Polyester compositions comprising amorphous copolyester having high glass transition temperature and articles made therefrom

Abstract

Described are polyester compositions comprising at least one amorphous copolyester which comprises terephthalic acid, an ester thereof, or mixtures thereof, ethylene glycol, 1,4-cyclohexanedimethanol, and 2,2,4,4-tetramethyl-l,3-cyclobutanediol, having high glass transition temperature, specific flexural properties, and impact property. The polyester composition may be manufactured into articles such as fibers, films, containers, bottles, or sheets.

Description

POLYESTER COMPOSITIONS COMPRISING AMORPHOUS COPOLYESTER HAVING HIGH GLASS TRANSITION TEMPERATURE AND ARTICLES MADE THEREFROMFIELD OF THE INVENTION

[0001] The present invention relates to polyester compositions comprising at least one amorphous copolyester made from terephthalic acid, ethylene glycol, 1,4-cyclohexanedimethanol and 2,2,4,4-tetramethyl-1,3-cyclobutanediol, the amorphous copolyester having good dimensional stability at high temperature and reduced costs.BACKGROUND OF THE INVENTION

[0002] Amorphous copolyesters can have desirable properties, such as excellent clarity and color, toughness, chemical resistance, and ease of processing. Such copolyesters are known to be useful for the manufacture of extruded sheets, packaging materials, and parts for medical devices. 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 sufficientmodifying ethylene glycol is included in the formulation to provide for long crystallization half-times. For example, 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.

[0003] Although certain copolyesters have been described as having a higher Tg, they can exhibit high inherent viscosities and high melt viscosities along with the high Tg, such that the equipment used in industry may be insufficient (or have difficulty) to manufacture or post-polymerization process these materials.

[0004] There is a commercial need for polymers that have high glass transition temperature that can be processed with typical melt-processing equipment, and that can maintain good mechanical properties, like flexural modulus, high heat distortiontemperature and high impact property while using less expensive raw materials and having better sustainable potential.SUMMARY OF THE INVENTION

[0005] It has been found that certain compositions comprising an amorphous copolyester formed from terephthalic acid residues, ethylene glycol residues, 1,4-cyclohexanedimethanol residues and 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues with certain glass transition temperatures can be provided that are superior to other copolyesters with respect to one or more of increased heat distortion temperature, increased flexural modulus, good color and clarity, and / or thermoformability, while maintaining other good (desired) physical properties and reduced costs.

[0006] In one aspect, the invention relates to a polyester composition comprising at least one amorphous copolyester which comprises:(a) a dicarboxylic acid component comprising:(i) 90 to 100 mole % of terephthalic acid residues;(ii) 0 to 10 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and;(b) a glycol component comprising:(i) 1 to 45 mole % of ethylene glycol residues; and (ii) 30 to 80 mole % of 1,4-cyclohexanedimethanol residues; and (iii) 15 to 38 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residueswherein the total mole % of the acid component (a) is 100 mole % and the total mole % of the glycol component (b) is 100 mole %, and wherein the inherent viscosity of the material is 0.3-1, or 0.3 to 0.8 dL / g in 60 / 40 (wt / wt) phenol / tetrachloroethan at a concentration of 0.5 g / 100 mL at 25 °C, a glass transition temperature of greater than 100°C as determined using ASTM D3418 test method, and a flexural modulus greater than 1700 MPa as determined using the ASTM D790 test method, a notched Izod impact strength of greater than 750 J / M according to ASTM D256.

[0007] In another aspect, the invention relates to a polyester composition comprising at least one amorphous copolyester which comprises:(a) a dicarboxylic acid component comprising:(i) 90 to 100 mole % of terephthalic acid residues;(ii) 0 to 10 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and;(b) a glycol component comprising:(i) 15 to 40 mole % of ethylene glycol residues; and(ii) 30 to 80 mole % of 1,4-cyclohexanedimethanol residues; and (iii) 15 to 38 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residueswherein the total mole % of the acid component (a) is 100 mole % and the total mole % of the glycol component (b) is 100 mole %, and wherein the inherent viscosity of the material is 0.3-1, or 0.3 to 0.8 dL / g in 60 / 40 (wt / wt) phenol / tetrachloroethan at a concentration of 0.5 g / 100 mL at 25 °C, a glass transition temperature of greater than 100 °C as determined using ASTM D3418 test method, and a flexural modulus greater than 1700 MPa as determined using the ASTM D790 test method, a notched Izod impact strength of greater than 750 J / M according to ASTM D256.

[0008] In another aspect, the invention relates to a polyester composition comprising at least one amorphous copolyester which comprises:(a) a dicarboxylic acid component comprising:(i) 90 to 100 mole % of terephthalic acid residues;(ii) 0 to 10 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and;(b) a glycol component comprising:(i) 15 to 40 mole % of ethylene glycol residues; and(ii) 30 to 65 mole % of 1,4-cyclohexanedimethanol residues; and (iii) 15 to 35 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residueswherein the total mole % of the acid component (a) is 100 mole % and the total mole % of the glycol component (b) is 100 mole %, and wherein the inherent viscosity of the material is 0.3-1, or 0.3 to 0.8 dL / g in 60 / 40 (wt / wt) phenol / tetrachloroethan at a concentration of 0.5 g / 100 mL at 25 °C, a glass transition temperature of greater than 100 °C as determined using ASTM D3418 test method, and a flexural modulus greaterthan 1700 MPa as determined using the ASTM D790 test method, a notched Izod impact strength of greater than 750 J / M according to ASTM D256.

[0009] In another aspect, the invention relates to a polyester composition comprising at least one amorphous copolyester which comprises:(a) a dicarboxylic acid component comprising:(i) 90 to 100 mole % of terephthalic acid residues;(ii) 0 to 10 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and;(b) a glycol component comprising:(i) 20 to 40 mole % of ethylene glycol residues; and(ii) 30 to 60 mole % of 1,4-cyclohexanedimethanol residues; and (iii) 15 to 35 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residueswherein the total mole % of the acid component (a) is 100 mole % and the total mole % of the glycol component (b) is 100 mole %, and wherein the inherent viscosity of the material is 0.3-1, or 0.3 to 0.8 dL / g in 60 / 40 (wt / wt) phenol / tetrachloroethan at a concentration of 0.5 g / 100 mL at 25 °C, a glass transition temperature of greater than 100 °C as determined using ASTM D3418 test method, and a flexural modulus greater than 1700 MPa as determined using the ASTM D790 test method, a notched Izod impact strength of greater than 750 J / M according to ASTM D256.

[0010] In another aspect, the invention relates to a polyester composition comprising at least one amorphous copolyester which comprises:(a) a dicarboxylic acid component comprising:(i) 90 to 100 mole % of terephthalic acid residues;(ii) 0 to 10 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and;(b) a glycol component comprising:(i) 15 to 40 mole % of ethylene glycol residues; and(ii) 30 to 60 mole % of 1,4-cyclohexanedimethanol residues; and (iii) 20 to 35 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residueswherein the total mole % of the acid component (a) is 100 mole % and the total mole % of the glycol component (b) is 100 mole %, and wherein the inherent viscosity of the material is 0.3-1, or 0.3 to 0.8 dL / g in 60 / 40 (wt / wt) phenol / tetrachloroethan at a concentration of 0.5 g / 100 mL at 25 °C, a glass transition temperature of greater than 100 °C as determined using ASTM D3418 test method, and a flexural modulus greater than 1700 MPa as determined using the ASTM D790 test method, a notched Izod impact strength of greater than 750 J / M according to ASTM D256.

[0011] In another aspect, the invention relates to a polyester composition comprising at least one amorphous copolyester which comprises:(a) a dicarboxylic acid component comprising:(i) 90 to 100 mole % of terephthalic acid residues;(ii) 0 to 10 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and;(b) a glycol component comprising:(i) 20 to 40 mole % of ethylene glycol residues; and(ii) 32 to 60 mole % of 1,4-cyclohexanedimethanol residues; and (iii) 20 to 35 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residueswherein the total mole % of the acid component (a) is 100 mole % and the total mole % of the glycol component (b) is 100 mole %, and wherein the inherent viscosity of the material is 0.3-1, or 0.3 to 0.8 dL / g in 60 / 40 (wt / wt) phenol / tetrachloroethan at a concentration of 0.5 g / 100 mL at 25 °C, a glass transition temperature of greater than 100 °C as determined using ASTM D3418 test method, and a flexural modulus greater than 1700 MPa as determined using the ASTM D790 test method, a notched Izod impact strength of greater than 750 J / M according to ASTM D256.DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention may be understood more readily by reference to the following detailed description of certain embodiments of the invention and the working examples. In accordance with the purpose(s) of this invention, certain embodiments of the invention are described in the Summary of the Invention and arefurther described herein below. Also, other embodiments or aspects of the invention are described herein.

[0013] It is believed that certain polyesters and / or polyester composition(s) of the invention formed from terephthalic acid, an ester thereof, and / or mixtures thereof, ethylene glycol, 1,4-cyclohexanedimethanol and 2,2,4,4-tetramethyl-1,3-cyclobutanediol, can have a unique combination of two or more of the following properties: certain notched Izod impact strengths, certain inherent viscosities, certain glass transition temperature (Tg); certain flexural modulus, good clarity, good color, good thermal stability (e.g., high heat deflection temperature) for a selected IV. In certain embodiments of the invention, certain polyesters and / or polyester compositions of the invention can have a unique combination of three or more of certain notched Izod impact strengths, certain inherent viscosities, certain glass transition temperature (Tg); certain flexural modulus, good clarity, good color, good thermal stability (e.g., high heat deflection temperature) for a selected IV.

[0014] As used herein, the term "polyester" includes copolyesters and is understood to mean a synthetic polymer prepared by the reaction of one or more difunctional and / or multifunctional carboxylic acids with one or more difunctional hydroxyl compounds and / or multifunctional hydroxyl compounds. Typically, 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. The term "glycol" as used in this application includes, but is not limited to, diols, glycols, and / or multifunctional hydroxyl compounds, for example, branching agents.Alternatively, the difunctional carboxylic acid may be a hydroxy carboxylic acid such as, for example, p-hydroxybenzoic acid, and the difunctional hydroxyl compound may be an aromatic nucleus bearing 2 hydroxyl substituents such as, for example, hydroquinone. The term "residue", as used herein, means any organic structure incorporated into a polymer through a polycondensation and / or an esterification reaction from the corresponding monomer. The term "repeating unit", as used herein, means an organic structure having a dicarboxylic acid residue and a diol residue bonded through a carbonyloxy group. Thus, for example, the dicarboxylic acid residues may be derived from a dicarboxylic acid monomer or its associated acid halides, esters, salts, anhydrides, or mixtures thereof. As used herein, therefore, theterm dicarboxylic acid is intended to include dicarboxylic acids and any derivative of a dicarboxylic acid, including its associated acid halides, esters, half-esters, salts, halfsalts, anhydrides, mixed anhydrides, or mixtures thereof, useful in a reaction process with a diol to make polyester. Furthermore, as used in this application, the term "diacid" includes multifunctional acids, for example, branching agents. As used herein, the term "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.

[0015] 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 are 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. For example, a polyester containing 10 mole % isophthalic acid, based on the total acid residues, means the polyester contains 10 mole % isophthalic acid residues out of a total of 100 mole % acid residues. Thus, there are 10 moles of isophthalic acid residues among every 100 moles of acid residues. In another example, a polyester containing 40 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, based on the total diol residues, means the polyester contains 40 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues out of a total of 100 mole % diol residues. Thus, there are 40 moles of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues among every 100 moles of diol residues.

[0016] In one embodiment or in combination with any other embodiment, wherein the ethylene glycol component (by mole % of the copolyester) is from 1-45%, or 1-40%, or 1-35%, or 1-30%, or 1-25%, or 1-20%, or 5-45%, or 5-40%, or 5-35%, or 5-30%, or 5-25%, or 5-20%, or 10-45%, or 10-40%, or 10-35%, or 10-30%, or 10-25%, or 10-20%, or 15-45%, or 15-40%, or 15-35%, or 15-30%, or 15-25%, or15-20%, or 20-45%, or 20-40%, or 20-35%, or 20-30%, or 20-25%, or 25-45%, or 25-40%, or 25-35%, or 25-30%, or 30-45%, or 30-40%, or 30-35%, or 35-45%, or 35-40%, or 40-45%.

[0017] In one embodiment or in combination with any other embodiment, wherein the 1,4-cyclohexanedimethanol component (by mole % of the copolyester) is from 30-80%, or 30-75%, or 30-70%, or 30-65%, or 30-60%, or 30-55%, or 30-50%, 30-45%, or 30-40%, or 30-35%, or 35-80%, or 35-75%, or 35-70%, or 35-65%, or 35-60%, or 35-55%, or 35-50%, 35-45%, or 35-40%, or 40-80%, or 40-75%, or 40-70%, or 40-65%, or 40-60%, or 40-55%, or 40-50%, 40-45%, or 45-80%, or 45-75%, or 45-70%, or 45-65%, or 45-60%, or 45-55%, or 45-50%, or 50-80%, or 50-75%, or 50-70%, or 50-65%, or 50-60%, or 50-55%, or 55-80%, or 55-75%, or 55-70%, or 55-65%, or 55-60%, or 60-80%, or 60-75%, or 60-70%, or 60-65%.

[0018] In one embodiment or in combination with any other embodiment, wherein the 2,2,4,4-tetramethyl-1,3-cyclobutanediol component (by mole % of the copolyester) is from 15-38%, or 15-35%, or 15-30%, or 15-25%, or 20-38%, or 20-35%, or 20-30%, or 20-25%, or 25-38%, or 25-35%, or 25-30%, or 30-38%, or 30-35%.

[0019] In aspects of the invention, the glycol component for the polyesters useful in the invention includes but are not limited to at least one of the following combinations of ranges: 15 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 30 to 65 mole % 1,4-cyclohexanedimethanol, and 1 to 45 mole % ethylene glycol; 15 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 30 to 65 mole % 1,4-cyclohexanedimethanol, and 15 to 40 mole % ethylene glycol; 15 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 30 to 65 mole % 1,4-cyclohexanedimethanol, and 20 to 40 mole % ethylene glycol; 15 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 35 to 65 mole % 1,4-cyclohexanedimethanol, and 1 to 45 mole % ethylene glycol; 15 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 35 to 65 mole % 1,4-cyclohexanedimethanol, and 15 to 40 mole % ethylene glycol; 15 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 35 to 65 mole % 1,4-cyclohexanedimethanol, and 20 to 40 mole % ethylene glycol; 15 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 30 to 60 mole % 1,4-cyclohexanedimethanol, and 5 to 45 mole % ethylene glycol; 15 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 30 to 60 mole % 1,4-cyclohexanedimethanol, and 15 to 40 mole % ethylene glycol; 15 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 30 to 60 mole % 1,4-cyclohexanedimethanol, and 20 to 40 mole % ethylene glycol.

[0020] In aspects of the invention, the glycol component for the polyesters useful in the invention includes but are not limited to at least one of the following combinations of ranges: 20 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 30 to 65 mole % 1,4-cyclohexanedimethanol, and 1 to 45 mole % ethylene glycol; 20 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 30 to 65 mole % 1,4-cyclohexanedimethanol, and 15 to 40 mole % ethylene glycol; 20 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 30 to 65 mole % 1,4-cyclohexanedimethanol, and 20 to 40 mole % ethylene glycol; 20 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 35 to 65 mole % 1,4-cyclohexanedimethanol, and 1 to 45 mole % ethylene glycol; 20 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 35 to 65 mole % 1,4-cyclohexanedimethanol, and 15 to 40 mole % ethylene glycol; 20 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 35 to 65 mole % 1,4-cyclohexanedimethanol, and 20 to 40 mole % ethylene glycol; 20 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 30 to 60 mole % 1,4-cyclohexanedimethanol, and 5 to 45 mole % ethylene glycol; 20 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 30 to 60 mole % 1,4-cyclohexanedimethanol, and 15 to 40 mole % ethylene glycol; 20 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 30 to 60 mole % 1,4-cyclohexanedimethanol, and 20 to 40 mole % ethylene glycol.

[0021] In aspects of the invention, the glycol component for the polyesters useful in the invention includes but are not limited to at least one of the following combinations of ranges: 25 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 30 to 65 mole % 1,4-cyclohexanedimethanol, and 1 to 45 mole % ethylene glycol; 25 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 30 to 65 mole % 1,4-cyclohexanedimethanol, and 15 to 40 mole % ethylene glycol; 25 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 30 to 65 mole % 1,4-cyclohexanedimethanol, and 20 to 40 mole % ethylene glycol; 25 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 35 to 65 mole % 1,4-cyclohexanedimethanol, and 1 to 45 mole % ethylene glycol; 25 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 35 to 65 mole % 1,4-cyclohexanedimethanol, and 15 to 40 mole % ethylene glycol; 25 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 35 to 65 mole % 1,4-cyclohexanedimethanol, and 20 to 40 mole % ethylene glycol; 25 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 30 to 60 mole % 1,4-cyclohexanedimethanol, and 5 to 45 mole % ethylene glycol; 25 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 30 to 60 mole % 1,4-cyclohexanedimethanol, and 15 to 40 mole % ethylene glycol; 25 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 30 to 60 mole % 1,4-cyclohexanedimethanol, and 20 to 40 mole % ethylene glycol.

[0022] In other aspects of the invention, the Tg of the amorphous copolyesters useful in the polyester compositions of the invention can include, but are not limited to greater than 100°C; or greater than 103°C; or greater than 105°C; or greater than 110°C; or greater than 100°C and less than 120°C; or greater than 100°C and less than 115°C; or greater than 100°C and less than 110°C; or 105°C to 120°C; or 105°C to 115°C; or 105°C to 110°C; or 110°C to 120°C; or 110°C to 115°C.

[0023] In other aspects of the invention, the heat deflection temperature of the amorphous copolyesters useful in the polyester compositions of the invention is 90°C or greater measured according to ASTM D648 at 0.455 MPa and / or 75°C or greater measured according to ASTM D648 at 1.82 MPa. The heat deflection temperature (HDT) was determined according to ASTM D648 using a 3.2mm thick injection molded bar and 1.82 or 0.455 MPa applied stress. Samples were conditioned for 48 hrs at 23°C and 50%RH prior to testing.

[0024] In embodiments, the heat deflection temperature of the copolyester composition measured according to ASTM D648 at 0.455 MPa is greater than 90°C; or greater than 95°C; 90 to 105° C; 90 to 100°C.; 90 to 95°C.; 95 to 105°C.; or 95 to

[0025] In embodiments, the heat deflection temperature of the copolyester composition measured according to ASTM D648 at 1.82 MPa is greater than 75°C; or greater than 80°C; 75 to 85° C; 75 to 80°C.; or 80 to 85°C.

[0026] For certain embodiments of the invention, the polyesters may exhibit any of the following inherent viscosities as determined in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.25 g / 50 ml at 25° C.: 0.3 to 0.8 dL / g; 0.3 to less than 0.80 dL / g; 0.3 to 0.78 dL / g.; 0.3 to less than 0.78 dL / g; 0.35 to 0.80 dL / g; 0.35 to less than 0.80 dL / g; 0.35 to 0.78 dL / g.; 0.35 to less than 0.78 dL / g; 0.40 to 0.80 dL / g; 0.40 to less than 0.80 dL / g; 0.40 to 0.78 dL / g; 0.40 to less than 0.78 dL / g; 0.44 to 0.80 dL / g.; 0.45 to less than 0.80 dL / g; 0.45 to 0.78 dL / g; 0.45 to less than 0.78 dL / g; 0.50 to 0.80 dL / g; 0.50 to less than 0.80 dL / g; 0.50 to 0.78 dL / g; 0.50 to less than 0.78 dL / g; 0.55 to 0.80 dL / g; 0.55 to less than 0.80 dL / g; 0.55 to 0.78 dL / g; 0.55 to less than 0.78 dL / g; 0.60 to 0.80 dL / g; 0.60 to less than 0.80 dL / g; 0.60 to 0.78 dL / g; 0.60 to less than 0.78 dL / g; 0.65 to 0.80 dL / g; 0.65 to less than 0.80 dL / g; or 0.65 to 0.78 dL / g; 0.65 to less than 0.78 dL / g; 0.70 to 0.80 dL / g; 0.70 to less than 0.80 dL / g; or 0.70 to 0.78 dL / g; 0.70 to less than 0.78 dL / g.

[0027] In one embodiment, terephthalic acid may be used as the starting material. In another embodiment, dimethyl terephthalate may be used as the starting material. In another embodiment, mixtures of terephthalic acid and dimethyl terephthalate may be used as the starting material and / or as an intermediate material.

[0028] In certain embodiments, 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. In certain embodiments, terephthalic acid residues can make up a portion or all of the dicarboxylic acid component used to form the polyesters useful in the invention. In certain embodiments, higher amounts of terephthalic acid can be used in order to produce a higher impact strength polyester. For purposes of this disclosure, the terms “terephthalic acid” and “dimethyl terephthalate” are used interchangeably herein. In one embodiment, dimethyl terephthalate is part or all of the dicarboxylic acid component used to make the polyesters useful in the present invention. In embodiments, 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.

[0029] In addition to terephthalic acid, the dicarboxylic acid component of the polyesters useful in the invention can comprise 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. Thus, if present, it is contemplated that the amount of one or more modifying aromatic dicarboxylic acids can range from any of these preceding endpoint values including, for example, 0.01 to 10 mole %, from 0.01 to 5 mole % and from 0.01 to 1 mole %. In one embodiment, 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. Examples of 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. In one embodiment, the modifying aromatic dicarboxylic acid is isophthalic acid.

[0030] The carboxylic 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. Certain embodiments can also comprise 0.01 to 10 mole %, such as 0.1 to 10 mole %, 1 or 10 mole %, 5 to 10 mole % of one or more modifying aliphatic dicarboxylic acids. Yet another embodiment contains 0 mole % modifying aliphatic dicarboxylic acids. The total mole % of the dicarboxylic acid component is 100 mole %. In one embodiment, adipic acid and / or glutaric acid are provided in the modifying aliphatic dicarboxylic acid component of the invention.

[0031] 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. In oneembodiment, the esters are chosen from at least one of the following: methyl, ethyl, propyl, isopropyl, and phenyl esters.

[0032] For the desired polyester, the molar ratio of cis / trans 2,2,4,4-tetramethyl- 1,3 -cyclobutanediol can vary from the pure form of each and mixtures thereof. In certain embodiments, 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 50 to 70 mole % cis and 50 to 30 mole % trans; or 60 to 70 mole % cis and 30 to 40 mole % trans; or greater than 70 mole % cis and less than 30 mole % trans; wherein the total mole percentages for cis- and trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol is equal to 100 mole %. In an additional embodiment, the molar ratio of cis / trans 2,2,4,4-tetramethyl-1,3-cyclobutanediol can vary within the range of 50 / 50 to 0 / 100, for example, between 40 / 60 to 20 / 80.

[0033] In one embodiment, the glycol component of the polyester portion of the polyester compositions useful in the invention can contain up to 30 mole % of one or more modifying glycols which are not 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-cyclohexanedimethanol or ethylene glycol. In one embodiment, the glycol component of the polyester portion of the polyester compositions useful in the invention can contain up to 10 mole %, or 9 mole %, or 8 mole %, or 7 mole %, or 6 mole %, or less of one or more modifying glycols which are not 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-cyclohexanedimethanol or ethylene glycol. In one embodiment, the glycol component of the polyester portion of the polyester compositions useful in the invention can contain up to 5 mole %, or 4 mole %, or 3 mole %, or 2 mole %, or 1 mole %, or less of one or more modifying glycols which are not 2,2,4,4-tetramethyl- 1.3-cyclobutanediol, 1,4-cyclohexanedimethanol or ethylene glycol. In certain embodiments, 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 2 mole % or less of one or more modifying glycols. In another embodiment, the polyesters useful in the invention can contain 0 mole % modifying glycols. It is contemplated however that some other glycol residuals may form in situ. For example, a certain amount of DEG will typically form in situ during the polymerization reactions. In some embodiments, DEG can be intentionally added as amonomer to the reaction mixture, and in other embodiments no DEG is intentionally added, but a small amount of DEG residues may be present in the final copolymer due to in situ formation.

[0034] In embodiments, modifying glycols for use in the polyesters can include diols other than 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-cyclohexanedimethanol and ethylene glycol and can contain 2 to 16 carbon atoms. Examples of modifying glycols include, but are not limited to, diethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5 -pentanediol, 1,6-hexanediol, p-xylene glycol, polytetramethylene glycol, and mixtures thereof. In another embodiment, the modifying glycols include, but are not limited to, at least one of 1,3-propanediol and 1,4-butanediol. In one embodiment, at least one modifying glycol is diethylene glycol. In one embodiment, the diethylene glycol is not added as a separate monomer but is formed during polymerization.

[0035] In some embodiments, the polyesters according to 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. In certain embodiments, the branching monomer or agent may be added prior to and / or during and / or after the polymerization of the polyester. In embodiments, the polyester(s) useful in the invention can thus be linear or branched.

[0036] 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 -hydroxy glutaric acid and the like. In one embodiment, 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, forexample, in U. S. Pat. Nos. 5,654,347 and 5,696,176, whose disclosure regarding branching monomers is incorporated herein by reference.

[0037] In one embodiment, 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.

[0038] In one embodiment, the polyesters useful in the invention and / or the polyester compositions of the invention 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. In various embodiments, the color values can be determined for polymers having the presence of and / or in the absence of toner(s).

[0039] In one embodiment, phosphorus compound(s) can be added to improve color of the copolyester composition. The phosphorus compound(s) can be an organic compound such as, for example, a phosphorus acid ester containing halogenated or non-halogenated organic substituents. In embodiments, the phosphorus compound(s) can comprise a wide range of phosphorus compounds, for example, phosphines, phosphites, phosphinites, phosphonites, phosphinates, phosphonates, phosphine oxides, and phosphates.

[0040] Examples of phosphorus compounds that may be useful in the invention can 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), tribenzyl phosphate, phenyl ethyl phosphate, trimethyl thionophosphate, phenyl ethyl thionophosphate, dimethyl methylphosphonate, diethyl methylphosphonate, diethyl pentylphosphonate, dilauryl methylphosphonate, diphenyl methylphosphonate, dibenzyl methylphosphonate, diphenyl cresylphosphonate, dimethyl cresylphosphonate, dimethyl methylthionophosphonate, phenyldiphenylphosphinate, benzyl diphenylphosphinate, methyl diphenylphosphinate, trimethyl phosphine oxide, triphenyl phosphine oxide, tribenzyl phosphine oxide, 4-methyl diphenyl phosphine oxide, triethyl phosphite, tributyl phosphite, trilauryl phosphite, triphenyl phosphite, tribenzyl phosphite, phenyl diethyl phosphite, phenyl dimethyl phosphite, benzyl dimethyl phosphite, dimethyl methylphosphonite, diethyl pentylphosphonite, diphenyl methylphosphonite, dibenzyl methylphosphonite, dimethyl cresylphosphonite, methyl dimethylphosphinite, methyl diethylphosphinite, phenyl diphenylphosphinite, methyl diphenylphosphinite, benzyl diphenylphosphinite, triphenyl phosphine, tribenzyl phosphine, and methyl diphenyl phosphine. In one embodiment, triphenyl phosphine oxide is excluded as a thermal stabilizer in the process(es) of making the polyesters of the invention and / or in the polyester composition(s) of the invention.

[0041] In one embodiment, phosphorus compounds 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. In another embodiment, phosphorus compounds 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.

[0042] 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 hydroxyl groups present on the phosphorus compound used. For example, 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.

[0043] In one embodiment, the phosphorus compounds 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.

[0044] In one aspect, the phosphorus compounds 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.

[0045] In one embodiment, for example, the phosphorus compounds useful in the invention can include at least one phosphate ester.

[0046] In one aspect, the phosphorus compounds 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, reaction products thereof, and mixtures thereof. The phosphate esters include esters in which the phosphoric acid is fully esterified or only partially esterified.

[0047] In one embodiment, for example, the phosphorus compounds useful in the invention can include at least one phosphate ester.

[0048] In another embodiment, 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.

[0049] In certain embodiments, the phosphate esters useful in the invention are those where the groups on the phosphate ester include are alkyl, alkoxy-alkyl, 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.

[0050] 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.

[0051] Representative of 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.

[0052] In one embodiment, the phosphate esters useful 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.

[0053] In one embodiment, at least one phosphorus compound useful in the invention comprises at least one aryl phosphate ester.

[0054] In one embodiment, at least one phosphorus compound useful in the invention comprises at least one unsubstituted aryl phosphate ester.

[0055] In one aspect, at least one phosphorus compound useful in the invention comprises at least one aryl phosphate ester which is not substituted with benzyl groups.

[0056] In one aspect, any of the phosphorus compounds useful in the invention may comprise at least one alkyl phosphate ester.

[0057] In one embodiment, the phosphate esters useful in the invention as thermal stabilizers and / or color stabilizers include but are not limited to, at least one of the following: trialkyl phosphates, triaryl phosphates, alkyl diaryl phosphates, and mixed alkyl aryl phosphates.

[0058] In one embodiment, the phosphate esters useful in the invention as thermal stabilizers and / or color stabilizers include but are not limited to, at least one of the following: triaryl phosphates, alkyl diaryl phosphates, and mixed alkyl aryl phosphates.

[0059] In one embodiment, the phosphate esters useful as thermal stabilizers and / or color stabilizers in the invention can include but are not limited to, at least one of the following: triaryl phosphates and mixed alkyl aryl phosphates.

[0060] In one embodiment, at least one phosphorus compound useful in the invention can comprise, but is not limited to, triaryl phosphates, such as, for example, triphenyl phosphate. In one embodiment, at least one thermal stabilizer comprises, but is not limited to Merpol A. In one embodiment, 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 & Co. The CAS Registry number for Merpol A is believed to be CAS Registry #37208-27-8.

[0061] In one aspect, any of the phosphorus compounds useful in the invention may comprise at least one triaryl phosphate ester which is not substituted with benzyl groups.

[0062] In one embodiment, the polyester compositions and / or processes of the invention may comprise 2-ethylhexyl diphenyl phosphate.

[0063] In one embodiment, any of the processes described herein for making any of the polyester compositions and / or polyesters can comprise at least one mixed alkyl aryl phosphite, such as, for example, bis(2,4-dicumylphenyl)pentaerythritol diphosphite also known as Doverphos S-9228 (Dover Chemicals, CAS#15486243-8).

[0064] In one embodiment, any of the processes described herein for making any of the polyester compositions and / or polyesters can comprise at least one phosphine oxide.

[0065] In one embodiment, 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, KH2PO4and Zn3(PO4)2.

[0066] The term “thermal stabilizer” is intended to include the reaction product(s) thereof. The term “reaction product” as used in connection with the thermal stabilizersof 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.

[0067] In one embodiment of the invention, the phosphorus compounds useful in the invention may act as thermal stabilizers. In one embodiment of the invention, the phosphorus compounds useful in the invention may not act as a thermal stabilizer but may act as a color stabilizer. In one embodiment of the invention, the phosphorus compounds useful in the invention may act as both a thermal stabilizer and a color stabilizer.

[0068] 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, for example, at least one phosphate ester(s). The amount of phosphorus compound(s), (for example, at least one phosphate ester), 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.

[0069] In one embodiment, amounts of the phosphate ester of the invention added during polymerization are chosen from the following: 10 to 200 ppm based on the total weight of the polyester composition and as measured in the form of phosphorus atoms in the final polyester. In embodiments of the invention, phosphorus can be present in an amount of 5 to 100, or 5 to 80, or 10 to 80, or 10 to 75, or 10 to 70, or 10 to 65 ppm, based on the total weight of the polyester composition and as measured in the form of phosphorus atoms in the final polyester.

[0070] In embodiments of the invention, certain agents which colorize the polymer can be added to the melt. In one embodiment, a bluing toner is added to the melt in order to reduce the b* of the resulting polyester polymer melt phase product. Such bluing agents include blue inorganic and organic toner(s). In addition, red toner(s) can also be used to adjust the a* color. Organic toner(s), e.g., blue and red organic toner(s), such as those toner(s) described in U. S. Pat. Nos. 5,372,864 and 5,384,377, which are incorporated by reference in their entirety, can be used. The organic toner(s) can be fed as a premix composition. The premix composition may bea neat blend of the red and blue compounds, or the composition may be pre-dissolved or slurried in one of the polyester's raw materials, e.g., ethylene glycol.

[0071] The total amount of toner components added can depend on the amount of inherent yellow color in the base polyester and the efficacy of the toner. In one embodiment, a concentration of up to about 15 ppm of combined organic toner components and a minimum concentration of about 0.5 ppm are used. In one embodiment, the total amount of bluing additive can range from 0.5 to 10 ppm. In an embodiment, the toner(s) can be added to the esterification zone or to the polycondensation zone. Preferably, the toner(s) are added to the esterification zone or to the early stages of the polycondensation zone, such as to a prepolymerization reactor.

[0072] The invention further relates to a polymer blend. In embodiments, the blend comprises:(a) from 5 to 95 weight % of at least one of the polyesters described above; and(b) from 5 to 95 weight % of at least one of the polymeric components.

[0073] Suitable examples of the polymeric components include, but are not limited to, nylon; polyesters different than those described herein such as PET; polyamides such as ZYTEL® from DuPont; polystyrene; polystyrene copolymers; styrene acrylonitrile copolymers; acrylonitrile butadiene styrene copolymers; poly (methylmethacrylate); acrylic copolymers; poly(ether-imides) such as ULTEM® (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 such as LEXAN® (a polycarbonate from General Electric); polysulfones; polysulfone ethers; and poly(ether-ketones) of aromatic dihydroxy compounds; or mixtures of any of the foregoing polymers. The blends can be prepared by conventional processing techniques known in the art, such as melt blending or solution blending.

[0074] In embodiments, the polyester compositions and the polymer blend compositions can also contain from 0.01 to 25% by weight of the overall compositioncommon additives such as colorants, toner(s), dyes, mold release agents, flame retardants, plasticizers, nucleating agents, stabilizers, including but not limited to, UV stabilizers, thermal stabilizers other than the phosphorus compounds describe herein, and / or reaction products thereof, fillers, and impact modifiers. Examples of commercially available impact modifiers include, but are not limited to, ethylene / propylene terpolymers, functionalized polyolefins such as those containing methyl acrylate and / or glycidyl methacrylate, styrene-based block copolymeric impact modifiers, and various acrylic core / shell type impact modifiers. Residues of such additives are also contemplated as part of the polyester composition.

[0075] Reinforcing materials may be added to 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. In one embodiment, the reinforcing materials include glass, such as, fibrous glass filaments, mixtures of glass and talc, glass and mica, and glass and polymeric fibers.

[0076] In one aspect, the invention relates to thermoplastic articles comprising the polyester compositions and / or polymer blends of the invention. In certain embodiments, the invention relates to film(s) and / or sheets comprising the polyester compositions and / or polymer blends of the invention. Methods of forming the polyesters and / or blends into film(s) and / or sheet(s) are well known in the art.Examples of film(s) and / or sheet(s) of the invention can include, without limitation, 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), pressure sensitive labels, stretched or stretchable films or sheets, uniaxially or biaxially oriented films, and / or multiwall films or sheets. Methods of making film and / or sheet include but are not limited to extrusion, calendering, compression molding, and solution casting.

[0077] In one embodiment, polyester compositions containing TMCD, CHDM and EG that provide improved calendering processes without the need for a branching monomer or branching agent are provided. In embodiments, the polyester compositions for calendering comprise: (a) at least one polyester comprising diacid residues, diol residues in which the polyester has a crystallization half time of at least5 minutes and an inherent viscosity of about 0.50 to about 0.80 dL / g; and (b) at least one release additive effective to prevent sticking of the polyester to calendering rolls. It is believed the polyester compositions of the present disclosure have an unexpected combination of excellent melt strength and melt viscosity with a good shear response that allows higher calendering line speeds before melt fracture occurs. Higher calendering line speeds, in turn, provides for more economical production of polyester sheet or film in commercial applications. In various embodiments, any of the types and / or amounts of diacid residues and diol residues discussed herein can be used for the polyester calendering compositions. In one embodiment, the polyester calendering composition does not contain any branching monomers or agents.

[0078] In one aspect, the invention relates to injection molded and / or blow molded articles comprising the polyester compositions and / or polymer blends of the invention.

[0079] In embodiments of the invention, certain polyesters and / or polyester compositions of the invention can have a unique combination of all of the following properties: certain notched Izod impact strength, certain inherent viscosities, certain glass transition temperature (Tg), certain flexural modulus, good clarity, good color, and good thermal stability.

[0080] In one embodiment, the processes of making the polyesters useful in the invention can comprise a batch or continuous process.

[0081] In one embodiment, the processes of making the polyesters useful in the invention comprise a continuous process.

[0082] Because of the long crystallization half-times (e.g., greater than 5 minutes) at 170°C exhibited by certain polyesters useful in the present invention, it can be possible to produce articles, including but not limited to, injection molded parts, injection blow molded articles, injection stretch blow molded articles, extruded film, extruded sheet, calendered film, pressure sensitive labels, stretched or stretchable films or sheets, uniaxially or biaxially oriented films, multiwall films or sheets, extrusion blow molded articles, extrusion stretch blow molded articles, and fibers. A thermoformable sheet is an example of an article of manufacture provided by this invention. The polyesters of the invention can be amorphous or semicrystalline. In one aspect, certain polyesters useful in the invention can have relatively lowcrystallinity. Certain polyesters useful in the invention can thus have a substantially amorphous morphology, meaning that the polyesters comprise substantially unordered regions of polymer.

[0083] Notched Izod impact strength, as described in ASTM D256, is a common method of measuring toughness. Notched Izod impact strength is measured herein at 23°C with a 10-mil notch in a 3.2mm (1 / 8-inch) thick bar determined according to ASTM D256. In one embodiment, certain polyesters useful in the invention can exhibit a notched Izod impact strength of at least 750 J / m at 23°C with a 10-mil notch in a 3.2mm (1 / 8-inch) thick bar determined according to ASTM D256. In one embodiment, certain polyesters useful in the invention can exhibit a notched Izod impact strength of from about 1000 J / m (0.56 ft-lb / in) to about 1300 J / m, or 1200 J / m to 1300 J / m at 23°C with a 10-mil notch in a 3.2mm (1 / 8-inch) thick bar determined according to ASTM D256.

[0084] In one embodiment, certain polyesters useful in the invention can exhibit at least one of the following densities: a density of greater than 1.2 g / ml at 23°C.

[0085] In one embodiment, certain polyesters useful in the invention can exhibit a flexural modulus at 23°C less than 2000 MPa (about 290,000 psi) as defined by ASTM D790. In another embodiment, certain polyesters useful in the invention can exhibit a flexural modulus at 23°C from about 1700 MPa to less than 2000 MPa as defined by ASTM D790. In another embodiment, certain polyesters useful in the invention can exhibit a flexural modulus at 23°C from about 1700 MPa to about 1900 MPa (377,100 psi) as defined by ASTM D790.

[0086] Certain polyesters useful in the invention can possess at least one of the following properties: a Tgof from about 100 to about 120 °C as measured by a TA 2100 Thermal Analyst Instrument at a scan rate of 20°C / min; a flexural modulus at 23°C less than 2000 MPa (about 290,000 psi), as defined by ASTM D790; and a notched Izod impact strength equal to or greater than 750 J / m and less than 1300 J / m according to ASTM D256 with a 10-mil notch using a 1 / 8-inch thick bar at 23°C.

[0087] In one embodiment, the melt viscosity of the polyester(s) useful in the invention can be less than 30,000 poise as measured a 1 radian / second on a rotary melt rheometer at 290°C. In another embodiment, the melt viscosity of thepolyester(s) useful in the invention can be less than 20,000 poise as measured a 1 radian / second on a rotary melt rheometer at 290°C.

[0088] In one embodiment, the melt viscosity of the polyester(s) useful in the invention can be less than 15,000 poise as measured at 1 radian / second (rad / sec) on a rotary melt rheometer at 290°C. In one embodiment, the melt viscosity of the polyester(s) useful in the invention can be less than 12,000 poise as measured at 1 radian / second (rad / sec) on a rotary melt rheometer at 290°C. In one embodiment, the melt viscosity of the polyester(s) useful in the invention in can be less than 10,000 poise as measured at 1 radian / second (rad / sec) on a rotary melt rheometer at 290°C.

[0089] 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.

[0090] In certain embodiments, the polyester compositions and / or polymer blends of the invention can be used in one or more of the following applications: graphic arts film, multiwall film or sheets, extruded articles, appliance parts, and glass laminates.

[0091] 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.

[0092] 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).

[0093] Examples of extruded articles comprising the polyester compositions useful in this invention include, but are not limited to, profile extruded tubing or channels, extrusion blow molded bottles, 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.

[0094] In one embodiment, 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.

[0095] ‘Outdoor sign,” as used herein, 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. In one embodiment, the outdoor sign comprises a polyester containing printed symbols, patterns, or designs. In one embodiment, 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.

[0096] “Appliance parts,” as used herein, refers to a rigid piece used in conjunction with an appliance. In one embodiment, the appliance part is partly or wholly separable from the appliance. In another embodiment, the appliance part is one that is typically made from a polymer. In one embodiment, the appliance part is visually clear.

[0097] Exemplary appliance parts include those requiring toughness and durability, 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 0°C (e.g., 2°C) to 5 °C, or freezer temperatures, e.g., at temperatures less than 0°C, such as temperatures ranging from -20 to 0°C, e.g., -18°C), such as refrigerator and freezer trays, bins, and shelves; parts having sufficient hydrolytic stability at temperatures above 90 °C, such as washing machine doors, steam cleaner canisters, tea kettles, and coffee pots; and vacuum cleaner canisters and dirt cups.

[0098] In one embodiment, 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.

[0099] In one embodiment, the polyesters useful have a heat deflection temperature at 264 psi greater than 90C.

[0100] For the purposes of this invention, the term "wt" means "weight".

[0101] The following examples further illustrate how the polyesters of the invention can be made and evaluated and are intended to be purely exemplary of theinvention and are not intended to limit the scope thereof. Unless indicated otherwise, parts are parts by weight, temperature is in degrees C or is at room temperature, and pressure is at or near atmospheric.EXAMPLES

[0102] The following examples illustrate in general how a copolyester is prepared and the effect of using ethylene glycol, 1,4-cyclohexanedimethanol and 2, 2,4,4-tetramethyl-L3 -cyclobutanediol on various polyester properties such as glass transition temperature, inherent viscosity, etc., compared to polyesters comprising 1,4-cyclohexanedimethanol and 2,2,4,4-tetramethyl-1,3-cyclobutanediol, but lacking ethylene glycol, or compared to polyesters comprising 1,4-cyclohexanedimethanol and ethylene glycol, but lacking 2,2,4,4-tetramethyl-1,3-cyclobutanediol.Additionally, based on the following examples, the skilled artisan will understand how the thermal stabilizers of the invention can be used in the preparation of polyesters containing them.

[0103] Measurement Method

[0104] 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.

[0105] Unless stated otherwise, the glass transition temperature (Tg) was determined using a TA DSC 2920 instrument from Thermal Analyst Instruments at a scan rate of 20° C. / min according to ASTM D3418.

[0106] The glycol content was determined by proton nuclear magnetic resonance (NMR) spectroscopy. All NMR spectra were recorded on a JEOL Eclipse Plus 600 MHz 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-tetramethyl-1,3-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.

[0107] Mechanical properties of all resins were characterized using the following methods:

[0108] Heat deflection temperature, at 264 and 66 psi, was determined according to ASTM D648.

[0109] Flexural modulus and flexural strength were determined according to ASTM D790.

[0110] Notched Izod impact strength, as described in ASTM D256, is a common method of measuring toughness.

[0111] All flex bars were molded on the Boy22A injection molding. All resins were dried in forced-air ovens for 4-6 hours at 20 °C below their Tg before molding. Once properly dried, the material was molded to give ’ / sX^xS-inch and ^x^xS-inch flexure bars using a barrel temperature of 270-280 °C and a mold temperature of 40-46 °C, depending on the composition. To ensure there was no contamination, the first 10 flex bars were discarded. The bars were submitted to analytical for further testing.Example 1

[0112] The process for the preparation of the copolyesters in Examples 1- 6 and comparative examples 1-4 as shown in Table 1 is exemplified by the preparation of the copolyester of Example 1, which has a target composition of 100 mol% terephthalic acid residues, 31.6 mol% EG residues, 33.9 mol% TMCD residues, and 34.5 mol% CHDM residues. A mixture of 145.65 g of terephthalic acid, 29.2 g of EG, 35.69 g of CHDM, 44.61 g of TMCD were placed in a 500-milliliter flask equipped with an inlet for nitrogen, a metal stirrer, and a short distillation column. 590 μL of a Titanium isopropoxide solution (0.01248 g / mL in n-butanol) and 0.26 g of a Fascat 4102 solution (2.82 wt% in n-butanol) were added to the flask. The flask was placed in a Wood’s metal bath already heated to 200 °C. The stirring speed was set to 200 RPM, and this was held for 60 minutes. The contents of the flask were heated to 210 °C over 10 minutes while the stirring, and then was held at that temperature for an additional 60 minutes. The contents were then raised to 275 °C slowly over 45 minutes. The content remained at 275 °C while the pressure was reduced to 7.5 torr over 10 minutes, followed by a further pressure reduction to 0.3 torr over another 10 minute period. Finally, the temperature was held at 275 °C while the stir rate slowlydecreased to 150 RPM an over the course of 90 minutes. A high melt viscosity, visually yellow, but transparent, polymer was obtained with an inherent viscosity of 0.66 dl / g. NMR analysis confirmed target monomer incorporations.Table 1. Composition of ExamplesTPA is terephthalic acidEG is ethylene glycolCHDM is 1,4-cyclohexanedimethanolTMCD is 2,2,4,4-tetramethyl-1,3-cyclobutanediolTable 2. Properties of referenced examples*NB is indicative that a sample that didn’t break, even when hit with the max energy output of the instrument

[0113] 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 affected within the spirit and scope of the invention.

Claims

What is claimed is:

1. A polyester composition comprising at least one amorphous copolyester which comprises:(a) a dicarboxylic acid component comprising:(i) 90 to 100 mole % of terephthalic acid residues;(ii) 0 to 10 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and(b) a glycol component comprising:(i) 1 to 45 mole % of ethylene glycol residues; and (ii) 30 to 80 mole % of 1,4-cyclohexanedimethanol residues; and (iii) 15 to 38 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residueswherein the total mole % of the acid component (a) is 100 mole % and the total mole % of the glycol component (b) is 100 mole %, and wherein the inherent viscosity of the material is 0.3-1, or 0.3 to 0.8 dL / g in 60 / 40 (wt / wt) phenol / tetrachloroethan at a concentration of 0.5 g / 100 mL at 25 °C, a glass transition temperature of greater than 100°C as determined using ASTM D3418 test method, and a flexural modulus from 1700 to 2100 MPa as determined using the ASTM D790 test method, a notched Izod impact strength of greater than 750 J / M according to ASTM D256.

2. The polyester composition of claim 1, wherein the glycol component comprises 20 to 35 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, 35 to 60 mole % 1,4-cyclohexanedimethanol residues and 20 to 40 mole % of ethylene glycol residues.

3. The polyester composition of claim 1, wherein the inherent viscosity is from 0.30 to less than 0.8 dL / g.

4. The polyester composition of claim 1, wherein glass transition temperature is from 100 to 120° C.

5. The polyester composition of claim 1, wherein the flexural modulus is from 1700 to less than 2000 MPa as determined using the ASTM D790 test method.

6. The polyester composition of claim 1, wherein the notched Izod impact strength is greater than 1200 J / M with a 10-mil notch in a 3.2 mm (½-inch) thick bar determined according to ASTM D256.

7. An article of manufacture comprising the polyester composition of claim 1.

8. A fiber, film, molded article, container, or sheet comprising a polyester composition according to Claim 1.

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