comprising the following steps:
- a dicarboxylic acid component comprising: (i) 70 to 100 mole % of terephthalic acid residues;
- Step (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 of alkyl phosphate esters, aryl phosphate esters, mixed alkyl aryl phosphate esters, reaction products thereof, and mixtures thereof;
- Step (II) heating the product of Step (I) at a temperature of 230 0 C to 320 0 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 a final polyester; wherein the total mole % of the dicarboxylic acid component of the final polyester is 100 mole %; and wherein the total mole % of the glycol component of the final polyester is 100 mole%.
- the invention comprises a process for making any of the polyesters useful in the invention comprising the following steps:
- Step (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 1.05-1.15/1.0; 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 of alkyl phosphate esters, aryl phosphate esters, mixed alkyl aryl phosphate esters, reaction products thereof, and mixtures thereof;
- Step (II) heating the product of Step (I) at a temperature of 230 0 C to 320 0 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 a final polyester; wherein the total mole % of the dicarboxylic acid component of the final polyester is 100 mole %; and wherein the total mole % of the glycol component of the final polyester is 100 mole %.
- the invention comprises a process for making any of the polyesters useful in the invention comprising the following steps:
- Step (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;
- Step (II) heating the product of Step (I) at a temperature of 23O°C to 32O 0 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, in the presence of 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 total mole % of the dicarboxylic acid component of the final polyester is 100 mole %; and wherein the total mole % of the glycol component of the final polyester is 100 mole %.
- the invention comprises a process for making any of the polyesters useful in the invention comprising the following steps: (I) heating a mixture at at least one temperature chosen from 150 0 C to 200 0 C, under at least one pressure chosen from the range of 0 psig to 75 psig wherein said mixture comprises:
- Step (ii) cyclohexanedimethanol residues; wherein the molar ratio of glycol component/dicarboxylic acid component added in Step (I) is 1.05-1.15/1.0; wherein the mixture in Step (I) is heated in the presence of 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;
- the invention comprises a process for making any of the polyesters useful in the invention comprising the following steps:
- Step (I) 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol residues; and (ii) cyclohexanedimethanol residues; wherein the molar ratio of glycol component/dicarb ⁇ xylic 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 of alkyl phosphate esters, aryl phosphate esters, mixed alkyl aryl phosphate esters, reaction products thereof, and mixtures thereof;
- Step (II) heating the product of Step (I) at a temperature of 250 0 C to 305°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 a final polyester; wherein the total mole % of the dicarboxylic acid component of the final polyester is 100 mole %; and wherein the total mole % of the glycol component of the final polyester is 100 mole %.
- the invention comprises a process for making any of the polyesters useful in the invention comprising the following steps:
- Step (ii) cyclohexanedimethanol residues; wherein the molar ratio of glycol component/dicarboxylic acid component added in Step (I) is 1.05-1.15/1.0; 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 of alkyl phosphate esters, aryl phosphate esters, mixed alkyl aryl phosphate esters, reaction products thereof, and mixtures thereof; (II) heating the product of Step (I) at a temperature of 250 0 C to 305 0 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,
- the invention comprises a process for making any of the polyesters useful in the invention comprising the following steps:
- Step (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 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; (II) heating the product of Step (I) at a temperature of 250°C to
- the invention comprises a process for making any of the polyesters useful in the invention comprising the following steps:
- Step (ii) cyclohexanedimethanol residues; wherein the molar ratio of glycol component/dicarboxylic acid component added in Step (I) is 1.05-1.15/1.0; wherein the mixture in Step (I) is heated in the presence of 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;
- Step (II) heating the product of Step (I) at a temperature of 250 0 C to 305 0 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, in the presence of 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 total mole % of the dicarboxylic acid component of the final polyester is 100 mole %; and wherein the total mole % of the glycol component of the final polyester is 100 mole %.
- the invention comprises a process for making any of the polyesters useful in the invention comprising the following steps:
- Step (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 of alkyl phosphate esters, aryl phosphate esters, mixed alkyl aryl phosphate esters, reaction products thereof, and mixtures thereof;
- Step (II) heating the product of Step (I) at a temperature of 230 0 C to 320 0 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 a final polyester; wherein the total mole % of the dicarboxylic acid component of the final polyester is 100 mole %; and wherein the total mole % of the glycol component of the final polyester is 100 mole %.
- the invention comprises a process for making any of the polyesters useful in the invention comprising the following steps:
- Step (ii) cyclohexanedimethanol residues; wherein the molar ratio of glycol component/dicarboxylic acid component added in Step (I) is 1.05-1.15/1.0; 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 of alkyl phosphate esters, aryl- phosphate esters, mixed alkyl aryl phosphate esters, reaction products thereof, and mixtures thereof; to form a polyester; and (II) heating the product of Step (I) at a temperature of 230 0 C to 320 0 C for 1 to 6 hours, under at least one pressure chosen from the range of the final pressure of Step (I
- the invention comprises a process for making any of the polyesters useful in the invention comprising the following steps:
- Step (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 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;
- Step (II) heating the product of Step (I) at a temperature of 230 0 C to 320 0 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, in the presence of 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; to form a polyester; and wherein the total mole % of the dicarboxylic acid component of the final polyester is 100 mole %; and wherein the total mole % of the glycol component of the final polyester is 100 mole %.
- the invention comprises a process for making any of the polyesters useful in the invention comprising the following steps:
- 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 1.05-1.15/1.0; wherein the mixture in Step (I) is heated- in the presence of 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;
- Step (II) heating the product of Step (I) at a temperature of 230 0 C to 320 0 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, in the presence of 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; to form a polyester; [0038] wherein the total mole % of the dicarboxylic acid component of the final polyester is 100 mole %; and wherein the total mole % of the glycol component of the final polyester is 100 mole %.
- the polyster compositions of the invention contain at least one polycarbonate.
- the polyester compositions of the invention contain no polycarbonate.
- the polyesters useful in the invention contain less than 15 mole % ethylene glycol residues, such as, for example, 0.01 to less than 15 mole % ethylene glycol residues.
- the polyesters useful in the invention contain no ethylene glycol residues.
- the polyesters useful in the invention contain 50 to 99.99 mole % ethylene glycol residues. [0044] In one aspect, the polyesters useful in the invention contain no branching agent, or alternatively, at least one branching agent is added either prior to or during polymerization of the polyester.
- the polyesters useful in the invention contain at least one branching agent without regard to the method or sequence in which it is added.
- the polyesters useful in the invention are made from no 1 , 3-propanediol, or, 1 , 4-butanediol, either singly or in combination.
- 1 , 3-propanediol or 1 , 4-butanediol, either singly or in combination may be used in the making of the polyesters useful in this invention.
- the mole % of cis-2,2,4,4-tetramethyi- 1 ,3-cyclobutanediol useful in certain polyesters useful in the invention is greater than 50 mole % or greater than 55 mole % of cis-2,2,4,4-tetramethyl-1 ,3- cyclobutanediol or greater than 70 mole % of cis-2,2,4,4-tetramethyl-1 ,3- cyclobutanediol; wherein the total mole percentage of cis-2,2,4,4-tetramethyl-1 ,3- cyclobutanediol and trans-2,2,4,4-tetramethyl-1 ,3-cyclobutanediol is equal to a total of 100 mole %.
- the mole % of the isomers of 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol useful in certain polyesters useful in the invention is from 30 to 70 mole % of cis-2,2,4,4-tetramethyl-1 ,3-cyclobutanediol or from 30 to 70 mole % of trans-2,2,4,4-tetramethyl-1 ,3-cyclobutanediol, or from 40 to 60 mole % of cis-2,2,4,4-tetramethyl-1 ,3-cyclobutanediol or from 40 to 60 mole % of trans-2,2,4,4-tetramethyl-1 ,3-cyclobutanediol, wherein the total mole percentage of cis-2,2,4,4-tetramethyl-1 ,3-cyclobutanediol and trans-2,2,4,4-tetramethyl-1 ,3- cyclobutanediol, where
- certain polyesters useful in the invention may be amorphous or semicrystalline. In one aspect, certain polyesters useful in the invention can have a relatively low crystallinity. Certain polyesters useful in the invention can thus have a substantially amorphous morphology, meaning that the polyesters comprise substantially unordered regions of polymer. [0050] In one aspect, the polyesters useful in the invention can comprise at least one phosphorus compound whether or not present as a thermal stabilizer, for example, at least one phosphate ester.
- the polyesters and/or polyester compositions useful in the invention can comprise phosphorus atoms.
- the polyesters and/or polyester compositions useful in the invention can comprise tin atoms.
- the polyesters useful in the invention can comprise phosphorus atoms and tin atoms.
- the polyester compositions useful in the invention contain at least one thermal stabilizer and/or reaction products thereof.
- the polyesters useful in the invention can comprise at least one thermal stabilizer which comprises at least one phosphorus compound.
- the phosphorus compounds useful in the invention comprise phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphonous acid, and various esters and salts thereof.
- the esters can be alkyl, branched alkyl, substituted alkyl, difunctional alkyl, alkyl ethers, aryl, and substituted aryl.
- the thermal stabilizers useful in the invention comprise at least one phosphorus compound chosen from at least one of substituted or unsubstituted alkyl phosphate esters, substituted or unsubstituted aryl phosphate esters, substituted or unsubstituted mixed alkyl aryl phosphate esters, diphosphites, salts of phosphoric acid, phosphine oxides, and mixed aryl alkyl phosphites, reaction products thereof, and mixtures thereof.
- the phosphate esters include esters in which the phosphoric acid is fully esterified or only partially esterified.
- the phosphorus compounds useful in the invention at least one thermal stabilizer chosen from at least one of substituted or unsubstituted alkyl phosphate esters, substituted or unsubstituted aryl phosphate esters, mixed substituted or unsubstituted alkyl aryl phosphate esters, reaction products thereof, and mixtures thereof.
- the phosphate esters include esters in which the phosphoric acid is fully esterified or only partially esterified.
- the phosphorus compounds useful in the invention are chosen from at least one of alkyl phosphate esters, aryl phosphate esters, mixed alkyl aryl phosphate esters, reaction products, thereof, and mixtures thereof.
- any of the polyester compositions of the invention may comprise at least one aryl phosphate ester.
- any of the polyester compositions of the invention may comprise at least one unsubstituted aryl phosphate ester.
- any of the polyester compositions of the invention may comprise at least one aryl phosphate ester which is not substituted with benzyl groups.
- any of the polyester compositions of the invention may comprise at least one triaryl phosphate ester.
- any of the polyester compositions of the invention may comprise at least one triaryl phosphate ester which is not substituted with benzyl groups.
- any of the polyester compositions of the invention may comprise at least one alkyl phosphate ester.
- any of the polyester compositions of the invention may comprise triphenyl phosphate and/or Merpol A. In one embodiment, any of the polyester compositions of the invention may comprise triphenyl phosphate.
- the phosphorus compounds useful in the invention can be chosen from at least one of the following: diphosphites, salts of phosphoric acid, phosphine oxides, and mixed aryl alkyl phosphites.
- the phosphorus compounds useful in the invention comprise, but are not limited to, at least one diphosphite.
- the phosphorus compounds useful in the invention comprise, but are not limited to, at least one diphosphite which contains a
- 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane structure such as, for example, Weston 619 (GE Specialty Chemicals, CAS# 3806-34-6) and/or
- the phosphorus compounds useful in the invention comprise at least one mixed alkyl aryl phosphite, such as, for example, bis(2,4- dicumylphenyl)pentaerythritol diphosphite also known as Doverphos S-9228
- the phosphorus compounds useful in the invention comprise at least one phosphine oxide.
- the phosphorus compounds useful in the invention comprise at least one salt of phosphoric acid such as, for example, KH 2 PO 4 and
- any of processes described herein for making the polyester compositions and/or polyesters comprise at least one of the phosphorus compounds described herein.
- any of processes described herein for making any of the polyester compositions and/or polyesters can comprise at least one diphosphite.
- any of the processes described herein for making any of the polyester compositions and/or polyesters can comprise, at least one diphosphite which contains a 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane structure, such as, for example, Weston 619 (GE Specialty Chemicals, CAS# 3806-34-6) and/or Doverphos S-9228 (Dover Chemicals, CAS# 154862-43-8).
- the pressure used in Step (I) of any of the processes of the invention consists of at least one pressure chosen from 0 psig to 75 psig. In one embodiment, the pressure used I Step (I) of any of the processes of the invention consists of at least one pressure chosen from 0 psig to 50 psig.
- the pressure used in Step (II) of any of the processes of the invention consists of at least one pressure chosen from 20 torr absolute to
- the pressure used in Step (II) of any of the processes of the invention consists of at least one pressure chosen from 10 torr absolute to 0.02 torr absolute; in one embodiment, the pressure used in Step (II) of any of the processes of the invention consists of at least one pressure chosen from 5 torr absolute to 0.02 torr absolute; in one embodiment, the pressure used in Step (II) of any of the processes of the invention consists of at least one pressure chosen from 3 torr absolute to 0.02 torr absolute; in one embodiment, the pressure used in Step (II) of any of the processes of the invention consists of at least one pressure chosen from 20 torr absolute to 0.1 torr absolute; in one embodiment, the pressure used in Step (II) of any of the processes of the invention consists of at least one pressure chosen from 10 torr absolute to 0.1 torr absolute; in one embodiment, the pressure used in Step (II) of any of the processes of the invention consists of at least one pressure chosen from 5 tor
- the molar ratio of glycol component/dicarboxylic acid component added in Step (I) of any of the processes of the invention is 1.0- 1.5/1.0; in one aspect, the molar ratio of glycol component/dicarboxylic acid component added in Step (I) of any of the processes of the invention is 1.01- 1.5/1.0; in one aspect, the molar ratio of glycol component/dicarboxylic acid component added in Step (I) of any of the processes of the invention is 1.01- 1.3/1.0; in one aspect, the molar ratio of glycol component/dicarboxylic acid component added in Step (I) of any of the processes of the invention is 1.01- 1.2/1.0; in one aspect, the molar ratio of glycol component/dicarboxylic acid component added in Step (I) of any of the processes of the invention is 1.01- 1.15/1.0; in one aspect, the molar ratio of glycol component/dicarboxylic acid component added in Step (I) of any of the processes of the invention is 1.01- 1.
- the molar ratio of glycol component/dicarboxylic acid component added in Step (I) of any of the processes of the invention is 1.05- 1.5/1.0; in one aspect, the molar ratio of glycol component/dicarboxylic acid component added in Step (I) of any of the processes of the invention is 1.05- 1.3/1.0; in one aspect, the motar ratio of glycol component/dicarboxylic acid component added in Step (I) of any of the processes of the invention is 1.05- 1.2/1.0; in one aspect, the molar ratio of glycol component/dicarboxylic acid component added in Step (I) of any of the processes of the invention is 1.05- 1.15/1.0; and in one aspect, the molar ratio of glycol component/dicarboxylic acid component added in Step (I) of any of the processes of the invention is 1.01 - 1.10/1.0.
- the heating time of Step (II) may be from 1 to 5 hours. In any of the process embodiments for making the polyesters useful in the invention, the heating time of Step (II) may be from 1 to 4 hours. In any of the process embodiments for making the polyesters useful in the invention, the heating time of Step (II) may be from 1 to 3 hours. In any of the process embodiments for making the polyesters useful in the invention, the heating time of Step (II) may be from 1.5 to 3 hours. In any of the process embodiments for making the polyesters useful in the invention, the heating time of Step (II) may be from 1 to 2 hours.
- any of the polyester compositions and/or processes of the invention may comprise at least one tin compound as described herein.
- any of the polyester compositions and/or processes of the invention may comprise 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.
- any of the polyester compositions and/or processes of making the polyesters useful in the invention may be prepared using at least one tin compound and at least one titanium compound as catalysts.
- the addition of the phosphorus compound(s) in the process(es) of the invention can result in a weight ratio of total tin atoms to total phosphorus atoms in the final polyester of 2-10:1. In one embodiment, the addition of the phosphorus compound(s) in the process(es) can result in a weight ratio of total tin atoms to total phosphorus atoms in the final polyester of 5-9:1. In one embodiment, the addition of the phosphorus compound(s) in the process(es) can result in a weight ratio of total tin atoms to total phosphorus atoms in the final polyester of 6-8:1.
- the addition of the phosphorus compound(s) in the process(es) can result in a weight ratio of total tin atoms to- total phosphorus atoms in the final polyester of 7:1.
- the amount of tin atoms in the final polyester useful in the invention can be from 15 to 400 ppm tin atoms based on the weight of the final polyester.
- the amount of tin atoms in the final polyester useful in the invention can be from 25 to 400 ppm tin atoms based on the weight of the final polyester.
- the amount of tin atoms in the final polyester useful in the invention can be from 40 to 200 ppm tin atoms based on the weight of the final polyester.
- the amount of tin atoms in the final polyester useful in the invention can be from 50 to 125 ppm tin atoms based on the weight of the final polyester.
- the amount of phosphorus atoms in the final polyester useful in the invention can be from 1 to 100 ppm phosphorus atoms based on the weight of the final polyester.
- the amount of phosphorus atoms in the final polyester useful in the invention can be from 4 to 60 ppm phosphorus atoms based on the weight of the final polyester.
- the amount of phosphorus atoms in the final polyester useful in the invention can be from 6 to 20 ppm phosphorus atoms based on the weight of the final polyester. [0091] In one embodiment, the amount of phosphorus atoms in the final polyester useful in the invention can be from 1 to 100 ppm phosphorus atoms based on the weight of the final polyester and the amount of tin atoms in the final polyester can be from 15 to 400 ppm tin atoms based on the weight of the final polyester.
- the amount of phosphorus atoms in the final polyester useful in the invention can be from 1 to 100 ppm phosphorus atoms based on the weight of the final polyester and the amount of tin atoms in the final polyester can be from 25 to 400- ppm tin atoms based on the weight of the final polyester.
- the amount of phosphorus atoms in the final polyester useful in the invention can be from 4 to 60 ppm phosphorus atoms based on the weight of the final polyester and the amount of tin atoms in the final polyester can be from 40 to 200 ppm tin atoms based on the weight of the final polyester.
- the amount of phosphorus atoms in the final polyester useful in the invention can be from 6 to 20 ppm phosphorus atoms based on the weight of the final polyester and the amount of tin atoms in the final polyester can be from 50 to 125 ppm tin atoms based on the weight of the final polyester.
- any of the processes described herein for making any of the polyester compositions and/or polyesters can comprise at least one mixed alkyl aryl phosphites, such as, for example, bis(2,4-dicumylphenyl)pentaerythritol diphosphite also known as Doverphos S-9228 (Dover Chemicals, CAS# 154862-
- any of the processes described herein for making any of the polyester compositions and/or polyesters can comprise, at least one one phosphine oxide.
- any of the processes described herein for making any of the polyester compositions and/or polyesters can comprise, at least one salt of phosphoric acid such as, for example, KHaPO 4 and Zn 3 (PO 4 ⁇ .
- the polyester compositions are useful in articles of manufacture including, but not limited to, extruded, calendered, and/or molded articles including, but not limited to, injection molded articles, extruded articles, cast extrusion articles, profile extrusion articles, melt spun articles, thermoformed articles, extrusion molded articles, injection blow molded articles, injection stretch blow molded- articles, extrusion blow molded articles and extrusion stretch blow molded articles.
- These articles can include, but are not limited to, films, bottles, containers, sheet and/or fibers.
- the polyester compositions useful in the invention may be used in various types of film and/or sheet, including but not limited to extruded film(s) and/or sheet(s), calendered film(s) and/or sheet(s), compression molded film(s) and/or sheet(s), solution casted film(s) and/or sheet(s).
- Methods of making film and/or sheet include but are not limited to extrusion, calendering, compression molding, and solution casting.
- use of these particular polyester compositions minimizes and/or eliminates the drying step prior to melt processing and/or thermoforming.
- the polyesters useful in the invention can contain no cyclohexanedimethanol residues.
- the processes of the invention can comprise a batch or continuous process.
- the processes of the invention comprise a batch process.
- Figure 1 is a graph showing the effect of comonomer on the fastest crystallization half-times of modified PCT copolyesters.
- Figure 2 is a graph showing the effect of comonomer on the brittle-to- ductile transition temperature (T bd ) in a notched Izod impact strength test (ASTM D256, 1/8-in thick, 10-mil notch).
- Figure 3 is a graph showing the effect of 2,2,4,4-tetramethyl-1 ,3- cyclobutanediol composition on the glass transition temperature (Tg) of the copolyester.
- polyesters and/or polyester composition ⁇ can have a unique combination of two or more physical properties such as moderate or high impact strengths, high glass transition temperatures, chemical resistance, hydrolytic stability, toughness, low ductile-to-brittle transition temperatures, good color and clarity, low densities, and long crystallization half-times, and good processability thereby easily permitting them to be formed into articles.
- the polyesters have a unique combination of the properties of good impact strength, heat resistance, chemical resistance, density and/or the combination of the properties of good impact strength, heat resistance, and processability and/or the combination of two or more of the described properties, that have never before been believed to be present in the polyester compositions which comprise the polyester(s) as disclosed herein.
- polystyrene resin is intended to include “copolyesters” and is understood to mean a synthetic polymer prepared by the reaction of one or more difunctional carboxylic acids and/or multifunctional carboxylic acids with one or more difunctional hydroxyl compounds and/or multifunctional hydroxyl compounds.
- the difunctional carboxylic acid can be a dicarboxylic acid and the difunctional hydroxyl compound can be a dihydric alcohol such as, for example, glycols and diols.
- glycols and diols can be a dihydric alcohol such as, for example, glycols and diols.
- glycocol as used herein includes, but is not limited to, diols, glycols, and/or multifunctional hydroxyl compounds.
- the difunctional carboxylic acid may be a hydroxy carboxylic acid such as, for example, p-hydroxybenzoic acid
- the difunctional hydroxyl compound may be an aromatic nucleus bearing 2 hydroxyl substituents such as, for example, hydroquinone.
- reduce means any organic structure incorporated into a polymer through a polycondensation and/or an esterification reaction from the corresponding monomer.
- peeling unit means an organic structure having a dicarboxylic acid residue and a diol residue bonded through a carbonyloxy group.
- the dicarboxylic acid residues may be derived from a dicarboxylic acid monomer or its associated acid halides, esters, salts, anhydrides, or mixtures thereof.
- dicarboxylic acid is intended to include dicarboxylic acids and any derivative of a dicarboxylic acid, including its associated acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof, useful in a reaction process with a diol to make polyester.
- the term “diacid” includes includes multifunctional acids, for example, branching agents.
- terephthalic acid is intended to include terephthalic acid itself and residues thereof as well as any derivative of terephthalic acid, including its associated acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof or residues thereof useful in a reaction process with a diol to make polyester.
- the intrinsic viscosity (It. V.) values described throughout this description are set forth in dL/g unit as calculated from the inherent viscosity (Ih.V.) measured at 25°C in 60/40 wt/wt phenol/tetrachloroethane. The inherent viscosity is calculated from the measured solution viscosity. The following equations describe these solution viscosity measurements, and subsequent calculations to Ih.V. and from Ih.V.
- ⁇ inh [In (t s /t 0 )]/C
- ⁇ inh Inherent viscosity at 25 0 C at a polymer concentration of 0.5 g/ 100 mL of 60% phenol and 40% 1 ,1 ,2,2- tetrachloroethane by weight
- In Natural logarithm
- t s Sample flow time through a capillary tube
- t 0 Solvent-blank flow time through a capillary tube
- C Concentration of polymer in grams per 100 mL of solvent (0.50%)
- the intrinsic viscosity is the limiting value at infinite dilution of the specific viscosity of a polymer. It is defined by the following equation:
- Instrument calibration involves triplicate testing of a standard reference material and then applying appropriate mathematical equations to produce the "accepted" Ih. V. values.
- the three values used for calibration shall be within a range of 0.010; if not, correct problems and repeat testing of standard until three consecutive results within this range are obtained.
- Calibration Factor Accepted Ih.V. of Reference Material / Average of
- the corrected Ih.V. based on calibration with standard reference materials, is calculated as follows:
- the intrinsic viscosity (It.V. or ⁇ int ) may be estimated using the Billmeyer equation as follows:
- terephthalic acid may be used as the starting material.
- dimethyl terephthalate may be used as the starting material.
- mixtures of terephthalic acid and dimethyl terephthalate may be used as the starting material and/or as an intermediate material.
- the polyesters used in the present invention typically can be prepared from dicarboxylic acids and diols which react in substantially equal proportions and are incorporated into the polyester polymer as their corresponding residues.
- the polyesters of the present invention therefore, can contain substantially equal molar proportions of acid residues (100 mole%) and diol (and/or multifunctional hydroxyl compound) residues (100 mole%) such that the total moles of repeating units is equal to 100 mole%.
- the mole percentages provided in the present disclosure therefore, may be based on the total moles of acid residues, the total moles of diol residues, or the total moles of repeating units.
- a polyester containing 30 mole% isophthalic acid means the polyester contains 30 mole% isophthalic acid residues out of a total of 100 mole% acid residues. Thus, there are 30 moles of isophthalic acid residues among every 100 moles of acid residues.
- a polyester containing 30 mole% 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol means the polyester contains 30 mole% 2,2,4,4-tetramethyl-1 ,3- cyclobutanediol residues out of a total of 100 mole% diol residues. Thus, there are 30 moles of 2,2,4,4 ⁇ tetramethyl-1 ,3-cyclobutanediol residues among every 100 moles of diol residues.
- the Tg of the polyesters useful in the invention can be at least one of the following ranges: 60 to 120°C; 60 to 115°C; 6Qto 110 0 C; 60 to 105 0 C; 60 to 100 0 C; 60 to 95°C; 60 to 90°C; 60 to 85°C; 60 to 80°C; 60 to 75°C; 65 to 120°C; 65 to 115°C; 65 to 110 0 C; 65 to 105°C; 65 to 100°C; 65 to 95°C; 65 to 90 0 C; 65 to 85°C; 65 to 80 0 C; 65 to 75°C; 70 to 120°C; 70 to 115°C; 70 to 110°C; 70 to 105 0 C; 70 to 100 0 C; 70 to 95°C; 70 to 90°C; 70 to 85°C; 70 to 80°C; 70 to 75°C; 75 to 120°C; 75 to 115 0 C; 75 to 110°C; 75 to 105°C;
- the glycol component for the polyesters useful in the invention include but are not limited to at least one or more of the following combinations of ranges: 0.01 to less than 5 mole % of 2,2,4,4-tetramethyl-1 ,3- cyclobutanediol residues, 0.01 to greater than 95 mole %of ethylene glycol residues, and 0 to 99.98 mole % of cyclohexanedimethanol; 0.01 to less than 5 mole % of 2,2,4,4-tetramethyl-i ,3-cyclobutanediol residues, 0.01 to greater than 99.98 mole %of ethylene glycol residues, and 0.01
- the glycol component for the polyesters useful the invention include but are not limited to at least of the following combinations of ranges: 0.01 to 5 mole % of 2,2,4,4-tetramethyl-i ,3-cyclobutanediol residues, 89 to 94.99 mole % of ethylene glycol residues, and 5 to 10 mole % of cyclohexanedimethanol; 0.01 to 5 mole % of 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol residues, 89 to 94.99 mole % of ethylene glycol residues, and 5 to 10 mole % of cyclohexanedimethanol; 0.01 to 5 mole % of 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol residues, 89 to 94.99 mole % of ethylene glycol residues, and 5 to 10 mole % of cyclohexanedim
- the glycol component may also contain one of the following ranges of 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol residues: 0.01 to 10 mole%; 0.01 to 9.5 mole % 0.01 to 9 mole %; 0.01 to 8.5 mole %; 0.01 to 8 mole %; 0.01 to 7.5 mole %; 0.01 to 7.0; 0.01 to 6.5 mole %; 0.Q1 to 6 mole %; 0.01 to 5.5 mole %; 0.01 to 5 mole %; 0.01 to less than 5 mole %; 0.01 to 4.5 mole %; 0.01 to 4 mole %; 0.01 to 3.5 mole %; 0.01 to 3 mole %; 0.01 to 2.5 mole %; 0.01 to 2.0- mole %; 0.01 to 2.5 mole %; 0.01 to 2 mole %; 0.01 to 1.5 mole %; 0.01 to 1.0 mole %; and 0.01 to 0.5
- the remainder of the glycol component can include, but is not limited, to any amount of cyclohexanedimethanol and/or ethylene glycol so long as the total amount of the glycol component equals 100 mole %.
- the polyesters useful in the polyester compositions of the invention may be made from 1 ,3-propanediol, 1 ,4- butanediol, or mixtures thereof. It is contemplated that compositions of the invention made from 1 ,3-propanediol, 1 ,4-butanediol, or mixtures thereof can possess at least one of the Tg ranges described herein, at least one of the intrinsic viscosity ranges described herein, and/or at least one of the glycol or diacid ranges described herein.
- the polyesters made from 1 ,3-propanediol or 1 ,4-butanediol or mixtures thereof may also be made from 1 ,4-cyclohexanedmethanol in at least one of the following amounts: from 0.1 to 95 mole %; 0.1 to 90 mole %; from 0.1 to 80 mole %; from 0.1 to 70 mole %; from 0.1 to 60 mole %; from 0.1 to 50 mole %; from 0.1 to 40 mole %; from 0.1 to 35 mole %; from 0.1 to 30 mole %; from 0.1 to 25 mole %; from 0.1 to 20 mole %; from 0.1 to 15 mole %; from 0.1 to 10 mole %; from 0.1 to 5 mole %; from 1 to 99 mole %; from 1 to 90 mole %; from 1 to 80 mole %; from 1 to 70 mole %; from 1 to 60 mole %; from 1
- the polyesters useful in the invention may exhibit at least one of the following intrinsic viscosities as determined in 60/40 (wt/wt) phenol/ tetrachloroethane at a concentration of 0.25 g/50 ml at 25 0 C: 0.10 to 1.2 dL/g; 0.10 to 1.1 dL/g; 0.10 to 1 dL/g; 0.10 to less than 1 dL/g; 0.10 to 0.98 dL/g; 0.10 to 0.95 dL/g; 0.10 to 0.90 dL/g; 0.10 to 0.85 dL/g; 0.10 to 0.80 dL/g; 0.10 to 0.75 dL/g; 0.10 to less than 0.75 dL/g; 0.10 to 0.72 dL/g; 0.10 to 0.70 dL/g; 0.10 to less than 0.70 dL/g; 0.10 to 0.68 dL/g; 0.10 to less than 0.68 d
- the polyesters useful in the invention may exhibit at least one of the following intrinsic viscosities as determined in 60/40 (wt/wt) phenol/ tetrachloroethane at a concentration of 0.25 g/50 ml at 25 0 C: 0.45 to 1.2 dL/g; 0.45 to 1.1 dL/g; 0.45 to 1 dL/g; 0-.45 to 0.98 dL/g; 0.45 to 0.95 dL/g; 0.45 to 0.90 dL/g; 0.45 to 0.85 dL/g; 0.45 to 0.80 dL/g; 0.45 to 0.75 dL/g; 0.45 to less than 0.75 dL/g; 0.45 to 0.72 dL/g; 0.45 to 0.70 dL/g; 0.45 to less than 0.70 dL/g; 0.45 to 0.68 dL/g; 0.45 to less than 0.68 dL/g; 0.45 to 0.65
- the molar ratio of cis/trans 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol can vary from the pure form of each or mixtures thereof.
- the molar percentages for cis and/or trans 2,2,4 ,4,-tetramethyl-1 ,3-cyclobutanediol are greater than 50 mole % cis and less than 50 mole % trans; or greater than 55 mole % cis and less than 45 mole % trans; or 30 to 70 mole % cis and 70 to 30 % trans; or 40 to 60 mole % cis and 60 to 40 mole % trans; or 50 to 70 mole % trans and 50 to 30 % cis; or 50 to 70 mole % cis and 50 to 30 % trans; or 60 to 70 mole % cis and 30 to 40 mole % trans; or greater than 70 mole % cis and less
- polyesters useful in the polyester composition(s) of the invention can possess at least one of the intrinsic viscosity ranges described herein and at least one of the monomer ranges for the compositions described herein unless otherwise stated. It is also contemplated that polyesters useful in the container(s) of the invention can possess at least one of the Tg ranges described herein and at least one of the monomer ranges for the compositions described herein unless otherwise stated. It is also contemplated that compositions useful in the containers ⁇ of the invention can possess at least one of the intrinsic viscosity ranges described herein, at least one of the Tg ranges described herein, and at least one of the monomer ranges for the compositions described herein unless otherwise stated.
- terephthalic acid or an ester thereof such as, for example, dimethyl terephthalate or a mixture of terephthalic acid residues and an ester thereof can make up a portion or all of the dicarboxylic acid component used to form the polyesters useful in the invention.
- terephthalic acid residues can make up a portion or all of the dicarboxylic acid component used to form the present polyester at a concentration of at least 70 mole %, such as at least 80 mole %, at least 90 mole % at least 95 mole %, at least 99 mole %, or even 100 mole %.
- terephthalic acid and “dimethyl terephthalate” are used interchangeably herein.
- dimethyl terephthalate is part or all of the dicarboxylic acid component used to make the polyesters useful in the present invention.
- the terms :"terephthalic acid” and “dimethyl terephthalate” are used interchangeably herein.
- ranges of from 70 to 100 mole %; or 80 to 100 mole %; or 90 to 100 mole %; or 99 to 100 mole %; or 100 mole % terephthalic acid and/or dimethyl terephthalate and/or mixtures thereof may be used.
- the dicarboxylic acid component of the polyester useful in the invention can comprise up to 30 mole %, up to 20 mole %, up to 10 mole %, up to 5 mole%, or up to 1 mole % of one or more modifying aromatic dicarboxylic acids. Yet another embodiment contains 0 mole % modifying aromatic dicarboxylic acids.
- modifying aromatic dicarboxylic acids can range from any of these preceding endpoint values including, for example, from 0.01 to 30 mole %, 0.01 to 20 mole %, from 0.01 to 10 mole %, from 0.01 to 5 mole % and from 0.01 to 1 mole %.
- modifying aromatic dicarboxylic acids that may be used in the present invention include but are not limited to those having up to 20 carbon atoms, and which can be linear, para-oriented, or symmetrical.
- modifying aromatic dicarboxylic acids which may be used in this invention include, but are not limited to, isophthalic acid, 4,4'- biphenyldicarboxylic acid, 1 ,4-, 1 ,5-, 2,6-, 2,7-naphthalenedicarboxylic acid, and trans-4,4'-stilbenedicarboxylic acid, and esters thereof.
- the modifying aromatic dicarboxylic acid is isophthalic acid.
- the amount of isophthalic acid is present in an amount from 0.01 to 5 mole%.
- the aliphatic dicarboxylic acid component of the polyesters useful in the invention can be further modified with up to 10 mole %, such as up to 5 mole % or up to 1 mole % of one or more aliphatic dicarboxylic acids containing 2-16 carbon atoms, such as, for example, cyclohexanedicarboxylic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic and dodecanedioic dicarboxylic acids.
- up to 10 mole % such as up to 5 mole % or up to 1 mole % of one or more aliphatic dicarboxylic acids containing 2-16 carbon atoms, such as, for example, cyclohexanedicarboxylic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic and dodecanedioic dicarboxylic acids.
- Certain embodiments can also comprise 0.01 or more mole %, such as 0.1 to 30 mole %, 1 to 30, 5 to 30 mole %, or 10 to 30 mole % of one or more modifying aliphatic dicarboxylic acids. Yet another embodiment contains 0 mole % modifying aliphatic dicarboxylic acids. Thus, if present, it is contemplated that the amount of one or more modifying aliphatic dicarboxylic acids can range from any of these preceding endpoint values including, for example, from 0.01 to 10 mole % and from 0.1 to 10 mole %. The total mole % of the dicarboxylic acid component is 100 mole %.
- the modifying dicarboxylic acids of the invention can include indan dicarboxylic acids, for example, indan-1 ,3-dicarboxylic acids and/or phenylindan dicarboxylic acids.
- the dicarboxylic acid may be chosen from at least one of 1 ,2,3-trimethyl-3-phenylindan-4',5-dicarboxylic acid and 1 ,1 ,3-trimethyl-5-carboxy-3-(4-carboxyphenyl)indan dicarboxylic acid.
- 2006/0004151 A1 entitled "Copolymers Containing Indan Moieties and Blends Thereof by Shaikh et al., assigned to General Electric Company may be used as at least one modifying dicarboxylic acid within the scope of this invention; United States Patent Application Publication No. 2006/0004151 A1 is incorporated herein by reference with respect to any of the indan dicarboxylic acids described therein.
- esters of terephthalic acid and the other modifying dicarboxylic acids or their corresponding esters and/or salts may be used instead of the dicarboxylic acids.
- Suitable examples of dicarboxylic acid esters include, but are not limited to, the dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, and diphenyl esters.
- the esters are chosen from at least one of the following: methyl, ethyl, propyl, isopropyl, and phenyl esters.
- the cyclohexanedimethanol may be cis, trans, or a mixture thereof, for example, a cis/trans ratio of 60:40 to 40:60 or a cis/trans ratio of 70:30 to 30:70.
- the trans-cyclohexanedimethanol can be present in an amount of 60 to 80 mole % and the cis-cyclohexanedimethanol can be present in an amount of 20 to 40 mole % wherein the total ratio of cis and trans cyclohexanedimethanol is equal to 100 mole %.
- the trans-cyclohexanedimethanol can be present in an amount of 60 mole % and the cis-cyclohexanedimethanol can be present in an amount of 40 mole %. In particular embodiments, the trans-cyclohexanedimethanol can be present in an amount of 70 mole % and the cis-cyclohexanedimethanol can be present in an amount of 30 mole %. Any of 1 ,1-, 1 ,2-, 1 ,3-, 1 ,4- isomers of cyclohexanedimethanol or mixtures thereof may be present in the glycol component of this invention.
- the polyesters useful in the invention comprise 1 ,4-cyclohexanedimethanol. In another embodiment, the polyesters useful in the invention comprise 1 ,4-cyclohexanedimethanol and 1 ,3- cyclohexanedimethanol.
- the glycol component of the polyester portion of the polyester compositions useful in the invention can contain 25 mole % or less of one or more modifying glycols which are not 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol or cyclohexanedimethanol or ethylene glycol; in one embodiment, the polyesters useful in the invention may contain less than 15 mole % or of one or more modifying glycols. In another embodiment, the polyesters useful in the invention can contain 10 mole % or less of one or more modifying glycols. In another embodiment, the polyesters useful in the invention can contain 5 mole % or less of one or more modifying glycols.
- the polyesters useful in the invention can contain 3 mole % or less of one or more modifying glycols. In another embodiment, the polyesters useful in the invention can contain 0 mole % modifying glycols. Certain embodiments can also contain 0.01 or more mole %, such as 0.1 or more mole %, 1 or more mole %, 5 or more mole %, or 10 or more mole % of one or more modifying glycols. Thus, if present, it is contemplated that the amount of one or more modifying glycols can range from any of these preceding endpoint values including, for example, from 0.01 to 15 mole % and from 0.1 to 10 mole %.
- Modifying glycols useful in the polyesters useful in the invention refer to diols other than 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol and cyclohexanedimethanol or ethylene glycol and can contain 2 to 16 carbon atoms.
- suitable modifying glycols include, but are not limited to, 1 ,2- propanediol, 1 ,3-propanediol, neopentyl glycol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, p-xylene glycol, polytetramethylene glycol, or mixtures thereof.
- the modifying glycols include, but are not limited to, 1 ,3- propanediol and 1 ,4-butanediol.
- ethylene glycol is excluded as a modifying diol.
- 1 ,3-propanediol and 1 ,4- butanediol are excluded as modifying diols.
- 2, 2- dimethyl-1 ,3-propanediol is excluded as a modifying diol.
- the polyesters and/or the polycarbonates useful in the polyesters compositions of the invention can comprise from 0 to 10 mole percent, for example, from 0.01 to 5 mole percent, from 0.01 to 1 mole percent, from 0.05 to 5 mole percent, from 0.05 to 1 mole percent, or from 0.1 to 0.7 mole percent, based the total mole percentages of either the diol or diacid residues; respectively, of one or more residues of a branching monomer, also referred to herein as a branching agent, having 3 or more carboxyl substituents, hydroxyl substituents, or a combination thereof.
- the branching monomer or agent may be added prior to and/or during and/or after the polymerization of the polyester.
- the polyester(s) useful in the invention can thus be linear or branched.
- the polycarbonate can also be linear or branched.
- the branching monomer or agent may be added prior to and/or during and/or after the polymerization of the polycarbonate.
- Examples of branching monomers include, but are not limited to, multifunctional acids or multifunctional alcohols such as trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, glycerol, pentaerythritol, citric acid, tartaric acid, 3-hydroxyglutaric acid and the like.
- the branching monomer residues can comprise 0.1 to 0.7 mole percent of one or more residues chosen from at least one of the following: trimellitic anhydride, pyromellitic dianhydride, glycerol, sorbitol, 1 ,2,6-hexanetriol, pentaerythritol, trimethylolethane, and/or trimesic acid.
- the branching monomer may be added to the polyester reaction mixture or blended with the polyester in the form of a concentrate as described, for example, in U.S. Patent Nos. 5,654,347 and 5,696,176, whose disclosure regarding branching monomers is incorporated herein by reference.
- Tg glass transition temperature
- the polyesters useful in the invention can have a crystallization half-time of 1.5 minutes or less at 170°C.
- Increasing the content of cyclohexanedimethanol in a copolyester based on terephthalic acid, ethylene glycol, and cyclohexanedimethanol can improve toughness which can be determined by the brittle-to-ductile transition temperature in a notched Izod impact strength test as measured by ASTM D256.
- the melt viscosity of the polyester(s) useful in the invention is less than 30,000 poise as measured a 1 radian/second on a rotary melt rheometer at 290 0 C. In another embodiment, the melt viscosity of the polyester(s) useful in the invention is less than 20,000 poise as measured a 1 radian/second on a rotary melt rheometer at 290 0 C.
- the melt viscosity of the polyester(s) useful in the invention is less than 15,000- poise as measured at 1 radian/second (rad/sec) on a rotary melt rheometer at 290 D C. In one embodiment, the melt viscosity of the polyester(s) useful in the invention is less than 10,000 poise as measured at 1 radian/second (rad/sec) on a rotary melt rheometer at 290 0 C. In another embodiment, the melt viscosity of the polyester(s) useful in the invention is less than 6,000 poise as measured at 1 radian/second on a rotary melt rheometer at 290 0 C. Viscosity at rad/sec is related to processability.
- Typical polymers have viscosities of less than 10,000 poise as measured at 1 radian/second when measured at their processing temperature. Polyesters are typically not processed above 290 0 C. Polycarbonate is typically processed at 290 0 C. The viscosity at 1 rad/sec of a typical 12 melt flow rate polycarbonate is 7000 poise at 290°C.
- certain polyesters useful in this invention can be visually clear.
- the term "visually clear” is defined herein as an appreciable absence of cloudiness, haziness, and/or muddiness, when inspected visually.
- polycarbonate including but not limited to, bisphenol A polycarbonates
- the blends can be visually clear.
- the polyesters useful in the invention may have a yellowness index (ASTM D-1925) of less than 50 or less than 20.
- the polyesters useful in the invention and/or the polyester compositions of the invention, with or without toners can have color values L * , a* and b* which can be determined using a Hunter Lab Ultrascan Spectra Colorimeter manufactured by Hunter Associates Lab Inc., Reston, Va.
- the color determinations are averages of values measured on either pellets of the polyesters or plaques or other items injection molded or extruded from them. They are determined by the L*a*b* color system of the CIE (International Commission on Illumination) (translated), wherein L* represents the lightness coordinate, a* represents the red/green coordinate, and b* represents the yellow/blue coordinate.
- CIE International Commission on Illumination
- the b* values for the polyesters useful in the invention can be from -10 to less than 10 and the L* values can be from 50 to 90.
- the b * values for the polyesters useful in the invention can be present in one of the following ranges: from -10 to 9; -10 to 8; -10 to 7; -10 to 6; -10 to 5; -10 to 4; -10 to 3; -10 to 2; from -5 to 9; -5 to 8; -5 to 7; -5 to 6; -5 to 5; -5 to 4; -5 to 3; -5 to 2; 0 to 9; 0 to 8; 0 to 7; 0 to 6; 0 to 5; ⁇ to 4; 0 to 3; 0 to 2; 1 to 10; 1 to 9; 1 to 8; 1 to 7; 1 to 6; 1 to 5; 1 to 4; 1 to 3; and 1 to 2.
- the L* value for the polyesters useful in the invention can be present in one of the following ranges: 50 to 60; 50 to 70; 50 to 80; 50 to 90; 60 to 70; 60 to 80; 60 to 90; 70 to 80; 79 to 90.
- the polyesters useful in the invention can exhibit at least one of the following densities: a density of less than 1.3 g/ml at 23°C; a density of less than 1.2 g/ml at 23°C; a density of less than 1.18 g/ml at 23°C; a density of 0.70 to 1.2 g/ml at 23°C; a density of 0.70 to 1.3 g/ml at 23°C; a density of 0.70 to less than 1.2 g/ml at 23°C; a density of 0.75 to 1.2 at 23°C; a density of 0.75 g/ml to less than 1.2 at 23°C; a density of 0.80 g/ml to 1.2 at 23°C; a density of 0.80 to less than 1.2 g/ml at 23°C; a density of 0.90 to 1.2 g/ml at 23°C; a density of 1.0 to 1.2 g/ml at 23°C; a
- the polyesters useful in the polyester compositions of the invention have an intrinsic viscosity of at least 0.70 to 1.2 dL/g or at least 0.72 to 1.2 dL/g or at least 0.76 dL/g to 1.2 dL/g obtained from a melt phase polymerization-process.
- Melt phase polymerization can be defined as a process for increasing molecular weight of a polymer in the melt phase [00144]
- the polyesters useful in the polyester compositions of the invention have an intrinsic viscosity of at least 0.70 to 1.2 dL/g or at least 0.72 to 1.2 dL/g or at least 0.76 dL/g to 1.2 dL/g obtained from a melt phase polymerization-process and are not solid stated to obtain the described intrinsic viscosities.
- Solid state polymerization is a process known to one of ordinary skill in the art.
- the 2,2,4 ,4-tetramethyl-1 ,3-cyclobutanediol used to make the polyesters useful in the invention is fed to a melt processing zone for making articles of manfacture
- the invention includes, but is not limited to, a shipping container containing particles of at least one of the polyester compositions of the invention wherein at least one of the polyesters useful in the invention has an intrinsic viscosity of at least 0.72 dL/g or at least 0.76 dL/g obtained from a melt phase polymerization-process which is not solid stated for the purpose of obtaining the stated intrinsic viscosities process.
- polyester particles (which term includes pellets) of the invention are directly or indirectly packaged as a bulk into shipping containers, which are then shipped to customers or third parties, such as converters for converting the particles into articles such as bottle preforms or other molded articles, or as dual ovemable food trays or lids; through such procedures as injection molding or thermoforming.
- polyester particles it is preferred to subject the polyester particles to any process embodiment described herein without solid state polymerizing the particles at any point prior to packaging the particles into shipping containers, and also preferably at any point prior to melt processing the particles (solids) to make articles.
- a high It.V. polyester polymer in the melt phase e.g. at least 0.70 dL/g, or at least 0.72 dL/g, or at least 0.74 dL/g, or at least 0.76dL/g
- Solid stating is commonly used for increasing the molecular weight (and the It.V) of the pellets in the solid state, usually by at least 0.05 ItV.
- the It.V. of solid stated polyester solids ranges from 0.70 dL/g to 1.15 dL/g.
- the crystallized pellets are subjected to a countercurrent flow of nitrogen gas heated to 180 0 C to 220 0 C, over a period of time as needed to increase the It.V. to the desired target. In one embodiment, the It.V.
- polyester polymer particles are not increased by more than 0.1 dL/g units, or by not more than 0.05 dL/g units, or by not more than 0.03 dl_/g units, or not subjected to solid state polymerization at all prior to loading into a shipping container or prior to introducing the polyester polymer particles into an melt processing zone for making articles.
- Shipping containers are containers used for shipping over land, sea or air. Examples include railcars, semi-tractor trailer containers, Gaylord boxes, ship hulls, or any other container which is used to transport finished polyester particles to a customer.
- the shipping containers contain a bulk of polyester polymer particles.
- a bulk occupies a volume of at least 3 cubic meters.
- the bulk in the shipping container occupies a volume of at least 5 cubic meters, or at least 10 cubic meters.
- the melt phase polyester polymers are solidified to a desired form.
- the shape of the polyester polymer particles from the melt phase or in a shipping container is not limited, and can include regular or irregular shaped discrete pellets without limitation on their dimensions, including stars, spheres, spheroids, globoids, cylindrically shaped pellets, conventional pellets, pastilles, and any other shape, but particles are distinguished from a sheet, film, preforms, strands or fibers. These shapes regarded as articles. In one embodiment, the particles are in the shape of spheres.
- the number average weight (not to be confused with the number average molecular weight) of the particles is not particularly limited.
- number average weight is meant the number of particles per given unit of weight.
- the particles have a number average weight of at least 0.1O g per 100 particles, more preferably greater than 1.0 g per 100 particles, and up to about 100 g per 100 particles.
- the method for solidifying the polyester polymer from the melt phase process is not limited.
- molten polyester polymer from the melt phase may be directed through a die, or merely cut, or both directed through a die followed by cutting the molten polymer.
- a gear pump may be used as the motive force to drive the molten polyester polymer through the die.
- the molten polyester polymer may be fed into a single or twin screw extruder and extruded through a die, optionally at a temperature of 19O 0 C or more at the extruder nozzle.
- the polyester polymer can be drawn into strands, contacted with a cool fluid, and cut into pellets, or the polymer can be pelletized at the die head, optionally underwater.
- the polyester polymer melt is optionally filtered to remove large particulates over a designated size before being cut.
- Any conventional hot pelletization or dicing method and apparatus can be used, including but not limited to dicing, strand pelletizing and strand (forced conveyance) pelletizing, pastillators, water ring pelletizers, hot face pelletizers, underwater pelletizers and centrifuged pelletizers.
- the polyester polymer is one which is crystallizable.
- the method and apparatus used to crystallize the polyester polymer is not limited, and includes thermal crystallization in a gas or liquid.
- the crystallization may occur in a mechanically agitated vessel; a fluidized bed; a bed agitated by fluid movement; an un-agitated vessel or pipe; crystallized in a liquid medium above the T 9 of the polyester polymer, preferably at 140 0 C to 190 0 C; or any other means known in the art.
- the polymer may be strain crystallized.
- the polymer may also be fed to a crystallizer at a polymer temperature below its T g (from the glass), or it may be fed to a crystallizer at a polymer temperature above its T 9 .
- molten polymer from the melt phase polymerization reactor may be fed through a die plate and cut underwater, and then immediately fed to an underwater thermal crystallization reactor where the polymer is crystallized underwater.
- the molten polymer may be cut, allowed to cool to below its T 9 , and then fed to an underwater thermal crystallization apparatus or any other suitable crystallization apparatus.
- the molten polymer may be cut in any conventional manner, allowed to cool to below its T 9 , optionally stored, and then crystallized.
- One type of solidification technique integrates cutting with crystallization by not allowing the heat energy imparted to the polymer in the melt phase manufacture to drop below the T 9 before the polymer is both cut and crystallized to at least 20% degree of crystallinity.
- the molten polyester polymer is directed through a die, cut at the die plate under water at high temperature and greater than atmospheric pressure, swept away from the cutter by the hot water and through a series of pipes to provide residence time to thermally crystallize the particles in the hot liquid water at a temperature greater than the T 9 of the polymer and preferably at about 130 to 18O 0 C, after which the water is separated from the crystallized particles and the particles are dried.
- the molten polyester polymer is cut underwater, the particles are immediately separated from the liquid water after cutting, the particles are dried, and while the particles are still hot and before the temperature of the particles drops below the T 9 of the polymer and desirably while the particle temperature is above 140 0 C, the particles are directed from the dryer onto a surface or vessel which allows the particles to form a moving bed with a bed height sufficient to allow the latent heat within the particles to crystallize the particles without the external application of a heating medium or pressurizing means.
- a surface or vessel is desirably an at least partially enclosed vibrating conveyor, such as is available from Brookman Kreyenborg GmbH.
- the degree of crystallinity is optionally at least 20%, or at least 25%, or at least 30%, or at least 35%, or at least 40%. In another embodiment, the degree of crystallinity does not exceed 70%, or does not exceed 65%, or does not exceed 60%.
- the residual acetaldehyde level of the polyester polymer particles can also be reduced by any conventional technique, such as by gas stripping or the use of AA scavengers or trapping agents.
- the residual AA level of the particles is 10 ppm or less, or 8 ppm or less, or 5 ppm or less, or 4 ppm or less, or 3 ppm or less, or 2 ppm or less, or 1 ppm or less, prior to loading into a shipping container or prior to introducing the particles into a dryer hopper associated with a melt processing zone for making articles or prior to introducing the particles into a melt processing zone for making articles.
- the shipper container can transport particles comprising the polyester compositions of the invention from one city to another city or from one state to another state or from one country to another country. [00158] In some embodiments, use of the polyester compositions useful in the invention minimizes and/or eliminates the drying step prior to melt processing and/or thermoforming.
- the polyesters useful in this invention can have any moisture content, in one embodiment, they may have a moisture content of 0.02 to 1.0 weight percent of the total weight of the polyester prior to melt processing. [00160] In certain embodiments, the polyesters are dried by conventional methods for less than 2 hours at 60 0 C to 100 0 C prior to melt processing. [00161] The polyesters and/or polyester compositions and/or process either useful or of the invention can comprise at least one thermal stabilizer.
- Thermal stabilizers are compounds that stabilize polyesters during polyester manufacture and/or post polymerization, including but not limited to phosphorous compounds including but not limited to phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphonous acid, and various esters and salts thereof. These can be present in the polyester compositions useful in the invention.
- the esters can be alkyl, branched alkyl, substituted alkyl, difunctional alkyl, alkyl ethers, aryl, and substituted aryl.
- the number of ester groups present in the particular phosphorous compound can vary from zero up to the maximum allowable based on the number of hydroxy! groups present on the thermal stabilizer used.
- thermal stabilizer is intended to include the reaction product(s) thereof.
- reaction product as used in connection with the thermal stabilizers of the invention refers to any product of a polycondensation or esterification reaction between the thermal stabilizer and any of the monomers used in making the polyester as well as the product of a polycondensation or esterification reaction between the catalyst and any other type of additive.
- the thermal stabilizer(s) useful in the invention can be an organic compound such as, for example, a phosphorus acid ester containing halogenated or non-halogenated organic substituents.
- the thermal stabilizer can comprise a wide range of phosphorus compounds well-known in the art such as, for example, phosphines, phosphites, phosphinites, phosphonites, phosphinates, phosphonates, phosphine oxides, and phosphates.
- phosphorus compounds well-known in the art such as, for example, phosphines, phosphites, phosphinites, phosphonites, phosphinates, phosphonates, phosphine oxides, and phosphates.
- thermal stabilizers include tributyl phosphate, triethyl phosphate, tri- butoxyethyl phosphate, t-butylphenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, ethyl dimethyl phosphate, isodecyl diphenyl phosphate, trilauryl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, t- butylphenyl diphenylphosphate, resorcinol bis(diphenyl phosphate), tribe ⁇ zyl phosphate, phenyl ethyl phosphate, trimethyl thionophosphate, phenyl ethyl thionophosphate, dimethyl methylphosphonate, diethyl methylphosphonate, diethyl pentylphosphonate, dilauryl methylphosphonate, diphenyl
- thermal stabilizers useful in the invention can be any of the previously described phosphorus-based acids wherein one or more of the hydrogen atoms of the acid compound (bonded to either oxygen or phosphorus atoms) are replaced with alkyl, branched alkyl, substituted alkyl, alkyl ethers, substituted alkyl ethers, alkyl-aryl, alkyl-substituted aryl, aryl, substituted aryl, and mixtures thereof.
- thermal stabilizers useful in the invention include but are not limited to, the above described compounds wherein at least one of the hydrogen atoms bonded to an oxygen atom of the compound is replaced with a metallic ion or an ammonium ion.
- the esters can contain alkyl, branched alkyl, substituted alkyl, alkyl ethers, aryl, and/or substituted aryl groups.
- the esters can also have at least one alkyl group and at least one aryl group.
- the number of ester groups present in the particular phosphorus compound can vary from zero up to the maximum allowable based on the number of hydroxy! groups present on the phosphorus compound used.
- an alkyl phosphate ester can include one or more of the mono-, di-, and tri alkyl phosphate esters; an aryl phosphate ester includes one or more of the mono-, di-, and tri aryl phosphate esters; and an alkyl phosphate ester and/or an aryl phosphate ester also include, but are not limited to, mixed alkyl aryl phosphate esters having at least one alkyl and one aryl group.
- the thermal stabilizers useful in the invention include but are not limited to alkyl, aryl or mixed alkyl aryl esters or partial esters of phosphoric acid, phosphorus acid, phosphinic acid, phosphonic acid, or phosphonous acid.
- the alkyl or aryl groups can contain one or more substituents.
- the phosphorus compounds useful in the invention comprise at least one thermal stabilizer chosen from at least one of substituted or unsubstituted alkyl phosphate esters, substituted or unsubstituted aryl phosphate esters, substituted or unsubstituted mixed alkyl aryl phosphate esters, diphosphites, salts of phosphoric acid, phosphine oxides, and mixed aryl alkyl phosphites, reaction products thereof, and mixtures thereof.
- the phosphate esters include esters in which the phosphoric acid is fully esterified or only partially esterified.
- the thermal stabilizers useful in the invention can include at least one phosphate ester.
- the phosphorus compounds useful in the invention comprise at least one thermal stabilizer chosen from at least one of substituted or unsubstituted alkyl phosphate esters, substituted or unsubstituted aryl phosphate esters, mixed substituted or unsubstituted alkyl aryl phosphate esters, reaction products thereof, and mixtures thereof.
- the phosphate esters include esters in which the phosphoric acid is fully esterified or only partially esterified.
- the thermal stabilizers useful in the invention can include at least one phosphate ester.
- the phosphate esters useful in the invention can include but are not limited to alkyl phosphate esters, aryl phosphate esters, mixed alkyl aryl phosphate esters, and/or mixtures thereof.
- the phosphate esters useful in the invention are those where the groups on the phosphate ester include are alkyl, alkoxy- alky ⁇ phenyl, or substituted phenyl groups. These phosphate esters are generally referred to herein as alkyl and/or aryl phosphate esters. Certain preferred embodiments include trialkyl phosphates, triaryl phosphates, alkyl diaryl phosphates, dialkyl aryl phosphates, and mixtures of such phosphates, wherein the alkyl groups are preferably those containing from 2 to 12 carbon atoms, and the aryl groups are preferably phenyl.
- Representative alkyl and branched alkyl groups are preferably those containing from 1-12 carbon atoms, including, but not limited to, ethyl, propyl, isopropyl, butyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl, decyl and dodecyl.
- Substituted alkyl groups include, but are not limited to, those containing at least one of carboxylic acid groups and esters thereof, hydroxyl groups, amino groups, keto groups, and the like.
- alkyl-aryl and substituted alkyl-aryl groups are those wherein the alkyl portion contains from 1-12 carbon atoms, and the aryl group is phenyl or substituted phenyl wherein groups such as alkyl, branched alkyl, aryl, hydroxyl, and the like are substituted for hydrogen at any carbon position on the phenyl ring.
- Preferred aryl groups include phenyl or substituted phenyl wherein groups such as alkyl, branched alkyl, aryl, hydroxyl and the like are substituted for hydrogen at any position on the phenyl ring.
- the phosphate esters useful as thermal stabilizers in the invention include but are not limited to dibutylphenyl phosphate, triphenyl phosphate, tricresyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, trioctyl phosphate, and/or mixtures thereof, including particularly mixtures of tributyl phosphate and tricresyl phosphate, and mixtures of isocetyl diphenyl phosphate and 2-ethylhexyl diphenyl phosphate.
- the phosphate esters useful as thermal stabilizers in the invention include but are not limited to, at least one of the following: trialkyl phosphates, triaryl phosphates, alkyl diaryl phosphates, and mixed alkyl aryl phosphates.
- the phosphate esters useful as thermal stabilizers in the invention include but are not limited to, at least one of the following: triaryl phosphates, alkyl diaryl phosphates, and mixed alkyl aryl phosphates.
- the phosphate esters useful as thermal stabilizers in the invention include but are not limited to, at least one of the following: triaryl phosphates and mixed alkyl aryl phosphates.
- At least one thermal stabilizer comprises, but is not limited to, triaryl phosphates, such as, for example, triphenyl phosphate. In one embodiment, at least one one thermal stabilizer comprises, but is not limited to
- At least one thermal stabilizer useful in the invention comprises, but is not limited to, triaryl phosphates, such as, for example, triphenyl phosphate.
- at least one one thermal stabilizer comprises, but is not limited to Merpol A.
- at least one thermal stabilizer useful in the invention comprises, but is not limited to, at least one of triphenyl phosphate and Merpol A.
- Merpol A is a phosphate ester commercially available from Stepan Chemical Co and/or E.I. duPont de Nemours
- the polyester compositions and/or processes of the invention may comprise 2-ethylhexyl diphenyl phosphate.
- the phosphorus compounds useful in the invention comprise, but are not limited to, at least one diphosphite.
- the phosphorus compounds useful in the invention comprise, but are not limited to, at least one diphosphite which contains a 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane structure, such as, for example, Weston 619 (GE Specialty Chemicals, CAS# 3806-34-6) and/or
- the phosphorus compounds useful in the invention comprise at least one phosphine oxide, such as, for example, triphenylphosphine oxide.
- the phosphorus compounds useful in the invention comprise at least one mixed alkyl aryl phosphites, such as, for example, bis(2,4- dicumylphenyl)pentaerythritol diphosphite also known as Doverphos S-9228
- any of processes described herein for making the polyester compositions and/or polyesters comprise at least one of the phosphorus compounds described herein.
- any of processes described herein for making any of the polyester compositions and/or polyesters can comprise at least one diphosphite.
- any of the processes described herein for making any of the polyester compositions and/or polyesters can comprise, at least one diphosphite which contains a 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane structure, such as, for example, Weston 619 (GE Specialty Chemicals, CAS#
- any of the processes described herein for making any of the polyester compositions and/or polyesters can comprise at least one phosphine oxide, such as, for example, triphenylphosphine oxide.
- any of the processes described herein for making any of the polyester compositions and/or polyesters can comprise at least one mixed alkyl aryl phosphites, such as, for example, bis(2,4-dicumylphenyl)pentaerythritol diphosphite also known as Doverphos S-9228 (Dover Chemicals, CAS# 154862-
- phosphorus When phosphorus is added to the polyesters and/or polyester compositions and/or process of making the polyesters of the invention, it is added in the form of a phosphorus compound as described herein, for example, at least one phosphate ester, at least one diphosphite, at least one salt of phosphoric acid.
- the amount of phosphorus compound(s), (for example, at least one diphosphite), is added to the polyesters of the invention and/or polyester compositions of the invention and/or processes of the invention can be measured in the form of phosphorus atoms present in the final polyester, for example, by weight measured in ppm.
- Amounts of thermal stabilizer added during polymerization or post manufacturing can include but are not limited to: 1 to 5000 ppm; 1 to 1000 ppm, 1 to 900 ppm, 1 to 800 ppm, 1 to 700 ppm. 1 to 600 ppm, 1 to 500 ppm, 1 to 400 ppm, 1 to 350 ppm, 1 to 300 ppm, 1 to 250 ppm, 1 to 200 ppm, 1 to 150 ppm, 1 to 100 ppm; 10 to 5000 ppm; 10 to 1000 ppm, 10 to 900 ppm, 10 to 800 ppm, 10 to 700 ppm.
- amounts of the phosphorus compound (for example, diphosphite, phosphate ester, etc.) of the invention added during polymerization are chosen from the following: 1 to 5000 ppm; 1 to 1000 ppm, 1 to 900 ppm, 1 to 800 ppm, 1 to 700 ppm. 1 to 600 ppm, 1 to 500 ppm, 1 to 400 ppm, 1 to 350 ppm, 1 to 300 ppm, 1 to 250 ppm, 1 to 200 ppm, 1 to 150 ppm, 1 to 100 ppm; 1 to 60 ppm; 2 to 5000 ppm; 2 to 1000 ppm, 2 to 900 ppm, 2 to 800 ppm, 2 to 700 ppm.
- Suitable catalysts for use in the processes of the invention to make the polyesters useful in the invention include at least one tin compound.
- the polyester compositions of the invention may also comprise at least one of the tin compounds useful in the processes of the invention.
- Other catalysts could possibly be used in the invention in combination with the at least one tin compound
- Other catalysts may include, but are not limited to, those based on titanium, gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium, aluminum compounds, and an aluminum compound with lithium hydroxide or sodium hydroxide.
- the catalyst can be a combination of at least one tin compound and at least one titanium compound.
- Catalyst amounts can range from 10 ppm to 20,000 ppm or 10 to10,000 ppm, or 10 to 5000 ppm or 10 to 1000 ppm or 10 to 500 ppm, or 10 to 300 ppm or 10 to 250 ppm based on the catalyst metal and based on the weight of the final polymer.
- the process can be carried out in either a batch or continuous process.
- the catalyst is a tin compound.
- the catalyst is solely a tin compound.
- the tin compound can be used in either the esterification reaction or the polycondensation reaction or both reactions.
- the catalyst is solely a tin compound used in the esterification reaction.
- the tin compound catalyst is used in amounts of from about 0.005% to about 0.2% based on the weight of the dicarboxylic acid or dicarboxylic acid ester. Generally, in one embodiment, less than about 700 ppm elemental tin based on polyester weight should be present as residue in the polyester based on the total weight of the polyester.
- tin When tin is added to to the polyesters and/or polyester compositions and/or process of making the polyesters of the invention, it is added to the process of making the polyester in the form of a tin compound.
- the amount of the tin compound added to the polyesters of the invention and/or polyester compositions of the invention and/or processes of the invention can be measured in the form of tin atoms present in the final polyester, for example, by weight measured in ppm.
- the catalyst is solely a tin compound used in the esterification reaction in the amount of 10 ppm to 20,0OQ ppm or 10 to10,000 ppm, or 10 to 5000 ppm or 10 to 4500 ppm or 10 to 4000 ppm or 10 to 3500 ppm or 10 to 3000 ppm or 10 to 2500 ppm or 10 to 2000 ppm or or 10 to 1500 ppm or 10 to 1000 ppm or 1 O to 500 ppm, or 10 to 300 ppm or 10 to 250 ppm or 15 ppm to 20,000 ppm or 15 to10,000 ppm, or 15 to 5000 ppm or or 15 to 4500 ppm or 15 to 4000 ppm or 15 to 3500 ppm or 15 to 3000 ppm or 15 to 2500 ppm or 15 to 2000 ppm or 15 to 1500 ppm or 15 to 1000 ppm or 15 to 500 ppm or 15 to 400 ppm or 15 to 300 ppm or 15
- the polyesters of the invention can be prepared using at least one tin compound as catalyst.
- tin compound as catalyst.
- these catalysts are tin compounds containing at least one organic radical.
- These catalysts include compounds of both divalent or tetravalent tin which have the general formulas set forth below:
- M is an alkali metal, e.g. lithium, sodium, or potassium
- M' is an alkaline earth metal such as Mg, Ca or Sr
- each R represents an alkyl radical containing- from 1 to 8 carbon atoms
- each R' radical represents a substituent selected from those consisting of alkyl radicals containing from 1 to 8 carbon atoms (i. e. R radicals) and aryl radicals of the benzene series containing from 6 to 9 carbon atoms (e.g. phenyl, tolyl, benzyl, phenylethyl, etc., radicals)
- Ac represents an acyl radical derived from an organic acid containing from 2 to 18 carbon atoms (e.g. acetyl, butyryl, lauroyl, benzoyl, stearoyl, etc. ).
- novel bimetallic alkoxide catalysts can be made as described by Meerwein, Ann. 476, 113 (1929). As shown by Meerwein, these catalysts are not merely mixtures of the two metallic alkoxides. They are definite compounds having a salt-like structure. These are the compounds depicted above by the Formulas A through H. Those not specifically described by Meerwein can be prepared by procedures analogous to the working examples and methods set forth by Meerwein.
- alkyl tin salts see CA. 31 , 4290.
- alkyl tin compounds see CA. 35, 2470 (1941): CA. 33, 5357 (1939).
- mixed alkyl aryl tin see CA. 31 , 4290 (1937): CA. 38, 331 (1944).
- tin compounds not covered by these citations see "Die Chemie der Metal- Organischen Kunststoffen.” by Krause and V. Grosse, published in Berlin, 1937, by Gebroder-Bomtrager.
- the tin alkoxides (Formulas I and J) and the bimetallic alkoxides (Formulas A through H) contain R substituents which can represent both straight chain and branched chain alkyf radicals, e.g. diethoxide, tetrameth ⁇ xide, tetrabutoxide, tetra-tert-butoxide, tetrahexoxide, etc.
- R substituents which can represent both straight chain and branched chain alkyf radicals, e.g. diethoxide, tetrameth ⁇ xide, tetrabutoxide, tetra-tert-butoxide, tetrahexoxide, etc.
- the alkyl derivatives (Formulas K and L) contain one or more alkyl radicals attached to a tin atom through a direct C-Sn linkage, e.g.
- the tin catalyst comprises dimethyl tin oxide.
- Complexes can be formed by reacting dialkyl tin oxides with alkali metal alkoxides in an alcohol solution to form compounds having Formula N, which compounds are especially useful catalysts, e.g. react dibutyl tin oxide with sodium ethoxide, etc. This formula is intended to represent the reaction products described. Tin compounds containing alkyl and alkoxy radicals are also useful catalysts (see Formula O), e.g. diethyl tin diethoxide, dibutyl tin dibutoxide, dihexyl tin dimethoxide, etc.
- Salts derived from dialkyl tin oxides reacted with carboxylic acids or hydrochloric acid are also of particular value as catalysts; see Formulas P and Q.
- these catalytic condensing agents include dibutyl tin diacetate, diethyl tin dibutyrate, dibutyl tin dilauroate, dimethyl tin dibenzoate, dibutyl tin dichloride, diethyl tin dichloride, dioctyl tin dichloride, dihexyl tin distearate, etc.
- the tin compounds having Formulas K, L and M can be prepared wherein one or more of the R 1 radicals represents an aryl radical of the benzene series, e.g. phenyl, tolyl, benzyl, etc.
- R 1 radicals represents an aryl radical of the benzene series, e.g. phenyl, tolyl, benzyl, etc.
- examples include diphenyl tin, tetraphenyl tin, diphenyl dibutyl tin, ditolyl diethyl tin, diphenyl tin oxide, dibenzyl tin, tetrabenzyl tin, di([B-phenylethyl) tin oxide, dibenzyl tin oxide, etc.
- catalysts useful in the present invention include, but are not limited to, one of more of the following: butyltin tris-2-ethylhexanoate, dibutyltin diacetate, dibutyltin oxide, and dimethyl tin oxide.
- catalysts useful in the present invention include, but are not limited to, one or more of the following: butyltin tris-2-ethylhexanoate, dibutyltin diacetate, dibutyltin oxide, and dimethyl tin oxide.
- Processes for preparing polyesters using tin-based catalysts are well known and described in the aforementioned U.S. Pat. No. 2,720, 507.
- the polyester portion of the polyester compositions useful in the invention can be made by processes known from the literature such as, for example, by processes in homogenous solution, by transesterification processes in the melt, and by two phase interfacial processes. Suitable methods include, but are not limited to, the steps of reacting one or more dicarboxylic acids with one or more glycols at a temperature of 100°C to 315°C at a pressure of 0.1 to 760 mm Hg for a time sufficient to form a polyester. See U.S. Patent No. 3,772,405 for methods of producing polyesters, the disclosure regarding such methods is hereby incorporated herein by reference.
- the polyester in general may be prepared by condensing the dicarboxylic acid or dicarboxylic acid ester with the glycol in the presence of the tin catalyst described herein at elevated temperatures increased gradually during the course of the condensation up to a temperature of about 225°-310° C, in an inert atmosphere, and conducting the condensation at low pressure during the latter part of the condensation, as described in further detail in U.S. Pat. No. 2, 720, 507 incorporated herein by reference.
- this invention relates to a process for preparing copolyesters of the invention.
- the process relates to preparing copolyesters comprising terephthalic acid, 2,2,4,4-tetramethyl-1 ,3- cyclobutanediol, and 1 ,4-cyclohexanedimethanol. This process comprises the steps of:
- Step (B) polycondensing the product of Step (A) by heating it at a temperature of 240 to 320 0 C for 1 to 6 hours;
- step (A) can be carried out until 50% by weight or more of the 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol has been reacted-.
- Step (A) may be carried out under pressure, ranging from 0 psig to 100 psig.
- reaction product as used in connection with any of the catalysts useful in the invention refers to any product of a polycondensation or esterification reaction with the catalyst and any of the monomers used in making the polyester as well as the product of a polycondensation or esterification reaction between the catalyst and any other type of additive.
- Step (B) and Step (C) can be conducted at the same time. These steps can be carried out by methods known in the art such as by placing the reaction mixture under a pressure ranging, from 0.002 psig to below atmospheric pressure, or by blowing hot nitrogen gas over the mixture.
- the invention comprises a process for making any of the polyesters useful in the invention, comprising the following steps:
- Step (i) 1 to 99 mole % of 2,2,4 ,4-tetramethyM ,3- cyclobutanediol residues; and (ii) 1 to 99 mole % of cyclohexanedimethanol residues; wherein the molar ratio of glycol compone ⁇ t/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;
- Step (II) heating the product of Step (I) at a temperature of 230 0 C to 320 0 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 a final polyester; wherein the total mole % of the dicarboxylic acid component of the final polyester is 100 mole %; and wherein the total mole % of the glycol component of the final polyester is 100 mole %.
- the invention comprises a process for making any of the polyesters useful in the invention comprising the following steps:
- Step (i) 1 to 99 mole % of 2,2,4 ,4-tetramethyM ,3- cyclobutanediol residues; and (ii) 1 to 99 mole % of 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 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
- Step (II) heating the product of Step (I) at a temperature of 230 0 C to 32O 0 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 a 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 %; wherein at least one phosphorus compound, for example, at least one phosphate ester, is added to either Step (I), Step (II) or both Steps (I) and (II); and wherein the addition of the phosphorus compound(s), for example, at least one phosphate ester, results in a weight ratio of total tin atoms to total phosphorus atoms in the final polyester useful in the invention of 2-10:1.
- At least one phosphorus compound can be added in Step (I), (II) and/or in both Steps (I) and (II) of the process.
- the phosphorus compound(s) are added in Step (I).
- the phosphorus compounds can comprise at least one phosphate ester, for example.
- thermal stabilizer, reaction products thereof, and mixtures thereof can be added either during esterification, polycondensation, or both and/or it can be added post-polymerization.
- the thermal stabilizer useful in any of the processes of the invention can be added during esterificaton.
- the thermal stabilizer added after both esterification and polycondensation it is added in the amount of 1 to 2 weight % based on the total weight of the final polyester.
- the thermal stabilizer can comprise at least one phosphorus compound useful in the invention.
- the thermal stabilizer can comprise at least one phosphate ester.
- the thermal stabilizer can comprise at least one phosphorus compound which is added during the esterificaton step. In one embodiment, the thermal stabilizer can comprise at least one phosphate ester, for example, which is added during the esterificaton step. [00219] In one embodiment, it is believed that when at least one thermal stabilizer comprising at least one phosphorus compound described herein are used during the processes of making the polyesters according to the present invention, the polyesters can be more easily produced without at least one of the following occurring: bubbling, splaying, color formation, foaming, off-gassing, and erratic melt levels, i.e., pulsating of the polyester or the polyester's production and processing systems.
- At least one process of the invention provides a means to more easily produce the polyesters useful in the invention in large quantities (for example, pilot run scale and/or commercial production) without at least one of the aforesaid difficulties occurring.
- large quantities includes quantities of polyester(s) useful in the invention which are produced in quantities larger than 100 pounds.
- large quantities includes quantities of polyester(s) useful in the invention which are produced in quantities larger than 1000 pounds.
- the processes of making the polyesters useful in the invention can comprise a batch or continuous process.
- the processes of making the polyesters useful in the invention comprise a continuous process.
- the pressure used in Step (II) of any of the processes of the invention consists of at least one pressure chosen from 20 torr absolute to 0.02 torr absolute; in one embodiment, the pressure used in Step (II) of any of the processes of the invention consists of at least one pressure chosen from 10 torr absolute to 0.02 torr absolute; in one embodiment, the pressure used in Step (II) of any of the processes of the invention consists of at least one pressure chosen from 5 torr absolute to 0.02 torr absolute; in one embodiment, the pressure used in Step (II) of any of the processes of the invention consists of at least one pressure chosen from 3 torr absolute to 0.02 torr absolute; in one embodiment, the pressure used in Step (II) of any of the processes of the invention consists of at least one pressure chosen from 20 torr absolute to 0.1 torr absolute; in one embodiment, the pressure used in Step (II) of any of the processes of the invention consists of at least one pressure chosen from 10 torr absolute to
- the molar ratio of glycol component/dicarboxylic acid component added in Step (I) of any of the processes of the invention is 1.0- 1.5/1.0; in one embodiment, the molar ratio of glycol component/dicarboxylic acid component added in Step (I) of any of the processes of the invention is 1.01- 1.5/1.0; in one embodiment, the molar ratio of glycol component/dicarboxylic acid component added in Step (I) of any of the processes of the invention is 1.01- 1.3/1.0; in one embodiment, the molar ratio of glycol component/dicarboxylic acid component added in Step (I) of any of the processes of the invention is 1.01- 1.2/1.0; in one embodiment, the molar ratio of glycol component/dicarboxylic acid component added in Step (I) of any of the processes of the invention is 1.01- 1.15/1.0; in one embodiment, the molar ratio of glycol component/dicarboxylic acid component added in Step (I) of any of the processes of the invention is 1.01- 1.
- the heating time of Step (II) can be from 1 to 5 hours or 1 to 4 hours or 1 to 3 hours or 1.5 to 3 hours or 1 to 2 hours. In one embodiment, the heating time of Step (II) can be from 1.5 to 3 hours.
- the addition of the phosphorus compound(s) in the process(es) of the invention can result in a weight ratio of total tin atoms to total phosphorus atoms in the final polyester useful in the invention of 2-10:1. In one embodiment, the addition of the phosphorus compound(s) in the process(es) can result in a weight ratio of total tin atoms to total phosphorus atoms in the final polyester of 5-9:1. In one embodiment, the addition of the phosphorus compound(s) in the process(es) can result in a weight ratio of total tin atoms to total phosphorus atoms in the final polyester of 6-8:1.
- the addition of the phosphorus compound(s) in the process(es) can result in a weight ratio of total tin atoms to total phosphorus atoms in the final polyester of 7:1.
- the weight of tin atoms and phosphorus atoms present in the final polyester can be measured in ppm and can result in a weight ratio of total tin atoms to total phosphorus atoms in the final polyester of any of the aforesaid weight ratios.
- the amount of tin atoms in the final polyester useful in the invention can be from 15 to 400 ppm tin atoms based on the weight of the final polyester.
- the amount of tin atoms in the final polyester useful in the invention can be from 25 to 400 ppm tin atoms based on the weight of the final polyester.
- the amount of tin atoms in the final polyester useful in the invention can be from 40 to 200 ppm tin atoms based on the weight of the final polyester.
- the amount of tin atoms in the final polyester useful in the invention can be from 50 to 125 ppm tin atoms based on the weight of the final polyester.
- the amount of phosphorus atoms in the final polyester useful in the invention can be from 1 to 100 ppm phosphorus atoms based on the weight of the final polyester.
- the amount of phosphorus atoms in the final polyester useful in the invention can be from 4 to 60 ppm phosphorus atoms based on the weight of the final polyester.
- the amount of phosphorus atoms in the final polyester useful in the invention can be from 6 to 20 ppm phosphorus atoms based on the weight of the final polyester.
- the amount of phosphorus atoms in the final polyester useful in the invention can be from 1 to 100 ppm phosphorus atoms based on the weight of the final polyester and the amount of tin atoms in the final polyester can be from 15 to 400 ppm tin atoms based on the weight of the final polyester.
- the amount of phosphorus atoms in the final polyester useful in the invention can be from 1 to 100 ppm phosphorus atoms based on the weight of the final polyester and the amount of tin atoms in the final polyester can be from 25 to 400 ppm tin atoms based on the weight of the final polyester.
- the amount of phosphorus atoms in the final polyester useful in the invention can be from 4 to 60 ppm phosphorus atoms based on the weight of the final polyester and the amount of tin atoms in the final polyester can be from 40 to 200 ppm tin atoms based on the weight of the final polyester.
- the amount of phosphorus atoms in the final polyester useful in the invention can be from 6 to 20 ppm phosphorus atoms based on the weight of the final polyester and the amount of tin atoms in the final polyester can be from 50 to 125 ppm tin atoms based on the weight of the final polyester.
- the invention further relates to the polyester compositions made by the process(es) described above.
- the invention further relates to a polymer blend.
- the blend comprises:
- Suitable examples of the polymeric components include, but are not limited to, nylon, polyesters different from those described herein, polyamides such as ZYTEL® from DuPont; polystyrene, polystyrene copolymers, stryrene acrylonitrile copolymers, acrylonitrile butadiene styrene copolymers, poly(methylmethacrylate), acrylic copolymers, poly(ether-imides) such as ULTEM ( B> (a poly(ether-imide) from General Electric); polyphenylene oxides such as poly(2,6-dimethylphenylene oxide) or poly(phenylene oxide)/polystyrene blends such as NORYL 1000® (a blend of poly(2,6-dimethylphenylene oxide) and polystyrene resins from General Electric); polyphenylene sulfides; polyphenylene sulfide/sulfones; poly(ester-carbonates); polycarbonates
- the blends can be prepared by conventional processing techniques known in the art, such as melt blending or solution blending.
- the polycarbonate is not present in the polyester composition. If polycarbonate is used in a blend in the polyester compositions useful in the invention, the blends can be visually clear.
- the polyester compositions useful in the invention also contemplate the exclusion of polycarbonate as well as the inclusion of polycarbonate.
- Polycarbonates useful in the invention may be prepared according to known procedures, for example, by reacting the dihydroxyaromatic compound with a carbonate precursor such as phosgene, a haloformate or a carbonate ester, a molecular weight regulator, an acid acceptor and a catalyst.
- a carbonate precursor such as phosgene, a haloformate or a carbonate ester
- a molecular weight regulator such as phosgene, a haloformate or a carbonate ester
- an acid acceptor such as sodium bicarbonate
- Methods for preparing polycarbonates are known in the art and are described, for example, in U.S. Patent 4,452,933, where the disclosure regarding the preparation of polycarbonates is hereby incorporated by reference herein.
- suitable carbonate precursors include, but are not limited to, carbonyl bromide, carbonyl chloride, or mixtures thereof; diphenyl carbonate; a di(halophenyl)carbonate, e.g., di(trichlorophenyl) carbonate, di(tribromophenyl) carbonate, and the like; di(alkylphenyl)carbonate, e.g., di(tolyl)carbonate; di(naphthyl)carbonate; di(chloronaphthy))carbonate, or mixtures thereof; and bis- haloformates of dihydric phenols.
- diphenyl carbonate e.g., di(trichlorophenyl) carbonate, di(tribromophenyl) carbonate, and the like
- di(alkylphenyl)carbonate e.g., di(tolyl)carbonate; di(naphthyl)carbonate; di(chlorona
- Suitable molecular weight regulators include, but are not limited to, phenol, cyclohexanol, methanol, alkylated phenols, such as octylphenol, para-tertiary-butyl-phenol, and the like. In one embodiment, the molecular weight regulator is phenol or an alkylated phenol.
- the acid acceptor may be either an organic or an inorganic acid acceptor.
- a suitable organic acid acceptor can be a tertiary amine and includes, but is not limited to, such materials as pyridine, triethylamine, dimethylaniline, tributylamine, and the like.
- the inorganic acid acceptor can be either a hydroxide, a carbonate, a bicarbonate, or a phosphate of an alkali or alkaline earth metal.
- the catalysts that can be used include, but are not limited to, those that typically aid the polymerization of the monomer with phosgene.
- Suitable catalysts include, but are not limited to, tertiary amines such as triethylamine, tripropylamine, N,N-dimethylaniline, quaternary ammonium compounds such as, for example, tetraethylammonium bromide, cetyl triethyl ammonium bromide, tetra-n-heptylammonium iodide, tetra-n-propyl ammonium bromide, tetramethyl ammonium chloride, tetra-methyl ammonium hydroxide, tetra-n-butyl ammonium iodide, benzyltrimethyl ammonium chloride and quaternary phosphonium compounds such as, for example, n-butyltriphenyl phosphonium bromide and methyltriphenyl phosphonium bromide.
- quaternary ammonium compounds such as, for example, n-butyltriphenyl
- the polycarbonates useful in the polyester compositions of the invention also may be copolyestercarbonates such as those described in U.S. Patents 3,169,121 ; 3,207,814; 4,194,038; 4,156,069; 4,430,484, 4,465,820, and 4,981 ,898, where the disclosure regarding copolyestercarbonates from each of the U.S. Patents is incorporated by reference herein.
- Copolyestercarbonates useful in this invention can be available commercially and/or can prepared by known methods in the art. For example, they can be typically obtained by the reaction of at least one dihydroxyaromatic compound with a mixture of phosgene and at least one dicarboxylic acid chloride, especially isophthaloyl chloride, terephthaloyl chloride, or both.
- polyester compositions and the polymer blend compositions containing the polyesters of this invention may also contain from 0.01 to 25% by weight or 0.01 to 20% by weight or 0.01 to 15% by weight or 0.01 to 10% by weight or 0.01 to 5% by weight of the total weight of the polyester composition of common additives such as colorants, dyes, mold release agents, flame retardants, plasticizers, nucleating agents, stabilizers, including but not limited to, UV stabilizers, thermal stabilizers and/or reaction products thereof, fillers, and impact modifiers.
- common additives such as colorants, dyes, mold release agents, flame retardants, plasticizers, nucleating agents, stabilizers, including but not limited to, UV stabilizers, thermal stabilizers and/or reaction products thereof, fillers, and impact modifiers.
- polyesters of the invention can comprise at least one chain extender.
- Suitable chain extenders include, but are not limited to, multifunctional (including, but not limited to, bifunctional) isocyanates, multifunctional epoxides, including for example ,epoxylated novolacs, and phenoxy resins.
- chain extenders may be added at the end of the polymerization process or after the polymerization process. If added after the polymerization process, chain extenders can be incorporated by compounding or by addition during conversion processes such as injection molding or extrusion.
- the amount of chain extender used can vary depending on the specific monomer composition used and the physical properties desired but is generally about 0.1 percent by weight to about 10 percent by weight, preferably about 0.1 to about 5 percent by weight based on the total weight of the polyester.
- Reinforcing materials may be useful in the compositions of this invention.
- the reinforcing materials may include, but are not limited to, carbon filaments, silicates, mica, clay, talc, titanium dioxide, Wollastonite, glass flakes, glass beads and fibers, and polymeric fibers and combinations thereof.
- the reinforcing materials are glass, such as fibrous glass filaments, mixtures of glass and talc, glass and mica, and glass and polymeric fibers.
- the invention further relates to articles of manufacture comprising any of the polyesters and blends described above.
- the invention further relates to articles of manufacture comprising any of the polyesters and blends described herein, extruded, calendered, and/or molded articles including but not limited to, injection molded articles, extruded articles, cast extrusion articles, profile extrusion articles, melt spun articles, thermoformed articles, extrusion molded articles, injection blow molded articles, injection stretch blow molded articles, extrusion blow molded articles, and extrusion stretch blow molded articles.
- These articles can include, but are not limited, to films, bottles (including, but not limited to, baby bottles), containers, sheet and/or fibers.
- the present polyesters and/or polyester blend compositions can be useful in forming fibers, films, molded articles, containers, and sheeting.
- the methods of forming the polyesters into fibers, films, molded articles, containers, and sheeting are well known in the art.
- Examples of potential molded articles include without limitation: medical devices such as dialysis equipment, medical packaging, healthcare supplies, commercial food service products such as food pans, tumblers and storage boxes, baby bottles, food processors, blender and mixer bowls, utensils, water bottles, crisper trays, washing machine fronts, and vacuum cleaner parts.
- Other potential molded articles could include, but are not limited to, ophthalmic lenses and frames. For instance, this material can be used to make bottles, including but not limited to, baby bottles, as it is clear, tough, heat resistant, and displays good hydrolytic stability.
- the invention further relates to articles of manufacture comprising the film(s) and/or sheet(s) containing polyester compositions described herein.
- the films and/or sheets useful in the present invention can be of any thickness which would be apparent to one of ordinary skill in the art.
- the film(s) of the invention have a thickness of no more than 40 mils.
- the film(s) of the invention have a thickness of no more than 35 mils.
- the film(s) of the invention have a thickness of no more than 30 mils.
- the film(s) of the invention have a thickness of no more than 25 mils.
- the film(s) of the invention have a thickness of no more than 20 mils.
- the sheet(s) of the invention have a thickness of no less than 20 mils. In another embodiment, the sheet(s) of the invention have a thickness of no less than 25 mils. In another embodiment, the sheet(s) of the invention have a thickness of no less than 30 mils. In another embodiment, the sheet(s) of the invention have a thickness of no less than 35 mils. In another embodiment, the sheet(s) of the invention have a thickness of no less than 40 mils. [00260] The invention further relates to the film(s) and/or sheet(s) comprising the polyester compositions of the invention. The methods of forming the polyesters into film(s) and/or sheet(s) are well known in the art.
- film(s) and/or sheet(s) of the invention including but not limited to extruded film(s) and/or sheet(s), calendered film(s) and/or sheet(s), compression molded film(s) and/or sheet(s), solution casted film(s) and/or sheet(s).
- Methods of making film and/or sheet include but are not limited to extrusion, calendering, compression molding, and solution casting.
- Examples of potential articles made from film and/or sheet useful in the invention include, but are not limited, to uniaxially stretched film, biaxially stretched film, shrink film (whether or not uniaxially or biaxially stretched, liquid crystal display film (including but not limited to diffuser sheets, compensation films and protective films), thermoformed sheet, graphic arts film, outdoor signs, skylights, coating(s), coated articles, painted articles, laminates, laminated articles, and/or multiwall films or sheets.
- Graphic art film is a film having a thermally-curable ink (e.g., heat-curable ink or air-curable ink) or radiation-curable ink (e.g., ultraviolet-curable ink) printed thereon or therein.
- thermally-curable ink e.g., heat-curable ink or air-curable ink
- radiation-curable ink e.g., ultraviolet-curable ink
- Cosmetic refers to capable of undergoing polymerization and/or crosslinking.
- the graphic art film may optionally also include varnishes, coatings, laminates, and adhesives.
- Exemplary thermally or air-cured inks involve pigment(s) dispersed in one or more standard carrier resins.
- the pigment can be 4B Toner (PR57), 2B Toner (PR48), Lake Red C (PR53), lithol red (PR49), iron oxide (PR101 ), Permanent Red R (PR4), Permanent Red 2G (PO5), pyrazolone orange (PO13), diaryl yellows (PY12, 13, 14), monoazo yellows (PY3,5,98), phthalocyanine green (PG7), phthalocyanine Blue, ⁇ form (PB15), ultramarine (PB62), permanent violet (PV23), titanium dioxide (PW6), carbon black (furnace/channel) (PB7), PMTA pink, green, blue, violet (PR81 , PG1 , PB1 , PV3,), copper ferrocyanide dye complexes (PR169, PG45, PB62, PV27), or the like.
- Pigmental identifications in the foregoing refer to the generic color index prepared by the Society of Dyers and Colourists.
- Such pigments and combinations thereof can be used to obtain various colors including, but not limited to, white, black, blue, violet, red, green, yellow, cyan, magenta, or orange.
- Examples of typical carrier resins used in standard inks include those which have nitrocellulose, amide, urethane, epoxide, acrylate, and/or ester functionalities.
- Standard carrier resins include one or more of nitrocellulose, polyamide, polyurethane, ethyl cellulose, cellulose acetate propionate,
- (meth)acrylates polyvinyl butyral), polyvinyl acetate), polyvinyl chloride), and the like.
- Such resins can be blended, with widely used blends including nitrocellulose/polyamide and nitrocellulose/polyurethane.
- Ink resin(s) riormally can be solvated or dispersed in one or more solvents.
- solvents employed include, but are not limited to, water, alcohols (e.g., ethanol, 1-propanol, isopropanol, etc.), acetates (e.g., n-propyl acetate), aliphatic hydrocarbons, aromatic hydrocarbons (e.g., toluene), and ketones.
- Such solvents typically can be incorporated in amounts sufficient to provide inks having viscosities, as measured on a #2 Zahn cup as known in the art, of at least 15 seconds, such as at least 20 seconds, at least 25 seconds, or from 25 to 35 seconds.
- the polyesters have sufficient Tg values to allow thermoformability, and to allow ease of printing onto the graphic art film.
- the graphic art film has at least one property chosen from thermoformability, toughness, clarity, chemical resistance, Tg, and flexibility.
- Graphic art films can be used in a variety of applications, such as, for example, in-mold decorated articles, embossed articles, hard-coated articles.
- the graphic art film can be smooth or textured.
- Exemplary graphic art films include, but are not limited to, nameplates; membrane switch overlays (e.g., for an appliance); point of purchase displays; flat or in-mold decorative panels on washing machines; flat touch panels on refrigerators (e.g., capacitive touch pad arrays); flat panel on ovens; decorative interior trim for automobiles (e.g., a polyester laminate) ; instrument clusters for automobiles; cell phone covers; heating and ventilation control displays; automotive console panels; automotive gear shift panels; control displays or warning signals for automotive instrument panels; facings, dials or displays on household appliances; facings, dials or displays on washing machines; facings, dials or displays on dishwashers; keypads for electronic devices; keypads for mobile phones, personal digital assistants (PDAs, or hand-held computers) or remote controls; displays for electronic devices; displays for hand-held electronic devices such as phones and PDAs; panels and housings for mobile or standard phones; logos on electronic devices; and logos for hand-held phones.
- PDAs personal digital assistants
- Multiwall film or sheet refers to sheet extruded as a profile consisting of multiple layers that are connected to each other by means of vertical ribs.
- Examples of multiwall film or sheet include but are not limited to outdoor shelters (for example, greenhouses and commercial canopies).
- extruded articles comprising the polyester compositions useful in this invention include, but are not limited to, thermoformed sheet, film for graphic arts applications, outdoor signs, skylights, multiwall film, plastic film for plastic glass laminates, and liquid crystal display (LCD) films, including but not limited to, diffuser sheets, compensation films, and protective films for LCDs.
- LCD liquid crystal display
- polyester compositions of the invention include but are not limited to safety/sport (examples including but not limited to: safety shields, face shields, sports goggles [racquetball, ski, etc.], police riot shields); corrugated sheet articles; recreation/outdoor vehicles and devices (examples including but not limited to: lawn tractors, snow mobiles, motorcycle windshield, camper windows, golf cart windshield, jet ski); residential and commercial lighting (examples including but not limited to: diffusers, office, home and commercial fixtures; High Intensity Discharge (HID) Lighting); telecommunications/business equipment/electronics (examples including but not limited to cell phone housing, TV housing, computer housing, stereo housing, PDAs, etc); optical media; tanning beds; multiwall sheet, extruded articles; rigid medical packaging; intravenous components; dialysis filter housing; blood therapy containers; sterilization containers (for example, infant care sterilization containers); pacifiers, tool handles (
- the invention further relates to bottles described herein.
- the methods of forming the polyesters into bottles are well known in the art.
- bottles include but are not limited to bottles such as pharmaceutical bottles, baby bottles; water bottles; juice bottles; large commercial water bottles having a weight from 200 to 800 grams; beverage bottles which include but are not limited to two liter bottles, 20 ounce bottles, 16.9 ounce bottles; medical bottles; personal care bottles, carbonated soft drink bottles; hot fill bottles; water bottles; alcoholic beverage bottles such as beer bottles and wine bottles; and bottles comprising at least one handle.
- These bottles include but are not limited to injection blow molded bottles, injection stretch blow molded bottles, extrusion blow molded bottles, and extrusion stretch blow molded bottles.
- Methods of making bottles include but are not limited to extrusion blow molding, extrusion stretch blow molding, injection blow molding, and injection stretch blow molding.
- the invention further relates to the preforms (or parisons) used to make each of said bottles.
- bottles include, but are not limited to, injection blow molded bottles, injection stretch blow molded bottles, extrusion blow molded bottles, and extrusion stretch blow molded bottles.
- Methods of making bottles include but are not limited to extrusion blow molding, extrusion stretch blow molding, thermoforming, injection blow molding, and injection stretch blow molding.
- containers include, but are not limited to, containers for cosmetics and personal care applications including bottles, jars, vials and tubes; sterilization containers; buffet steam pans; food pans or trays; frozen food trays; microwaveable food trays; hot fill containers, amorphous lids or sheets to seal or cover food trays; food storage containers; for example, boxes; tumblers, pitchers, cups, bowls, including but not limited to those used in restaurant smallware; beverage containers; retort food containers; centrifuge bowls; vacuum cleaner canisters, and collection and treatment canisters.
- "Restaurant smallware” refers to any container used for eating or serving food.
- Examples of restaurant smallware include pitchers, cups, mugs optionally including handles (including decorative mugs, single-or double walled mugs, pressurized mugs, vacuum mugs), bowls (e.g., serving bowls, soup bowls, salad bowls), and plates (e.g., eating and serving plates, such as buffet plates, saucers, dinner plates).
- handles including decorative mugs, single-or double walled mugs, pressurized mugs, vacuum mugs
- bowls e.g., serving bowls, soup bowls, salad bowls
- plates e.g., eating and serving plates, such as buffet plates, saucers, dinner plates.
- the containers used as restaurant smallware are capable of withstanding refrigerator temperatures ranging from greater than 0 0 C (e.g., 2 0 C) to 5°C.
- the restaurant smallware containers can withstand steam treatments and/or commercial dishwasher conditions.
- the restaurant smallware containers are capable of withstanding microwave conditions.
- restaurant smallware containers have at least one property chosen from toughness, clarity, chemical resistance, Tg, hydrolytic stability, and dishwasher stability.
- the medical devices comprising the polyester compositions of the invention include but are not limited to medical devices comprising an ultraviolet light (UV)-curable, silicone-based coating, on at least a portion of a surface of a medical device comprising a polyester comprising a cyclobutanediol, which improves protein resistance and biocompatibility, may be coated on various substrates, and overcomes several difficulties identified in previously disclosed methods.
- UV ultraviolet light
- the present invention comprises a thermoplastic article, typically in the form of sheet material, having a decorative material embedded therein which comprise any of the compositions described herein.
- Food storage container are capable of storing and/or serving hot and/or cold food and/or beverages at temperatures customarily used for storing and serving foods and beverages, e.g., ranging from deep freezer temperatures to hot temperatures such as those in a low temperature oven or those used in hot beverage dispensers.
- the food storage container can be sealed to reduce the rate of food oxidation.
- the food storage container can be used to display and serve the food to dining customers.
- the food storage containers are capable of being stored in a freezer, e.g., at temperatures less than 0 0 C, such as temperatures ranging from -20 to 0 0 C (e.g., -18°C).
- the food storage containers are capable of storing food in the refrigerator at temperatures ranging from greater than 0 0 C (e.g., 2°C) to 5°C.
- the food storage containers can withstand steam treatments and/or commercial dishwasher conditions.
- the food storage containers are capable of withstanding microwave conditions.
- Examples of food storage containers include buffet steam pans, buffet steam trays, food pans, hot and cold beverage dispensers (e.g. refrigerator beverage dispensers, automated hot or cold beverage dispensers), and food storage boxes.
- food storage containers have at least one additional property chosen from toughness, clarity, chemical resistance, Tg, and hydrolytic stability.
- thermoplastic article which is obtained by applying heat and pressure to one or more laminates or "sandwiches", wherein at least one of said laminates comprises, in order, (1) at least one upper sheet material, (2) at least one decorative material, and (3) at least one lower sheet material.
- an adhesive layer may be used between (1 ) and (2) and/or between (2) and (3).
- Any of layers (1), (2) and/or (3) of the "sandwich” may comprise any of the compositions of the invention.
- Ophthalmic product refers to prescription eyeglass lenses, nonprescription eyeglass lenses, sunglass lenses, and eyeglass and sunglass frames.
- the ophthalmic product is chosen from tinted eyeglass lenses and hardcoated eyeglass lenses.
- the eyeglass lenses such as the tinted eyeglass lenses or hardcoated eyeglass lenses, comprise at least one polarizing film or polarizing additive.
- the ophthalmic product when the product is a lens, the ophthalmic product has a refractive index ranging from 1.54 to 1.56.
- the ophthalmic product can have at least one property chosen from toughness, clarity, chemical resistance (e.g., for withstanding lens cleaners, oils, hair products, etc.), Tg, and hydrolytic stability.
- Outdoor sign refers to a surface formed from the polyester described herein, or containing symbols (e.g., numbers, letters, words, pictures, etc.), patterns, or designs coated with the polyester or polyester film described herein.
- the outdoor sign comprises a polyester containing printed symbols, patterns, or designs.
- the sign is capable of withstanding typical weather conditions, such as rain, snow, ice, sleet, high humidity, heat, wind, sunlight, or combinations thereof, for a sufficient period of time, e.g., ranging from one day to several years or more.
- typical weather conditions such as rain, snow, ice, sleet, high humidity, heat, wind, sunlight, or combinations thereof.
- Exemplary outdoor signs include, but are not limited to, billboards, neon signs, electroluminescent signs, electric signs, fluorescent signs, and light emitting diode (LED) displays.
- Other exemplary signs include, but are not limited to, painted signs, vinyl decorated signs, thermoformed signs, and hardcoated signs.
- the outdoor sign has at least one property chosen from thermoformability, toughness, clarity, chemical resistance, and Tg.
- a "vending machine display panel,” as used herein, refers to a front or side panel on a vending machine that allows a customer to view the items for sale, or advertisement regarding such items.
- the vending machine display panel can be a visually clear panel of a vending machine through which a consumer can view the items on sale.
- the vending machine display panel can have sufficient rigidity to contain the contents within the machine and/or to discourage vandalism and/or theft.
- the vending machine display panel can have dimensions well known in the art, such as planar display panels in snack, beverage, popcorn, or sticker/ticket vending machines, and capsule display panels as in, e.g., gumball machines or bulk candy machines.
- the vending machine display panel can optionally contain advertising media or product identification indicia. Such information can be applied by methods well known in the art, e.g., silk screening.
- the vending machine display panel can be resistant to temperatures ranging from -100 to 120 0 C.
- the vending machine display panel can be UV resistant by the addition of, e.g., at least one UV additive, as disclosed herein.
- the vending machine display panel has at least one property chosen from thermoformability, toughness, clarity, chemical resistance, and Tg.
- Point of purchase display refers to a wholly or partially enclosed casing having at least one visually clear panel for displaying an item.
- Point of purchase displays are often used in retail stores to for the purpose of catching the eye of the customer.
- Exemplary point of purchase displays include enclosed wall mounts, countertops, enclosed poster stands, display cases (e.g., trophy display cases)-, sign frames, and cases for computer disks such as CDs and DVDs.
- the point of purchase display can include shelves, and additional containers, such as holders for magazines or pamphlets.
- the display can be as small as a case for jewelry, or a larger enclosed cabinet for displaying multiple trophies.
- the point of purchase display has at least one property chosen from toughness, clarity, chemical resistance, Tg, and hydrolytic stability.
- Intravenous component refers to components made from a polymeric material used for administering fluids (e.g., medicaments, nutrients) to the bloodstream of a patient.
- the intravenous component is a rigid component.
- Exemplary intravenous components include y-site connector - assemblies, luer components, filters, stopcocks, manifolds, and valves.
- a y-site connector has a "Y" shape including a first arm having a first passage, a second arm having a second passage, and a third arm connected with said first and second arms and having a third passage communicating with said first and second passages.
- Luer components can include luer locks, connections, and valves.
- the intravenous component can withstand sterilization treatments, such as high pressure steam sterilization, ethylene oxide gas sterilization, radiation sterilization, and dry-heating sterilization.
- the intravenous component has at least one property chosen from toughness, clarity, chemical resistance, Tg, and hydrolytic stability.
- a "dialysis filter housing,” as used herein, refers to a protective casing having a plurality of openings for holding a plurality of hollow fibers or tubing, which can be used for introducing and discharging a dialyzate to a patient.
- a cross-sectional area of one opening in the protective casing ranges from 0.001 cm 2 to less than 50 cm 2 .
- the dialysis filter housing has at least one property chosen from toughness, clarity, chemical resistance, Tg, and hydrolytic stability.
- “Blood therapy containers,” as used herein, refers to those containers used in administering and withdrawing blood to and from a patient.
- Exemplary blood therapy containers include oxygenators, cassettes, centrifuge bowls, collection and treatment canisters, pump cartridges, venal port housings, and dialyzer housings.
- Oxygenators can remove carbon dioxide from the venous blood of the patient, introduce oxygen to the withdrawn blood to convert it into arterial blood, and introduce the oxygenated blood to the patient.
- Other containers can be used to temporarily house the withdrawn or stored blood prior to its administration to the patient.
- the blood therapy container can withstand sterilization treatments, such as high pressure steam sterilization, ethylene oxide gas sterilization, radiation sterilization, and dry-heating sterilization.
- the blood therapy container has at least one property chosen from toughness, clarity, chemical resistance, Tg, and hydrolytic stability.
- “Appliance parts,” as used herein, refers to a rigid piece used in conjunction with an appliance.
- the appliance part is partly or wholly separable from the appliance.
- the appliance part is one that is typically made from a polymer.
- the appliance part is visually clear.
- Exemplary appliance parts include those requiring toughness and durable, such as cups and bowls used with food processers, mixers, blenders, and choppers; parts that can withstand refrigerator and freezer temperatures (e.g., refrigerator temperatures ranging from greater than O 0 C (e.g., 2 0 C) to 5°C, or freezer temperatures, e.g., at temperatures less than 0 0 C, such as temperatures ranging from -20 to 0 0 C, e.g., -18°C), such as refrigerator and freezer trays, bins, and shelves; parts having sufficient hydrolytic stability at temperatures up to 90°C, such as washing machine doors, steam cleaner canisters, tea kettles, and coffee pots; and vacuum cleaner canisters and dirt cups.
- refrigerator and freezer temperatures e.g., refrigerator temperatures ranging from greater than O 0 C (e.g., 2 0 C) to 5°C, or freezer temperatures, e.g., at temperatures less than 0 0 C, such as temperatures ranging from -20 to 0 0
- these appliance parts have at least one property chosen from toughness, clarity, chemical resistance, Tg, hydrolytic stability, and dishwasher stability.
- the appliance part can also be chosen from steam cleaner canisters, which, in one embodiment, can have at least one property chosen from toughness, clarity, chemical resistance, Tg, and hydrolytic stability.
- the polyester useful in the appliance part has a Tg of 105 to 140°C and the appliance part is chosen from vacuum cleaner canisters and dirt cups.
- the polyester useful in the appliance part has a Tg of 120 to 150 0 C and the appliance part is chosen from steam cleaner canisters, tea kettles and coffee pots.
- Skylight refers to a light permeable panel secured to a roof surface such that the panel forms a portion of the ceiling.
- the panel is rigid, e.g., has dimensions sufficient to achieve stability and durability, and such dimensions can readiliy be determined by one skilled in the art.
- the skylight panel has a thickness greater than 3/16 inches, such as a thickness of at least 1/2 inches.
- the skylight panel is visually clear.
- the skylight panel can transmit at least 35% visible light, at least 50%, at least 75%, at least 80%, at least 90%, or even at least 95% visible light.
- the skylight panel comprises at least one UV additive that allows the skylight panel to block up to 80%, 90%, or up to 95% UV light.
- the skylight has at least one property chosen from thermoformability, toughness, clarity, chemical resistance, and Tg.
- Outdoor shelters refer to a roofed and/or walled structure capable of affording at least some protection from the elements, e.g., sunlight, rain, snow, wind, cold, etc., having at least one rigid panel.
- the outdoor shelter has at least a roof and/or one or more walls.
- the outdoor shelter has dimensions sufficient to achieve stability and durability, and such dimensions can readiliy be determined by one skilled in the art.
- the outdoor shelter panel has a thickness greater than 3/16 inches.
- the outdoor shelter panel is visually clear.
- the outdoor shelter panel can transmit at least 35% visible light, at least 50%, at least 75%, at least 80%, at least 90%, or even at least 95% visible light.
- the outdoor shelter panel comprises at least one UV additive that allows the outdoor shelter to block up to 80%, 90%, or up to 95% UV light.
- Exemplary outdoor shelters include security glazings, transportation shelters (e.g., bus shelters), telephone kiosks, and smoking shelters.
- the shelter has at least one property chosen from thermoformability, toughness, clarity, chemical resistance, and Tg.
- the shelter has at least one property chosen from toughness, clarity, chemical resistance, and Tg.
- a "canopy,” as used herein, refers to a roofed structure capable of affording at least some protection from the elements, e.g., sunlight, rain, snow, wind, cold, etc.
- the roofed structure comprises, either in whole or in part, at least one rigid panel, e.g., has dimensions sufficient to achieve stability and durability, and such dimensions can readiliy be determined by one skilled in the art.
- the canopy panel has a thickness greater than 3/16 inches, such as a thickness of at least 1/2 inches.
- the canopy panel is visually clear.
- the canopy panel can transmit at least 35% visible light, at least 50%, at least 75%, at least 80%, at least 90%, or even at least 95% visible light.
- the canopy panel comprises at least one UV additive that allows the canopy to block up to 80%, 90%, or up to 95% UV light.
- Exemplary canopies include covered walkways, roof lights, sun rooms, airplane canopies, and awnings.
- the canopy has at least one property chosen from toughness, clarity, chemical resistance, Tg, and flexibility.
- a "sound barrier,” as used herein, refers to a rigid structure capable of reducing the amount of sound transmission from one point on a side of the structure to another point on the other side when compared to sound transmission between two points of the same distance without the sound barrier.
- the effectiveness in reducing sound transmission can be assessed by methods known in the art. In one embodiment, the amount of sound transmission that is reduced ranges from 25 % to 90 %.
- the sound barrier can be rated as a sound transmission class value, as described in, for example, ASTM E90, "Standard Test Method for Laboratory Measurement of Airborne Sound Transmission Loss of Building Partitions and Elements," and ASTM E413, "Classification of Rating Sound Insulation.”
- An STC 55 barrier can reduce the sound of a jet engine, ⁇ 130 dBA, to 60 dBA, which is the sound level within a typical office.
- a sound proof room can have a sound level ranging from 0-20 dBA.
- One of ordinary skill in the art can construct and arrange the sound barrier to achieve a desired STC rating.
- the sound barrier has an STC rating of at least 20, such as a rating ranging from 20 to 60.
- the sound barrier comprises a plurality of panels connected and arranged to achieve the desired barrier outline.
- the sound barriers can be used along streets and highways to dampen automotive noises. Alternatively, the sound barriers can be used in the home or office, either as a discrete panel or panels, or inserted within the architecture of the walls, floors, ceilings, doors, and/or windows.
- the sound barrier is visually clear.
- the sound barrier can transmit at least 35% visible light, at least 50%, at least 75%, at least 80%, at least 90%, or even at least 95% visible light.
- the sound barrier comprises at least one UV additive that allows the sound barrier to block up to 80%, 90%, or up to 95% UV light.
- the sound barrier has at least one property chosen from toughness, clarity, chemical resistance, and Tg.
- a "greenhouse,” as used herein, refers to an enclosed structure used for the cultivation and/or protection of plants.
- the greenhouse is capable of maintaining a humidity and/or gas (oxygen, carbon dioxide, nitrogen, etc.) content desirable for cultivating plants while being capable of affording at least some protection from the elements, e.g., sunlight, rain, snow, wind, cold, etc.
- the roof of the greenhouse comprises, either in whole or in part, at least one rigid panel, e.g., has dimensions sufficient to achieve stability and durability, and such dimensions can readiliy be determined by one skilled in the art.
- the greenhouse panel has a thickness greater than 3/16 inches, such as a thickness of at least 1/2 inches.
- the greenhouse panel is visually clear. In another embodiment, substantially all of the roof and walls of the greenhouse are visually clear. In one embodiment, the greenhouse panel can transmit at least 35% visible light, at least 50%, at least 75%, at least 80%, at least 90%, or even at least 95% visible light. In another embodiment, the greenhouse panel comprises at least one UV additive that allows the greenhouse panel to block up to 80%, 90%, or up to 95% UV light.
- the greenhouse panel has at least one property chosen from toughness, clarity, chemical resistance, and Tg.
- An "optical medium,” as used herein, refers to an information storage medium in which information is recorded by irradiation with a laser beam, e.g., light in the visible wavelength region, such as light having a wavelength ranging from 600 to 700 nm.
- a laser beam e.g., light in the visible wavelength region, such as light having a wavelength ranging from 600 to 700 nm.
- the irradiated area of the recording layer is locally heated to change its physical or chemical characteristics, and pits are formed in the irradiated area of the recording layer. Since the optical characteristics of the formed pits are different from those of the area having been not irradiated, the digital information is optically recorded.
- the recorded information can be read by reproducing procedure generally comprising the steps of irradiating the recording layer with the laser beam having the same wavelength as that employed in the recording procedure, and detecting the light- reflection difference between the pits and their periphery.
- the optical medium comprises a transparent disc having a spiral pregroove, a recording dye layer placed in the pregroove on which information is recorded by irradiation with a laser beam, and a light-reflecting layer.
- the optical medium is optionally recordable by the consumer.
- the optical medium is chosen from compact discs (CDs) and digital video discs (DVDs).
- the optical medium can be sold with prerecorded information, or as a recordable disc.
- At least one of the following comprises the polyester of the invention: the substrate, at least one protective layer of the optical medium, and the recording layer of the optical medium.
- the optical medium has at least one property chosen from toughness, clarity, chemical resistance, Tg, and hydrolytic stability.
- “Infant-care sterilization container,” as used herein, refers to a container configured to hold infant-care products for use in in-home sterilization of the infant-care products.
- the infant-care sterilization container is a baby bottle sterilization container.
- infant-care sterilization containers have at least one additional property chosen from toughness, clarity, chemical resistance, Tg, hydrolytic stability, and dishwasher stability.
- Pacifiers as used herein, comprise a flexible nipple (e.g., for an infant to suck and/or bite) surrounded by a rigid mouth shield, where the rigid mouth shield is optionally connected to a handle, allowing the infant or supervising adult a convenient structure for gripping and/or holding the pacifier.
- the handle may be rigid or flexible.
- the pacifier can be made of multiple components.
- the nipple can pass through an aperture in the center of the mouth shi ⁇ ld.
- the handle may or may not be integrally connected to the mouth shield.
- the handle can be rigid or flexible.
- the nipple and- mouth shield of the pacifier is formed as an integral unit.
- the selection of plastic is governed by the need to provide a relatively rigid mount shield and handle.
- the nipple of the pacifier may be more rigid yet still be desirable for an infant to suck or bite.
- pacifiers have at least one property chosen from toughness, clarity, chemical resistance, Tg, hydrolytic stability, and dishwasher stability.
- a "retort food container,” as used herein, refers to flexible container or pouch for storing food and/or beverages, in which the food and/or beverage is hermetically sealed for long-term unrefrigerated storage.
- the food can be sealed under vacuum or an inert gas.
- the retort food container can comprise at least one polyester layer, e.g., a single layer or multi-layer container.
- a multi-layer container includes a light reflecting inner layer, e.g., a metallized film.
- At least one foodstuff chosen from vegetables, fruit, grain, soups, meat, meat products, dairy products, sauces, dressings, and baking supplies is contained in the retort food container.
- the retort food container has at least one property chosen from toughness, clarity, chemical resistance, Tg, and hydrolytic stability.
- a "glass laminate,” as used herein, refers to at least one coating on a glass, where at least one of the coatings comprises the polyester.
- the coating can be a film or a sheet.
- the glass can be clear, tinted, or reflective.
- the laminate is permanently bonded to the glass, e.g., applying the laminate under heat and pressure to form a single, solid laminated glass product. One or both faces of the glass can be laminated.
- the glass laminate contains more than one coating comprising the polyester compositions of the present invention.
- the glass laminate comprises multiple glass substrates, and more than one coating comprising the polyester compositions of the present invention.
- Exemplary glass laminates include windows (e.g., windows for high rise buildings, building entrances), safety glass, windshields for transportation applications (e.g., automotive, buses, jets, armored vehicles), bullet proof or resistant glass, security glass (e.g., for banks), hurricane proof or resistant glass, airplane canopies, mirrors, solar glass panels, flat panel displays, and blast resistant windows.
- the glass laminate can be visually clear, be frosted, etched, or patterned.
- the glass laminate can be resistant to temperatures ranging from -100 to 120°C.
- the glass laminate can be UV resistant by the addition of, e.g., at least one UV additive, as disclosed herein.
- Methods for laminating the films and/or sheets of the present invention to the glass are well known to one of ordinary skill in the art. Lamination without the use of an adhesive layer may be performed by vacuum lamination. To obtain an effective bond between the glass layer and the laminate, in one embodiment, the glass has a low surface roughness.
- a double-sided adhesive tape, an adhesive layer, or a gelatin layer obtained by applying, for example, a hotmelt, a pressure- or thermo- sensitive adhesive, or a UV or electron-beam curable adhesive, can be used to bond the laminate of the present invention to the glass.
- the adhesive layer may be applied to the glass sheet, to the laminate, or to both, and may be protected by a stripping layer, which can be removed just before lamination.
- the glass laminate has at least one property chosen from toughness, clarity, chemical resistance, hydrolytic stability, and Tg.
- the abbreviation "wt" means "weight".
- polyesters The inherent viscosity of the polyesters was determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at 25°C, and is reported in dL/g.
- the glass transition temperature (T 9 ) was determined using a TA DSC 2920 instrument from Thermal Analyst Instruments at a scan rate of 20°C/min according to ASTM D3418.
- the glycol content and the cis/trans ratio of the compositions were determined by proton nuclear magnetic resonance (NMR) spectroscopy. All NMR spectra were recorded on a JEOL Eclipse Plus 600MHz nuclear magnetic resonance spectrometer using either chloroform-trifluoroacetic acid (70-30 volume/volume) for polymers or, for oligomeric samples, 60/40(wt/wt) phenol/ tetrachloroethane with deuterated chloroform added for lock.
- Peak assignments for 2,2,4,4-tetramethyM ,3-cyclobutanediol resonances were made by comparison to model mono- and dibenzoate esters of 2,2,4,4-tetramethyl- 1 ,3-cyclobutanediol. These model compounds closely approximate the resonance positions found in the polymers and oligomers.
- the crystallization half-time, i V2 was determined by measuring the light transmission of a sample via a laser and photo detector as a function of time on a temperature controlled hot stage. This measurement was done by exposing the polymers to a temperature, Tm a x, and then cooling it to the desired temperature.
- T max is defined as the temperature required to melt the crystalline domains of the sample (if crystalline domains are present).
- the T ma ⁇ reported in the examples below represents the temperature at which each sample was heated to condition the sample prior to crystallization half time measurement.
- the T max temperature is dependant on composition and is typically different for each polyester. For example, PCT may need to be heated to some temperature greater than 290 0 C to melt the crystalline domains.
- Density was determined using a gradient density column at 23°C.
- the melt viscosity reported herein was measured by using a Rheometrics Dynamic Analyzer (RDA II). The melt viscosity was measured as a function of shear rate, at frequencies ranging from 1 to 400 rad/sec, at the temperatures reported.
- the zero shear melt viscosity ( ⁇ o ) is the melt viscosity at zero shear rate estimated by extrapolating the data by known models in the art. This step is automatically performed by the Rheometrics Dynamic Analyzer (RDA II) software.
- the polymers were dried at a temperature ranging from 80 to 100 0 C in a vacuum oven for 24 hours and injection molded on a Boy 22S molding machine to give 1/8x1/2x5-inch and 1/4x1/2x5-inch flexure bars. These bars were cut to a length of 2.5 inch and notched down the Vz inch width with a 10-mil notch in accordance with ASTM D256. The average Izod impact strength at 23°C was determined from measurements on 5 specimens.
- the brittle-to-ductile transition temperature is defined as the temperature at which 50% of the specimens fail in a brittle manner as denoted by ASTM D256.
- Color values reported herein are CIELAB L*, a*, and b* values measured following ASTM D 6290-98 and ASTM E308-99, using measurements from a Hunter Lab Ultrascan XE Spectrophotometer (Hunter Associates Laboratory Inc., Reston, VA) with the following parameters: (1) D65 illuminant, (2) 10 degree observer, (3) reflectance mode with specular angle included, (4) large area view, (5) 1" port size. The measurements were performed on polymer granules ground to pass a 6 mm sieve.
- the percent foam in the polyesters of the invention was measured as follows. A 20 mL Headspace Vial supplied by MicroLiter Analytical Supplies, Suwanee, Ga. was placed on laboratory scale, 5 grams of dried polymer was added and the weight was recorded. Water was then carefully added until the vial was full and this weight was then recorded. The difference in weight (wt1) was recorded and used to estimate the vial volume with polymer containing no foam. This value was used for all subsequent runs. For each test, 5 grams of dried polymer sample was added to a clean Headspace Vial. A septum cap was attached to the top of the vial and the vial purged with dry nitrogen gas for approximately one minute.
- the purge line was removed and a dry nitrogen line equipped with a bubbler was inserted into the septum cap to ensure inert gas at atmospheric (ambient) pressure was maintained in the vial during the heating time.
- the vial was then placed into a pre-heated 300 0 C heating block (drilled out for a loose but close fit for vial) and held in the block for 15 minutes.
- the vial was then removed and air-cooled on a laboratory bench. After the vial was cooled, the vial top was removed and the vial was placed on a laboratory scale and weighed. Once the weight was recorded, water was carefully added to completely fill the vial.
- the density of the dry polyesters of the invention comprising about 45 mole % 2,2,4 ,4-tetramethyl-1 ,3-cyclobutanediol was 1.17 g/mL. This 1.17 g/mL value did not change significantly for the polyesters tested with a composition in the range from 40% to 50% mol TMCD.
- the density value for dry polyesters of about 20 mole % TCMD was 1.18 g/mL.
- the % Foam is a volume % of void volume in the after-test polymer. A visual grade of the final polymer sample after heating and cooling can also be determined.
- tin (Sn) in the examples below is reported in part per million (ppm) of metal and was measured by x-ray fluorescence (xrf) using a PANanalytical Axios Advanced wavelength dispersive x-ray fluorescence spectrometer.
- the amount of phosphorous is similarly reported as ppm of elemental phosphorus and was also measured by xrf using the same instrument.
- 10-mil films of selected polyester samples were compression molded using a Carver press at 240 0 C. Inherent viscosity was measured on these films as described above.
- the cis/trans ratio of the 1 ,4 cyclohexanedimethanol used in the following examples was approximately 30/70, and could range from 35/65 to 25/75.
- the cis/trans ratio of the 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol used in the following examples was approximately 50/50.
- the samples had sufficiently similar inherent viscosities thereby effectively eliminating this as a variable in the crystallization rate measurements.
- Crystallization half-time measurements from the melt were made at temperatures from 140 to 200°C at 10°C increments and are reported in Table 1. The fastest crystallization half-time for each sample was taken as the minimum value of crystallization half-time as a function of temperature, typically occurring around 170 to 180°C. The fastest crystallization half-times for the samples are plotted in Figure 1 as a function of mole% comonomer modification to PCT.
- the balance of the diol component of the polyesters in Table 1 is 1 , 4- cyclohexanedimethanol; and the balance of the dicarboxylic acid component of the polyesters in Table 1 is dimethyl terephthalate; if the dicarboxylic acid is not described, it is 100 mole % dimethyl terephthalate.
- Example 3 A film was pressed from the ground polyester of Example 1 G at 240 0 C. The resulting film had an inherent viscosity value of 0.575 dL/g.
- A is lsophthalic Acid
- C is 2,2,4 ,4-Tetramethyl-1 ,3-cyclobutanediol (approx. 50/50 cis/trans)
- D is 2,2,4,4-Tetramethyl-1 ,3-cyclobutanediol (98/2 cis/trans)
- E is 2,2,4 ,4-Tetramethyl-1 ,3-cyclobutanediol (5/95 cis/trans)
- This example illustrates the preparation of a copolyester with a target composition of 80 mol% dimethyl terephthalate residues, 20 mol % dimethyl isophthalate residues, and 100 mol% 1 ,4-cyclohexanedimethanol residues (28/72 cis/trans).
- a mixture of 56.63 g of dimethyl terephthalate, 55.2 g of 1 ,4-cyclohexanedimethanol, 14.16 g of dimethyl isophthalate, and 0.0419 g of dibutyl tin oxide was placed in a 500-milliliter flask equipped with an inlet for nitrogen, a metal stirrer, and a short distillation column.
- the flask was placed in a Wood's metal bath already heated to 210 0 C.
- the stirring speed was set to 200 RPM throughout the experiment.
- the contents of the flask were heated at 210 0 C for 5 minutes and then the temperature was gradually increased to 290 0 C over 30 minutes.
- This example illustrates the preparation of a copolyester with a target composition of 100 mol% dimethyl terephthalate residues, 20 mol % ethylene glycol residues, and 80 mol% 1 ,4-cyclohexanedimethanol residues (32/68 cis/trans).
- a mixture of 77.68 g of dimethyl terephthalate, 50.77 g of 1 ,4-cyclohexanedimethanol, 27.81 g of ethylene glycol, and 0.0433 g of dibutyl tin oxide was placed in a 500-milliliter flask equipped with an inlet for nitrogen, a metal stirrer, and a short distillation column.
- the flask was placed in a Wood's metal bath already heated to 200 0 C.
- the stirring speed was set to 200 RPM throughout the experiment.
- the contents of the flask were heated at 200 0 C for 60 minutes and then the temperature was gradually increased to 210 0 C over 5 minutes.
- the reaction mixture was held at 210 0 C for 120 minutes and then heated up to 280 0 C in 30 minutes. Once at 280 0 C, vacuum was gradually applied over the next 5 minutes until the pressure inside the flask reached 100 mm of Hg. The pressure inside the flask was further reduced to 0.3 mm of Hg over the next 10 minutes. A pressure of 0.3 mm of Hg was maintained for a total time of 90 minutes to remove excess unreacted diols. A high melt viscosity, visually clear and colorless polymer was obtained with a glass transition temperature of 87.7°C and an inherent viscosity of 0.71 dl/g. NMR analysis showed that the polymer was composed of 19.8 mol% ethylene glycol residues.
- This example illustrates the preparation of a copolyester with a target composition of 100 mol% dimethyl terephthalate residues, 20 mol % 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol residues, and 80 mol% 1 ,4-cyclohexanedimethanol residues (31/69 cis/trans).
- This example illustrates the preparation of a copolyester with a target composition of 100 mol% dimethyl terephthalate residues, 40 mol % dimethyl isophthalate residues, and 100 mol% 1 ,4-cyclohexanedimethanol residues (28/72 cis/trans).
- the reaction mixture was held at 290 0 C for 60 minutes and then vacuum was gradually applied over the next 5 minutes until the pressure inside the flask reached 100 mm of Hg. The pressure inside the flask was further reduced to 0.3 mm of Hg over the next 5 minutes. A pressure of 0.3 mm of Hg was maintained for a total time of 90 minutes to remove excess unreacted diols.
- a high melt viscosity, visually clear and colorless polymer was obtained with a glass transition temperature of 81.2 0 C and an inherent viscosity of 0.67 dl/g. NMR analysis showed that the polymer was composed of 100 mol% 1 ,4-cyclohexanedimethanol residues and 40.2 mol% dimethyl isophthalate residues.
- This example illustrates the preparation of a copolyester with a target composition of 100 mol% dimethyl terephthalate residues, 40 mol % ethylene glycol residues, and 60 mol% 1 ,4-cyclohexanedimethanol residues (31/69 cis/trans).
- a mixture of 81.3 g of dimethyl terephthalate, 42.85 g of 1 ,4-cyclohexanedimethanol, 34.44 g of ethylene glycol, and 0.0419 g of dibutyl tin oxide was placed in a 500-milliliter flask equipped with an inlet for nitrogen, a metal stirrer, and a short distillation column.
- the flask was placed in a Wood's metal bath already heated to 200 0 C.
- the stirring speed was set to 200 RPM throughout the experiment.
- the contents of the flask were heated at 200°C for 60 minutes and then the temperature was gradually increased to 210 0 C over 5 minutes.
- the reaction mixture was held at 210 0 C for 120 minutes and then heated up to 280 0 C in 30 minutes. Once at 280°C, vacuum was gradually applied over the next 5 minutes until the pressure inside the flask reached 100 mm of Hg. The pressure inside the flask was further reduced to 0.3 mm of Hg over the next 10 minutes. A pressure of 0.3 mm of Hg was maintained for a total time of 90 minutes to remove excess unreacted diols. A high melt viscosity, visually clear and colorless polymer was obtained with a glass transition temperature of 82.1 °C and an inherent viscosity of 0.64 dl/g. NMR analysis showed that the polymer was composed of 34.5 mol% ethylene glycol residues.
- This example illustrates the preparation of a copolyester with a target composition of 100 mol% dimethyl terephthalate residues, 40 mol % 2,2,4 ,4-tetramethyl-1 ,3-cyclobutanediol residues, and 60 mol% 1 ,4-cyclohexanedimethanol residues (31/69 cis/trans).
- a mixture of 77.4 g of dimethyl terephthalate, 36.9 g of 1 ,4-cyclohexanedimethanol, 32.5 g of 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol, and 0.046 g of dibutyl tin oxide was placed in a 500-milliliter flask equipped with an inlet for nitrogen, a metal stirrer, and a short distillation column. The flask was placed in a Wood's metal bath already heated to 210 0 C. The stirring speed was set to 200 RPM throughout the experiment.
- the contents of the flask were heated at 210 0 C for 3 minutes and then the temperature was gradually increased to 260 0 C over 30 minutes.
- the reaction mixture was held at 260°C for 120 minutes and then heated up to 290 0 C in 30 minutes.
- vacuum was gradually applied over the next 5 minutes until the pressure inside the flask reached 100 mm of Hg.
- the pressure inside the flask was further reduced to 0.3 mm of Hg over the next 5 minutes. A pressure of 0.3 mm of Hg was maintained for a total time of 90 minutes to remove excess unreacted diols.
- This example illustrates the preparation of a copolyester with a target composition of 100 mol% dimethyl terephthalate residues, 20 mol % 2,2,4 ,4-tetramethyl-1 ,3-cyclobutanediol residues (98/2 cis/trans), and 80 mol% 1 ,4-cyclohexanedimethanol residues (31/69 cis/trans).
- a mixture of 77.68 g of dimethyl terephthalate, 48.46 g of 1 ,4-cyclohexanedimethanol, 20.77 g of 2,2,4 ,4-tetra methyl- 1 ,3-cyclobutanediol, and 0.046 g of dibutyl tin oxide was placed in a 500-milliliter flask equipped with an inlet for nitrogen, a metal stirrer, and a short distillation column. The flask was placed in a Wood's metal bath already heated to 210 0 C. The stirring speed was set to 200 RPM throughout the experiment.
- the contents of the flask were heated at 21O 0 C for 3 minutes and then the temperature was gradually increased to 260 0 C over 30 minutes.
- the reaction mixture was held at 260 0 C for 120 minutes and then heated up to 290 0 C in 30 minutes.
- vacuum was gradually applied over the next 5 minutes until the pressure inside the flask reached 100 mm of Hg and the stirring speed was also reduced to 100 RPM.
- the pressure inside the flask was further reduced to 0.3 mm of Hg over the next 5 minutes and the stirring speed was reduced to 50 RPM.
- a pressure of 0.3 mm of Hg was maintained for a total time of 60 minutes to remove excess unreacted diols.
- This example illustrates the preparation of a copolyester with a target composition of 100 mol% dimethyl terephthalate residues, 20 mol % 2,2,4.4-tetramethyl-1 ,3-cyclobutanediol residues (5/95 cis/trans), and 80 mol% 1 ,4-cyclohexanedimethanol residues (31/69 cis/trans).
- a mixture of 77.68 g of dimethyl terephthalate, 48.46 g of 1 ,4-cyclohexanedimethanol, 20.77 g of 2,2,4 ,4-tetramethyl-1 ,3-cyclobutanediol, and 0.046 g of dibutyl tin oxide was placed in a 500-milliliter flask equipped with an inlet for nitrogen, a metal stirrer, and a short distillation column. The flask was placed in a Wood's metal bath already heated to 210 0 C. The stirring speed was set to 200 RPM at the beginning of the experiment.
- the contents of the flask were heated at 210 0 C for 3 minutes and then the temperature was gradually increased to 260 0 C over 30 minutes.
- the reaction mixture was held at 260°C for 120 minutes and then heated up to 290°C in 30 minutes.
- vacuum was gradually applied over the next 5 minutes with a set point of 100 mm of Hg and the stirring speed was also reduced to 100 RPM.
- the pressure inside the flask was further reduced to a set point of 0.3 mm of Hg over the next 5 minutes and the stirring speed was reduced to 50 RPM. This pressure was maintained for a total time of 60 minutes to remove excess unreacted diols.
- Copolyesters based on 2,2,4,4-tetramethyl-i ,3-cyclobutanediol were prepared as described below. The cis/trans ratio of the 1 ,4- cyclohexanedimethanol was approximately 31/69 for all samples. Copolyesters based on ethylene glycol and 1 ,4-cyclohexanedimethanol were commercial polyesters.
- the copolyester of Example 2A (Eastar PCTG 5445) was obtained from Eastman Chemical Co.
- the copolyester of Example 2B was obtained from Eastman Chemical Co. under the trade name Spectar.
- Example 2C and Example 2D were prepared on a pilot plant scale (each a 15-lb batch) following an adaptation of the procedure described in Example 1A and having the inherent viscosities and glass transition temperatures described in Table 2 below.
- Example 2C was prepared with a target tin amount of 300ppm (Dibutyltin Oxide). The final product contained 295 ppm tin.
- Example 2D was prepared with a target tin amount of 300ppm (Dibutyltin Oxide). The final product contained 307 ppm tin.
- the Izod impact strength undergoes a major transition in a short temperature span.
- the Izod impact strength of a copolyester based on 38 mol% ethylene glycol undergoes this transition between 15 and 2O 0 C.
- This transition temperature is associated with a change in failure mode; brittle/low energy failures at lower temperatures and ductile/high energy failures at higher temperatures.
- the transition temperature is denoted as the brittle-to-ductile transition temperature, T bd , and is a measure of toughness.
- T bd is reported in Table 2 and plotted against mol% comonomer in Figure 2.
- the balance of the glycol component of the polyesters in the Table is 1 ,4- cyclohexanedimethanol. All polymers were prepared from 100 mole % dimethyl terephthalate.
- C is 2,2,4,4-Tetramethyl-i ,3-cyclobutanediol (50/50 cis/trans)
- This example illustrates that a polyester based on 100% 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol has a slow crystallization half-time.
- a polyester based solely on terephthalic acid and 2,2,4,4-tetramethyl- 1 ,3-cyclobutanediol was prepared in a method similar to the method described in Example 1 A with the properties shown on Table 3. This polyester was made with 300 ppm dibutyl tin oxide. The trans/cis ratio of the 2,2,4 ,4-tetramethyl-1 ,3- cyclobutanediol was 65/35.
- Sheets comprising a polyester that had been prepared with a target composition of 100 mole % terephthalic acid residues, 80 mole % 1 ,4-cyclohexanedimethanol residues, and 20 mole % 2,2,4,4-tetramethyl- 1 ,3-cyclobutanediol residues were produced using a 3.5 inch single screw extruder.
- a sheet was extruded continuously, gauged to a thickness of 177 mil and then various sheets were sheared to size.
- Inherent viscosity and glass transition temperature were measured on one sheet. The sheet inherent viscosity was measured to be 0.69 dl/g. The glass transition temperature of the sheet was measured to be 106 0 C.
- Sheets were then conditioned at 50% relative humidity and 60 0 C for 2 weeks. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine.
- the thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below.
- Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part. The draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Example G).
- the thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H).
- the results below demonstrate that these thermoplastic sheets with a glass transition temperature of 106°C can be thermoformed under the conditions shown below, as evidenced by these sheets having at least 95% draw and no blistering, without predrying the sheets prior to thermoforming.
- Sheets comprising a polyester that had been prepared with a target composition of 100 mole % terephthalic acid residues, 80 mole % 1,4-cyclohexanedimethanol residues, and 20 mole % 2,2,4,4-tetramethyl- 1 ,3-cyclobutanediol residues were produced using a 3.5 inch single screw.
- a sheet was extruded continuously, gauged to a thickness of 177 mil and then various sheets were sheared to size. Inherent viscosity and glass transition temperature were measured on one sheet. The sheet inherent viscosity was measured to be 0.69 dl/g. The glass transition temperature of the sheet was measured to be 106 0 C.
- Sheets were then conditioned at 100% relative humidity and 25°C for 2 weeks. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine.
- the thermoforming oven heaters were set to 60/40/40% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below.
- Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part. The draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Example G).
- the thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H).
- the results below demonstrate that these thermoplastic sheets with a glass transition temperature of 106 0 C can be thermoformed under the conditions shown below, as evidenced by the production of sheets having at least 95% draw and no blistering, without predrying the sheets prior to thermo
- Kelvx 201 Sheets consisting of Kelvx 201 were produced using a 3.5 inch single screw extruder.
- Kelvx is a blend consisting of 69.85% PCTG (Eastar from Eastman Chemical Co. having 100 mole % terephthalic acid residues, 62 mole % 1 ,4-cyclohexanedimethanol residues, and 38 mole % ethylene glycol residues); 30% PC (bisphenol A polycarbonate); and 0.15% Western 619 (stabilizer sold by Crompton Corporation).
- a sheet was extruded continuously, gauged to a thickness of 177 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 100 0 C.
- Sheets were then conditioned at 50% relative humidity and 60 0 C for 2 weeks. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine.
- the thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below.
- Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part. The draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Example E).
- the thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H).
- the results below demonstrate that these thermoplastic sheets with a glass transition temperature of 100 0 C can be thermoformed under the conditions shown below, as evidenced by the production of sheets having at least 95% draw and no blistering, without predrying the sheets prior to thermo
- Sheets consisting of Kelvx 201 were produced using a 3.5 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 177 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 100 0 C. Sheets were then conditioned at 100% relative humidity and 25°C for 2 weeks. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine. The thermoforming oven heaters were set to 60/40/40% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below.
- Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part.
- the draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Example H).
- the thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H).
- N none
- L low
- H high
- Sheets consisting of PCTG 25976 (100 mole % terephthalic acid residues, 62 mole % 1 ,4-cyclohexanedimethanol residues, and 38 mole % ethylene glycol residues) were produced using a 3.5 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 118 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 87°C. Sheets were then conditioned at 50% relative humidity and 60 0 C for 4 weeks. The moisture level was measured to be 0.17 wt%. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine.
- thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below. Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part. The draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Example A). The thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H). The results below demonstrate that these thermoplastic sheets with a glass transition temperature of 87°C can be thermoformed under the conditions shown below, as evidenced by the production of sheets having greater than 95% draw and no blistering, without predrying the sheets prior to thermoforming.
- a miscible blend consisting of 20 wt% Teijin L-1250 polycarbonate (a bisphenol-A polycarbonate), 79.85 wt% PCTG 25976, and 0.15 wt% Weston 619 was produced using a 1.25 inch single screw extruder. Sheets consisting of the blend were then produced using a 3.5 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 118 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 94 0 C. Sheets were then conditioned at 50% relative humidity and 60 0 C for 4 weeks. The moisture level was measured to be 0.25 wt%.
- Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine.
- the thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below.
- Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part.
- the draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Example A).
- the thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H).
- N none
- L low
- H high
- a miscible blend consisting of 30 wt% Teijin L-1250 polycarbonate, 69.85 wt%. PCTG 25976, and 0.15 wt% Weston 619 was produced using a 1.25 inch single screw extruder. Sheets consisting of the blend were then produced using a 3.5 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 118 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 99°C. Sheets were then conditioned at 50% relative humidity and 60 0 C for 4 weeks. The moisture level was measured to be 0.25 wt%.
- Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine.
- the thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below.
- Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part.
- the draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Example A).
- the thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H).
- N none
- L low
- H high
- NA not applicable. A value of zero indicates that the sheet was not formed because it did not pull into the mold (likely because it was too cold).
- a miscible blend consisting of 40 wt% Teijin L-1250 polycarbonate, 59.85 wt% PCTG 25976, and 0.15 wt% Weston 619 was produced using a 1.25 inch single screw extruder. Sheets consisting of the blend were then produced using a 3.5 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 118 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 105 0 C. Sheets were then conditioned at 50% relative humidity and 60°C for 4 weeks. The moisture level was measured to be 0.265 wt%.
- Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine.
- the thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below.
- Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part.
- the draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Examples 8A to 8E).
- the thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H).
- N none
- L low
- H high
- a miscible blend consisting of 50 wt% Teijin L-1250 polycarbonate, 49.85 wt% PCTG 25976, and 0.15 wt% Weston 619 was produced using a 1.25 inch single screw extruder.
- a sheet was extruded continuously, gauged to a thickness of 118 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 111 0 C. Sheets were then conditioned at 50% relative humidity and 60 0 C for 4 weeks. The moisture level was measured to be 0.225 wt%. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine.
- thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below. Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part. The draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Examples A to D). The thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H). The results below demonstrate that these thermoplastic sheets with a glass transition temperature of 111°C can be thermoformed under the conditions shown below, as evidenced by the production of sheets having greater than 95% draw and no blistering, without predrying the sheets prior to thermoforming.
- NA not applicable. A value of zero indicates that the sheet was not formed because it did not pull into the mold (likely because it was too cold).
- a miscible blend consisting of 60 wt% Teijin L-1250 polycarbonate, 39.85 wt% PCTG 25976, and 0.15 wt% Weston 619 was produced using a 1.25 inch single screw extruder. Sheets consisting of the blend were then produced using a 3.5 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 118 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 117°C. Sheets were then conditioned at 50% relative humidity and 6O 0 C for 4 weeks. The moisture level was measured to be 0.215 wt%.
- Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine.
- the thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below.
- Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part.
- the draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Example A).
- the thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H).
- N none
- L low
- H high
- a miscible blend consisting of 65 wt% Teijin L-1250 polycarbonate, 34.85 wt% PCTG 25976, and 0.15 wt% Weston 619 was produced using a 1.25 inch single screw extruder. Sheets consisting of the blend were then produced using a 3.5 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 118 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 120 0 C. Sheets were then conditioned at 50% relative humidity and 60°C for 4 weeks. The moisture level was measured to be 0.23 wt%.
- Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine.
- the thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below.
- Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part.
- the draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Example A).
- the thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H).
- N none
- L low
- H high
- a miscible blend consisting of 70 wt% Teijin L-1250 polycarbonate, 29.85 wt% PCTG 25976, and 0.15 wt% Weston 619 was produced using a 1.25 inch single screw extruder. Sheets consisting of the blend were then produced using a 3.5 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 118 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 123°C. Sheets were then conditioned at 50% relative humidity and 60 0 C for 4 weeks. The moisture level was measured to be 0.205 wt%.
- Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine.
- the thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below.
- Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part.
- the draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Examples A and B).
- the thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H).
- N none
- L low
- H high
- NA not applicable. A value of zero indicates that the sheet was not formed because it did not pull into the mold (likely because it was too cold).
- Sheets consisting of Teijin L-1250 polycarbonate were produced using a 3.5 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 118 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 149°C. Sheets were then conditioned at 50% relative humidity and 60 0 C for 4 weeks. The moisture level was measured to be 0.16 wt%. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine. The thermoforming oven heaters were set to 70/60/60% output using top heat only.
- thermoformed part was left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below.
- Part quality was determined by measuring the volume of the thermoformed part, calculating the draw and visually inspecting the thermoformed part. The draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Example A). The thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H).
- N none
- L low
- H high
- NA not applicable. A value of zero indicates that the sheet was not formed because it did not pull into the mold (likely because it was too cold).
- polyesters comprising at least one thermal stabilizer, reaction products thereof, and mixtures thereof, resulting in improved stability of the polyester melts during processing.
- DMT dimethyl terephthalate
- CHDM 1 ,4-cyclohexanedimethanol
- TMCD 2,2,4 ,4-tetramethyl-1 ,3-cyclobutanediol
- the mole% of TMCD for the experiments of this example is reported in Table 4 below, with the glycol balance being CHDM.
- the DMT was purchased from Cape Industries, the CHDM (min. 98 %) and the TMCD (min. 98 %) were from Eastman Chemical Company.
- the tin compound was either dimethyltin oxide (from Strem Chemical Co. or Gelest, Inc.) or butyltin-tris-2-ethylhexonate (from Aldrich or Arkema).
- the phosphorus compound was triphenyl phosphate (TPP, from Aldrich (98 %) or FERRO, Corp.). Unless otherwise indicated below, the source of phosphorous was added upfront, with the rest of the polyester reagents.
- the cis/trans ratio of the CHDM was as described above while the cis/trans ratio of the TMCD is reported in Table 4.
- Example 17S and Example 17T are comparative examples.
- Example 17S represents a polyester prepared in a similar manner to Example 2OA below with no phosphorus thermal stabilizer, having an IV of 0.54 dL/g and containing 100 mole % terephthalic acid residues, 43.8 mole % TMCD residues and 56.2 mole %CHDM acid residues.
- Example 17T represents a commercial Kelvx polymer containing 65 mole % terephthalic acid residues, 35 mole % isophthalic acid residues, and 100 mole % 1 ,4-cyclohexanedimethanol residues.
- the polyesters of this example were prepared in a 500 ml round bottom flask fitted with a stirrer and a polymer head that allowed both a nitrogen purge and vacuum when necessary.
- the glycol/acid ratio was 1.2/1 with the excess being 2% CHDM and the rest of the 20% excess being TMCD.
- the catalyst was weighed into the flask, either as a solid or liquid.
- Triphenyl phosphate was weighed into the flask as a solid in the amount recited in Table 4 for each experiment. 100 ppm (0.0109g as a liquid) of tetramethyl ammonium hydroxide (TMAH) was used in the preparation of Example 17N.
- TMAH tetramethyl ammonium hydroxide
- This example illustrates the preparation of polyesters comprising at least one thermal stabilizer, reaction products thereof, and mixtures thereof, employing different process conditions from Example 17, resulting in improved stability of the polyester melts during processing.
- polyesters were prepared as described below from 100 mole% DMT, CHDM, and TMCD.
- the mole% of TMCD for the experiments of this example is reported in Table 6 below, with the glycol balance being CHDM.
- the DMT, CHDM, and TMCD were of the same origin as in Example 17.
- the catalyst was dimethyltin oxide (Strem Chemical Co., Batch B4058112), butyltin- tris-2-ethylhexonate (Aldrich, Batch 06423CD, or Arkema), or dibutyl tin oxide (Arkema).
- the thermal stabilizer was triphenyl phosphate, also with the same origin as in Example 17.
- a 500 ml round bottom flask was charged with 0.4 moles of DMT (77.6 grams), 0.224 moles of CHDM (32.3 grams), 0.256 moles of TMCD (36.8 grams), and 0.0460 grams of dibutyl tin oxide.
- the flask was equipped with a stainless steel stirrer and polymer head that allowed both nitrogen purge and- vacuum capabilities.
- the flask was immersed in a Belmont metal bath at 200 0 C and stirred at 25 RPM until the contents melted. The stirring was increased to 200 RPM and these conditions were held for 3 hours and 15 minutes.
- the temperature was increased to 22O 0 C and these conditions held for an additional 30 minutes.
- the temperature was increased to 29O 0 C over 20 minutes.
- the actual tin concentration for each polyester in this example is reported in Table 6 [00426]
- the glycol/acid ratio for all but two runs in this example was 1.2/1 with the excess being 2% CHDM and the rest of the 20% excess being TMCD.
- the glycol/acid ratio for Example 18H was 1.1/1 , with the excess being TMCD.
- the glycol/acid ratio for Example 181 was 1.05/1 , with the excess being TMCD.
- the catalyst was weighed into the flask, either as a solid or liquid. Triphenyl phosphate was weighed into the flask as a solid in the amounts recited in Table 6.
- the TPP in Example 18K was added late from a methanol solution.
- This example illustrates the preparation of polyesters utilizing different thermal stabilizers and showing their effect on the stability of the polyester melts during processing.
- polyesters were prepared as described below from 100 mole% DMT, and different concentrations of CHDM, and TMCD.
- the mole% of TMCD for the experiments of this example is reported in Table 8 below, with the glycol balance being CHDM.
- the DMT, CHDM, and TMCD were of the same origin as in Example 17.
- the catalyst was either dimethyltin oxide (Strem Chemical Co., Batch B4058112) or butyltin-tris-2-ethylhexonate (Aldrich, Batch 06423CD).
- the thermal stabilizer is indicated in Table 8 and was chosen from Merpol A (an octyl alcohol phosphate ester mixture from DuPont), triethylphosphate (Aldrich), lrgafos 168 (tris(2,4-di-tert-butylphenyl)phosphate, Ciba Specialty Chemicals), Doverphos 9228 (CAS# 154862-43-8, bis(2,4- dicumylphenyl) pentaerythritol diphosphate, Dover), Weston 619g (CAS# 85190- 63-2, 2-propanol, 1 ,1M"-nitrilotris-, mixt.
- the data in Table 9 shows the stability of polymer melts using different sources of phosphorous as thermal stabilizers.
- the data shows that phosphate esters and phosphorous compounds that can be hydrolyzed to phosphate esters provide stable melt and acceptable polyester products.
- the melt level stability and the visual grading reported in Table 9 are based on the scales disclosed in Example 17.
- polyesters were prepared as follows. A mixture of 77.6 g (0.4 mol) dimethyl terephthalate, 32.3 g (0.224 mol) 1 ,4-cyclohexanedimethanol, 36.8 g (0.256 mol) 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol was placed in a 500-ml flask equipped with an inlet for nitrogen, a metal stirrer, and a short distillation column. The catalyst was also added to the reaction flask. The amount and type of catalyst are in detailed in Table 8. The phosphorus compounds were also added to the reaction flask. The theoretical and measured amount of phosphorus compound for each experiment in this example is detailed in Table 8.
- polyesters were prepared as follows. A mixture of 77.6 g (0.4 mol) dimethyl terephthalate, 33.31 g (0.231 mol) 1 ,4-cyclohexanedimethanol, 35.91 g (0.249 mol) 2,2,4,4-tetramethyl-i ,3-cyclobutanediol was placed in a 500- ml flask equipped with an inlet for nitrogen, a metal stirrer, and a short distillation column. The catalyst was also added to the reaction flask. The amount and type of catalyst are in detailed in Table 8.
- the source of phosphorous was weighed into the flask in the amounts recited in Table 8, which includes the theoretical and measured amount of phosphorus compound for each experiment.
- the flask was placed in a Wood's metal bath already heated to 200 0 C.
- the temperature/pressure/stir rate sequence controlled by the Camile software for each example is reported below.
- the glycol/acid ratio for all experiments in this example was 1.2/1 with the excess being 2% CHDM and the rest of the 20% excess being TMCD.
- the catalyst was weighed into the flask, either as a solid or liquid.
- the set points and data collection were facilitated by a Camile process control system. Once the reactants were melted, stirring was initiated and slowly increased as indicated below in the corresponding Camile sequences. The temperature of the reactor also gradually increased with run time.
- the temperature/pressure/stir rate sequence controlled by the Camile software for each example is reported in the following tables.
- the final polymerization temperature (Pz Temp.) for the experiments of this example was 265°C.
- This example illustrates the preparation of polyesters at a pilot plant scale comprising at least one thermal stabilizer, reaction products thereof, and mixtures thereof, resulting in improved stability of the polyester melts during processing.
- polyesters were prepared as described below from 100 mole% DMT, CHDM, and TMCD.
- the mole% of TMCD for the experiments of this example is reported in Table 10 below, with the glycol balance being CHDM.
- the DMT, CHDM, and TMCD were of the same origin as in Example 17.
- the catalyst was either dimethyltin oxide (Strem Chemical Co., Batch B4058112) or butyltin-tris-2-ethylhexonate (Aldrich, Batch 06423CD).
- the thermal stabilizer was triphenyl phosphate (TPP) (Aldrich). Unless otherwise indicated below, the source of phosphorous was added upfront, with the rest of the polyester reagents.
- the cis/trans ratio of the CHDM was as described above while the cis/trans ratio of the TMCD is reported in Table 10. Table lO
- the reaction mixture temperature was increased to 250 0 C and the pressure was increased to 20 psig.
- the reaction mixture was held for 2 hours at 250 0 C and 20 psig pressure.
- the pressure was then decreased to 0 psig at a rate of 3 psig/minute.
- the agitator speed was then decreased to 15 RPM, the temperature of the reaction mixture was then increased to 270 0 C, and the pressure was decreased to ⁇ 1-mm.
- the reaction mixture was held at 270°C and a pressure of ⁇ 1 mm of Hg for 3.75 hours.
- the pressure of the vessel was then increased to 1 atmosphere using nitrogen gas.
- the molten polymer was then extruded from the pressure vessel using an extrusion die.
- the extruded polymer strands were then pulled through a cold water bath to cool them after which the strands were pelletized.
- the pelletized polymer had an inherent viscosity of 0.553. NMR analysis showed that the polymer was composed- of 53.9 mol% 1 ,4-cyclohexanedimethanol moiety and 46.1 mol% 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol moiety.
- Example 2OB to Example 2OD were prepared in a similar manner to Example 2OA, having the composition disclosed in Table 10.
- Example 2OE represents PCTG Eastar DN001 from Eastman Chemical Company, having an IV of 0.73 dL/g with a nominal composition of 100 mole% terephthalic acid residues, 62 mole% CHDM residues and 38 mole % ethylene glycol residues.
- Example 2OF represents the polycarbonate Makrolon 2608 from Bayer, with a nominal composition of 100 mole% bisphenol A residues and 100 mole% diphenyl carbonate residues.
- Example 2OG represents an Eastman Chemical Company polyester, with a nominal composition of 100 mole% terephthalic acid residues, 55 mole% CHDM residues and 45 mole % TMCD residues.
- Example 2OH represents PETG Eastar 6763 from Eastman Chemical Company, with a nominal composition of 100 mole% terephthalic acid, 31 mole% cyclohexanedimenthanol (CHDM) and 69 mole % ethylene glycol.
- CHDM cyclohexanedimenthanol
- the polyester of Example 2Ol is a blend of 10 different polyesters, each prepared in the following manner. 84.96 lbs (198.83 gram-mol) dimethyl terephthalate were reacted in the presence of 200 ppm of tin catalyst (as butyltin- tris-ethylhexanoate) with 50.45 to 51.46-lbs (159.06 162.24 gram-mol, depednign on the batch) 1 ,4-cyclohexanedimethanol and 24.22 to 31.53-lbs (76.36 to 99.41 gram-mol, also depending on the batch) 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol.
- tin catalyst as butyltin- tris-ethylhexanoate
- the reaction was carried out under a nitrogen gas purge in an 74-gallon stainless steel pressure vessel fitted with a condensing column, a vacuum system, and a HELICONE-type agitator, to provide glycol/dimethyl terephthalate molar ratios of 1.2/1 to 1.3/1.
- the reaction mixture temperature was increased to 250 0 C and the pressure was increased to 20 psig.
- the reaction mixture was held for 2 hours at 250 0 C and 20 psig pressure. The pressure was then decreased to 0 psig at a rate of 3 psig/minute.
- the agitator speed was then decreased to 15 RPM, the temperature of the reaction mixture was then increased to 260-270 0 C, and the pressure was decreased- to 90 mm of Hg.
- the reaction mixture was held at 260-270°C and 90-mm pressure for 1 hour.
- the temperature of the reaction mixture was then increased to 275-290°C and the pressure was decreased to ⁇ 1 mm of Hg.
- the reaction mixture was held at 275-290 0 C and ⁇ 1 mm of Hg for 1.5-3 hours to complete the polycondensation stage.
- the pressure of the pressure vessel was then increased to 1 atmosphere using nitrogen gas.
- the molten polymer was then extruded from the pressure vessel into a cold water bath.
- the cooled, extruded polymer was ground to pass a 6-mm screen.
- Plaques (4 inch x 4 inch x 1/8 inch thick) were prepared in a Toyo 110 injection molding press from the polyesters of Table 10. Pellets of each polyester were feed into the press and heated to the temperatures reported in Table 11. The residence time of the molten polymer in the barrel before injection is also reported in Table 11. Once the part had cooled sufficiently, it was visually analyzed and the splay generated during the injection molding process was recorded.
- the polymers were extruded on a 1.5" Killion extruder using a General Purpose screw. The polymers were extruded at temperatures of 572°F (300 0 C) and 527°F (275 0 C). The following extruder conditions were used for each polymer in the 572°F extrusions:
- polyesters of the present invention offer an advantage over the commercially available polyesters with regard to at least one of bubbling, splaying, color formation, foaming, off-gassing, and erratic melt levels in the polyester's production and processing systems.
- the invention has been described in detail with reference to the embodiments disclosed herein, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
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Abstract
Description
Claims
Applications Claiming Priority (47)
Application Number | Priority Date | Filing Date | Title |
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US73138905P | 2005-10-28 | 2005-10-28 | |
US73145405P | 2005-10-28 | 2005-10-28 | |
US73905805P | 2005-11-22 | 2005-11-22 | |
US73886905P | 2005-11-22 | 2005-11-22 | |
US75068205P | 2005-12-15 | 2005-12-15 | |
US75069205P | 2005-12-15 | 2005-12-15 | |
US75069305P | 2005-12-15 | 2005-12-15 | |
US75054705P | 2005-12-15 | 2005-12-15 | |
US39077306A | 2006-03-28 | 2006-03-28 | |
US11/390,654 US20060287477A1 (en) | 2005-06-17 | 2006-03-28 | Greenhouses comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4- cyclohexanedimethanol |
US11/390,809 US7959998B2 (en) | 2005-03-02 | 2006-03-28 | Transparent, oxygen-scavenging compositions containing polyesters comprising a cyclobutanediol and articles prepared therefrom |
US11/391,156 US7812112B2 (en) | 2005-06-17 | 2006-03-28 | Outdoor signs comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
US11/390,750 US20060287480A1 (en) | 2005-06-17 | 2006-03-28 | Outdoor shelters comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
US11/390,811 US7868128B2 (en) | 2005-06-17 | 2006-03-28 | Skylights and windows comprising polyester compositions formed from 2,2,4,4,-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
US11/390,671 US8063172B2 (en) | 2005-06-17 | 2006-03-28 | Film(s) and/or sheet(s) made using polyester compositions containing low amounts of cyclobutanediol |
US11/390,847 US20060287484A1 (en) | 2005-06-17 | 2006-03-28 | Opththalmic devices comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
US11/390,629 US7803439B2 (en) | 2005-06-17 | 2006-03-28 | Blood therapy containers comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
US11/390,858 US7951900B2 (en) | 2005-06-17 | 2006-03-28 | Dialysis filter housings comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
US11/390,846 US7955674B2 (en) | 2005-03-02 | 2006-03-28 | Transparent polymer blends containing polyesters comprising a cyclobutanediol and articles prepared therefrom |
US11/390,630 US7807774B2 (en) | 2005-06-17 | 2006-03-28 | Vending machines comprising polyester compositions formed from 2,2,4,4,-tetramethyl-1,3,-cyclobutanediol and 1,4-cyclohexanedimethanol |
US11/391,063 US7576171B2 (en) | 2005-06-17 | 2006-03-28 | Pacifiers comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
US11/390,883 US7834129B2 (en) | 2005-06-17 | 2006-03-28 | Restaurant smallware comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
US11/391,124 US20060234073A1 (en) | 2005-03-02 | 2006-03-28 | Multilayered, transparent articles containing polyesters comprising a cyclobutanediol and a process for their preparation |
US11/390,908 US7462684B2 (en) | 2005-03-02 | 2006-03-28 | Preparation of transparent, multilayered articles containing polyesters comprising a cyclobutanediol and homogeneous polyamide blends |
US11/390,631 US7855267B2 (en) | 2005-06-17 | 2006-03-28 | Film(s) and/or sheet(s) comprising polyester compositions which comprise cyclobutanediol and have a certain combination of inherent viscosity and moderate glass transition temperature |
US11/391,137 US7985827B2 (en) | 2005-06-17 | 2006-03-28 | Polyester compositions which comprise cyclobutanediol having certain cis/trans ratios |
US11/390,752 US8063173B2 (en) | 2005-06-17 | 2006-03-28 | Polyester compositions containing low amounts of cyclobutanediol and articles made therefrom |
US11/390,836 US20060286330A1 (en) | 2005-06-17 | 2006-03-28 | Sterilization containers comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
US11/390,865 US20060287485A1 (en) | 2005-06-17 | 2006-03-28 | Sound barriers comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
US11/390,655 US8067525B2 (en) | 2005-06-17 | 2006-03-28 | Film(s) and/or sheet(s) comprising polyester compositions which comprise cyclobutanediol and have a certain combination of inherent viscosity and high glass transition temperature |
US11/390,814 US20060286327A1 (en) | 2005-06-17 | 2006-03-28 | Retort containers comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
US11/390,853 US20070270569A1 (en) | 2005-06-17 | 2006-03-28 | Film(s) and/or sheet(s) made from polyester compositions containing cyclobutanediol and articles made therefrom |
US11/390,827 US7893188B2 (en) | 2005-06-17 | 2006-03-28 | Baby bottles comprising polyester compositions which comprise cyclobutanediol |
US11/390,955 US7915376B2 (en) | 2005-06-17 | 2006-03-28 | Containers comprising polyester compositions which comprise cyclobutanediol |
US11/390,812 US7959836B2 (en) | 2005-03-02 | 2006-03-28 | Process for the preparation of transparent, shaped articles containing polyesters comprising a cyclobutanediol |
US11/391,125 US20070010650A1 (en) | 2005-06-17 | 2006-03-28 | Tough amorphous polyester compositions |
US11/390,864 US7812111B2 (en) | 2005-06-17 | 2006-03-28 | LCD films comprising polyester compositions formed from 2,2,4,4-tetramethy1-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
US11/390,882 US20060287486A1 (en) | 2005-06-17 | 2006-03-28 | Optical media comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
US11/390,826 US7906610B2 (en) | 2005-06-17 | 2006-03-28 | Food service products comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
US11/390,751 US7803440B2 (en) | 2005-06-17 | 2006-03-28 | Bottles comprising polyester compositions which comprise cyclobutanediol |
US11/390,672 US20060287479A1 (en) | 2005-06-17 | 2006-03-28 | Polyester compositions containing cyclobutanediol and articles made therefrom |
US11/391,485 US7842776B2 (en) | 2005-06-17 | 2006-03-28 | Appliance parts comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
US11/390,793 US20060286389A1 (en) | 2005-06-17 | 2006-03-28 | Protein-resistant articles comprising cyclobutanediol |
US11/390,563 US7902320B2 (en) | 2005-06-17 | 2006-03-28 | Graphic art films comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
US11/390,794 US8119761B2 (en) | 2005-06-17 | 2006-03-28 | Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and high glass transition temperature and articles made therefrom |
US11/390,722 US7893187B2 (en) | 2005-06-17 | 2006-03-28 | Glass laminates comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
PCT/US2006/042291 WO2007053548A2 (en) | 2005-10-28 | 2006-10-27 | Polyester compositions comprising minimal amounts of cyclobutanediol |
Publications (1)
Publication Number | Publication Date |
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EP1940910A2 true EP1940910A2 (en) | 2008-07-09 |
Family
ID=39481116
Family Applications (2)
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EP06827056A Withdrawn EP1940910A2 (en) | 2005-10-28 | 2006-10-27 | Polyester compositions comprising minimal amounts of cyclobutanediol |
EP06836589A Withdrawn EP1940953A1 (en) | 2005-10-28 | 2006-10-27 | Polyester compositions which comprise cyclobutanediol and at least one phosphorus compound |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
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EP06836589A Withdrawn EP1940953A1 (en) | 2005-10-28 | 2006-10-27 | Polyester compositions which comprise cyclobutanediol and at least one phosphorus compound |
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EP (2) | EP1940910A2 (en) |
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2006
- 2006-10-27 EP EP06827056A patent/EP1940910A2/en not_active Withdrawn
- 2006-10-27 EP EP06836589A patent/EP1940953A1/en not_active Withdrawn
Non-Patent Citations (1)
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