Copolyester composition having a low coefficient of friction

Abstract

A polymer composition comprising a copolyester containing 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) and cyclohexanedimethanol (CHDM) residues is provided, which exhibits a significant improvement in impact toughness and a reduction in the coefficient of friction, while the physical properties after modification (e.g., heat distortion temperature (HDT) and flexural modulus) are maintained with respect to the unmodified composition.

Description

Technical Field

[0001] The present invention generally belongs to the field of polymer science. In particular, the present invention relates to certain copolyester compositions having a low surface energy.

Background Art

[0002] High molecular weight thermoplastic linear copolyesters can generally be formed by reacting one or more diesters with one or more diols under suitable polymerization conditions. A diester composition containing a dialkyl ester of terephthalic acid is reacted with a diol composition containing a first diol component containing 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) and a second diol component containing 1,4-cyclohexanedimethanol (CHDM) to form certain copolyesters useful for a variety of applications. Such copolyesters are described, for example, in U.S. Pat. Nos. 7,781,562 and 8,586,701 assigned to the assignee of the present invention, the contents and descriptions of which are incorporated herein by reference. The usefulness of these copolyesters and the compositions containing them as components are numerous and diverse, for example, as described in U.S. Pat. No. 7,576,171 (pacifier); 7,951,900 (housing for a dialysis filter); 7,803,439 (blood treatment container); and 8,133,967 (restaurant ware), the contents and descriptions of which are also incorporated herein by reference, all of which are also assigned to the assignee of the present invention.

[0003] The above linear copolyesters have achieved commercial success to a certain extent because a combination of performance parameters (e.g., toughness, glass transition temperature, density, crystallization rate, melt viscosity, and chemical resistance) provides many advantages to both product manufacturers and consumers who purchase these products. However, in the ongoing efforts to expand the sales, use, and applicability of compositions containing these copolyesters into new markets, polymer manufacturers are still trying to adjust the properties and parameters of the compositions to meet the specifications of product manufacturers in yet-to-be-developed product applications.

[0004] Copolyesters based on 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol (TMCD) and cyclohexanedimethanol (CHDM) can have medium to high surface energy. High surface energy can be advantageous for certain secondary operations (e.g., weldability, paintability, etc.), but polymer products made from compositions based on such copolyesters can have medium to high coefficient of friction (COF). If the COF is overly high, it can result in polymer products that are not suitable for use in certain durable product applications that require repeated material interactions at various contact pressures. Manipulation of the surface properties of the polymer (e.g., coefficient of friction by incorporation of additives) can correspondingly cause a significant decrease in other physical properties or result in a trade - off in the performance of the base resin.

[0005] Accordingly, there is a need for improved polymer compositions based on TMCD and CHDM that reduce the coefficient of friction without compromising other desirable qualities of the polymer composition and the durable articles manufactured therefrom. SUMMARY OF THE INVENTION

[0006] The present invention provides a means for reducing the friction of a copolyester containing residues of TMCD and CHDM while substantially maintaining or improving processability by incorporating various additives. In one embodiment, by incorporating additives including specific waxes and organosiloxanes, a reduction in the coefficient of friction was achieved while maintaining one or more physical properties. Further, certain embodiments of the present invention improve the flow length during injection molding while reducing the coefficient of friction.

[0007] The friction-modified, impact-tough copolyester polymer containing residues of TMCD and CHDM can exhibit an adjustable friction profile equivalent to that of conventional engineering polymers (e.g., acrylonitrile-butadiene-styrene polymer (ABS) or polycarbonate) that can exhibit similar frictional responses (static and kinetic coefficients of friction) over a wide range of contact pressures and part geometries. However, it should be noted that the physical properties after modification (e.g., heat distortion temperature (HDT) and modulus of elasticity) are maintained compared to the unmodified copolyester composition, while the impact toughness is retained or improved.

[0008] In an embodiment, a polymer composition is provided that includes a copolyester and one or more additives in an amount sufficient to reduce the coefficient of friction of the polymer composition. The copolyester can include a dicarboxylic acid component containing terephthalic acid residues and a glycol component containing 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues and 1,4-cyclohexanedimethanol (CHDM) residues, and has an intrinsic viscosity (determined at 25 °C at a concentration of 0.5 g / 100 ml in 60 / 40 (wt / wt) phenol / tetrachloroethane) of 0.1 to 1.2 dL / g and a glass transition temperature (Tg) of 100 to 200 °C. The one or more additives can be selected from waxes and siloxanes.

[0009] The additives used for friction modification can include from low molecular weight waxes to high molecular weight organosiloxanes. In an embodiment, depending on the selected friction additive(s), the additive can be incorporated at a content of 0.1 wt% to 12 wt%.

Best Mode for Carrying Out the Invention

[0010] In a first aspect, the present invention provides a polymer composition comprising: (a) A copolyester comprising the following components: (i) A dicarboxylic acid component comprising the following: a. 70 to 100 mol% of terephthalic acid residues, b. 0 to 30 mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms, and c. 0 to 10 mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms, and (ii) A glycol component comprising the following: a. 10 to 90 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol (TMCD) residues, and b. 10 to 90 mol% of 1,4 - cyclohexanedimethanol (CHDM) residues (the total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the glycol component is 100 mol%), (the intrinsic viscosity of the polyester is 0.1 to 1.2 dL / g as determined at 25 °C in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml, and the Tg of the polyester is 100 to 200 °C), (b) About 0.1 to about 12 weight percent of a friction additive selected from wax and siloxane, and (c) Optionally, 0 to about 15 weight percent of at least one impact modifier.

[0011] As used herein, the term "polyester" 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 polyfunctional carboxylic acids with one or more difunctional hydroxyl compounds and / or polyfunctional hydroxyl compounds (e.g., branching agents). Usually, the difunctional carboxylic acid can be a dicarboxylic acid, and the difunctional hydroxyl compound can be a dihydric alcohol (e.g., glycols and diols). The term "glycol" as used herein includes, but is not limited to, diols, glycols, and / or polyfunctional hydroxyl compounds (e.g., branching agents). The term "residue" as used herein means any organic structure incorporated into the polymer through polycondensation and / or esterification reactions from the corresponding monomer. The term "repeat unit" as used herein means an organic structure having a dicarboxylic acid residue and a diol residue bonded through an ester group. Thus, for example, a dicarboxylic acid residue can be derived from a dicarboxylic acid monomer or its related acid halides, esters, salts, anhydrides, and / or mixtures thereof. Further, as used herein, the term "diacid" includes polyfunctional acids (e.g., branching agents). Thus, as used herein, the term "dicarboxylic acid" is intended to include dicarboxylic acids and any derivatives of dicarboxylic acids (e.g., related acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, and / or mixtures thereof) useful in the reaction process with diols for making polyesters. As used herein, the term "terephthalic acid" is intended to include terephthalic acid itself and its residues, as well as any derivatives of terephthalic acid (e.g., related acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, and / or mixtures thereof) or their residues useful in the reaction process with diols for making polyesters.

[0012] The polyesters used in the present invention can generally be prepared from dicarboxylic acids and diols that react in substantially equal proportions and are incorporated into the polyester polymer as the corresponding residues. Thus, the polyesters of the present invention can contain substantially equal molar ratios of acid residues (100 mol%) as well as diol (and / or polyfunctional hydroxyl compound) residues (100 mol%), such that the total molar number of repeating units is equal to 100 mol%. Accordingly, the molar percentages provided in the present invention may be based on the total molar number of acid residues, the total molar number of diol residues, or the total molar number of repeating units.

[0013] In certain embodiments, terephthalic acid or its esters (e.g., dimethyl terephthalate) or a mixture of terephthalic acid residues and their esters can constitute some or all of the dicarboxylic acid component used to form the polyesters useful in the present invention. In certain embodiments, terephthalic acid residues can constitute some or all of the dicarboxylic acid component used to form the polyesters useful in the present disclosure. For the purposes of the present disclosure, the terms “terephthalic acid” and “dimethyl terephthalate” are used interchangeably herein.

[0014] Instead of the dicarboxylic acid, esters of terephthalic acid with other dicarboxylic acids, or their corresponding esters and / or salts can be used. Suitable examples of dicarboxylic acid esters include, but are not limited to, dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, and diphenyl esters. In one embodiment, the ester is selected from at least one of the following: methyl ester, ethyl ester, propyl ester, isopropyl ester, and phenyl ester.

[0015] In certain embodiments, the polyester composition comprises a copolyester comprising: (a) A dicarboxylic acid component comprising: i) 70 to 100 mol% of terephthalic acid residues, ii) 0 to 30 mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms, and iii) aliphatic dicarboxylic acid residues having up to 16 carbon atoms and 0 to 10 mol%, and (b) a glycol component comprising: i) 10 to 90 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol (TMCD) residues, and ii) 10 to 90 mol% of 1,4 - cyclohexanedimethanol (CHDM) residues (the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the glycol component is 100 mol%), (the intrinsic viscosity of the polyester is 0.1 to 1.2 dL / g as determined at 25 °C in phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml and a weight ratio of 60 / 40 (wt / wt), and the Tg of the polyester is 100 to 200 °C).

[0016] In an embodiment, the polyester composition comprises at least one polyester comprising: (a) a dicarboxylic acid component comprising: i) 70 to 100 mol% of terephthalic acid residues, ii) 0 to 30 mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms, and iii) 0 to 10 mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms, and (b) a glycol component comprising: i) 15 to 70 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol residues, and ii) 30 to 85 mol% of 1,4 - cyclohexanedimethanol residues (the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the glycol component is 100 mol%), (the intrinsic viscosity of the polyester is 0.35 to 1.2 dL / g as determined at 25 °C in phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml and a weight ratio of 60 / 40 (wt / wt), and the Tg of the polyester is 100 to 160 °C).

[0017] In an embodiment, the polyester composition comprises at least one polyester comprising: (a) A dicarboxylic acid component comprising: i) 70 to 100 mol% of terephthalic acid residues, ii) 0 to 30 mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms, and iii) 0 to 10 mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms, and (b) A glycol component comprising: i) 20 to 40 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol residues, and ii) 60 to 80 mol% of 1,4 - cyclohexanedimethanol residues (the total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the glycol component is 100 mol%), (The intrinsic viscosity of the polyester is 0.35 to 0.85 dL / g as determined at 25 °C with a concentration of 0.5 g / 100 ml in 60 / 40 (wt / wt) phenol / tetrachloroethane, and the Tg of the polyester is 100 to 120 °C).

[0018] In an embodiment, the polyester composition comprises at least one polyester comprising: (a) A dicarboxylic acid component comprising: i) 70 to 100 mol% of terephthalic acid residues, ii) 0 to 30 mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms, and iii) 0 to 10 mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms, and (b) A glycol component comprising: i) 40 to 55 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol residues, and ii) 45 to 60 mol% of 1,4 - cyclohexanedimethanol residues (the total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the glycol component is 100 mol%), (The intrinsic viscosity of the polyester is 0.35 to 0.85 dL / g as determined at 25 °C in a concentration of 0.5 g / 100 ml of 60 / 40 (wt / wt) phenol / tetrachloroethane, and the Tg of the polyester is 120 to 140 °C).

[0019] In an embodiment, the polyester composition comprises at least one polyester comprising: (a) A dicarboxylic acid component comprising: i) 70 to 100 mol% of terephthalic acid residues, ii) 0 to 30 mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms, and iii) 0 to 10 mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms, and (b) A glycol component comprising: i) 15 to 70 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and ii) 30 to 85 mol% of 1,4-cyclohexanedimethanol residues (the total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the glycol component is 100 mol%), (The intrinsic viscosity of the polyester is 0.35 to 0.85 dL / g as determined at 25 °C in a concentration of 0.5 g / 100 ml of 60 / 40 (wt / wt) phenol / tetrachloroethane, and the Tg of the polyester is 100 to 140 °C).

[0020] In an embodiment, the polyester composition comprises at least one polyester comprising: (a) A dicarboxylic acid component comprising: i) 70 to 100 mol% of terephthalic acid residues, ii) 0 to 30 mol% of aromatic dicarboxylic acid residues having up to 20 carbon atoms, and iii) 0 to 10 mol% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms, and (b) A glycol component comprising: i) 15 to 90 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and ii) 10 to 85 mol% of 1,4 - cyclohexanedimethanol residues (the total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the glycol component is 100 mol%). (The intrinsic viscosity of the polyester is 0.1 to 1.2 dL / g as determined at 25 °C with a concentration of 0.5 g / 100 ml in 60 / 40 (wt / wt) phenol / tetrachloroethane, and the Tg of the polyester is 100 to 200 °C).

[0021] In an embodiment, any one of the polyesters or polyester compositions described herein may further contain residues of at least one branching agent. In an embodiment, any one of the polyesters or polyester compositions described herein may contain at least one heat stabilizer or a reaction product thereof.

[0022] In an embodiment, the polyester composition contains at least one polycarbonate. In other embodiments, the polyester composition does not contain a polycarbonate.

[0023] In an embodiment, the polyester may contain less than 15 mol% of ethylene glycol residues, for example, 0.01 to less than 15 mol% of ethylene glycol residues. In an embodiment, the polyesters useful in the present invention contain less than 10 mol%, or less than 5 mol%, or less than 4 mol%, or less than 2 mol%, or less than 1 mol% of ethylene glycol residues, for example, 0.01 to less than 10 mol%, or 0.01 to less than 5 mol%, or 0.01 to less than 4 mol%, or 0.01 to less than 2 mol%, or 0.01 to less than 1 mol% of ethylene glycol residues. In one embodiment, the polyesters useful in the present invention do not contain ethylene glycol residues.

[0024] In an embodiment, the glycol component of the polyester may include, but is not limited to, at least one of the following combinations: 10 to 99 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 90 mol% of 1,4-cyclohexanedimethanol; 10 to 95 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 90 mol% of 1,4-cyclohexanedimethanol; 10 to 90 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 90 mol% of 1,4-cyclohexanedimethanol; 10 to 85 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 90 mol% of 1,4-cyclohexanedimethanol; 10 to 80 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 90 mol% of 1,4-cyclohexanedimethanol, 10 to 75 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 90 mol% of 1,4-cyclohexanedimethanol; 10 to 70 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 90 mol% of 1,4-cyclohexanedimethanol; 10 to 65 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 90 mol% of 1,4-cyclohexanedimethanol; 10 to 60 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 90 mol% of 1,4-cyclohexanedimethanol; 10 to 55 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 90 mol% of 1,4-cyclohexanedimethanol; 10 to 50 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50 to 90 mol% of 1,4-cyclohexanedimethanol; less than 10 to 50 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and more than 50 to 90 mol% of 1,4-cyclohexanedimethanol; 10 to 45 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55 to 90 mol% of 1,4-cyclohexanedimethanol; 10 to 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60 to 90 mol% of 1,4-cyclohexanedimethanol;10 to 35 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 65 to 90 mol% of 1,4 - cyclohexanedimethanol; less than 10 to 35 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and more than 65 to 90 mol% or less of 1,4 - cyclohexanedimethanol; 10 to 30 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 70 to 90 mol% of 1,4 - cyclohexanedimethanol; 10 to 25 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and more than 75 to 90 mol% of 1,4 - cyclohexanedimethanol; 11 to 25 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 75 to 89 mol% of 1,4 - cyclohexanedimethanol; 12 to 25 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 75 to 88 mol% of 1,4 - cyclohexanedimethanol; and 13 to 25 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 75 to 87 mol% of 1,4 - cyclohexanedimethanol.;

[0025] In other embodiments, the glycol component of the polyester may include, but is not limited to, at least one of the following combinations: 14 to 99 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 1 to 86 mol% of 1,4 - cyclohexanedimethanol; 14 to 95 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 5 to 86 mol% of 1,4 - cyclohexanedimethanol; 14 to 90 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 10 to 86 mol% of 1,4 - cyclohexanedimethanol; 14 to 85 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 15 to 86 mol% of 1,4 - cyclohexanedimethanol; 14 to 80 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 20 to 86 mol% of 1,4 - cyclohexanedimethanol, 14 to 75 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 25 to 86 mol% of 1,4 - cyclohexanedimethanol; 14 to 70 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 30 to 86 mol% of 1,4 - cyclohexanedimethanol; 14 to 65 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 35 to 86 mol% of 1,4 - cyclohexanedimethanol; 14 to 60 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 40 to 86 mol% of 1,4 - cyclohexanedimethanol; 14 to 55 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 45 to 86 mol% of 1,4 - cyclohexanedimethanol; and 14 to 50 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 50 to 86 mol% of 1,4 - cyclohexanedimethanol.

[0026] In other embodiments, the glycol component of the polyester may include, but is not limited to, at least one of the following combinations: 15 to 99 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 85 mol% of 1,4-cyclohexanedimethanol; 15 to 95 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 85 mol% of 1,4-cyclohexanedimethanol; 15 to 90 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 85 mol% of 1,4-cyclohexanedimethanol; 15 to 85 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 85 mol% of 1,4-cyclohexanedimethanol; 15 to 80 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 85 mol% of 1,4-cyclohexanedimethanol, 15 to 75 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 85 mol% of 1,4-cyclohexanedimethanol; 15 to 70 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 85 mol% of 1,4-cyclohexanedimethanol; 15 to 65 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 85 mol% of 1,4-cyclohexanedimethanol; 15 to 60 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 85 mol% of 1,4-cyclohexanedimethanol; 15 to 55 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 85 mol% of 1,4-cyclohexanedimethanol; and 15 to 50 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50 to 85 mol% of 1,4-cyclohexanedimethanol.

[0027] In other embodiments, the glycol component of the polyester may include, but is not limited to, at least one of the following combinations within the following ranges: 2,2,4,4-tetramethyl-1,3-cyclobutanediol of less than 15 to 50 mol% and 1,4-cyclohexanedimethanol of more than 50 to 85 mol% or less; 2,2,4,4-tetramethyl-1,3-cyclobutanediol of 15 to 45 mol% and 1,4-cyclohexanedimethanol of 55 to 85 mol%; 2,2,4,4-tetramethyl-1,3-cyclobutanediol of 15 to 40 mol% and 1,4-cyclohexanedimethanol of 60 to 85 mol%; 2,2,4,4-tetramethyl-1,3-cyclobutanediol of 15 to 35 mol% and 1,4-cyclohexanedimethanol of 65 to 85 mol%; 2,2,4,4-tetramethyl-1,3-cyclobutanediol of 15 to 30 mol% and 1,4-cyclohexanedimethanol of 70 to 85 mol%; 2,2,4,4-tetramethyl-1,3-cyclobutanediol of 15 to 25 mol% and 1,4-cyclohexanedimethanol of 75 to 85 mol%; 2,2,4,4-tetramethyl-1,3-cyclobutanediol of 15 to 20 mol% and 1,4-cyclohexanedimethanol of 75 to 80 mol%; and 2,2,4,4-tetramethyl-1,3-cyclobutanediol of 17 to 23 mol% and 1,4-cyclohexanedimethanol of 77 to 83 mol%.

[0028] In other embodiments, the glycol component of the polyester may include, but is not limited to, at least one of the following combinations: 20 to 99 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 1 to 80 mol% of 1,4 - cyclohexanedimethanol; 20 to 95 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 5 to 80 mol% of 1,4 - cyclohexanedimethanol; 20 to 90 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 10 to 80 mol% of 1,4 - cyclohexanedimethanol; 20 to 85 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 15 to 80 mol% of 1,4 - cyclohexanedimethanol; 20 to 80 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 20 to 80 mol% of 1,4 - cyclohexanedimethanol, 20 to 75 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 25 to 80 mol% of 1,4 - cyclohexanedimethanol; 20 to 70 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 30 to 80 mol% of 1,4 - cyclohexanedimethanol; 20 to 65 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 35 to 80 mol% of 1,4 - cyclohexanedimethanol; 20 to 60 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 40 to 80 mol% of 1,4 - cyclohexanedimethanol; 20 to 55 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 45 to 80 mol% of 1,4 - cyclohexanedimethanol; 20 to 50 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 50 to 80 mol% of 1,4 - cyclohexanedimethanol; 20 to 45 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 55 to 80 mol% of 1,4 - cyclohexanedimethanol; 20 to 40 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 60 to 80 mol% of 1,4 - cyclohexanedimethanol; 20 to 35 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 65 to 80 mol% of 1,4 - cyclohexanedimethanol;20 to 30 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 70 to 80 mol% of 1,4 - cyclohexanedimethanol; and 20 to 25 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 75 to 80 mol% of 1,4 - cyclohexanedimethanol.;

[0029] In other embodiments, the glycol component of the polyester may include, but is not limited to, at least one of the following combinations: 25 to 99 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 75 mol% of 1,4-cyclohexanedimethanol; 25 to 95 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 75 mol% of 1,4-cyclohexanedimethanol; 25 to 90 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 75 mol% of 1,4-cyclohexanedimethanol; 25 to 85 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 75 mol% of 1,4-cyclohexanedimethanol; 25 to 80 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 75 mol% of 1,4-cyclohexanedimethanol, 25 to 75 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 75 mol% of 1,4-cyclohexanedimethanol; 25 to 70 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 75 mol% of 1,4-cyclohexanedimethanol; 25 to 65 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 75 mol% of 1,4-cyclohexanedimethanol; 25 to 60 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 75 mol% of 1,4-cyclohexanedimethanol; 25 to 55 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 75 mol% of 1,4-cyclohexanedimethanol; 25 to 50 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50 to 75 mol% of 1,4-cyclohexanedimethanol; 25 to 45 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55 to 75 mol% of 1,4-cyclohexanedimethanol; 25 to 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60 to 75 mol% of 1,4-cyclohexanedimethanol; 25 to 35 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65 to 75 mol% of 1,4-cyclohexanedimethanol;as well as 25 to 30 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70 to 75 mol% of 1,4-cyclohexanedimethanol.;

[0030] In other embodiments, the glycol component of the polyester may include, but is not limited to, at least one of the following combinations: 30 to 99 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 1 to 70 mol% of 1,4 - cyclohexanedimethanol; 30 to 95 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 5 to 70 mol% of 1,4 - cyclohexanedimethanol; 30 to 90 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 10 to 70 mol% of 1,4 - cyclohexanedimethanol; 30 to 85 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 15 to 70 mol% of 1,4 - cyclohexanedimethanol; 30 to 80 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 20 to 70 mol% of 1,4 - cyclohexanedimethanol; 30 to 75 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 25 to 70 mol% of 1,4 - cyclohexanedimethanol; 30 to 70 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 30 to 70 mol% of 1,4 - cyclohexanedimethanol; 30 to 65 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 35 to 70 mol% of 1,4 - cyclohexanedimethanol; 30 to 60 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 40 to 70 mol% of 1,4 - cyclohexanedimethanol; 30 to 55 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 45 to 70 mol% of 1,4 - cyclohexanedimethanol; 30 to 50 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 50 to 70 mol% of 1,4 - cyclohexanedimethanol; less than 30 to 50 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and more than 50 to 70 mol% of 1,4 - cyclohexanedimethanol; 30 to 45 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 55 to 70 mol% of 1,4 - cyclohexanedimethanol; 30 to 40 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol and 60 to 70 mol% of 1,4 - cyclohexanedimethanol;30 to 35 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65 to 70 mol% of 1,4-cyclohexanedimethanol.;

[0031] In addition to the diols described above, in certain embodiments, the polyester may also be made from 1,3-propanediol, 1,4-butanediol, or mixtures thereof. Compositions made from 1,3-propanediol, 1,4-butanediol, or mixtures thereof are contemplated to have 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. Additionally or alternatively, the polyester made from 1,3-propanediol or 1,4-butanediol or mixtures thereof may also be made from at least one of the following amounts of 1,4-cyclohexanedimethanol: 0.1 to 99 mol%; 0.1 to 90 mol%; 0.1 to 80 mol%; 0.1 to 70 mol%; 0.1 to 60 mol%; 0.1 to 50 mol%; 0.1 to 40 mol%; 0.1 to 35 mol%; 0.1 to 30 mol%; 0.1 to 25 mol%; 0.1 to 20 mol%; 0.1 to 15 mol%; 0.1 to 10 mol%; 0.1 to 5 mol%; 1 to 99 mol%; 1 to 90 mol%, 1 to 80 mol%; 1 to 70 mol%; 1 to 60 mol%; 1 to 50 mol%; 1 to 40 mol%; 1 to 35 mol%; 1 to 30 mol%; 1 to 25 mol%; 1 to 20 mol%; 1 to 15 mol%; 1 to 10 mol%; 1 to 5 mol%; 5 to 99 mol%, 5 to 90 mol%, 5 to 80 mol%; 5 to 70 mol%; 5 to 60 mol%; 5 to 50 mol%; 5 to 40 mol%; 5 to 35 mol%; 5 to 30 mol%; 5 to 25 mol%; 5 to 20 mol%; and 5 to 15 mol%; 5 to 10 mol%; 10 to 99 mol%; 10 to 90 mol%; 10 to 80 mol%; 10 to 70 mol%; 10 to 60 mol%; 10 to 50 mol%; 10 to 40 mol%; 10 to 35 mol%; 10 to 30 mol%; 10 to 25 mol%; 10 to 20 mol%; 10 to 15 mol%; 20 to 99 mol%; 20 to 90 mol%; 20 to 80 mol%; 20 to 70 mol%; 20 to 60 mol%; 20 to 50 mol%; 20 to 40 mol%; 20 to 35 mol%; 20 to 30 mol%; as well as 20 to 25 mol.

[0032] In certain embodiments, the glycol component of the polyester portion of the polyester composition may contain up to 25 mol% of one or more modified glycols that are not 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol or 1,4 - cyclohexanedimethanol; in one embodiment, the polyester useful in the present invention may contain less than 15 mol% of one or more modified glycols. In another embodiment, the polyester may contain up to 10 mol% of one or more modified glycols. In another embodiment, the polyester may contain up to 5 mol% of one or more modified glycols. In another embodiment, the polyester may contain up to 3 mol% of one or more modified glycols. In another embodiment, the polyester may contain 0 mol% of modified glycols. Certain embodiments may also contain 0.01 mol% or more, for example, 0.1 mol% or more, 1 mol% or more, 5 mol% or more, or 10 mol% or more of one or more modified glycols. Thus, when present, it is contemplated that the amount of one or more modified glycols can be in the range of any of these above - mentioned endpoint values (e.g., 0.01 - 15 mol% and 0.1 - 10 mol%).

[0033] In an embodiment, the modified glycol useful for the polyester refers to a diol other than 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol, and may contain 2 to 16 carbon atoms. Examples of suitable modified glycols in certain embodiments include, but are not limited to, ethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, p-xylene glycol, or mixtures thereof. In one embodiment, the modified glycol is ethylene glycol. In another embodiment, the modified glycol is 1,3-propanediol and / or 1,4-butanediol. In another embodiment, ethylene glycol is excluded as the modified diol. In another embodiment, 1,3-propanediol and 1,4-butanediol are excluded as the modified diol. In another embodiment, 2,2-dimethyl-1,3-propanediol is excluded as the modified diol.

[0034] In an embodiment, the polyester and / or polycarbonate (if included) useful for the polyester composition may each contain one or more residues of a branching monomer (also referred to herein as a branching agent) having three or more carboxyl substituents, hydroxyl substituents, or combinations thereof, based on the total molar percentage of either the diol residue or the diacid residue, for example, 0 to 10 mol%, such as 0.01 to 5 mol%, 0.01 to 1 mol%, 0.05 to 5 mol%, 0.05 to 1 mol%, or 0.1 to 0.7 mol%. In certain embodiments, the branching monomer or branching agent may be added before and / or during and / or after the polymerization of the polyester.

[0035] In an embodiment, the polyester can be made from monomers that do not contain 1,3-propanediol or 1,4-butanediol alone or in combination. In other aspects, 1,3-propanediol or 1,4-butanediol, alone or in combination, can be used in the preparation of the polyester useful in the present invention.

[0036] In an embodiment, the mole % of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol in a specific polyester is more than 50 mol% or more than 55 mol% of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol, or more than 70 mol% of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol, and 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 100 mol% in total.

[0037] In an embodiment, the mole % of the isomers of 2,2,4,4-tetramethyl-1,3-cyclobutanediol in a specific polyester is 30 to 70 mol% of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol, or 30 to 70 mol% of trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol, or 40 to 60 mol% of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol, or 40 to 60 mol% of trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol, and 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 100 mol% in total.

[0038] In a particular embodiment, the polyester can be amorphous or semi-crystalline. In one aspect, a specific polyester can have a relatively low crystallinity. Thus, a specific polyester can have a substantially amorphous form, which means that the polyester contains substantially disordered polymer regions.

[0039] In embodiments, the polyester(s) and / or polyester composition(s) can have a unique combination of two or more physical properties (e.g., high impact strength, medium to high glass transition temperature, chemical resistance, hydrolysis stability, toughness, transition temperature from low ductility to brittleness, good color and transparency, low density, long semi-crystallization time, and good processability), thereby enabling them to be easily formed into articles. In some embodiments, the polyester can have a unique combination of good impact strength, heat resistance, chemical resistance, density properties, and / or a combination of good impact strength, heat resistance, and processability properties, and / or a combination of two or more of the described properties.

[0040] In embodiments, the polyester can be prepared from a dicarboxylic acid and a diol that react in a substantially equimolar ratio and are incorporated into the polyester polymer as the corresponding residues. Thus, the polyester can contain a substantially equal molar ratio of acid residues (100 mol%) and diol (and / or polyfunctional hydroxyl compound) residues (100 mol%), such that the total molar number of repeating units is equal to 100 mol%. Accordingly, the molar percentages provided in the present disclosure can be based on the total molar number of acid residues, the total molar number of diol residues, or the total molar number of repeating units. For example, a polyester containing 30 mol% isophthalic acid based on the total acid residues means a polyester containing 30 mol% isophthalic acid residues out of 100 mol% of the total acid residues. Thus, there are 30 mol of isophthalic acid residues per 100 mol of acid residues. In another example, a polyester containing 30 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol based on the total diol residues means a polyester containing 30 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues out of 100 mol% of the total diol residues. Thus, there are 30 mol of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues per 100 mol of diol residues.

[0041] In an embodiment, the Tg of the polyester can be at least one of the following ranges: 100 to 200 °C; 100 to 190 °C; 100 to 180 °C; 100 to 170 °C; 100 to 160 °C; 100 to 155 °C; 100 to 150 °C; 100 to 145 °C; 100 to 140 °C; 100 to 138 °C; 100 to 135 °C; 100 to 130 °C; 100 to 125 °C; 100 to 120 °C; 100 to 115 °C; 100 to 110 °C; 105 to 200 °C; 105 to 190 °C; 105 to 180 °C; 105 to 170 °C; 105 to 160 °C; 105 to 155 °C; 105 to 150 °C; 105 to 145 °C; 105 to 140 °C; 105 to 138 °C; 105 to 135 °C; 105 to 130 °C; 105 to 125 °C; 105 to 120 °C; 105 to 115 °C; 105 to 110 °C; above 105 to 125 °C; above 105 to 120 °C; above 105 to 115 °C; above 105 to 110 °C; 110 to 200 °C; 110 to 190 °C; 110 to 180 °C; 110 to 170 °C; 110 to 160 °C; 110 to 155 °C; 110 to 150 °C; 110 to 145 °C; 110 to 140 °C; 110 to 138 °C; 110 to 135 °C; 110 to 130 °C; 110 to 125 °C; 110 to 120 °C; 110 to 115 °C; 115 to 200 °C; 115 to 190 °C; 115 to 180 °C; 115 to 170 °C; 115 to 160 °C; 115 to 155 °C; 115 to 150 °C; 115 to 145 °C; 115 to 140 °C; 115 to 138 °C; 115 to 135 °C; 110 to 130 °C; 115 to 125 °C; 115 to 120 °C; 120 to 200 °C; 120 to 190 °C; 120 to 180 °C; 120 to 170 °C; 120 to 160 °C; 120 to 155 °C; 120 to 150 °C; 120 to 145 °C; 120 to 140 °C; 120 to 138 °C; 120 to 135 °C; 120 to 130 °C; 125 to 200 °C; 125 to 190 °C; 125 to 180 °C; 125 to 170 °C; 125 to 160 °C; 125 to 155 °C; 125 to 150 °C; 125 to 145 °C; 125 to 140 °C; 125 to 138 °C; 125 to 135 °C; 127 to 200 °C; 127 to 190 °C; 127 to 180 °C; 127 to 170 °C; 127 to 160 °C; 127 to 150 °C; 127 to 145 °C; 127 to 140 °C; 127 to 138 °C; 127 to 135 °C; 130 to 200 °C; 130 to 190 °C; 130 to 180 °C; 130 to 170 °C; 130 to 160 °C; 130 to 155 °C; 130 to 150 °C; 130 to 145 °C;130~140 °C; 130~138 °C; 130~135 °C; 135~200 °C; 135~190 °C; 135~180 °C; 135~170 °C; 135~160 °C; 135~155 °C; 135~150 °C; 135~145 °C; 135~140 °C; 140~200 °C; 140~190 °C; 140~180 °C; 140~170 °C; 140~160 °C; 140~155 °C; 140~150 °C; 140~145 °C; 148~200 °C; 148~190 °C; 148~180 °C; 148~170 °C; 148~160 °C; 148~155 °C; 148~150 °C; 150~200 °C; 150~190 °C; 150~180 °C; 150~170 °C; 150~160 °C; 155~190 °C; 155~180 °C; 155~170 °C; and 155~165 °C.;

[0042] In certain embodiments, the polyester can exhibit at least one of the following intrinsic viscosities (determined at 25 °C at a concentration of 0.5 g / 100 ml in 60 / 40 (wt / wt) phenol / tetrachloroethane): 0.10 to 1.2 dL / g; 0.10 to 1.1 dL / g; 0.10 to 1 dL / g; less than 0.10 to 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; less than 0.10 to 0.75 dL / g; 0.10 to 0.72 dL / g; 0.10 to 0.70 dL / g; less than 0.10 to 0.70 dL / g; 0.10 to 0.68 dL / g; less than 0.10 to 0.68 dL / g; 0.10 to 0.65 dL / g; 0.20 to 1.2 dL / g; 0.20 to 1.1 dL / g; 0.20 to 1 dL / g; less than 0.20 to 1 dL / g; 0.20 to 0.98 dL / g; 0.20 to 0.95 dL / g; 0.20 to 0.90 dL / g; 0.20 to 0.85 dL / g; 0.20 to 0.80 dL / g; 0.20 to 0.75 dL / g; less than 0.20 to 0.75 dL / g; 0.20 to 0.72 dL / g; 0.20 to 0.70 dL / g; less than 0.20 to 0.70 dL / g; 0.20 to 0.68 dL / g; less than 0.20 to 0.68 dL / g; 0.20 to 0.65 dL / g; 0.35 to 1.2 dL / g; 0.35 to 1.1 dL / g; 0.35 to 1 dL / g; less than 0.35 to 1 dL / g; 0.35 to 0.98 dL / g; 0.35 to 0.95 dL / g; 0.35 to 0.90 dL / g; 0.35 to 0.85 dL / g; 0.35 to 0.80 dL / g; 0.35 to 0.75 dL / g; less than 0.35 to 0.75 dL / g; 0.35 to 0.72 dL / g; 0.35 to 0.70 dL / g; less than 0.35 to 0.70 dL / g; 0.35 to 0.68 dL / g; less than 0.35 to 0.68 dL / g; 0.35 to 0.65 dL / g; 0.40 to 1.2 dL / g; 0.40 to 1.1 dL / g; 0.40 to 1 dL / g; less than 0.40 to 1 dL / g; 0.40 to 0.98 dL / g; 0.40 to 0.95 dL / g; 0.40 to 0.90 dL / g; 0.40 to 0.85 dL / g; 0.40 to 0.80 dL / g; 0.40 to 0.75 dL / g; less than 0.40 to 0.75 dL / g; 0.40 to 0.72 dL / g; 0.40 to 0.70 dL / g; 0.40 to 0.Less than 70 dL / g; 0.40 to 0.68 dL / g; less than 0.40 to 0.68 dL / g; 0.40 to 0.65 dL / g; greater than 0.42 to 1.2 dL / g; greater than 0.42 to 1.1 dL / g; greater than 0.42 to 1 dL / g; greater than 0.42 to less than 1 dL / g; greater than 0.42 to 0.98 dL / g; greater than 0.42 to 0.95 dL / g; greater than 0.42 to 0.90 dL / g; greater than 0.42 to 0.85 dL / g; greater than 0.42 to 0.80 dL / g; greater than 0.42 to 0.75 dL / g; greater than 0.42 to less than 0.75 dL / g; greater than 0.42 to 0.72 dL / g; greater than 0.42 to less than 0.70 dL / g; greater than 0.42 to 0.68 dL / g; greater than 0.42 to less than 0.68 dL / g; and greater than 0.42 to 0.65 dL / g.

[0043] In certain embodiments, the polyester may exhibit at least one of the following intrinsic viscosities (determined at 25 °C at a concentration of 0.5 g / 100 ml in 60 / 40 (wt / wt) phenol / tetrachloroethane): 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 dL / g; 0.50 to 1.2 dL / g; 0.50 to 1.1 dL / g; 0.50 to 1 dL / g; 0.50 to less than 1 dL / g; 0.50 to 0.98 dL / g; 0.50 to 0.95 dL / g; 0.50 to 0.90 dL / g; 0.50 to 0.85 dL / g; 0.50 to 0.80 dL / g; 0.50 to 0.75 dL / g; 0.50 to less than 0.75 dL / g; 0.50 to 0.72 dL / g; 0.50 to 0.70 dL / g; 0.50 to less than 0.70 dL / g; 0.50 to 0.68 dL / g; 0.50 to less than 0.68 dL / g; 0.50 to 0.65 dL / g; 0.55 to 1.2 dL / g; 0.55 to 1.1 dL / g; 0.55 to 1 dL / g; 0.55 to less than 1 dL / g; 0.55 to 0.98 dL / g; 0.55 to 0.95 dL / g; 0.55 to 0.90 dL / g; 0.55 to 0.85 dL / g; 0.55 to 0.80 dL / g; 0.55 to 0.75 dL / g; 0.55 to less than 0.75 dL / g; 0.55 to 0.72 dL / g; 0.55 to 0.70 dL / g; 0.55 to less than 0.70 dL / g; 0.55 to 0.68 dL / g; 0.55 to less than 0.68 dL / g; 0.55 to 0.65 dL / g; 0.58 to 1.2 dL / g; 0.58 to 1.1 dL / g; 0.58 to 1 dL / g; 0.58 to less than 1 dL / g; 0.58 to 0.98 dL / g; 0.58 to 0.95 dL / g; 0.58 to 0.90 dL / g; 0.58 to 0.85 dL / g; 0.58 to 0.80 dL / g; 0.58 to 0.75 dL / g; 0.58 to less than 0.75 dL / g; 0.58 to 0.72 dL / g; 0.58 to 0.70 dL / g; 0.58 to less than 0.70 dL / g; 0.58 to 0.68 dL / g; less than 0.58 to 0.68 dL / g; 0.58 to 0.65 dL / g; 0.60 to 1.2 dL / g; 0.60 to 1.1 dL / g; 0.60 to 1 dL / g; less than 0.60 to 1 dL / g; 0.60 to 0.98 dL / g; 0.60 to 0.95 dL / g; 0.60 to 0.90 dL / g; 0.60 to 0.85 dL / g; 0.60 to 0.80 dL / g; 0.60 to 0.75 dL / g; less than 0.60 to 0.75 dL / g; 0.60 to 0.72 dL / g; 0.60 to 0.70 dL / g; less than 0.60 to 0.70 dL / g; 0.60 to 0.68 dL / g; less than 0.60 to 0.68 dL / g; 0.60 to 0.65 dL / g; 0.65 to 1.2 dL / g; 0.65 to 1.1 dL / g; 0.65 to 1 dL / g; less than 0.65 to 1 dL / g; 0.65 to 0.98 dL / g; 0.65 to 0.95 dL / g; 0.65 to 0.90 dL / g; 0.65 to 0.85 dL / g; 0.65 to 0.80 dL / g; 0.65 to 0.75 dL / g; less than 0.65 to 0.75 dL / g; 0.65 to 0.72 dL / g; 0.65 to 0.70 dL / g; less than 0.65 to 0.70 dL / g; 0.68 to 1.2 dL / g; 0.68 to 1.1 dL / g; 0.68 to 1 dL / g; less than 0.68 to 1 dL / g; 0.68 to 0.98 dL / g; 0.68 to 0.95 dL / g; 0.68 to 0.90 dL / g; 0.68 to 0.85 dL / g; 0.68 to 0.80 dL / g; 0.68 to 0.75 dL / g; less than 0.68 to 0.75 dL / g; 0.68 to 0.72 dL / g; greater than 0.76 dL / g to 1.2 dL / g; greater than 0.76 dL / g to 1.1 dL / g; greater than 0.76 dL / g to 1 dL / g; greater than 0.76 dL / g to less than 1 dL / g; greater than 0.76 dL / g to 0.98 dL / g; greater than 0.76 dL / g to 0.95 dL / g; greater than 0.76 dL / g to 0.90 dL / g; greater than 0.80 dL / g to 1.2 dL / g; greater than 0.80 dL / g to 1.1 dL / g; greater than 0.80 dL / g to 1 dL / g; greater than 0.80 dL / g to less than 1 dL / g; greater than 0.80 dL / g to 1.2 dL / g; greater than 0.80 dL / g to 0.98 dL / g; greater than 0.80 dL / g to 0.95 dL / g; greater than 0.80 dL / g to 0.90 dL / g.

[0044] In certain embodiments, unless otherwise specified, it is contemplated that the polyester composition can have at least one of the intrinsic viscosity ranges described herein and at least one of the monomer ranges of the compositions described herein. Also, unless otherwise specified, it is contemplated that the polyester composition can have at least one of the Tg ranges described herein and at least one of the monomer ranges of the compositions described herein. Further, unless otherwise specified, it is contemplated that the polyester composition can have at least one of the Tg ranges described herein, at least one of the intrinsic viscosity ranges described herein, and at least one of the monomer ranges of the compositions described herein.

[0045] In embodiments, the molar ratio of cis / trans 2,2,4,4-tetramethyl-1,3-cyclobutanediol can vary from their respective pure forms or mixtures thereof. In certain embodiments, the molar percentage of cis and / or trans 2,2,4,4,-tetramethyl-1,3-cyclobutanediol is greater than 50 mol% cis and less than 50 mol% trans; or greater than 55 mol% cis and less than 45 mol% trans; or 30 - 70 mol% cis and 70 - 30% trans; or 40 - 60 mol% cis and 60 - 40 mol% trans; or 50 - 70 mol% trans and 50 - 30% cis; or 50 - 70 mol% cis and 50 - 30% trans; or 60 - 70 mol% cis and 30 - 40 mol% trans; or greater than 70 mol% cis and less than 30 mol% trans; and the sum of the molar percentages of cis and trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol is equal to 100 mol%. The molar ratio of cis / trans 1,4-cyclohexanedimethanol can vary within the range of 50 / 50 to 0 / 100 (e.g., 40 / 60 to 20 / 80).

[0046] In certain embodiments, terephthalic acid or its esters, such as dimethyl terephthalate, or a mixture of terephthalic acid and its esters, constitute most or all of the dicarboxylic acid component used to form the polyester. In certain embodiments, the terephthalic acid residues can constitute a portion or all of the dicarboxylic acid component used to form the polyester at a concentration of at least 70 mol% (e.g., at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol%, or 100 mol%). In certain embodiments, a greater amount of terephthalic acid can be used to produce a polyester with higher impact strength. In one embodiment, dimethyl terephthalate is a portion or all of the dicarboxylic acid component used to create the polyesters useful in the present invention. For the purposes of this disclosure, references to the residues of "terephthalic acid" and "dimethyl terephthalate" are used interchangeably herein. For example, a reference to the polymer residue of terephthalic acid (TPA) also includes the polymer residue derived from dimethyl terephthalic acid (DMT). In all embodiments, a range of 70 to 100 mol%, or 80 to 100 mol%, or 90 to 100 mol%, or 99 to 100 mol%, or 100 mol% of terephthalic acid and / or dimethyl terephthalate and / or mixtures thereof can be used.

[0047] In certain embodiments, in addition to terephthalic acid, the dicarboxylic acid component of the polyester may include one or more modified aromatic dicarboxylic acids in amounts up to 30 mol%, up to 20 mol%, up to 10 mol%, up to 5 mol%, or up to 1 mol%. Yet another embodiment contains 0 mol% of the modified aromatic dicarboxylic acid. Thus, when present, the amount of one or more modified aromatic dicarboxylic acids is contemplated to be in the range of any of these above-described endpoint values (e.g., 0.01 - 30 mol%, 0.01 - 20 mol%, 0.01 - 10 mol%, 0.01 - 5 mol%, and 0.01 - 1 mol%). In one embodiment, modified aromatic dicarboxylic acids that can be used include those having up to 20 carbon atoms, but are not limited thereto, and which can be linear, para-oriented, or symmetric. Examples of modified aromatic dicarboxylic acids that can be used include 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, but are not limited thereto. In one embodiment, the modified aromatic dicarboxylic acid is isophthalic acid.

[0048] In embodiments, the carboxylic acid component of the polyester can further be modified with one or more aliphatic dicarboxylic acids containing 2 - 16 carbon atoms in amounts up to 10 mol% (e.g., up to 5 mol% or up to 1 mol%) (e.g., dicarboxylic acids of malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and dodecanedioic acid). Certain embodiments can further include one or more modified aliphatic dicarboxylic acids in amounts of 0.01 mol% or more (e.g., 0.1 mol% or more, 1 mol% or more, 5 mol% or more, or 10 mol% or more). Yet another embodiment contains 0 mol% of the modified aliphatic dicarboxylic acid. Thus, when present, the amount of one or more modified aliphatic dicarboxylic acids is contemplated to be in the range of any of these above-described endpoint values (e.g., 0.01 - 10 mol% and 0.1 - 10 mol%). The total mol% of the dicarboxylic acid component is 100 mol%.

[0049] Instead of the dicarboxylic acid, an ester of terephthalic acid and another modified dicarboxylic acid, or their corresponding esters and / or salts can be used. Suitable examples of dicarboxylic acid esters include, but are not limited to, dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, and diphenyl esters. In one embodiment, the ester is selected from at least one of the following: methyl ester, ethyl ester, propyl ester, isopropyl ester, and phenyl ester.

[0050] In embodiments of the polyester containing CHDM, 1,4-cyclohexanedimethanol can be cis, trans, or a mixture thereof. For example, the cis / trans ratio can be from 60:40 to 40:60. In one embodiment, trans-1,4-cyclohexanedimethanol can be present in an amount of 60 to 80 mol%.

[0051] In embodiments, the polyester(s) can be linear or branched. In embodiments, the polycarbonate (if included) can also be linear or branched. In certain embodiments, a branching monomer or branching agent can be added before and / or during and / or after the polymerization of the polycarbonate.

[0052] Examples of branching monomers include, but are not limited to, polyfunctional acids or polyfunctional alcohols (e.g., trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, glycerol, pentaerythritol, citric acid, tartaric acid, 3-hydroxyglutaric acid, etc.). In one embodiment, the branched monomer residue may contain one or more residues in a molar percentage of 0.1 to 0.7 selected 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. Pat. Nos. 5,654,347 and 5,696,176, the disclosures of which are incorporated herein by reference.

[0053] The glass transition temperature (Tg) of the polyester can be measured by using a TA DSC2920 manufactured by Thermal Analyst Instrument with a scan rate of 20 °C / min.

[0054] The long crystallization time (e.g., 5 minutes or more) at 170 °C exhibited by a particular polyester can be beneficial for the production of certain injection-molded articles, compression-molded articles, and solution-cast articles. The polyester can be amorphous or semi-crystalline. In one aspect, a particular polyester can have a relatively low crystallinity. Thus, a particular polyester can have a substantially amorphous form, which means that the polyester contains substantially disordered polymer regions.

[0055] In one embodiment, the semi-crystallization time of the "amorphous" polyester can be more than 5 minutes at 170 °C, or more than 10 minutes at 170 °C, or more than 50 minutes at 170 °C, or more than 100 minutes at 170 °C. In one embodiment, the semi-crystallization time is more than 1,000 minutes at 170 °C. In another embodiment of the present invention, the semi-crystallization time of the polyester useful in the present invention is more than 10,000 minutes at 170 °C. The semi-crystallization time of the polyester used herein can be measured using methods well known to those skilled in the art. For example, the semi-crystallization time t 1 / 2 of the polyester can be determined by measuring the light transmittance of the sample via a laser and a photodetector as a function of time on a temperature-controlled hot stage. This measurement can be performed by exposing the polymer to temperature T max and then cooling it to the desired temperature. Thereafter, the sample can be held at the desired temperature by the hot stage, but the transmittance measurement is performed as a function of time. Initially, the sample may be visually transparent and have a high light transmittance, but it becomes opaque as the sample crystallizes. The semi-crystallization time is the time when the light transmittance is intermediate between the initial transmittance and the final transmittance. T max is defined as the temperature required to melt the crystalline domains of the sample (if crystalline domains are present). Before measuring the semi-crystallization time, the sample can be heated and adjusted to T max . The absolute T max temperature varies for each composition. For example, PCT can be heated to several temperatures above 290 °C to melt the crystalline regions.

[0056] In embodiments, certain polyesters are visually transparent. The term "visually transparent" is defined as having little to no haze, cloudiness, and / or turbidity upon visual inspection. In one embodiment, when the polyester is blended with a polycarbonate (e.g., bisphenol A polycarbonate), the blend can be visually transparent. In embodiments, the polyester can have one or more of the properties described herein. In embodiments, the polyester can have a yellowness index (ASTM D-1925) of less than 50 (e.g., less than 20).

[0057] The copolyester portion of the polymer composition of the present invention can be produced by processes known in the literature (e.g., processes in homogeneous solution, transesterification processes in the melt, and two-phase interfacial processes). Suitable methods include, but are not limited to, reacting one or more dicarboxylic acids with one or more glycols at a temperature of 100°C to 315°C, a pressure of 0.1 to 760 mmHg, for a time sufficient to form the polyester. For methods of making polyesters, see: U.S. Patent No. 3,772,405 (the disclosure of such methods is incorporated herein by reference).

[0058] Generally, the copolyester can be prepared by a process comprising: (I) heating a mixture comprising monomers useful in any of the polyesters of the present invention in the presence of a catalyst at a temperature of 150 to 240°C for a time sufficient to produce an initial polyester; (II) heating the initial polyester of step (I) at a temperature of 240 to 320°C for 1 to 4 hours; and (III) removing unreacted glycol.

[0059] Suitable catalysts used in this process include, but are not limited to, organozinc or tin compounds. The use of this type of catalyst is well-known in the art. Examples of catalysts useful in the present invention include, but are not limited to, zinc acetate, butyltin tris-2-ethylhexanoate, dibutyltin diacetate, and dibutyltin oxide. Other catalysts may include, but are not limited to, those based on titanium, zinc, manganese, lithium, germanium, and cobalt. The amount of catalyst can range from 10 ppm to 20,000 ppm, or 10 to 10,000 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, based on the weight of the catalyst metal and the final polymer. This process can be carried out either in a batch process or a continuous process.

[0060] Typically, step (I) can be carried out until at least 50% by weight of 2,2,4,4-tetramethyl-1,3-cyclobutanediol has reacted. Step (I) can be carried out under a pressure in the range of atmospheric pressure to 100 psig. The term "reaction product" as used in connection with any of the catalysts useful in the present invention refers to any product of a polycondensation or esterification reaction using either the catalyst and any of the monomers used in the production of the polyester, as well as the product of a polycondensation or esterification reaction between the catalyst and any other type of additive.

[0061] Typically, steps (II) and (III) can be carried out simultaneously. These steps can be carried out by known methods in the art by placing the reaction mixture under a pressure of 0.002 psig to less than atmospheric pressure, or by blowing hot nitrogen gas into the mixture.

[0062] In an embodiment, the polyester composition can be a polymer blend, the blend comprising: (a) 5 to 95% by weight of at least one of the polyesters described herein, and (b) 5 to 95% by weight of at least one polymer component. Suitable examples of the polymer component include, but are not limited to: nylon, polyesters different from those described herein, polyamides (e.g., ZYTEL® (DuPont)), polystyrene, polystyrene copolymers, styrene acrylonitrile copolymers, acrylonitrile butadiene styrene copolymers, poly(methyl methacrylate), acrylic copolymers, poly(ether imide) (e.g., ULTEM™ resin (SABIC's poly(ether imide))), polyphenylene oxide (e.g., poly(2,6-dimethylphenylene oxide) or poly(phenylene oxide)) / polystyrene blend (e.g., NORYL® resin (a blend of SABIC's poly(2,6-dimethylphenylene oxide) and polystyrene resin)), polyphenylene sulfide, polyphenylene sulfide / sulfone, poly(ester carbonate), polycarbonate (e.g., LEXAN® (SABIC's polycarbonate)), polysulfone, polysulfone ether, and poly(ether ketone) of an aromatic dihydroxy compound; or a mixture of any of the other polymers described above. The blend can be prepared by conventional processing techniques known in the art (e.g., melt blending or solution blending). In one embodiment, the polycarbonate is not present in the polyester composition. When polycarbonate is used in the blend of the polyester composition useful in the present invention, the blend can be visually transparent. However, the polyester compositions useful in the present invention contemplate both the exclusion and the inclusion of polycarbonate.

[0063] In addition to the additives and any impact modifiers (described herein), the polyester compositions and polymer blend compositions may also contain additional additives selected from antioxidants, heat stabilizers, release agents, antistatic agents, whitening agents, colorants, flow aids, processing aids, plasticizers, anti-fogging additives, minerals, UV stabilizers, lubricants, chain extenders, nucleating agents, reinforcing fillers, other fillers, glass fibers, carbon fibers, flame retardants, dyes, pigments, colorants, additional resins, and combinations thereof. In certain embodiments, the polyester compositions and polymer blend compositions may also contain common additives (e.g., colorants, dyes, release agents, flame retardants, plasticizers, nucleating agents, stabilizers (e.g., but not limited to, UV stabilizers, heat stabilizers, and / or their reaction products), and fillers) in an amount of 0.01 to 25 wt% of the total composition. For example, the UV additives can be incorporated into the article (e.g., through addition to the bulk or addition to a hard coat).

[0064] In some embodiments, during the process of manufacturing the polyesters useful in the present invention, certain agents (e.g., toners or dyes) for coloring the polymer can be added to the melt. In one embodiment, a blue toner is added to the melt to adjust the b* of the resulting polyester polymer melt phase product. Such blueing agents include blue inorganic and organic toners and / or dyes. Additionally, a red toner and / or dye can be used to adjust the a* color. In one embodiment, with or without the toner, the polymers or polymer blends useful in the present invention, and / or the polymer compositions of the present invention can have lightness L*, a*, and b*, which can be determined using a Hunter Lab Ultrascan spectral colorimeter manufactured by Hunter Associates Lab Inc. (Reston, VA). The color determination is the average of the values measured on pellets or powders of the polymer, or plaques or other articles injection molded or extruded from the polymer. They are determined by the CIE (International Commission on Illumination) L*a*b* color space (translation), where L* represents the lightness coordinate, a* represents the red / green coordinate, and b* represents the yellow / blue coordinate. Organic toners, e.g., blue and red organic toners, e.g., the toners described in U.S. Patent Nos. 5,372,864 and 5,384,377 (incorporated herein by reference in their entirety) can be used. The organic toners can be supplied as a premix composition. Whether the premix composition is a pure blend of a red compound and a blue compound, or the composition is pre-dissolved or slurried in one of the raw materials of the polyester (e.g., ethylene glycol).

[0065] The total amount of toner components to be added can be determined by the amount of inherent yellow in the base polyester and the effectiveness of the toner. In one embodiment, a concentration of up to about 15 ppm and a minimum concentration of about 0.5 ppm of the combined organic toner components can be used. In one embodiment, the total amount of the blue additive can be in the range of 0.5 to 10 ppm. In one embodiment, the toner(s) can be added to the esterification zone or the polycondensation zone. Advantageously, the toner(s) is added to the initial stage of the esterification zone or the polycondensation zone, for example, to a prepolymerization reactor, or added to an extruder or a calender during processing.

[0066] In an embodiment, the polyester can include at least one chain extender. Suitable chain extenders include, but are not limited to, polyfunctional (including, but not limited to, bifunctional) isocyanates, polyfunctional epoxides (such as those including epoxidized novolac), and phenoxy resins. In certain embodiments, the chain extender can be added at the end of the polymerization process or after the polymerization process. When added after the polymerization process, the chain extender can be incorporated by mixing during a conversion process (such as injection molding or extrusion molding) or by addition. The amount of chain extender used can vary depending on the specific monomer composition used and the desired physical properties, but generally ranges from 0.1 weight percent to 10 weight percent (such as 0.1 to 5 weight percent) based on the total weight of the polyester.

[0067] A heat stabilizer is a compound that stabilizes polyester during and / or after the production of the polyester, and this includes, but is not limited to, phosphorus compounds (including, but not limited to, 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 ether, aryl, and substituted aryl. In one embodiment, the number of ester groups present in a particular phosphorus compound can vary from zero to the maximum allowable, based on the number of hydroxyl groups present on the heat stabilizer used. The term "heat stabilizer" is intended to include its reaction product(s). The term "reaction product" as used in connection with the heat stabilizers of the present invention refers to any product of a polycondensation or esterification reaction between a heat stabilizer and any of the monomers used in the production of the polyester, as well as the product of a polycondensation or esterification reaction between a catalyst and other types of additives. In embodiments, these can be present in the polyester composition.

[0068] In embodiments, a reinforcing agent can be useful in the polyester composition. The reinforcing agent can include, but is not limited to, carbon fibers, silicates, mica, clay, talc, titanium dioxide, wollastonite, glass flakes, glass beads and fibers, and polymer fibers, and combinations thereof. In one embodiment, the reinforcing agent is glass (e.g., glass fibers, a mixture of glass and talc, a mixture of glass and mica, and a mixture of glass and polymer fibers).

[0069] In another embodiment, the present invention further relates to a manufactured article comprising either the polyester or blend described herein. In embodiments, the article can be an extruded article, a calendered article, and / or a molded article, which includes, but is not limited to, an injection molded article, an extruded article, a cast extruded article, a profile extruded article, a melt spun article, a thermoformed article, an extruded article, an injection blow molded article, an injection stretch blow molded article, an extrusion blow molded article, and an extrusion stretch blow molded article. These articles can include, but are not limited to, films, bottles (including but not limited to baby bottles), containers, sheets, and / or fibers.

[0070] In embodiments, the article can be intended for use where the article (or its components) come into surface-to-surface contact (with another article or component) when movement is predicted upon surface contact, e.g., where the surfaces are predicted to be able to slide relative to each other. Such uses can include, for example, articles, parts, or components that are releasably joined to each other by frictional engagement. Examples of such uses can include durable or decorative articles (e.g., structural adornments) having articles, parts, or components that interact during use as described above. In embodiments, the polyester composition or an article made therefrom can be for uses currently manufactured from ABS plastic (e.g., general adornments, electronic devices, or medical devices). Additional examples of articles can include transparent or opaque food contact uses, e.g., food containers, lids, bottles (e.g., sports bottles and lids), as well as fasteners and hinges therefor (e.g., fastener and hinge integral components and / or assemblies).

[0071] In an embodiment, the copolyester and / or polyester blend composition may be useful for forming fibers, films, molded articles, containers, and sheets. Methods for molding polyesters into fibers, films, molded articles, containers, and sheets are well known in the art. Examples of potential molded articles include, but are not limited to: medical devices (e.g., dialysis devices), medical packaging, healthcare products, commercial food service products (e.g., food pots, tumblers and storage boxes, baby bottles, food processors, blenders, and mixing bowls), appliances, water barrels, vegetable compartment trays, decorative items, the front of washing machines, and parts of vacuum cleaners.

[0072] In another embodiment, the present invention further relates to a manufactured article comprising a film(s) and / or sheet(s) containing the polyester composition described herein.

[0073] The films and / or sheets useful in the present invention can be of any thickness that is apparent to those skilled in the art. In one embodiment, the thickness of the film(s) of the present invention is 40 mils or less. In one embodiment, the thickness of the film(s) of the present invention is 35 mils or less. In one embodiment, the thickness of the film(s) of the present invention is 30 mils or less. In one embodiment, the thickness of the film(s) of the present invention is 25 mils or less. In one embodiment, the thickness of the film(s) of the present invention is 20 mils or less.

[0074] In an embodiment, the (friction) additive can be selected from a wide range of waxes and siloxanes. Waxes useful in the polymer compositions of the present invention can include known higher alkanes and lipids that are lipophilic malleable solids at room temperature (i.e., 23 °C). Natural waxes are found in plants and animals and also in petroleum products. In one embodiment, the wax is a mixture of saturated alkanes, naphthenes, and alkyl and naphthene-substituted aromatic compounds. In another embodiment, the wax can be montan wax extracted from certain coal and lignite sources. In another embodiment, the wax can be a polyolefin wax or a polyalkylene wax. Natural waxes can include beeswax, which is mainly myricyl palmitate, cetyl palmitate, lanolin, carnauba wax, or rice bran wax.

[0075] In an embodiment, the siloxane can be a compound containing Si-O-Si bonds. Examples include compounds having the structures of H(OSiH2)nOH and (OSiH2)n. In other embodiments, the siloxane can be a silicone or polysiloxane having a (-RSi-O-SiR-) structure, where R is an organic group (e.g., an alkyl or aryl group). Examples of such polysiloxanes are polydimethylsiloxane or "PDMS" and polydiphenylsiloxane.

[0076] Examples of commercially available waxes and siloxanes can include: Genioplast S, a pelletized silicone gum formulation from Wacker Chemie AG; Tegomer H-Si (e.g., H-Si 6441P) (polyester-modified siloxane), Tegomer V-Si (e.g., V-Si 4042) (vinyl-terminated organo-modified silicone (OMS)), Tegomer M-Si (e.g., M-Si2650) (aryl-terminated OMS), Tegomer E-Si (e.g., E-Si2330) (epoxy-terminated OMS), or Tegomer DA800 (copolyester dispersion) (all from Evonik Industries AG); MCR-E21 or ECMS-227 functionalized siloxanes from Gelest; Dowsil (trademark) Si powder resin modifier or DowSil 4-7081 from Dow Chemical Company; Loxiol P or P861, polyol esters from Emery Oleochemicals GmbH; Modiper 1401, Modiper 4300, or Modiper 4400 (polyethylene-based (graft) copolymer) from NOF Corporation; A-C Wax 307, 316, or 325 (polyethylene polymer powder) from Honeywell, Licowax OP, E, PED191, 371FP, or WE40 from Clariant; Hystrene (fatty acid) from PMC Group; Licocare RBW101, 102, 106, 300, 330, 360 Vita, as well as Ceridust 1060 and 1041 TP Vita from Clariant; Repellant polymer PM-870 or FX 5911 (fluorine compound flakes) from 3M; and Incroslip or Incromax 100 (bio-based slip additives) from Croda. It should be noted that some of these additives can provide functionality to the copolyester resin. For example, Modiper 4300 and 4400 can also function as impact modifiers.

[0077] The wax and siloxane used as the above component (b) are usually present in an amount of about 0.1 to about 12% by weight ratio. In other embodiments, they are present in an amount of about 0.1 to about 10, or 1 to about 10 weight percent based on the total copolyester composition. In embodiments, the component (b) additive includes wax and is present in an amount of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 8 wt%, or 0.1 to 6 wt%, or 0.1 to 4 wt%, or 0.1 to 3 wt%, or 0.1 to 2 wt%, or 0.1 to 1.5 wt%, or 0.1 to 1.3 wt%, or 0.1 to 1.2 wt%, or 0.1 to 1.1 wt%, or 0.1 to 1.0 wt%, 0.2 to 4 wt%, or 0.2 to 3 wt%, or 0.2 to 2 wt%, or 0.2 to 1.5 wt%, or 0.2 to 1.3 wt%, or 0.2 to 1.2 wt%, or 0.2 to 1.1 wt%, or 0.2 to 1.0 wt%, or 0.3 to 4 wt%, or 0.3 to 3 wt%, or 0.3 to 2 wt%, or 0.3 to 1.5 wt%, or 0.3 to 1.3 wt%, or 0.3 to 1.2 wt%, or 0.3 to 1.1 wt%, or 0.3 to 1.0 wt%, or 0.4 to 4 wt%, or 0.4 to 3 wt%, or 0.4 to 2 wt%, or 0.4 to 1.5 wt%, or 0.4 to 1.3 wt%, or 0.4 to 1.2 wt%, or 0.4 to 1.1 wt%, or 0.4 to 1.0 wt%, or 0.5 to 4 wt%, or 0.5 to 3 wt%, or 0.5 to 2 wt%, or 0.5 to 1.5 wt%, or 0.5 to 1.3 wt%, or 0.5 to 1.2 wt%, or 0.5 to 1.1 wt%, or 0.5 to 1.0 wt% based on the total weight of the polyester composition.

[0078] In an embodiment, the component (b) additive contains siloxane and is present in an amount of 0.1 to 12 wt%, or 1 to 12 wt%, or 1 to 11 wt%, or 1 to 10 wt%, or 1 to 9 wt%, or 1 to 8 wt%, or 2 to 12 wt%, or 2 to 11 wt%, or 2 to 10 wt%, or 2 to 9 wt%, or 2 to 8 wt%, or 3 to 12 wt%, or 3 to 11 wt%, or 3 to 10 wt%, or 3 to 9 wt%, or 3 to 8 wt%, or 4 to 12 wt%, or 4 to 11 wt%, or 4 to 10 wt%, or 4 to 9 wt%, or 4 to 8 wt%, or 5 to 12 wt%, or 5 to 11 wt%, or 5 to 10 wt%, or 5 to 9 wt%, or 5 to 8 wt%, or 6 to 12 wt%, or 6 to 11 wt%, or 6 to 10 wt%, or 6 to 9 wt%, or 6 to 8 wt% based on the total weight of the polyester composition.

[0079] Regarding any component (c) impact modifier, such compounds are generally elastomeric compounds or polymers that serve to absorb or dissipate the kinetic energy of impact. A wide range of materials can be useful for any component (c). Examples of impact modifiers can be those containing at least one functional group capable of reacting with at least one end group of a macrocyclic polyester oligomer / polymer. Examples of suitable impact modifiers include, but are not limited to, various known graft copolymers, core-shell polymers, and block copolymers. These polymers can include at least one monomer selected from the group consisting of alkenes, alkadienes, arenes, acrylates, and alcohols. (See, for example: EP1,694,771B1). As an example, a core-shell polymer can be mentioned in which the core consists of a rubbery polymer and the shell consists of a styrene copolymer (see, for example: U.S. Patent No. 5,321,056, incorporated herein by reference). Other examples include core-shells and functional polyolefins as described in US2014 / 0256848A1 (incorporated herein by reference). See also: EP2139948B1.

[0080] In embodiments, examples of commercially available impact modifiers can include, but are not limited to, ethylene / propylene terpolymers, functionalized polyolefins containing methyl acrylate and / or glycidyl methacrylate, styrene-based block copolymer impact modifiers, and various acrylic core / shell type impact modifiers. Residues of such additives are also considered part of the polyester composition.

[0081] It should also be noted that certain friction additives can also function as impact modifiers. Therefore, in certain embodiments, it is contemplated that an additive identified as a friction additive can be included as an impact modifier in addition to one of the other identified friction additives. For example, Modiper4300 can function as an impact modifier and can be added together with a wax additive (e.g., Licowax OP), where Licowax OP is an additive of component (b) and Modiper4300 is an additive of optional component (c).

[0082] Commercially available examples can include the following: Modiper® 4300 and Modiper® 4400, available from NOF Corporation Kane Ace® M300, available from Kaneka Americas Holding, Inc. Kane Ace® B564, available from Kaneka Americas Holding, Inc. Kane Ace® ECO1000, available from Kaneka Americas Holding, Inc. Kane Ace® MR02, available from Kaneka Americas Holding, Inc. Kane Ace® MR03, available from Kaneka Americas Holding, Inc., and Lotader® 8900, available from Arkema.

[0083] The impact modifiers utilized as any of the above components (c) are typically present in an amount of from 0 to about 12 weight percent. In other embodiments, they are present in an amount of from 0 to 10, or 0 to 8, or 0 to 6, or 0 to 5, or 0 to 4, or 0 to 3, or 0 to 4, or 0 to 1, or less than 0 to 1, or 0 to 0.9, or 0 to 0.8, or 0 to 0.7, or 0 to 0.6, or 0 to 0.5 weight percent, based on the total weight of the polyester composition.

[0084] The present invention can be further illustrated by the following examples of preferred embodiments, which are included for illustrative purposes only and are not to be construed as limiting the scope of the invention unless otherwise specifically stated.

[0085] Experimental Section Section 1. Testing of Base Resins Several commercially available resins were subjected to a series of tests. This testing was designed to establish a baseline for the performance of the copolyester composition from the perspective of physical properties and friction performance.

[0086] Using established test methods defined by ASTM, physical properties typically reported in a technical data sheet (TDS) were evaluated using injection molded tensile or flexure test specimens. For commercially available resins, the drying conditions and processing conditions reported in the technical data sheet were utilized for molding. In the case of modified resins, the processing conditions utilized were selected based on those of the base resin.

[0087] Multiple tests were completed on all samples, and the modified resins are detailed in Section 3 below. These test methods are categorized as follows: ● Specific physical properties commonly found in technical data sheets. Specific tests included tensile properties (ASTM D638), flexural properties (ASTM D790), notched Izod impact properties (ASTM D256), and heat deflection properties (ASTM D648). In all cases, both the commercial resin and the modified resin were tested according to standard conditioning and test protocols. ● Coefficient of static friction and coefficient of dynamic friction (μ s and μ k ), respectively) of the base resin reported using an in-house custom test method equivalent to the conventional standardized sliding friction thread test (ASTM D1894). These values were measured using a Bruker tribometer by intentionally contacting the surfaces of pairs of 4-inch × 4-inch × 1 / 8-inch plaques manufactured using injection molding. To avoid contamination of the friction data measurements, gloves were always worn to avoid direct contact with the test specimens. After molding, a pair of plaques was used to measure the coefficient of friction according to the following definitions. ○ Static COF (μ s ) is measured at the limit where both the contact force (F z ) between two plaques and the relative velocity (v x ) between the two contacting plaques approach zero. For example: ■ F z = 0.05 N, v x = 0.01 mm / sec ○ Dynamic COF (μ k ), defined as the friction measured at a constant force and relative velocity between two contacting plaques. For example: ■ F z = 3.00 N, v x = 10.0 mm / sec

[0088] An overview of the commercial resins evaluated as examples of "controls" or "comparisons" is shown in Table 1 below.

Table 1

[0089] The overview of the physical properties of the control / comparison materials is shown in Table 2 below.

Table 2

[0090] The overview of the physical property data in Table 2 reveals that Resins C-01 and C-02 (ABS and polycarbonate (PC), respectively) exhibit higher rigidity in both tensile modulus and flexural modulus than all other materials evaluated. Resin C-03 (cellulose material) shows similar tensile properties to C-01, except for the modulus, and similar levels of impact toughness when measured by the notched Izod test. The toughness of Resins C-06, C-07, C-09, and C-10 is significantly lower than that of C-01, while the rigidity of Resins C-04, C-05, and C-08 is the lowest among the commercial resins evaluated.

[0091] The frictional performance of the materials in Table 1 was evaluated to quantify the coefficient of static friction and coefficient of kinetic friction (μ s and μ k ). The coefficient of friction (COF) values are listed in Table 3 below.

Table 3

[0092] Section 2. Modification By incorporating various additives, twin-screw mixing and various additives (plural possible) were used to generate modified development samples in order to modify performance, particularly the friction profile. These additives can vary in chemical nature, including, for example, ranging from short-chain molecules (such as waxes) to high molecular weight or ultra-high molecular weight organosiloxanes (such as PDMS). In the mixed formulations, it was found that the additives can function as internal lubricants and / or external lubricants depending on the specific additive chemistry, molecular weight, loading level, and functionality. The additives utilized are listed in Table 4 below. [Table 4]

[0093] In addition to the above additives, additional additives that can be incorporated into potential formulations are additives that are specifically designed to modify impact toughness. Additives utilized for impact modification are typically incorporated at loading levels of less than 15 wt%, and span multiple chemical natures and morphologies (such as core-shell, branched, reactive, MBS, acrylic, EGMA, etc.). A non-exhaustive overview of possible impact modifiers that can potentially be used in combination with the above modifiers is considered in the present specification above.

Examples

[0094] Section 3. Examples By using friction additives for modification, multiple samples of TMCD- and CHDM-containing copolyesters were generated (e.g., Eastman Tritan™ TX1500 copolyester (Sample C-04, without release agent), Eastman Tritan™ TX1000 copolyester (Sample C-08)). Physical properties before and after the thermal aging protocol were measured. The friction performance of each was also evaluated using a tribometer (as described above). The results are reported in the following table summarizing the performance of the modified formulations compared to the control examples.

[0095] Table 5 summarizes the formulations (TX-01 to TX-09) evaluated in this study that contain specific compositions of friction additives, compared to the control or control cases. The "base resins" used for the friction-modified Tritan™ samples were Tritan™ TX1500 (C-04, no release agent) and Tritan™ TX1000 (C-08). However, it should be noted that the findings from this study provide insights into the use of other TMCD- and CHDM-based resins (e.g., Tritan™ TX1001, TX1501, TX2001, TX3001).

Table 5-1

Table 5-2

Table 5-3

[0096] The physical properties and performance of the resins in the examples of TX1500, TX1000, and TX1001 were measured according to the procedures and test methods described above for all control resins, comparative resins, and / or commercially available resins in Table 5. Spiral flow results are also provided to evaluate the flow characteristics brought about by the addition of friction-reducing additives. Spiral flow measurements were carried out using a Boy 22A Pro 22-ton reciprocating screw injection molding machine under the following conditions. The flow length ratio (L / t) was calculated by dividing the spiral flow length (L) by the cavity thickness (t). To allow the process to reach equilibrium, approximately 15 injection cycles were discarded, and then at least 10 repeated measurements were collected and averaged. Before entering the spiral flow cavity, the spiral flow mold was fed with a 2.25-inch sprue with a diameter of 0.28 inches. No release spray was used. All resins were vacuum dried at 60°C overnight before molding. The molding conditions used for the spiral flow test are described in Table 5A below.

Table 6

[0097] An overview of the physical properties (in particular, tensile properties, notched Izod impact toughness, flexural modulus, and heat deflection temperature) is shown in Tables 6 and 7. In all cases, the samples were equilibrated at 23 °C for 72 hours before testing. [Table 7] [Table 8]

[0098] Summarizing Tables 6 and 7, it was found that the tensile performance (yield strength, yield strain, breaking strength, breaking strain) was maintained even in formulations with different types of friction additives and load levels, compared to C-01 and unmodified TX1501 and TX1001 (C-04 and C-05). Specifically, some examples (e.g., TX-96, TX-97, and TX-99) maintained similar tensile modulus and / or flexural modulus compared to the unmodified TX1001 formulation of C-05; some examples showed an improvement in tensile modulus and / or flexural modulus compared to unmodified TX1001; and some examples (e.g., TX-93, TX-96, and TX-99) showed similar notched Izod performance and / or heat deflection performance compared to unmodified TX1001.

[0099] After a simple accelerated aging protocol, the physical properties of the TX1001 formulation were also evaluated. This was accomplished by subjecting the samples to a thermal aging protocol and then performing physical property tests on the thermally aged test specimens according to the standard ASTM test methods as described above. The purpose of performing the tests both before and after thermal exposure was to determine whether any substantial changes in performance and physical properties were observed in the examples of the modified copolyesters resulting from the friction modification and additives. Table 8 summarizes the tensile properties measured after standard conditions (72 hours at 23 °C and 50% RH) and after a thermal aging protocol (200 hours at 60 °C), which shows minimal variation in tensile and impact properties compared to Samples C-01 and C-05.

Table 9

[0100] Finally, the friction performance of specific modified samples of TX1500 and TX1000 was compared to control samples C-04 and C-08. The results are presented in Tables 9 and 10 below. Table 11 also includes data on the haze % of specific TX1000 samples.

Table 10

Table 11-1

Table 11-2

Table 11-3

[0101] Although the invention has been described in detail with reference to its specific embodiments, it will be understood that changes and modifications can affect the spirit and scope of the invention.

Claims

1. A polymer composition, (a) Copolyester, (i) Dicarboxylic acid component, a. 70-100 mol% of terephthalic acid residues, b. Aromatic dicarboxylic acid residues having up to 20 carbon atoms in an amount of 0 to 30 mol%, and c. The dicarboxylic acid component comprising an aliphatic dicarboxylic acid residue having up to 16 carbon atoms in an amount of 0 to 10 mol%, and (ii) Glycol component, a. 10 to 99 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues, and b. A glycol component comprising 10 to 90 mol% of 1,4-cyclohexanedimethanol (CHDM) residues, wherein the total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the glycol component is 100 mol%, The intrinsic viscosity of the polyester is 0.1 to 1.2 dL / g, determined at a concentration of 0.5 g / 100 ml in 60 / 40 (wt / wt) phenol / tetrachloroethane at 25°C, and the Tg of the polyester is 100 to 200°C. (b) A friction additive selected from waxes and siloxanes, in an amount of about 0.1 to about 12 weight percent, and (c) The polymer composition optionally comprising 0 to about 12 weight percent of at least one impact modifier.

2. The composition according to claim 1, wherein the friction additive is a wax.

3. The composition according to claim 2, wherein the friction additive is present in an amount of about 0.1 to about 3 weight percent.

4. The composition according to claim 1, wherein the friction additive is a siloxane.

5. The composition according to claim 4, wherein the friction additive is present in an amount of about 0.1 to about 10 weight percent.

6. The composition according to claim 1, wherein the polyester composition is a copolyester comprising a diol residue containing 5 to 42 mole percent of TMCD residues and 58 to 95 mole percent of CHDM residues.

7. The composition according to claim 6, wherein the polyester composition is a copolyester comprising a diol residue containing 20 to 30 mole percent of TMCD residues and 70 to 80 mole percent of CHDM residues.

8. The composition according to claim 6, wherein the polyester composition is a copolyester containing a diol residue comprising 30 to 40 mole percent of TMCD residues and 60 to 70 mole percent of CHDM residues.

9. The composition according to claim 1, wherein the friction additive (b) comprises two or more friction additives.

10. The composition according to claim 1, wherein the composition comprises (a) 5 to 95% by weight of the copolyester (a), and (d) 5 to 95% by weight of at least one polymer component other than (a).

11. The composition according to claim 10, wherein (d) is selected from polyamide; polystyrene; styrene acrylonitrile; acrylonitrile butadiene styrene; poly(methyl methacrylate); acrylic; poly(etherimide); polyamide; polystyrene; polystyrene copolymer; styrene acrylonitrile copolymer; acrylonitrile butadiene styrene copolymer; poly(methyl methacrylate); acrylic copolymer; poly(etherimide); polyphenylene oxide; poly(phenylene oxide) / polystyrene blend; polycarbonate; poly(ester carbonate); polyphenylene sulfide / sulfone; polysulfone; polysulfone ether; and poly(ether ketone), or a mixture thereof.

12. The composition according to claim 1, wherein the composition has a static COF of 0.6 or less and a dynamic COF of 0.5 or less.

13. The composition according to claim 1, wherein the composition has a haze of 5% or less.

14. The composition according to claim 1, wherein the composition has 6 or fewer b*.

15. The composition according to claim 1, wherein the flow length ratio (L / t) (280°C and 1.6 mm) of the composition is 100 or more.

16. The composition according to claim 1, wherein the composition comprises antioxidants, heat stabilizers, mold release agents, antistatic agents, whitening agents, colorants, flow aids, processing aids, plasticizers, anti-fogging additives, minerals, UV stabilizers, lubricants, chain extenders, nucleating agents, reinforcing fillers, other fillers, glass fibers, carbon fibers, flame retardants, dyes, pigments, colorants, additional resins, and additional additives selected from combinations thereof.

17. A molded or formed article comprising the polymer composition according to any one of claims 1 to 16.

18. The article according to claim 17, wherein the article is selected from extruded articles, calendered articles, and / or molded articles.

19. The article according to claim 18, wherein the article is selected from injection molded articles, extruded articles, cast extruded articles, shaped extruded articles, melt-spun articles, thermoformed articles, extruded articles, injection blow molded articles, injection stretch blow molded articles, extruded blow molded articles, and extruded stretch blow molded articles.