Copolyester composition with low coefficient of friction

Abstract

Provided are polymer compositions comprising a copolyester comprising 2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) and cyclohexanedimethanol (CHDM) residues that exhibit significantly improved impact toughness and reduced coefficient of friction after modification as compared to unmodified compositions, and that exhibit significantly improved impact toughness and reduced coefficient of friction after modification as compared to non-modified compositions. And meanwhile, physical characteristics such as heat distortion temperature (HDT) and bending modulus are still maintained.

Description

Field of the Invention

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

[0003] 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. Specific copolyesters useful for a wide variety of applications can be formed by reacting a diester composition comprising a dialkyl ester of terephthalic acid with a diol composition comprising a first diol component comprising 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) and a second diol component comprising 1,4-cyclohexanedimethanol (CHDM). 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 utility of these copolyesters and compositions containing the copolyesters as components are varied and are described, for example, in U.S. Pat. Nos. 7,576,171 (pacifiers); 7,951,900 (dialysis filter housings); 7,803,439 (hemotherapy containers); and 8,133,967 (restaurant smallware), the contents and descriptions of which are also incorporated herein by reference and all of which are also assigned to the assignee of the present invention.

[0004] The aforementioned linear copolyesters have achieved tremendous commercial success, in part due to their combination of performance parameters such as toughness, glass transition temperature, density, crystallization rate, melt viscosity and chemical resistance, which provide many benefits to product manufacturers and consumers who purchase these products. However, in the ongoing effort to expand the sale, use and applicability of compositions containing these copolyesters into new markets, polymer manufacturers seek to tailor composition characteristics and parameters to meet product manufacturer specifications in heretofore unexplored product applications.

[0005] Copolyesters based on 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) and cyclohexanedimethanol (CHDM) can have moderate to high surface energies. High surface energies can be advantageous for certain secondary operations (e.g., weldability, coatability, etc.), however polymer articles made from compositions based on such copolyesters can have moderate to high coefficients of friction (COF). Excessively high COFs can render polymer articles unsuitable for certain durable product applications that require repeated material-to-material interactions within a certain range of contact pressures. Manipulation of polymer surface properties, such as coefficient of friction, by incorporation of additives can result in a correspondingly large decrease in other physical properties, or result in trade-offs in base resin properties.

[0006]

[0006] Therefore, a need exists for improved polymer compositions based on TMCD and CHDM having a reduced coefficient of friction without compromising other desirable qualities of the polymer compositions and durable articles made therefrom. Summary of the invention

[0007] The present invention provides a means for reducing the friction of copolyesters containing TMCD and CHDM residues while substantially maintaining or improving processability by incorporating various additives. In one embodiment, the reduction in the coefficient of friction is achieved by incorporating additives including certain waxes and organosilicone while maintaining one or more physical properties. In addition, certain embodiments of the present invention improve the flow length during injection molding while reducing the coefficient of friction.

[0008] Friction-modified, impact-toughened copolyester polymers containing TMCD and CHDM residues exhibit tunable friction profiles comparable to those of conventional engineering polymers such as acrylonitrile-butadiene-styrene polymers (ABS) or polycarbonate, exhibiting similar friction responses (static and dynamic coefficients of friction) over a wide range of contact pressures and part geometries. However, it is noteworthy that physical properties such as heat distortion temperature (HDT) and modulus are maintained after modification, while impact toughness is maintained or improved compared to the unmodified copolyester composition.

[0009] In an embodiment, a polymer composition is provided, comprising a copolyester and one or more additives in an amount sufficient to reduce the coefficient of friction of the polymer composition. The copolyester may comprise: a dicarboxylic acid component comprising terephthalic acid residues and a diol component comprising: 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues; and 1,4-cyclohexanedimethanol (CHDM) residues; an intrinsic viscosity of 0.1 to 1.2 dL / g, as measured at a concentration of 0.5 g / 100 ml in 60 / 40 (weight / weight) phenol / tetrachloroethane at 25°C; and a glass transition temperature (Tg) of 100°C to 200°C. The one or more additives may be selected from waxes and silicones.

[0010] Additives for friction modification may include small molecule waxes to high molecular weight organosilicones. In embodiments, the additive may be incorporated at a loading of 0.1 wt % to 12 wt % depending on the friction additive selected. DETAILED DESCRIPTION

[0011] In a first aspect, the present invention provides a polymer composition comprising:

[0012] (a) a copolyester comprising:

[0013] (i) a dicarboxylic acid component comprising:

[0014] a. 70 to 100 mol % of terephthalic acid residues;

[0015] b. 0 to 30 mol % of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

[0016] c. 0 to 10 mol % of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

[0017] (ii) a diol component comprising:

[0018] a. 10 to 90 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues; and

[0019] b. 10 to 90 mole % of 1,4-cyclohexanedimethanol (CHDM) residues, wherein the total mole % of the dicarboxylic acid component is 100 mole % and the total mole % of the diol component is 100 mole %; and

[0020] wherein the polyester has an intrinsic viscosity of 0.1 to 1.2 dL / g as measured at a concentration of 0.5 g / 100 ml in 60 / 40 (wt / wt) phenol / tetrachloroethane at 25°C; and wherein the polyester has a Tg of 100°C to 200°C; and

[0021] (b) from about 0.1 to about 12 weight percent of a friction additive selected from waxes and silicones; and

[0022] (c) Optionally, 0 to about 15 weight percent of at least one impact modifier.

[0023] As used herein, the term "polyester" is intended to include "copolyesters" and should be 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 hydroxy compounds and / or polyfunctional hydroxy compounds (e.g., branching agents). Typically, the difunctional carboxylic acid can be a dicarboxylic acid, and the difunctional hydroxy compound can be a dihydric alcohol, such as a diol and a diol. The term "diol" as used herein includes, but is not limited to, diols, diols and / or polyfunctional hydroxy compounds, such as branching agents. As used herein, the term "residue" means any organic structure incorporated into a polymer by polycondensation and / or esterification of the corresponding monomers. As used herein, the term "repeat unit" means an organic structure having a dicarboxylic acid residue and a diol residue bonded by an ester group. Thus, for example, a dicarboxylic acid residue can be derived from a dicarboxylic acid monomer or its associated acyl halide, ester, salt, anhydride and / or mixtures thereof. In addition, as used herein, the term "diacid" includes polyfunctional acids, such as branching agents. Thus, as used herein, the term "dicarboxylic acid" is intended to include dicarboxylic acids and any derivatives of dicarboxylic acids, including their associated acyl halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides and / or mixtures thereof, which can be used in the reaction process with diols to prepare polyesters. As used herein, the term "terephthalic acid" is intended to include terephthalic acid itself and its residues, and any derivatives of terephthalic acid, including its associated acyl halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides and / or mixtures thereof, or residues thereof, which can be used in the reaction process with diols to prepare polyesters.

[0024] The polyesters used in the present invention can generally be prepared from dicarboxylic acids and diols, which react in substantially equal proportions and are incorporated into the polyester polymer as their respective residues. Thus, the polyesters of the present invention may contain substantially equal molar proportions of acid residues (100 mole %) and diol (and / or polyfunctional hydroxy compound) residues (100 mole %), such that the total number of moles of repeating units is equal to 100 mole %. Thus, the mole percentages provided in the present invention may be based on the total number of moles of acid residues, the total number of moles of diol residues, or the total number of moles of repeating units.

[0025] In certain embodiments, terephthalic acid or its esters (e.g., dimethyl terephthalate) or a mixture of terephthalic acid residues and their esters may constitute part or all of the dicarboxylic acid component used to form the polyesters useful in the present invention. In certain embodiments, terephthalic acid residues may constitute part 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.

[0026] Can use terephthalic acid ester and other dicarboxylic acids or their corresponding ester and / or salt to replace dicarboxylic acid.Suitable example of dicarboxylic acid ester includes but not limited to dimethyl ester, diethyl ester, dipropyl ester, diisopropyl ester, dibutyl ester and diphenyl ester.In one embodiment, ester is selected from at least one of following: methyl ester, ethyl ester, propyl ester, isopropyl ester and phenyl ester.

[0027] In certain embodiments, the polyester composition comprises a copolyester comprising:

[0028] (a) a dicarboxylic acid component comprising:

[0029] i) 70 to 100 mole % of terephthalic acid residues;

[0030] ii) 0 to 30 mol % of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

[0031] iii) 0 to 10 mol % of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

[0032] (b) a diol component comprising:

[0033] i) 10 to 90 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues; and

[0034] ii) 10 to 90 mole % of 1,4-cyclohexanedimethanol (CHDM) residues, wherein the total mole % of the dicarboxylic acid components is 100 mole % and the total mole % of the diol components is 100 mole %; and

[0035] wherein the polyester has an intrinsic viscosity of 0.1 to 1.2 dL / g as measured at a concentration of 0.5 g / 100 ml in 60 / 40 (wt / wt) phenol / tetrachloroethane at 25°C; and wherein the polyester has a Tg of 100°C to 200°C.

[0036] In embodiments, the polyester composition comprises at least one polyester comprising:

[0037] (a) a dicarboxylic acid component comprising:

[0038] i) 70 to 100 mole % of terephthalic acid residues;

[0039] ii) 0 to 30 mol % of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

[0040] iii) 0 to 10 mol % of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

[0041] (b) a diol component comprising:

[0042] i) 15 to 70 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

[0043] ii) 30 to 85 mole % of 1,4-cyclohexanedimethanol residues, wherein the total mole % of the dicarboxylic acid components is 100 mole % and the total mole % of the diol components is 100 mole %; and

[0044] wherein the polyester has an intrinsic viscosity of 0.35 to 1.2 dL / g as measured at a concentration of 0.5 g / 100 ml in 60 / 40 (wt / wt) phenol / tetrachloroethane at 25°C; and wherein the polyester has a Tg of 100°C to 160°C.

[0045] In embodiments, the polyester composition comprises at least one polyester comprising:

[0046] (a) a dicarboxylic acid component comprising:

[0047] i) 70 to 100 mole % of terephthalic acid residues;

[0048] ii) 0 to 30 mol % of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

[0049] iii) 0 to 10 mol % of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

[0050] (b) a diol component comprising:

[0051] i) 20 to 40 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

[0052] ii) 60 to 80 mole % of 1,4-cyclohexanedimethanol residues, wherein the total mole % of the dicarboxylic acid components is 100 mole % and the total mole % of the diol components is 100 mole %; and

[0053] wherein the polyester has an intrinsic viscosity of 0.35 to 0.85 dL / g as measured at a concentration of 0.5 g / 100 ml in 60 / 40 (wt / wt) phenol / tetrachloroethane at 25°C; and wherein the polyester has a Tg of 100°C to 120°C.

[0054] In embodiments, the polyester composition comprises at least one polyester comprising:

[0055] (a) a dicarboxylic acid component comprising:

[0056] i) 70 to 100 mole % of terephthalic acid residues;

[0057] ii) 0 to 30 mol % of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

[0058] iii) 0 to 10 mol % of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

[0059] (b) a diol component comprising:

[0060] i) 40 to 55 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

[0061] ii) 45 to 60 mole % of 1,4-cyclohexanedimethanol residues, wherein the total mole % of the dicarboxylic acid components is 100 mole % and the total mole % of the diol components is 100 mole %; and

[0062] wherein the polyester has an intrinsic viscosity of 0.35 to 0.85 dL / g as measured at a concentration of 0.5 g / 100 ml in 60 / 40 (wt / wt) phenol / tetrachloroethane at 25°C; and wherein the polyester has a Tg of 120°C to 140°C.

[0063] In embodiments, the polyester composition comprises at least one polyester comprising:

[0064] (a) a dicarboxylic acid component comprising:

[0065] i) 70 to 100 mole % of terephthalic acid residues;

[0066] ii) 0 to 30 mol % of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

[0067] iii) 0 to 10 mol % of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

[0068] (b) a diol component comprising:

[0069] i) 15 to 70 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

[0070] ii) 30 to 85 mole % of 1,4-cyclohexanedimethanol residues, wherein the total mole % of the dicarboxylic acid components is 100 mole % and the total mole % of the diol components is 100 mole %; and

[0071] wherein the polyester has an intrinsic viscosity of 0.35 to 0.85 dL / g as measured at a concentration of 0.5 g / 100 ml in 60 / 40 (wt / wt) phenol / tetrachloroethane at 25°C; and wherein the polyester has a Tg of 100°C to 140°C.

[0072] In embodiments, the polyester composition comprises at least one polyester comprising:

[0073] (a) a dicarboxylic acid component comprising:

[0074] i) 70 to 100 mole % of terephthalic acid residues;

[0075] ii) 0 to 30 mol % of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

[0076] iii) 0 to 10 mol % of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

[0077] (b) a diol component comprising:

[0078] i) 15 to 90 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

[0079] ii) 10 to 85 mole % of 1,4-cyclohexanedimethanol residues, wherein the total mole % of the dicarboxylic acid components is 100 mole % and the total mole % of the diol components is 100 mole %; and

[0080] wherein the polyester has an intrinsic viscosity of 0.1 to 1.2 dL / g as measured at a concentration of 0.5 g / 100 ml in 60 / 40 (wt / wt) phenol / tetrachloroethane at 25°C; and wherein the polyester has a Tg of 100°C to 200°C.

[0081] In embodiments, any of the polyesters or polyester compositions described herein may further comprise the residue of at least one branching agent.In embodiments, any of the polyesters or polyester compositions described herein may comprise at least one thermal stabilizer or a reaction product thereof.

[0082] In embodiments, the polyester composition contains at least one polycarbonate. In other embodiments, the polyester composition does not contain a polycarbonate.

[0083] In embodiments, the polyesters may contain less than 15 mole % ethylene glycol residues, such as 0.01 to less than 15 mole % ethylene glycol residues. In embodiments, the polyesters useful in the present invention contain less than 10 mole %, or less than 5 mole %, or less than 4 mole %, or less than 2 mole %, or less than 1 mole % ethylene glycol residues, such as, for example, 0.01 to less than 10 mole %, or 0.01 to less than 5 mole %, or 0.01 to less than 4 mole %, or 0.01 to less than 2 mole %, or 0.01 to less than 1 mole % ethylene glycol residues. In one embodiment, the polyesters useful in the present invention contain no ethylene glycol residues.

[0084] In an embodiment, the diol component of the polyester may include, but is not limited to, at least one of the following range combinations: 10 to 99 mol % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 90 mol % 1,4-cyclohexanedimethanol; 10 to 95 mol % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 90 mol % 1,4-cyclohexanedimethanol; 10 to 90 mol % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 90 mol % 1,4-cyclohexanedimethanol; 10 to 85 mol % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 90 mol % 1,4-cyclohexanedimethanol; 10 to 80 mol % 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; 10 to less than 50 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater 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 mole % of 1,4-cyclohexanedimethanol; 10 to less than 35 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 65 to a maximum of 90 mole % of 1,4-cyclohexanedimethanol; 10 to 30 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70 to 90 mole % of 1,4-cyclohexanedimethanol; 10 to 25 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 75 to 90 mole % of 1,4-cyclohexanedimethanol; 11 to 25 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75 to 89 mole % 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. ;

[0085] In other embodiments, the diol component of the polyester may include, but is not limited to, at least one of the following range 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.

[0086] In other embodiments, the diol component of the polyester may include, but is not limited to, at least one of the following range 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.

[0087] In other embodiments, the diol component of the polyester may include, but is not limited to, at least one of the following range combinations: 15 to less than 50 mole percent 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50 to a maximum of 85 mole percent 1,4-cyclohexanedimethanol; 15 to 45 mole percent 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55 to 85 mole percent 1,4-cyclohexanedimethanol; 15 to 40 mole percent 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60 to 85 mole percent 1,4-cyclohexanedimethanol; 15 to 35 mole percent 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65 to 85 mol % of 1,4-cyclohexanedimethanol; 15 to 30 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70 to 85 mol % of 1,4-cyclohexanedimethanol; 15 to 25 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75 to 85 mol % of 1,4-cyclohexanedimethanol; 15 to 20 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75 to 80 mol % of 1,4-cyclohexanedimethanol; and 17 to 23 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 77 to 83 mol % of 1,4-cyclohexanedimethanol.

[0088] In other embodiments, the diol component of the polyester may include, but is not limited to, at least one of the following range 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 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 8 0 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.

[0089] In other embodiments, the diol component of the polyester may include, but is not limited to, at least one of the following range 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; and 25 to 30 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70 to 75 mol % of 1,4-cyclohexanedimethanol.

[0090] In other embodiments, the diol component of the polyester may include, but is not limited to, at least one of the following range 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 10 to 70 mol % of 1,4-cyclohexanedimethanol. 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; 30 to less than 50 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater 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.

[0091] In addition to the diols listed above, in certain embodiments, the polyesters may be prepared from 1,3-propylene glycol, 1,4-butanediol, or mixtures thereof. It is contemplated that compositions prepared from 1,3-propylene glycol, 1,4-butanediol, or mixtures thereof may 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 diol or dibasic acid ranges described herein. Additionally or alternatively, polyesters prepared from 1,3-propylene glycol or 1,4-butanediol, or mixtures thereof, may also be prepared from 1,4-cyclohexanedimethanol in at least one of the following amounts: 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 %; and 20 to 25 mol %.

[0092] In certain embodiments, the diol component of the polyester portion of the polyester composition may contain 25 mol % or less of one or more modified diols 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 diols. In another embodiment, the polyester may contain 10 mol % or less of one or more modified diols. In another embodiment, the polyester may contain 5 mol % or less of one or more modified diols. In another embodiment, the polyester may contain 3 mol % or less of one or more modified diols. In another embodiment, the polyester may contain 0 mol % of modified diols. Certain embodiments may also contain 0.01 mol % or more, such as 0.1 mol % or more, 1 mol % or more, 5 mol % or more, or 10 mol % or more of one or more modified diols. Therefore, if present, it is expected that the amount of one or more modified diols may be within the range of any of these aforementioned endpoint values, including, for example, 0.01 to 15 mol % and 0.1 to 10 mol %.

[0093] In an embodiment, the modified diols that can be used for polyesters refer to diols other than 2,2,4,4,-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol, and may contain 2 to 16 carbon atoms. In certain embodiments, examples of suitable modified diols include, but are not limited to, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, p-xylene glycol, or a mixture thereof. In one embodiment, the modified diol is ethylene glycol. In another embodiment, the modified diol is 1,3-propylene glycol and / or 1,4-butanediol. In another embodiment, ethylene glycol is excluded as a modified diol. In another embodiment, 1,3-propylene glycol and 1,4-butanediol are excluded as modified diols. In another embodiment, 2,2-dimethyl-1,3-propylene glycol is excluded as a modified diol.

[0094] In embodiments, the polyester and / or polycarbonate (if included) useful in the polyester composition may contain 0 to 10 mol%, e.g., 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%, based on the total mol% of diol or diacid residues; each containing 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 branching agent may be added before and / or during and / or after the polymerization of the polyester.

[0095] In embodiments, the polyesters may be prepared 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, may be used to prepare the polyesters useful in the present invention.

[0096] In embodiments, the mole percent of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol in certain polyesters is greater than 50 mole percent, or greater than 55 mole percent of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol, or greater than 70 mole percent of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol; wherein the total mole percent of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol and trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol equals a total of 100 mole percent.

[0097] In embodiments, the mole percent of isomers of 2,2,4,4-tetramethyl-1,3-cyclobutanediol in certain polyesters is from 30 to 70 mole percent cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol or from 30 to 70 mole percent trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol, or from 40 to 60 mole percent cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol or from 40 to 60 mole percent trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol, wherein the total mole percent of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol and trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol equals a total of 100 mole percent.

[0098] In certain embodiments, the polyester can be amorphous or semi-crystalline. In one aspect, certain polyesters can have a relatively low degree of crystallinity. Thus, certain polyesters can have a substantially amorphous morphology, meaning that the polyester comprises substantially disordered polymer regions.

[0099] In embodiments, the polyesters and / or polyester compositions may have a unique combination of two or more physical properties, such as high impact strength, moderate to high glass transition temperature, chemical resistance, hydrolytic stability, toughness, low tough-brittle transition temperature, good color and clarity, low density, long crystallization half-life, and good processability, making them easy to shape into articles. In some embodiments, the polyesters may have a unique combination of properties such as good impact strength, heat resistance, chemical resistance, density, and / or a combination of properties such as good impact strength, heat resistance, and processability, and / or a combination of two or more of the properties.

[0100] In embodiments, polyesters may be prepared from dicarboxylic acids and diols that react in substantially equal proportions and are incorporated into polyester polymers as their respective residues. Thus, polyesters may contain substantially equal molar proportions of acid residues (100 mole %) and diol (and / or polyfunctional hydroxy compound) residues (100 mole %) such that the total moles of repeating units are equal to 100 mole %. Thus, the mole percentages provided in the present disclosure 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 30 mole % of isophthalic acid based on total acid residues means that the polyester contains 30 mole % of isophthalic acid residues in a total of 100 mole % of acid residues. Thus, there are 30 moles of isophthalic acid residues in every 100 moles of acid residues. In another example, a polyester containing 30 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol based on total diol residues means that the polyester contains 30 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues out of a total of 100 mole % of diol residues. Thus, there are 30 moles of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues for every 100 moles of diol residues.

[0101] In an embodiment, the Tg of the polyester may be at least one of the following ranges: 100°C to 200°C; 100°C to 190°C; 100°C to 180°C; 100°C to 170°C; 100°C to 160°C; 100°C to 155°C; 100°C to 150°C; 100°C to 145°C; 100°C to 140°C; 100°C to 138°C; 100°C to 135°C; 100°C to 130°C; 100°C to 125°C; 100°C to 120°C; 100°C to 115°C; 100°C to 110°C; 105°C to 200°C; 105°C to 190°C; 105°C to 180°C; 105°C to 170°C; 105°C to 160°C; 105°C to 155°C; 10 5℃ to 150℃; 105℃ to 145℃; 105℃ to 140℃; 105℃ to 138℃; 105℃ to 135℃; 105℃ to 130℃; 105℃ to 125℃; 105℃ to 120℃; 105℃ to 115℃; 105℃ to 110℃ greater than 105℃ to 125℃; greater than 105℃ to 120℃; greater than 105℃ to 115℃; greater than 105℃ to 110℃; 110℃ to 200℃; 110℃ to 190℃; 110℃ to 180℃; 110℃ to 170℃; 110℃ to 160℃; 110℃ to 155℃; 110℃ to 150℃; 110℃ to 145℃; 110℃ to 140℃; 110℃ to 138℃; 110 ℃ to 135℃; 110℃ to 130℃; 110℃ to 125℃; 110℃ to 120℃; 110℃ to 115℃; 115℃ to 200℃; 115℃ to 190℃; 115℃ to 180℃; 115℃ to 170℃; 115℃ to 160℃; 115℃ to 155℃; 115℃ to 150℃; 115℃ to 14 5℃; 115℃ to 140℃; 115℃ to 138℃; 115℃ to 135℃; 110℃ to 130℃; 115℃ to 125℃; 115℃ to 120℃; 120℃ to 200℃; 120℃ to 190℃; 120℃ to 180℃; 120℃ to 170℃; 120℃ to 160℃; 120℃ to 155℃; 1 20℃ to 150℃; 120℃ to 145℃; 120℃ to 140℃; 120℃ to 138℃; 120℃ to 135℃; 120℃ to 130℃; 125℃ to 200℃; 125℃ to 190℃; 125℃ to 180℃; 125℃ to 170℃; 125℃ to 160℃; 125℃ to 155℃; 125℃ to 150℃; 125℃ to 145℃; 125℃ to 140℃; 125℃ to 138℃; 125℃ to 135℃; 127℃ to 200℃; 127℃ to 190℃; 127℃ to 180℃; 127℃ to 170℃; 127℃ to 160℃; 127℃ to 150℃; 127℃ to 145℃; 127℃ to 140℃;127℃ to 138℃; 127℃ to 135℃; 130℃ to 200℃; 130℃ to 190℃; 130℃ to 180℃; 130℃ to 170℃; 130℃ to 160℃; 130℃ to 155℃; 130℃ to 150℃; 130℃ to 145℃; 130℃ to 140℃; 130℃ to 138℃; 130℃ to 135℃; 135℃ to 200℃; 135℃ to 190℃; 135℃ to 180℃; 135℃ to 170℃; 135℃ to 160℃; 135℃ to 155℃; 135℃ to 150℃; 135℃ to 145℃; 135℃ to 140℃; 140℃ to 200℃; 1 40°C to 190°C; 140°C to 180°C; 140°C to 170°C; 140°C to 160°C; 140°C to 155°C; 140°C to 150°C; 140°C to 145°C; 148°C to 200°C; 148°C to 190°C; 148°C to 180°C; 148°C to 170°C; 148°C to 160°C; 148°C to 155°C; 148°C to 150°C; 150°C to 200°C; 150°C to 190°C; 150°C to 180°C; 150°C to 170°C; 150°C to 160°C; 155°C to 190°C; 155°C to 180°C; 155°C to 170°C; and 155°C to 165°C.

[0102] For certain embodiments, the polyester may exhibit at least one of the following intrinsic viscosities as measured at a concentration of 0.5 g / 100 ml in 60 / 40 (wt / wt) phenol / tetrachloroethane at 25° C.: 0.10 to 1.2 dL / g; 0.10 to 1.1 dL / g; 0.10 to 1 dL / g; 0.10 to less than 1 dL / g; 0.10 to 0.98 dL / g; 0.10 to 0.95 dL / g; 0.10 to 0.90 dL / g; 0.10 to 0.85 dL / g; 0.10 to 0.80 dL / g; 0.10 to 0.75 dL / g; 0.10 to less than 0.75 dL / g; 0.10 to 0.72 dL / g; 0.10 to 0.70 dL / g g; 0.10 to less than 0.70 dL / g; 0.10 to 0.68 dL / g; 0.10 to less than 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; 0.20 to less than 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; 0.20 to less than 0.75 dL / g; 0.20 to 0.72 dL / g; 0.20 to 0.70 dL / g; 0.20 to less than 0. 70 dL / g; 0.20 to 0.68 dL / g; 0.20 to less than 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; 0.35 to less than 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; 0.35 to less than 0.75 dL / g; 0.35 to 0.72 dL / g; 0.35 to 0.70 dL / g; 0.35 to less than 0.70 dL / g; 0.35 to 0.68 dL / g; 0.35 to less than 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; 0.40 to less than 1 dL / g; 0.40 to 0.98 dL / g; 0.40 to 0.95 dL / g; 0.40 to 0. 90dL / g; 0.40 to 0.85dL / g; 0.40 to 0.80dL / g; 0.40 to 0.75dL / g; 0.40 to less than 0.75dL / g; 0.40 to 0.72dL / g; 0.40 to 0.70dL / g; 0.40 to less than 0.70dL / g; 0.40 to 0.68dL / g; 0.40 to less than 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.

[0103] For certain embodiments, the polyester may exhibit at least one of the following inherent viscosities as measured at a concentration of 0.5 g / 100 ml in 60 / 40 (weight / weight) phenol / tetrachloroethane at 25° C.: 0.45 to 1.2 dL / g; 0.45 to 1.1 dL / g; 0.45 to 1 dL / g; 0.45 to 0.98 dL / g; 0.45 to 0.95 dL / g; 0.45 to 0.90 dL / g; 0.45 to 0.85 dL / g; 0.45 to 0.80 dL / g; 0.45 to 0.75 dL / g; 0.45 to less than 0.75 dL / g; 0.45 to 0.72 dL / g; 0.45 to 0.70 dL / g; 0.45 to less than 0.7 0dL / g; 0.45 to 0.68dL / g; 0.45 to less than 0.68dL / g; 0.45 to 0.65dL / g; 0.50 to 1.2dL / g; 0.50 to 1.1dL / g; 0.50 to 1dL / g; 0.50 to less than 1dL / g; 0.50 to 0.98dL / g; 0.50 to 0.95dL / g; 0.50 to 0.90dL / g; 0.50 to 0.85dL / g; 0.50 to 0.80dL / g; 0.50 to 0.75dL / g; 0.50 to less than 0.75dL / g; 0.50 to 0.72dL / g; 0.50 to 0.70dL / g; 0.50 to less than 0.70dL / 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; 0.58 to less than 0.68dL / g; 0.58 to 0.65dL / g; 0.60 to 1.2dL / g; 0.60 to 1.1dL / g; 0.60 to 1dL / g; 0.60 to less than 1dL / g; 0.60 to 0.98dL / g; 0.60 to 0.95dL / g; 0.60 to 0.90dL / g; 0.60 to 0.85dL / g; 0.60 to 0.80dL / g; 0.60 to 0.75dL / g; 0.60 to less than 0.75dL / g; 0.60 to 0.72dL / g; 0.60 to 0.70dL / g; 0.60 to less than 0.70dL / g; 0.60 to 0.68dL / g L / g; 0.60 to less than 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; 0.65 to less than 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; 0.65 to less than 0.75 dL / g; 0.65 to 0.72 dL / g; 0.65 to 0.70 dL / g; 0.65 to less than 0.70 dL / g g; 0.68 to 1.2 dL / g; 0.68 to 1.1 dL / g; 0.68 to 1 dL / g; 0.68 to less than 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; 0.68 to less than 0.75 dL / g; 0.68 to 0.72 dL / g; greater than 0.76 dug 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 1dL / g; greater than 0.76dL / g to 0.98dL / g; greater than 0.76dL / g to 0.95dL / g; greater than 0.76dL / g to 0.90dL / g; greater than 0.80dL / g to 1.2dL / g; greater than 0.80dL / g to 1.1dL / g; greater than 0.80dL / g to 1dL / g; greater than 0.80dL / g to less than 1dL / g; greater than 0.80dL / g to 1.2dL / g; greater than 0.80dL / g to 0.98dL / g; greater than 0.80dL / g to 0.95dL / g; greater than 0.80dL / g to 0.90dL / g. .

[0104] In certain embodiments, unless otherwise stated, it is contemplated that the polyester composition may have at least one of the intrinsic viscosity ranges described herein and at least one of the monomer ranges for the composition described herein. Unless otherwise stated, it is also contemplated that the polyester composition may have at least one of the Tg ranges described herein and at least one of the monomer ranges for the composition described herein. Unless otherwise stated, it is also contemplated that the polyester composition may 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 for the composition described herein.

[0105] In embodiments, the molar ratio of cis / trans 2,2,4,4-tetramethyl-1,3-cyclobutanediol may vary depending on the respective pure forms or mixtures thereof. In certain embodiments, the mole percentage of cis and / or trans 2,2,4,4,-tetramethyl-1,3-cyclobutanediol is greater than 50 mole % cis and less than 50 mole % trans; or greater than 55 mole % cis and less than 45 mole % trans; or 30 to 70 mole % cis and 70 to 30% trans; or 40 to 60 mole % cis and 60 to 40 mole % trans; or 50 to 70 mole % trans and 50 to 30% cis or 50 to 70 mole % cis and 50 to 30% trans; or 60 to 70 mole % cis and 30 to 40 mole % trans; or greater than 70 mole % cis and less than 30 mole % trans; wherein the sum of the mole percentages of cis and trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol is equal to 100 mole %. The molar ratio of cis / trans 1,4-cyclohexanedimethanol may vary within the range of 50 / 50 to 0 / 100, such as between 40 / 60 and 20 / 80.

[0106] In certain embodiments, terephthalic acid or its ester (such as dimethyl terephthalate) or a mixture of terephthalic acid and its ester constitutes most or all of the dicarboxylic acid component for forming polyester. In certain embodiments, terephthalic acid residues may constitute a part or all of the dicarboxylic acid component for forming polyester, and the concentration of terephthalic acid residues is at least 70 mol%, such as at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol% or 100 mol%. In certain embodiments, a larger amount of terephthalic acid can be used to produce a polyester with higher impact strength. In one embodiment, dimethyl terephthalate is a part or all of the dicarboxylic acid component for preparing polyesters that can be used in the present invention. For the purpose of this disclosure, the reference to the residues of "terephthalic acid" and "dimethyl terephthalate" can be used interchangeably herein. For example, the reference to the polymer residues of terephthalic acid (TPA) also includes the polymer residues derived from dimethyl terephthalate (DMT). In all embodiments, a range of 70 to 100 mole %; or 80 to 100 mole %; or 90 to 100 mole %; or 99 to 100 mole %; or 100 mole % of terephthalic acid and / or dimethyl terephthalate and / or mixtures thereof may be used.

[0107] In addition to terephthalic acid, in certain embodiments, the dicarboxylic acid component of polyester may also include up to 30 mol %, up to 20 mol %, up to 10 mol %, up to 5 mol % or up to 1 mol % of one or more modified aromatic dicarboxylic acids. Another embodiment contains 0 mol % of modified aromatic dicarboxylic acids. Therefore, if present, it is expected that the starting value of the range of the amount of one or more modified aromatic dicarboxylic acids may be any one of these front end values, including, for example, 0.01 to 30 mol %, 0.01 to 20 mol %, 0.01 to 10 mol %, 0.01 to 5 mol % and 0.01 to 1 mol %. In one embodiment, the modified aromatic dicarboxylic acids that can be used include but are not limited to those with up to 20 carbon atoms, and may be linear, para-oriented or symmetrical. Examples of modified aromatic dicarboxylic acids that may be used include, but are not limited to, isophthalic acid, 4,4'-biphenyl dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, and trans-4,4'-stilbene dicarboxylic acid and esters thereof. In one embodiment, the modified aromatic dicarboxylic acid is isophthalic acid.

[0108] In embodiments, the carboxylic acid component of polyester can be further modified with up to 10 mol %, for example up to 5 mol % or up to 1 mol % of one or more aliphatic dicarboxylic acids containing 2-16 carbon atoms such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and dodecanedioic acid dicarboxylic acid. Some embodiments can also include 0.01 mol % or more, such as 0.1 mol % or more, 1 mol % or more, 5 mol % or more or 10 mol % or more of one or more modified aliphatic dicarboxylic acids. Another embodiment contains 0 mol % of modified aliphatic dicarboxylic acids. Therefore, if present, it is expected that the starting value of the range of the amount of one or more modified aliphatic dicarboxylic acids can be any one of these front end values, including for example 0.01 to 10 mol % and 0.1 to 10 mol %. The total mole % of dicarboxylic acid component is 100 mol %.

[0109] Can use terephthalic acid ester and other modified dicarboxylic acids or their corresponding ester and / or salt to replace dicarboxylic acid.Suitable example of dicarboxylic acid ester includes but not limited to dimethyl ester, diethyl ester, dipropyl ester, diisopropyl ester, dibutyl ester and diphenyl ester.In one embodiment, ester is selected from at least one of following: methyl ester, ethyl ester, propyl ester, isopropyl ester and phenyl ester.

[0110] In embodiments of polyesters containing CHDM, 1,4-cyclohexanedimethanol may be cis, trans, or mixtures thereof, such as in a cis / trans ratio of 60:40 to 40:60. In one embodiment, trans-1,4-cyclohexanedimethanol may be present in an amount of 60 to 80 mole percent.

[0111] In embodiments, the polyesters may be linear or branched. In embodiments, the polycarbonates (if included) may also be linear or branched. In certain embodiments, branching monomers or branching agents may be added before and / or during and / or after polymerization of the polycarbonate.

[0112] Examples of branching monomers include, but are not limited to, polyfunctional acids or polyfunctional alcohols such as trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, glycerol, pentaerythritol, citric acid, tartaric acid, 3-hydroxyglutaric acid, and the like. In one embodiment, the branching monomer residues may comprise 0.1 to 0.7 mole percent of one or more residues selected from at least one of trimellitic anhydride, pyromellitic dianhydride, glycerol, sorbitol, 1,2,6-hexanetriol, pentaerythritol, trimethylolethane, and / or trimesic acid. The branching monomers may be added to the polyester reaction mixture or blended with the polyester in the form of a concentrate, such as described in U.S. Pat. Nos. 5,654,347 and 5,696,176, the disclosures of which regarding branching monomers are incorporated herein by reference.

[0113] The glass transition temperature (Tg) of the polyester can be measured using a TA DSC2920 from Thermal Analyst Instrument at a scanning rate of 20°C / min.

[0114] The long crystallization half-life at 170° C. (e.g., greater than 5 minutes) exhibited by certain polyesters can be beneficial for the production of certain injection molded, compression molded, and solution cast articles. The polyesters can be amorphous or semi-crystalline. In one aspect, certain polyesters can have a relatively low degree of crystallinity. Thus, certain polyesters can have a substantially amorphous morphology, meaning that the polyester comprises substantially disordered polymer regions.

[0115] In one embodiment, the "amorphous" polyester may have a crystallization half-time of greater than 5 minutes at 170°C, or greater than 10 minutes at 170°C, or greater than 50 minutes at 170°C, or greater than 100 minutes at 170°C. In one embodiment of the present invention, the crystallization half-time is greater than 1,000 minutes at 170°C. In another embodiment of the present invention, the crystallization half-time of the polyester useful in the present invention is greater than 10,000 minutes at 170°C. The crystallization half-time of the polyester as used herein can be measured using methods well known to those skilled in the art. For example, the crystallization half-time of the polyester t 1 / 2 It can be determined by measuring the light transmittance of a sample over time on a temperature-controlled hot stage using a laser and a photodetector. This measurement can be performed by exposing the polymer to a temperature T max This is done by heating the sample to a temperature of 100 °C and then cooling it to the desired temperature. The sample can then be held at the desired temperature by a hot stage while transmittance measurements are taken over time. Initially, the sample may be visually transparent with high light transmittance, but becomes opaque as the sample crystallizes. The crystallization half-life is the time it takes for the light transmittance to be halfway between the initial transmittance and the final transmittance. max Defined as the temperature required to melt the crystalline domains of the sample (if any). The sample can be heated to T max , in order to condition the samples before crystallization half-time measurements. The absolute T for each composition max The temperature is different. For example, PCT may have to be heated to a temperature above 290°C to melt the crystalline domains.

[0116] In embodiments, certain polyesters are visually transparent. The term "visually transparent" is defined herein as being significantly free of turbidity, haziness, and / or turbidity when visually inspected. In one embodiment, when the polyester is blended with a polycarbonate (including bisphenol A polycarbonate), the blend may be visually transparent. In embodiments, the polyester may have one or more properties described herein. In embodiments, the polyester may have a yellowness index (ASTM D-1925) of less than 50, such as less than 20.

[0117] The copolyester portion of the polymer composition of the present invention can be prepared by methods known in the literature, such as, for example, by methods in homogeneous solution, by transesterification methods in the melt, and by two-phase interface methods. Suitable methods include, but are not limited to, reacting one or more dicarboxylic acids with one or more diols at a temperature of 100° C. to 315° C., at a pressure of 0.1 to 760 mmHg, for a time sufficient to form polyesters. For methods of producing polyesters, see U.S. Pat. No. 3,772,405, the disclosure of which is hereby incorporated by reference herein.

[0118] Generally, the copolyester can be prepared by a process comprising: (I) heating a mixture comprising monomers of any polyester useful in the present invention at a temperature of 150°C to 240°C for a time sufficient to produce an initial polyester in the presence of a catalyst; (II) heating the initial polyester of step (I) at a temperature of 240°C to 320°C for 1 to 4 hours; and (III) removing any unreacted diol.

[0119] Catalysts suitable for use in the process include, but are not limited to, organozinc or tin compounds. The use of catalysts of this type is well known in the art. Examples of catalysts that can be used in the present invention include, but are not limited to, zinc acetate, butyltin tri-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 the catalyst may be based on the catalyst metal and based on the weight of the final polymer in the range of 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. The process may be performed in an intermittent or continuous process.

[0120] Typically, step (I) may be performed until 50 weight percent or more of the 2,2,4,4-tetramethyl-1,3-cyclobutanediol has reacted. Step (I) may be performed at a pressure ranging from atmospheric pressure to 100 psig. The term "reaction product" used in conjunction with any catalyst useful in the present invention refers to any product of a polycondensation or esterification reaction using the catalyst and any monomer used to prepare polyesters, as well as the product of a polycondensation or esterification reaction between the catalyst and any other type of additive.

[0121] Typically, step (II) and step (III) can be performed simultaneously. These steps can be performed by methods known in the art, such as by placing the reaction mixture under a pressure ranging from 0.002 psig to below atmospheric pressure, or by blowing hot nitrogen over the mixture.

[0122] In an embodiment, the polyester composition can be a polymer blend, wherein the blend comprises: (a) 5 to 95 weight percent of at least one polyester described herein; and (b) 5 to 95 weight percent of at least one polymer component. Suitable examples of polymer components include, but are not limited to, nylon, polyesters other than those described herein, polyamides (such as nylon 9000 from DuPont), ... ); polystyrene, polystyrene copolymers, styrene acrylonitrile copolymers, acrylonitrile butadiene styrene copolymers, poly(methyl methacrylate), acrylic acid copolymers, poly(ether-imides) such as ULTEM TM Resin (poly(ether-imide) from SABIC); polyphenylene ether such as poly(2,6-dimethylphenylene ether) or poly(phenylene ether) / polystyrene blends such as NORYL TM resin (a blend of poly(2,6-dimethylphenylene oxide) and polystyrene resin from SABIC); polyphenylene sulfide; polyphenylene sulfide / sulfone; poly(ester-carbonate); polycarbonates such as (polycarbonate from SABIC); polysulfone; polysulfone ether; and poly(ether-ketone) of aromatic dihydroxy compounds; or any other mixture of the foregoing polymers. The blends can be prepared by conventional processing techniques known in the art, such as melt blending or solution blending. In one embodiment, polycarbonate is not present in the polyester composition. If polycarbonate is used in a blend useful in the polyester composition of the present invention, the blend can be visually transparent. However, the polyester composition useful in the present invention also contemplates the exclusion of polycarbonate as well as the inclusion of polycarbonate.

[0123] In addition to additives and optional impact modifiers (as discussed herein), the polyester compositions and polymer blend compositions may also contain additional additives selected from antioxidants, heat stabilizers, mold release agents, antistatic agents, brighteners, colorants, flow aids, processing aids, plasticizers, anti-fog 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 from 0.01% to 25% of common additives such as colorants, dyes, mold release agents, flame retardants, plasticizers, nucleating agents, stabilizers (including but not limited to UV stabilizers, heat stabilizers and / or reaction products thereof), and fillers, based on the weight of the overall composition. For example, UV additives may be incorporated into the article, for example, by addition to the body or hardcoat.

[0124] In some embodiments, during the preparation of the polyesters useful in the present invention, certain agents that color the polymers may be added to the melt, including toners or dyes. In one embodiment, a bluing toner is added to the melt to adjust the b* of the resulting polyester polymer melt phase product. Such bluing agents include blue inorganic and organic toners and / or dyes. In addition, red toners and / or dyes may also be used to adjust the a* color. In one embodiment, the polymers or polymer blends useful in the present invention and / or the polymer compositions of the present invention (with or without toners) may have color values ​​L*, a*, and b* that can be measured using a HunterLab Ultrascan Spectra Colorimeter manufactured by Hunter Associates Lab Inc., Reston, Va. The color measurement result is the average of the values ​​measured for the pellets or powder of the polymer or the plaques or other articles thereof that are injection molded or extruded. They are measured by the L*a*b* color system of CIE (International Commission on Illumination) (translation), where L* represents the photometric coordinate, a* represents the red / green coordinate, and b* represents the yellow / blue coordinate. Organic toners, for example, blue and red organic toners, such as those 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 toners can be fed as a premixed composition. The premixed composition can be a neat blend of the red and blue compounds, or the composition can be pre-dissolved or slurried in one of the polyester raw materials (e.g., ethylene glycol).

[0125] The total amount of toner components added may depend on the amount of inherent yellow 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 may be used. In one embodiment, the total amount of bluing additive may be in the range of 0.5 to 10 ppm. In one embodiment, the toner may be added to the esterification zone or the polycondensation zone. Advantageously, the toner is added to the esterification zone or to the early stages of the polycondensation zone, such as to the prepolymerization reactor or to the extruder or calender during processing.

[0126] In an embodiment, the polyester may include at least one chain extender. Suitable chain extenders include, but are not limited to, multifunctional (including but not limited to difunctional) isocyanates, multifunctional epoxides (including, for example, epoxidized phenolic resins), and phenoxy resins. In certain embodiments, the chain extender may be added at the end of the polymerization process or after the polymerization process. If added after the polymerization process, the chain extender may be incorporated by compounding or by addition during a conversion process such as injection molding or extrusion. The amount of chain extender used may vary depending on the specific monomer composition used and the desired physical properties, but is typically 0.1 weight percent to 10 weight percent, such as 0.1 to 5 weight percent, based on the total weight of the polyester.

[0127] Heat stabilizers are compounds that stabilize polyesters during polyester manufacturing and / or post-polymerization processes, including but not limited to phosphorus compounds, including but not limited to phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphous acid, and various esters and salts thereof. 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 a maximum value that can be allowed based on the number of hydroxyl groups present on the heat stabilizer used. The term "heat stabilizer" is intended to include its reaction products. The term "reaction product" used in conjunction with the heat stabilizer of the present invention refers to any product of a polycondensation or esterification reaction between a heat stabilizer and any monomer used to prepare polyester, as well as a product of a polycondensation or esterification reaction between a catalyst and any other type of additive. In an embodiment, these may be present in a polyester composition.

[0128] In embodiments, reinforcing materials can be used for polyester compositions. Reinforcing materials can include, but are not limited to, carbon filaments, silicates, mica, clay, talc, titanium dioxide, wollastonite, glass flakes, glass beads and fibers and polymer fibers and combinations thereof. In one embodiment, reinforcing materials are glass, such as fiberglass filaments, a mixture of glass and talc, a mixture of glass and mica, and a mixture of glass and polymer fibers.

[0129] In another embodiment, the present invention also relates to an article comprising any of the polyesters and blends described herein. In an embodiment, the article can be an extruded article, a calendered article and / or a molded article, including but not limited to injection molded articles, extruded articles, cast extruded articles, profile extruded articles, melt-spun articles, thermoformed articles, extrusion molded articles, injection blow molded articles, injection stretch blow molded articles, extrusion blow molded articles, and extrusion stretch blow molded articles. These articles can include but are not limited to films, bottles (including but not limited to baby bottles), containers, sheets and / or fibers.

[0130] In an embodiment, the article may be intended for use in applications where the article (or a component thereof) has surface-to-surface contact (with another article or component) where movement is expected to occur at the surface contact, for example, the surfaces are expected to slide against each other. Such applications may include articles, parts or components that are releasably connected to each other (e.g., connected by friction). Examples of such applications may include durable articles or toys (e.g., puzzle toys) having articles, parts or components that interact when used as described above. In an embodiment, the polyester composition or an article made therefrom may be an application currently made of ABS plastic (e.g., a common toy, electronic product, or medical device). Other examples of articles may include transparent or opaque food contact applications, for example, food containers, lids, bottles (including sports bottles and lids) and fasteners and hinges thereof, including fastener and hinge integrated components and / or assemblies.

[0131] In embodiments, the copolyester and / or polyester blend compositions can be used to form fibers, films, molded articles, containers, and sheets. Methods of molding polyesters into fibers, films, molded articles, containers, and sheets are well known in the art. Examples of possible molded articles include, but are not limited to, medical devices (such as dialysis equipment), medical packaging, health care products, commercial food service products (such as food trays, cups, and storage boxes), baby bottles, food processors, blenders and mixing bowls, tableware, water bottles, crisper trays, toys, washing machine fronts, and vacuum cleaner parts.

[0132] In another embodiment, the present invention is also directed to articles comprising films and / or sheets comprising the polyester compositions described herein.

[0133] Films and / or sheets useful for the present invention may have any thickness that will be apparent to one of ordinary skill in the art. In one embodiment, the film of the present invention has a thickness of no more than 40 mils. In one embodiment, the film of the present invention has a thickness of no more than 35 mils. In one embodiment, the film of the present invention has a thickness of no more than 30 mils. In one embodiment, the film of the present invention has a thickness of no more than 25 mils. In one embodiment, the film of the present invention has a thickness of no more than 20 mils.

[0134] In an embodiment, the (friction) additive may be selected from a wide variety of waxes and silicones. Waxes that can be used in the polymer composition of the present invention may include known higher alkanes and lipids, which are lipophilic, ductile solids at room temperature (i.e., 23° C.). Natural waxes are found in plants and animals, and are also found in petroleum products. In one embodiment, the wax is a mixture of saturated alkanes, naphthenes, and alkyl and cycloalkane-substituted aromatic compounds. In another embodiment, the wax may be a montan wax extracted from certain coal and lignite sources. In another embodiment, the wax may be a polyolefin or polyethylene wax (polyalkylene wax). Naturally occurring waxes may include beeswax, primarily beeswax palmitate, cetyl palmitate, lanolin, carnauba wax, or rice bran wax.

[0135] In an embodiment, the siloxane may be a compound containing Si-O-Si bonds. Examples include compounds having the structures H(OSiH2)nOH and (OSiH2)n. In other embodiments, the siloxane may be an organosilicon or polysiloxane having the structure (-RSi-O-SiR-), where R is an organic group, such as an alkyl or aryl group. Examples of such polysiloxanes are polydimethylsiloxane or "PDMS" and polydiphenylsiloxane.

[0136] Commercially available examples of waxes and silicones may include Genioplast S, a pelletized silicone gum formulation from Wacker Chemie AG; Tegomer H-Si (e.g., H-Si 6441P) (polyester-modified silicone), Tegomer V-Si (e.g., V-Si 4042) (vinyl-terminated organic modified silicone (OMS)), Tegomer M-Si (e.g., M-Si 2650) (aryl-terminated OMS), Tegomer E-Si (e.g., E-Si 2330) (epoxy-terminated OMS) or Tegomer DA 800 (copolyester dispersion), all from Evonik Industries AG; MCR-E21 or ECMS-227 functionalized silicones from Gelest; Dowsil T MSi powder resin modifier or DowSil 4-7081 from Dow Chemical Company; Loxiol P or P861, polyol esters from Emery Oleochemicals GmbH; Modiper 1401, 4300 or 4400 (polyethylene-based (graft) copolymers) from Nippon Oil & Fat Corporation; A-C Wax 307, 316 or 325 (polyethylene polymer powder) from Honeywell; Licowax OP, E, PED191, 371FP or WE 40 from Clariant; Hystrene (fatty acid) from PMC Group; Licocare RBW 101, 102, 106, 300, 330, 360 Vita and Ceridust 1060 and 1041TP Vita from Clariant; repellent polymer PM-870 or FX 5911 (fluorochemical 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 other functions to the copolyester resin. For example, Modiper 4300 and 4400 can also be used as impact modifiers.

[0137] The waxes and silicones used as component (b) above are generally present in an amount of about 0.1 to about 12 weight percent. 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 polyester composition. In an embodiment, component (b) additive comprises a 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 %, 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 %.

[0138] In an embodiment, component (b) additive comprises 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%, based on the total weight of the polyester composition. %, or 3 to 9 weight %, or 3 to 8 weight %, or 4 to 12 weight %, or 4 to 11 weight %, or 4 to 10 weight %, or 4 to 9 weight %, or 4 to 8 weight %, or 5 to 12 weight %, or 5 to 11 weight %, or 5 to 10 weight %, or 5 to 9 weight %, or 5 to 8 weight %, or 6 to 12 weight %, or 6 to 11 weight %, or 6 to 10 weight %, or 6 to 9 weight %, or 6 to 8 weight %.

[0139] About optional component (c) impact modifier, such compound is usually elastomeric compound or polymer, it is used to absorb or dissipate the kinetic energy of impact. Wide variety of materials can be used for optional component (c). Examples of impact modifiers can be those including at least one functional group capable of reacting with at least one end group of 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 may include at least one monomer selected from the group consisting of olefins, dienes, aromatic hydrocarbons, acrylates and alcohols. (See, for example, EP 1,694,771B1). An example includes core-shell polymers, wherein the core is composed of rubbery polymers and the shell is composed of styrene copolymers (see, for example, U.S. Patent No. 5,321,056, which is incorporated herein by reference.) Other examples include core-shell and functional polyolefins, such as those described in US2014 / 0256848A1 incorporated herein by reference. See also EP 2139 948 B1.

[0140] In embodiments, examples of commercially available impact modifiers may include, but are not limited to, ethylene / propylene terpolymers; functionalized polyolefins such as those containing methyl acrylate and / or glycidyl methacrylate; styrene-based block copolymer impact modifiers; and various acrylic core / shell impact modifiers. Residues of such additives are also contemplated as being part of the polyester composition.

[0141] It should also be noted that certain friction additives may also function as impact modifiers. Thus, in certain embodiments, it is contemplated that an additive identified as a friction additive may be included as an impact modifier in addition to one of the other identified friction additives. For example, Modiper 4300 may be used as an impact modifier and may be added with a wax additive such as Licowax OP, wherein Licowax OP is a component (b) additive and Modiper 4300 is an optional component (c) additive.

[0142] Commercially available examples may include:

[0143] 4300 and 4400, available from Nippon Oil & Fat Corporation;

[0144] Kane M300, available from Kaneka Americas Holding, Inc.;

[0145] Kane B564, available from Kaneka Americas Holding, Inc.;

[0146] Kane ECO 1000, available from Kaneka Americas Holding, Inc.;

[0147] Kane MR02, available from Kaneka Americas Holding, Inc.;

[0148] Kane MR03, available from Kaneka Americas Holding, Inc.; and

[0149] 8900, available from Arkema.

[0150] Impact modifiers used as the optional component (c) described above are typically present in an amount of 0 to about 12 weight percent. In other embodiments, they are present in an amount of 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 0 to less than 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.

[0151] The present invention can be further illustrated by the following examples or preferred embodiments thereof, but it should be understood that these examples are included for illustrative purposes only and are not intended to limit the scope of the present invention unless otherwise specifically stated.

[0152] Experimental Section

[0153] Part 1. Base resin testing

[0154] A series of tests were performed on several commercially available resins. This test was designed to benchmark the performance of copolyester compositions with respect to physical properties and friction performance.

[0155] Physical properties typically reported in the Technical Data Sheet (TDS) were evaluated using injection molded tensile or flexural bars using established test methods as defined by ASTM. For commercially available resins, molding was performed using the drying and processing conditions reported on the Technical Data Sheet. For modified resins, the processing conditions used were selected using the processing conditions of the base resin.

[0156] Multiple tests were completed on all samples and modified resins as detailed in Section 3 below. These test methods are broken down as follows:

[0157] Specific physical properties are usually found on technical data sheets. Specific tests include tensile properties (ASTM D638), flexural properties (ASTM D790), notched Izod impact properties (ASTM D256), and heat deformation properties (ASTM D648). In all cases, commercial resins and modified resins follow standard conditioning and testing protocols.

[0158] The friction profile of the base resin is reported as static and dynamic coefficients of friction (μ s and μ k ). These values ​​were measured using a Bruker Tribometer by intentionally contacting the surface of a pair of 4"x4"x1 / 8" plates produced using injection molding. Gloves were worn at all times to avoid direct contact with the test specimens to avoid contaminating the friction data measurements. Once molded, the coefficient of friction was measured using a pair of plates according to the following definition:

[0159] ○Static COF(μ s ), the contact force between the two plates (F z ) and the relative velocity between the two contacting plates (v x ) are close to zero, for example:

[0160] ■F z =0.05N,v x =0.01mm / s

[0161] ○ Dynamic COF(μ k ), defined as the friction force measured between two contacting plates at constant force and relative velocity, e.g.:

[0162] ■F z =3.00N, v x =10.0mm / s

[0163] A summary of the commercial resins evaluated as "control" or "counter" examples is shown in Table 1 below.

[0164] Table 1. Summary of “control” or “comparative” materials evaluated

[0165]

[0166]

[0167] A summary of the physical properties of the control / comparative materials is shown in Table 2 below.

[0168]

[0169] Review of the physical property data in Table 2 reveals that resins C-01 and C-02 (ABS and polycarbonate (PC), respectively) exhibit higher stiffness in tensile and flexural modulus than all other materials evaluated. In addition to modulus, resin C-03 (a cellulosic material) exhibits similar tensile properties compared to C-01, as well as impact toughness of similar magnitude as measured by notched Izod testing. Resins C-06, C-07, C-09, and C-10 have significantly lower toughness than C-01, while resins C-04, C-05, and C-08 have the lowest stiffness of the commercial resins evaluated.

[0170] The friction properties of the materials in Table 1 were evaluated to quantify the static and kinetic friction coefficients (μ s and μ k ). The coefficient of friction (COF) values ​​are listed in Table 3 below.

[0171] Table 3. Summary of friction characteristics:

[0172]

[0173] Inspection of Table 3 shows that C-01 (ABS) and C-02 (PC) have similar friction profiles when measured according to a skateboard-type test, referring to the coefficient of static friction and the coefficient of dynamic friction (Table 3). In addition, resin C-01 provides lower friction performance than all of the resins evaluated. Therefore, in order to achieve the functionality of applications that previously used ABS materials and required similar friction behavior, it will be necessary to modify the friction performance of other resins (e.g., C-03 to C-10) to match the performance of C-01 in the friction test, while still maintaining (or not significantly reducing) the physical properties, most notably stiffness and impact toughness, compared to the unmodified base resin.

[0174] Part 2. Modification

[0175] Modified development samples were generated using twin screw compounding and various additives to modify properties, most notably by incorporating various additives to modify the friction profile. These additives can vary in chemistry, ranging from short chain molecules (e.g., waxes) to high molecular weight or ultra-high molecular weight organosiloxanes (e.g., PDMS). In the composite formulations, it was found that the additives could act as internal and / or external lubricants, depending on the specific additive chemistry, molecular weight, loading level, and function. The additives used are listed in Table 4 below.

[0176] Table 4. Additives used to modify resins

[0177] sample additive T-01 Tegomer H-Si 6441 P T-02 Tegomer V-Si 4042 T-03 Tegomer M-Si 2650 T-04 Tegomer E-Si 2330 T-05 Tegomer DA 800 T-06 Modiper 1401 T-07 Modiper 4300 T-08 Modiper 4400 T-09 DowSil 4-7081 T-10 AC Wax 307 T-11 AC Wax 316 T-12 AC Wax 325 T-13 Loxiol P T-14 3M PM-870 T-15 Not used T-16 Licowax OP T-17 Hystrene 5016 T-18 Licowax E T-19 Licowax PED191 T-20 Licowax 371 FP T-21 Licowax WE 40 T-22 Licowax E / WE 40 T-23 FX 5911 T-24 Incroslip T-25 Incromax 100 T-26 Genioplast S

[0178] In addition to the above additives, other additives that may be incorporated into potential formulations are additives specifically designed to modify impact toughness. Additives for impact modification are typically incorporated at loading levels below 15 wt. % and cover a variety of chemistries and forms including: core-shell, branched, reactive, MBS, acrylic, EGMA, etc. A non-exhaustive summary of potential impact modifiers that may be used with the above modifiers is discussed herein above.

[0179] Part 3. Examples

[0180] Various copolyester samples containing TMCD and CHDM were produced by modification with friction additives, such as Eastman Tritan TM TX1500 copolyester (sample C-04, but without mold release additive), Eastman Tritan TM TX1000 copolyester (Sample C-08). Physical properties were measured before and after the heat aging protocol. The friction performance of each formulation was also evaluated using a tribometer (as discussed above). The results are reported in the table below, which summarizes the performance of the modified formulations compared to the control examples.

[0181] Table 5 summarizes the specific compositions of the formulations TX-01 to TX-09 evaluated in this study, including the friction additives, compared to the control or comparative examples. TM The "base resin" used in the sample is Tritan TM TX1500 (C-04 without mold release additive) and Tritan TM TX1000(C-08), but the experience of this study will help understand other TMCD and CHDM base resins (e.g., Tritan TM The usage of TX1001, TX1501, TX2001, TX3001).

[0182] Table 5. Exemplary formulations evaluated

[0183]

[0184]

[0185]

[0186] The physical properties and performance of TX1500, TX1000 and TX1001 exemplary resins are measured according to the procedures and test methods previously mentioned for all control, comparative and / or commercial resins in Table 5. Spiral flow results are also provided to evaluate the flow characteristics caused by the addition of friction reducing additives. The spiral flow measurement was performed on a Boy22A Pro 22-ton reciprocating screw injection molding machine using the following conditions. The flow length ratio (L / t) was calculated by dividing the spiral flow length (L) by the cavity thickness (t). About 15 injection cycles were discarded to allow the process to reach equilibrium, after which at least 10 repeated measurements were collected and averaged. Before entering the spiral flow cavity, the spiral flow mold was fed through a 2.25" gate with a diameter of 0.28". No demolding spray was used. All resins were vacuum dried overnight at 60°C before molding. The molding conditions for the spiral flow test are listed in Table 5A below.

[0187] Table 5A - Spiral Flow Molding Conditions

[0188]

[0189] A summary of the physical properties including tensile properties, notched Izod impact toughness, flexural modulus, and heat deflection temperature are shown in Tables 6 and 7. In all cases, the samples were equilibrated at 23°C for 72 hours prior to testing.

[0190] Table 6. Summary of TDS properties of TX1500 formulations:

[0191]

[0192] *TX-04 cannot be molded

[0193] Table 7. Summary of TDS properties of TX1001 formulations:

[0194]

[0195] Reviewing Tables 6 and 7, it is found that the formulations with different friction additive types and loading levels maintain tensile properties (yield strength, yield strain, breaking strength, breaking strain) compared to C-01 and unmodified TX1 501 and TX1001 (C-04 and C-05). Specifically, some examples (e.g., TX-96, TX-97, and TX-99) maintain similar tensile and / or flexural moduli compared to the unmodified TX1001 formulation of C-05; some examples show improved tensile and / or flexural moduli compared to unmodified TX1001; and some examples (e.g., TX-93, TX-96, and TX-99) show similar notched Izod performance and / or hot deformation performance compared to unmodified TX1001.

[0196] The physical properties of the TX1001 formulation were also evaluated after a simple accelerated aging protocol. This was accomplished by subjecting the samples to a heat aging protocol and then testing the heat aged test bars for physical properties according to standard ASTM test methods as summarized previously. The goal of completing the testing before and after heat exposure was to determine if any substantial changes in performance and physical properties resulting from the friction modifications and additives were observed in the modified copolyester examples. Table 8 summarizes the tensile properties measured after standard conditioning (72 hours at 23°C and 50% RH) and heat aging protocols (200 hours at 60°C), which show minimal changes in tensile and impact properties when compared to samples C-01 and C-05.

[0197] Table 8. Summary of TDS properties of exemplary formulations after heat aging.

[0198]

[0199] Finally, the friction performance of certain modified samples of TX1500 and TX1000 were compared to control samples C-04 and C-08. The results are listed below in Tables 9 and 10. Table 11 also includes the % haze data for certain TX1000 samples.

[0200] Table 9. Summary of friction properties of TX1500 / TX1501.

[0201]

[0202] Table 10. Summary of friction / haze properties of TX1000 / TX1001.

[0203]

[0204]

[0205]

[0206] The invention has been described in detail with particular reference to certain embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

Claims

1. A polymer composition comprising: (a) a copolyester comprising: (i) a dicarboxylic acid component comprising: 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 diol component comprising: a. 10 to 99 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues; and b. 10 to 90 mole % of 1,4-cyclohexanedimethanol (CHDM) residues, wherein the total mole % of the dicarboxylic acid component is 100 mole % and the total mole % of the diol component is 100 mole %; and wherein the polyester has an intrinsic viscosity of 0.1 to 1.2 dL / g as measured at a concentration of 0.5 g / 100 ml in 60 / 40 (wt / wt) phenol / tetrachloroethane at 25°C; and wherein the polyester has a Tg of 100°C to 200°C; and (b) from about 0.1 to about 12 weight percent of a friction additive selected from waxes and silicones; and (c) Optionally, 0 to about 12 weight percent of at least one impact modifier.

2. The composition of claim 1 wherein the friction additive is a wax.

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

4. The composition of claim 1 wherein the friction additive is a silicone.

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

6. The composition of any one of claims 1 to 5, wherein the polyester composition is a copolyester comprising diol residues comprising 5 to 42 mole percent TMCD residues and 58 to 95 mole percent CHDM residues.

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

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

9. The composition according to any one of claims 1 to 8, wherein the friction additive (b) comprises 2 or more friction additives.

10. The composition of any one of claims 1 to 9, wherein the composition comprises: (a) 5 to 95 weight percent of the copolyester (a); and (d) 5 to 95 weight percent of at least one polymer component other than (a).

11. The composition of claim 10 wherein (d) is selected from the group consisting of polyamides; polystyrene; styrene acrylonitrile; acrylonitrile butadiene styrene; poly(methyl methacrylate); acrylics; poly(ether-imides); polyamides; polystyrene; polystyrene copolymers; styrene acrylonitrile copolymers; acrylonitrile butadiene styrene copolymers; poly(methyl methacrylate); acrylic copolymers; poly(ether-imides); polyphenylene ether; poly(phenylene ether) / polystyrene blends; polycarbonates; poly(ester-carbonates); polyphenylene sulfide / sulfone; polysulfone; polysulfone ether; and poly(ether-ketone) or mixtures thereof.

12. The composition of any one of claims 1 to 11, wherein the composition has a static COF of 0.6 or less and a dynamic COF of 0.5 or less.

13. The composition of any one of claims 1 to 12, wherein the composition has a haze of 5% or less.

14. The composition of any one of claims 1 to 13, wherein the composition has a b* of 6 or less.

15. The composition according to any one of claims 1 to 14, wherein the composition has a flow length ratio (L / t) at 280C and 1.6 mm of 100 or more.

16. The composition of any one of claims 1 to 15, wherein the composition comprises additional additives selected from antioxidants, heat stabilizers, mold release agents, antistatic agents, brighteners, colorants, flow aids, processing aids, plasticizers, anti-fog 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.

17. A shaped 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 an extruded article, a calendered article and / or a molded article.

19. The article of claim 18, wherein the article is selected from the group consisting of injection molded articles, extruded articles, cast extruded articles, profile extruded articles, melt spun articles, thermoformed articles, extrusion molded articles, injection blow molded articles, injection stretch blow molded articles, extrusion blow molded articles, and extrusion stretch blow molded articles.

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