Copolyester composition having a low coefficient of friction

Abstract

A polymer composition is provided that includes a copolyester containing 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) and ethylene glycol (EG) residues, which exhibits a significant improvement in impact toughness and a reduction in the coefficient of friction, while maintaining the modified physical properties (e.g., heat distortion temperature (HOT) and flexural modulus) relative to the unmodified composition.

Description

Technical Field

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

Background Art

[0002] High molecular weight thermoplastic linear copolyesters can generally be formed by reacting one or more diesters with one or more diols under suitable polymerization conditions. By reacting a diester composition containing a dialkyl ester of terephthalic acid with a diol composition containing a first diol component containing 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) and a second diol component containing ethylene glycol (EG), certain copolyesters useful for a variety of applications can be formed.

[0003] These copolyesters provide a desirable combination of performance parameters (e.g., toughness, glass transition temperature, density, crystallization rate, melt viscosity, and chemical resistance), which provides many advantages to both 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 adjust the properties and parameters of the compositions to meet the specifications of product manufacturers in undeveloped product applications.

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

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

[0006] The present invention provides means for reducing the friction of copolyesters containing TMCD and EG residues while substantially maintaining or improving impact toughness by incorporating various additives. In one embodiment, reduction of the coefficient of friction is achieved by incorporating additives including certain waxes and organosiloxanes, while impact modification is achieved by incorporating a wide range of reactive and / or non - reactive impact modifiers. Further, certain embodiments of the present invention maintain transparency while improving impact toughness and reducing the coefficient of friction.

[0007] The friction-modified, impact-tough polymer composition of the present invention containing residues of TMCD and EG exhibits a similar adjustable frictional response (static and kinetic friction coefficients) over a wide range of contact pressures and part shapes, showing a friction profile equivalent to that of conventional engineering polymers (e.g., acrylonitrile-butadiene-styrene polymer (ABS) or polycarbonate). However, notably, the physical properties after modification (e.g., heat distortion temperature (HDT) and flexural modulus) are maintained compared to the unmodified copolyester composition, while the impact toughness is significantly improved.

[0008] In an embodiment, a polymer composition is provided that includes a copolyester, one or more additives in an amount sufficient to reduce the coefficient of friction (COF) of the polymer composition, and one or more additives in an amount sufficient to increase impact toughness. The copolyester can include a dicarboxylic acid component containing terephthalic acid residues and a glycol component containing 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues and ethylene glycol (EG) residues, and has an intrinsic viscosity (determined at 25 °C at a concentration of 0.5 g / 100 ml in 60 / 40 (wt / wt) phenol / tetrachloroethane) of 0.1 to 1.2 dL / g and a glass transition temperature (Tg) of 85 to 200 °C. The one or more additives for reducing COF can be selected from waxes and siloxanes.

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

[0010] In an embodiment, the one or more additives for increasing impact toughness can be selected from elastomeric compounds or polymers that serve to absorb or dissipate the kinetic energy of impact.

Mode for Carrying Out the Invention

[0011] In a first aspect, the present invention provides a polymer composition comprising: (a) a copolyester comprising (i) diacid residues comprising from about 90 to 100 mole percent terephthalic acid residues and from 0 to about 10 mole percent isophthalic acid residues, and (ii) diol residues comprising from 58 to 95 mole percent ethylene glycol residues and from 5 to 42 mole percent 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol residues (the copolyester comprising a total of 100 mole percent diacid residues and a total of 100 mole percent diol residues), (b) from about 0.1 to about 12 weight percent of a friction additive selected from waxes and siloxanes; and (c) from about 0.5 to about 15 weight percent of at least one impact modifier.

[0012] As used herein, the term "polyester" is intended to include "copolyesters" and is understood to mean a synthetic polymer prepared by the reaction of one or more difunctional carboxylic acids and / or polyfunctional carboxylic acids with one or more difunctional hydroxyl compounds and / or polyfunctional hydroxyl compounds (e.g., branching agents). Typically, the difunctional carboxylic acid can be a dicarboxylic acid and the difunctional hydroxyl compound can be a dihydric alcohol (e.g., glycols and diols). The term "glycol" as used herein includes, but is not limited to, diols, glycols, and / or polyfunctional hydroxyl compounds (e.g., branching agents). The term "residue" as used herein means any organic structure incorporated into the polymer through a polycondensation and / or esterification reaction from the corresponding monomer. The term "repeat unit" as used herein means an organic structure having a dicarboxylic acid residue and a diol residue linked via an ester group. Thus, for example, a dicarboxylic acid residue can be derived from a dicarboxylic acid monomer or its related acid halide, ester, salt, anhydride, and / or mixtures thereof. Further, as used herein, the term "diacid" includes polyfunctional acids (e.g., branching agents). Thus, as used herein, the term "dicarboxylic acid" is intended to include dicarboxylic acids and any derivatives of dicarboxylic acids (e.g., related acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, and / or mixtures thereof) useful in the reaction process with a diol to make a polyester. As used herein, the term "terephthalic acid" is intended to include terephthalic acid itself and its residues, as well as any derivatives of terephthalic acid (e.g., related acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, and / or mixtures thereof) or their residues useful in the reaction process with a diol to make a polyester.

[0013] The polyesters used in the present invention can usually be prepared from dicarboxylic acids and diols that react in substantially equal proportions and are incorporated into the polyester polymer as the corresponding residues. Thus, the polyesters of the present invention can contain substantially equal molar ratios of acid residues (100 mol%) as well as diol (and / or polyfunctional hydroxyl compound) residues (100 mol%), such that the total molar number of repeating units is equal to 100 mol%. Accordingly, the molar percentages provided in the present invention may be based on the total molar number of acid residues, the total molar number of diol residues, or the total molar number of repeating units.

[0014] In certain embodiments, terephthalic acid or its esters (e.g., dimethyl terephthalate) or a mixture of terephthalic acid residues and their esters can constitute some or all of the dicarboxylic acid component used to form the polyesters useful in the present invention. In certain embodiments, terephthalic acid residues can constitute some or all of the dicarboxylic acid component used to form the polyesters useful in the present disclosure. For the purposes of the present disclosure, the terms "terephthalic acid" and "dimethyl terephthalate" are used interchangeably herein.

[0015] Instead of the dicarboxylic acid, esters of terephthalic acid with other dicarboxylic acids, or their corresponding esters and / or salts can be used. Suitable examples of dicarboxylic acid esters include, but are not limited to, dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, and diphenyl esters. In one embodiment, the ester is selected from at least one of the following: methyl ester, ethyl ester, propyl ester, isopropyl ester, and phenyl ester.

[0016] In certain embodiments, the polyester composition comprises a copolyester comprising: (a) diacid residues comprising from about 90 to 100 mole percent of TPA residues and 0 to about 10 mole percent of IPA residues; and (b) diol residues comprising 58 to 95 mole percent of EG residues; and 5 to 42 mole percent of TMCD residues (the copolyester comprising a total of 100 mole percent of diacid residues and a total of 100 mole percent of diol residues).

[0017] In embodiments, the copolyester comprises diol residues comprising 10 to 42 mole percent of TMCD residues and 58 to 90 mole percent of EG residues. In one embodiment, the copolyester comprises diol residues comprising 5 to 40 mole percent of TMCD residues and 60 to 95 mole percent of EG residues.

[0018] In embodiments, the copolyester comprises diol residues comprising 20 to 37 mole percent of TMCD residues and 63 to 80 mole percent of EG residues. In one embodiment, the copolyester comprises diol residues comprising 22 to 35 mole percent of TMCD residues and 65 to 78 mole percent of EG residues.

[0019] In an embodiment, the copolyester comprises a dicarboxylic acid component comprising a) (i) 90 to 100 mol% of terephthalic acid residues and (ii) about 0 to about 10 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and a glycol component comprising b) (i) about 10 to about 27 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues and (ii) about 90 to about 73 mol% of ethylene glycol residues; the total mol% of the dicarboxylic acid component being 100 mol% and the total mol% of the glycol component being 100 mol%; the intrinsic viscosity (IV) of the polyester (determined at 25 °C at a concentration of 0.25 g / 50 ml in 60 / 40 (wt / wt) phenol / tetrachloroethane) being 0.50 to 0.8 dL / g; and the L* lightness of the polyester (determined in the L*a*b* color system measured according to ASTM D6290-98 and ASTM E308-99) for polymer granules ground to pass through a 1 mm sieve being 90 or greater. In an embodiment, the L* lightness of the polyester (determined in the L*a*b* color system measured according to ASTM D6290-98 and ASTM E308-99) for polymer granules ground to pass through a 1 mm sieve is greater than 90.

[0020] In certain embodiments, the glycol component of the copolyester comprises: (i) about 15 to about 25 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues; and (ii) about 85 to about 75 mol% of ethylene glycol residues; or (i) about 20 to about 25 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues; and (ii) about 80 to about 75 mol% of ethylene glycol residues; or (i) about 21 to about 24 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues; and (ii) about 76 to about 79 mol% of ethylene glycol residues.

[0021] In one embodiment, the copolyester comprises: (a) A dicarboxylic acid component comprising: (i) From about 90 to about 100 mol% of terephthalic acid residues, (ii) From about 0 to about 10 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and (b) A glycol component comprising: (i) From about 10 to about 27 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol residues, and (ii) From about 73 to about 90 mol% of ethylene glycol residues, and (iii) Less than about 5 mol%, or less than 2 mol% of any other optional modified glycol, (where the total mol% of the dicarboxylic acid component is 100 mol%, the total mol% of the glycol component is 100 mol%, and the intrinsic viscosity of the copolyester (determined at 25 °C at a concentration of 0.25 g / 50 ml in 60 / 40 (wt / wt) phenol / tetrachloroethane) is from 0.50 to 0.8 dL / g).

[0022] In an embodiment, the copolyester has at least one of the following properties selected from: T g (measured with a TA2100 Thermal Analyst Instrument at a scan rate of 20 °C / min) is from about 90 °C to about 108 °C; the flexural modulus at 23 °C (defined by ASTM D790) is greater than about 2000 MPa (290,000 psi); the notched Izod impact strength (by ASTM D256 with a 10 - mil notch using a 1 / 8 - inch - thick specimen at 23 °C) is greater than about 25 J / m (0.47 ft - lb / in). In one embodiment, the L* lightness of the copolyester (determined in the L*a*b* color system measured according to ASTM D6290 - 98 and ASTM E308 - 99) for polymer granules ground to pass through a 1 - mm sieve) is 90 or greater, or greater than 90.

[0023] In one embodiment, the copolyester further comprises the following: (II) a catalyst / stabilizer component comprising: (i) titanium atoms in the range of 10 to 50 ppm based on the polymer weight, (ii) optionally, manganese atoms in the range of 10 to 100 ppm based on the polymer weight, and (iii) phosphorus atoms in the range of 10 to 200 ppm based on the polymer weight. In one embodiment, the 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues are a mixture comprising more than 50 mol% of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and less than 50 mol% of trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.

[0024] In embodiments, the glycol component of the copolyester can include, but is not limited to, at least one of the following combinations: about 10 to about 30 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and about 90 to about 70 mol% of ethylene glycol; about 10 to about 27 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and about 90 to about 73 mol% of ethylene glycol; about 15 to about 26 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and about 85 to about 74 mol% of ethylene glycol; about 18 to about 26 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and about 82 to about 77 mol% of ethylene glycol; about 20 to about 25 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and about 80 to about 75 mol% of ethylene glycol; about 21 to about 24 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and about 79 to about 76 mol% of ethylene glycol; or about 22 to about 24 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and about 78 to about 76 mol% of ethylene glycol.

[0025] In certain embodiments, the copolyester can exhibit at least one of the following intrinsic viscosities (determined at 25 °C at a concentration of 0.25 g / 50 ml in 60 / 40 (wt / wt) phenol / tetrachloroethane): 0.50 to 0.8 dL / g, 0.55 to 0.75 dL / g, 0.57 to 0.73 dL / g, 0.58 to 0.72 dL / g, 0.59 to 0.71 dL / g, 0.60 to 0.70 dL / g, 0.61 to 0.69 dL / g, 0.62 to 0.68 dL / g, 0.63 to 0.67 dL / g, 0.64 to 0.66 dL / g. Or about 0.65 dL / g.

[0026] In certain embodiments, the Tg of the copolyester can be selected from one of the following ranges: 85 to 100 °C, 86 to 99 °C, 87 to 98 °C, 88 to 97 °C, 89 to 96 °C, 90 to 95 °C, 91 to 95 °C, 92 to 94 °C.

[0027] In another embodiment, the copolyester contains a diol residue comprising 30 to 42 mole percent of TMCD residues and 58 to 70 mole percent of EG residues. In one embodiment, the copolyester contains a diol residue comprising 33 to 38 mole percent of TMCD residues and 62 to 67 mole percent of EG residues.

[0028] In an embodiment, the copolyester comprises: a) a dicarboxylic acid component including (i) 90 to 100 mol% of terephthalic acid residues and (ii) about 0 to about 10 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and b) a glycol component including (i) about 30 to about 42 mol% of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol (TMCD) residues and (ii) about 70 to about 58 mol% of ethylene glycol residues; wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the glycol component is 100 mol%; the intrinsic viscosity (IV) of the polyester (determined at 25 °C at a concentration of 0.25 g / 50 ml in 60 / 40 (wt / wt) phenol / tetrachloroethane) is 0.50 to 0.7 dL / g; and the L* lightness of the polyester (determined in the L*a*b* color system measured according to ASTM D6290 - 98 and ASTM E308 - 99) for polymer granules ground to pass through a 1 mm sieve is 90 or greater. In an embodiment, the L* lightness of the polyester (determined in the L*a*b* color system measured according to ASTM D6290 - 98 and ASTM E308 - 99) for polymer granules ground to pass through a 1 mm sieve is greater than 90.

[0029] In certain embodiments, the glycol component comprises: (i) from about 32 to about 42 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues and (ii) from about 68 to about 58 mole % of ethylene glycol residues; or (i) from about 34 to about 40 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues and (ii) from about 66 to about 60 mole % of ethylene glycol residues; or (i) greater than 34 to about 40 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues and (ii) less than 66 to about 60 mole % of ethylene glycol residues; or (i) from 34.2 to about 40 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues and (ii) from 65.8 to about 60 mole % of ethylene glycol residues; or (i) from about 35 to about 39 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues and (ii) from about 65 to about 61 mole % of ethylene glycol residues; or (i) from about 36 to about 37 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues and (ii) from about 64 to about 63 mole % of ethylene glycol residues.

[0030] In one embodiment, the copolyester comprises: (a) A dicarboxylic acid component comprising: (i) from about 90 to about 100 mole % of terephthalic acid residues, (ii) from about 0 to about 10 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and (b) A glycol component comprising: (i) from about 30 to about 42 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and (ii) from about 70 to about 58 mole % of ethylene glycol residues, and (iii) less than about 5 mole %, or less than 2 mole %, of any other optional modifying glycol, (the total mole % of the dicarboxylic acid component being 100 mole %, the total mole % of the glycol component being 100 mole %, The intrinsic viscosity of the polyester is 0.50 to 0.70 dL / g (determined at 25°C at a concentration of 0.25 g / 50 ml in 60 / 40 (wt / wt) phenol / tetrachloroethane). In an embodiment, the copolyester has at least one of the following properties selected from the following: T g (Measured with a TA2100 Thermal Analyst Instrument at a scan rate of 20°C / min) is from about 100°C to about 110°C; the flexural modulus at 23°C (defined by ASTM D790) is 2000 MPa (about 290,000 psi) or more, or more than 2200 MPa (319,000 psi); the notched Izod impact strength (by ASTM D256 with a 10-mil notch using a 1 / 8-inch thick specimen at 23°C) is from about 30 J / m (0.56 ft-lb / in) to about 80 J / m (1.50 ft-lb / in); the loss of intrinsic viscosity after holding at a temperature of 293°C (560°F) for 2 minutes is less than 5%. In one embodiment, the L* lightness of the polyester composition (determined in the L*a*b* color system measured according to ASTM D6290-98 and ASTM E308-99) for polymer granules ground to pass through a 1 mm sieve is 90 or more, or greater than 90.

[0031] In one embodiment, the copolyester comprises a diol component having at least 30 mole percent of TMCD residues (based on the diol) and a catalyst / stabilizer component comprising (i) titanium atoms in the range of 10 to 60 ppm based on the polymer weight, (ii) manganese atoms in the range of 10 to 100 ppm based on the polymer weight, and (iii) phosphorus atoms in the range of 10 to 200 ppm based on the polymer weight. In one embodiment, the 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues are a mixture comprising more than 50 mole percent cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and less than 50 mole percent trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.

[0032] In an embodiment, the glycol component of the copolyester includes, but is not limited to, at least one of the following combinations: about 30 to about 42 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and about 58 to 70 mol% of ethylene glycol; about 32 to about 42 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and about 58 to 68 mol% of ethylene glycol; about 32 to about 36 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and about 64 to 68 mol% of ethylene glycol; about 33 to about 41 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and about 59 to 67 mol% of ethylene glycol; about 34 to about 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and about 60 to 66 mol% of ethylene glycol; more than 34 to about 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and less than 60 to 66 mol% of ethylene glycol; 34.2 to 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and about 60 to 65.8 mol% of ethylene glycol; about 35 to about 39 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and about 61 to 65 mol% of ethylene glycol; about 35 to about 38 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and about 62 to 65 mol% of ethylene glycol; or about 36 to about 37 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and about 63 to 64 mol% of ethylene glycol.

[0033] In certain embodiments, the polyester can exhibit at least one of the following intrinsic viscosities (determined at 25 °C at a concentration of 0.25 g / 50 ml in 60 / 40 (wt / wt) phenol / tetrachloroethane): 0.50 to 0.70 dL / g; 0.55 to 0.65 dL / g; 0.56 to 0.64 dL / g; 0.56 to 0.63 dL / g; 0.56 to 0.62 dL / g; 0.56 to 0.61 dL / g; 0.57 to 0.64 dL / g; 0.58 to 0.64 dL / g; 0.57 to 0.63 dL / g; 0.57 to 0.62 dL / g; 0.57 to 0.61 dL / g; 0.58 to 0.60 dL / g or about 0.59 dL / g.

[0034] In an embodiment, the copolyester contains 0 to 10 mole percent of CHDM residues. In certain embodiments, the copolyester may contain less than 10 mol%, or less than 5 mol%, or less than 4 mol%, or less than 3 mol%, or less than 2 mol%, or less than 1 mol% of CHDM residues, or may contain no CHDM residues at all.

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

[0036] In an embodiment, the mole percent of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol in a particular polyester is greater than 50 mol% or greater than 55 mol% of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol, or greater than 70 mol% of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol, and the total mole percentage of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol and trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol is equal to 100 mol% in total.

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

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

[0039] In an embodiment, the polyester(s) and / or polyester composition(s) can have a unique combination of two or more physical properties (e.g., high impact strength, medium to high glass transition temperature, chemical resistance, hydrolysis stability, toughness, low ductility to brittle transition temperature, good color and transparency, low density, long crystallization half-life, and good processability), thereby making it possible to easily mold them into articles. In some embodiments, the polyester can have a unique combination of properties of good impact strength, heat resistance, chemical resistance, density, and / or a combination of properties of good impact strength, heat resistance, and processability, and / or a combination of two or more of the described properties.

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

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

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

[0043] In certain embodiments, the polyester may exhibit at least one of the following intrinsic viscosities (determined at 25 °C at a concentration of 0.5 g / 100 ml in 60 / 40 (wt / wt) phenol / tetrachloroethane): 0.45 to 1.2 dL / g; 0.45 to 1.1 dL / g; 0.45 to 1 dL / g; 0.45 to 0.98 dL / g; 0.45 to 0.95 dL / g; 0.45 to 0.90 dL / g; 0.45 to 0.85 dL / g; 0.45 to 0.80 dL / g; 0.45 to 0.75 dL / g; 0.45 to less than 0.75 dL / g; 0.45 to 0.72 dL / g; 0.45 to 0.70 dL / g; 0.45 to less than 0.70 dL / g; 0.45 to 0.68 dL / g; 0.45 to less than 0.68 dL / g; 0.45 to 0.65 dL / g; 0.50 to 1.2 dL / g; 0.50 to 1.1 dL / g; 0.50 to 1 dL / g; 0.50 to less than 1 dL / g; 0.50 to 0.98 dL / g; 0.50 to 0.95 dL / g; 0.50 to 0.90 dL / g; 0.50 to 0.85 dL / g; 0.50 to 0.80 dL / g; 0.50 to 0.75 dL / g; 0.50 to less than 0.75 dL / g; 0.50 to 0.72 dL / g; 0.50 to 0.70 dL / g; 0.50 to less than 0.70 dL / g; 0.50 to 0.68 dL / g; 0.50 to less than 0.68 dL / g; 0.50 to 0.65 dL / g; 0.55 to 1.2 dL / g; 0.55 to 1.1 dL / g; 0.55 to 1 dL / g; 0.55 to less than 1 dL / g; 0.55 to 0.98 dL / g; 0.55 to 0.95 dL / g; 0.55 to 0.90 dL / g; 0.55 to 0.85 dL / g; 0.55 to 0.80 dL / g; 0.55 to 0.75 dL / g; 0.55 to less than 0.75 dL / g; 0.55 to 0.72 dL / g; 0.55 to 0.70 dL / g; 0.55 to less than 0.70 dL / g; 0.55 to 0.68 dL / g; 0.55 to less than 0.68 dL / g; 0.55 to 0.65 dL / g; 0.58 to 1.2 dL / g; 0.58 to 1.1 dL / g; 0.58 to 1 dL / g; 0.58 to less than 1 dL / g; 0.58 to 0.98 dL / g; 0.58 to 0.95 dL / g; 0.58 to 0.90 dL / g; 0.58 to 0.85 dL / g; 0.58 to 0.80 dL / g; 0.58 to 0.75 dL / g; 0.58 to less than 0.75 dL / g; 0.58 to 0.72 dL / g; 0.58 to 0.70 dL / g; 0.58 to less than 0.70 dL / g; 0.58 to 0.68 dL / g; less than 0.58 to 0.68 dL / g; 0.58 to 0.65 dL / g; 0.60 to 1.2 dL / g; 0.60 to 1.1 dL / g; 0.60 to 1 dL / g; less than 0.60 to 1 dL / g; 0.60 to 0.98 dL / g; 0.60 to 0.95 dL / g; 0.60 to 0.90 dL / g; 0.60 to 0.85 dL / g; 0.60 to 0.80 dL / g; 0.60 to 0.75 dL / g; less than 0.60 to 0.75 dL / g; 0.60 to 0.72 dL / g; 0.60 to 0.70 dL / g; less than 0.60 to 0.70 dL / g; 0.60 to 0.68 dL / g; less than 0.60 to 0.68 dL / g; 0.60 to 0.65 dL / g; 0.65 to 1.2 dL / g; 0.65 to 1.1 dL / g; 0.65 to 1 dL / g; less than 0.65 to 1 dL / g; 0.65 to 0.98 dL / g; 0.65 to 0.95 dL / g; 0.65 to 0.90 dL / g; 0.65 to 0.85 dL / g; 0.65 to 0.80 dL / g; 0.65 to 0.75 dL / g; less than 0.65 to 0.75 dL / g; 0.65 to 0.72 dL / g; 0.65 to 0.70 dL / g; less than 0.65 to 0.70 dL / g; 0.68 to 1.2 dL / g; 0.68 to 1.1 dL / g; 0.68 to 1 dL / g; less than 0.68 to 1 dL / g; 0.68 to 0.98 dL / g; 0.68 to 0.95 dL / g; 0.68 to 0.90 dL / g; 0.68 to 0.85 dL / g; 0.68 to 0.80 dL / g; 0.68 to 0.75 dL / g; less than 0.68 to 0.75 dL / g; 0.68 to 0.72 dL / g; greater than 0.76 dL / g to 1.2 dL / g; greater than 0.76 dL / g to 1.1 dL / g; greater than 0.76 dL / g to 1 dL / g; greater than 0.76 dL / g to less than 1 dL / g; greater than 0.76 dL / g to 0.98 dL / g; greater than 0.76 dL / g to 0.95 dL / g; greater than 0.76 dL / g to 0.90 dL / g; greater than 0.80 dL / g to 1.2 dL / g; greater than 0.80 dL / g to 1.1 dL / g; greater than 0.80 dL / g to 1 dL / g; greater than 0.80 dL / g to less than 1 dL / g; greater than 0.80 dL / g to 0.98 dL / g; greater than 0.80 dL / g to 0.95 dL / g; greater than 0.80 dL / g to 0.90 dL / g.

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

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

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

[0047] In certain embodiments, in addition to terephthalic acid, the dicarboxylic acid component of the polyester can 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. In yet another embodiment, 0 mol% of the modified aromatic dicarboxylic acid is contained. Thus, when present, the amount of one or more modified aromatic dicarboxylic acids is contemplated to be in the range of any of these above-described end point values (e.g., 0.01 - 30 mol%, 0.01 - 20 mol%, 0.01 - 10 mol%, 0.01 - 5 mol%, and 0.01 - 1 mol%). In one embodiment, the modified aromatic dicarboxylic acids that can be used include those having up to 20 carbon atoms, but are not limited thereto, and this can be linear, para-oriented, or symmetric. Examples of modified aromatic dicarboxylic acids that can be used include isophthalic acid, 4,4'-biphenyldicarboxylic acid, 1,4-, 1,5-, 2,6-, 2,7-naphthalenedicarboxylic acid, and trans-4,4'-stilbenedicarboxylic acid, and esters thereof, but are not limited to these. In one embodiment, the modified aromatic dicarboxylic acid is isophthalic acid.

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

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

[0050] In embodiments of the polyester containing CHDM, 1,4-cyclohexanedimethanol may be cis, trans, or a mixture thereof. For example, the cis / trans ratio may be from 60:40 to 40:60.

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

[0052] Examples of branching monomers include, but are not limited to, polyfunctional acids or polyfunctional alcohols (such as trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, glycerol, pentaerythritol, citric acid, tartaric acid, 3-hydroxyglutaric acid, etc.). In one embodiment, the branching monomer residue may contain from 0.1 to 0.7 mole percent of one or more residues selected from at least one of the following: trimellitic anhydride, pyromellitic dianhydride, glycerol, sorbitol, 1,2,6-hexanetriol, pentaerythritol, trimethylolethane, and / or trimesic acid. The branching monomer may be added to the polyester reaction mixture or blended with the polyester, for example, in the form of concentrates described in U.S. Pat. Nos. 5,654,347 and 5,696,176 (the disclosures of which regarding the branching monomer are incorporated herein by reference).

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

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

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

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

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

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

[0059] Suitable catalysts used in this process include, but are not limited to, organozinc or tin compounds. The use of this type of catalyst is well known in the art. Examples of catalysts useful in the present invention include, but are not limited to, zinc acetate, butyltin tris-2-ethylhexanoate, dibutyltin diacetate, and dibutyltin oxide. Other catalysts may include, but are not limited to, those based on titanium, zinc, manganese, lithium, germanium, and cobalt. The amount of catalyst can range from 10 ppm to 20,000 ppm, or 10 to 10,000 ppm, or 10 to 5000 ppm, or 10 to 1000 ppm, or 10 to 500 ppm, or 10 to 300 ppm, or 10 to 250 ppm based on the weight of the catalyst metal and the final polymer. This process can be carried out in either a batch process or a continuous process.

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

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

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

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

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

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

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

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

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

[0069] In another embodiment, the present invention further relates to a manufactured article comprising any of the polyesters and blends described herein. The extruded articles, calendered articles, and / or molded articles include, but are not limited to, injection molded articles, extruded articles, cast extruded articles, profile extruded articles, melt spun articles, thermoformed articles, blow 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.

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

[0071] The copolyesters and / or polyester blend compositions of the present invention may be useful for forming fibers, films, molded articles, containers, and sheets. Methods for shaping polyesters into fibers, films, molded articles, containers, and sheets are well known in the art. Examples of potential molded articles include, but are not limited to: medical devices (e.g., dialysis devices), medical packaging, healthcare supplies, commercial food service products (e.g., food pans, tumblers and storage containers, baby bottles, food processors, blenders, and mixing bowls), appliances, water bottles, vegetable crisper trays, decorative items, the front of washing machines, and parts of vacuum cleaners, as well as associated lids, latches, and hinges therefor.

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

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

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

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

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

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

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

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

[0080] In embodiments, examples of commercially available impact modifiers can 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 type impact modifiers. Residues of such additives are also considered part of the polyester composition.

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

[0082] Examples of commercially available products include: Modiper® 4300 and Modiper® 4400, available from NOF Corporation Kane Ace® M300, available from Kaneka Americas Holding, Inc. Kane Ace® B564, available from Kaneka Americas Holding, Inc. Kane Ace® ECO1000, available from Kaneka Americas Holding, Inc. Kane Ace® MR02, available from Kaneka Americas Holding, Inc. Kane Ace® MR03, available from Kaneka Americas Holding, Inc., and Lotader® 8900, available from Arkema.

[0083] The impact modifier of the above component (c) may be present in an amount of 0.5 to about 15% by weight. In other embodiments, they are 0.5 to 14, or 0.5 to 12, or 0.5 to 10, or 0.5 to 8, or 0.5 to 6, or 0.5 to 5, or 0.5 to 4, or 0.5 to 3, or 0.5 to 2, or 0.5 to 1, or 1 to 14, or 1 to 12, or 1 to 10, or 1 to 8, or 1 to 6, or 1 to 5, or 1 to 4, or 1 to 3, or 1 to 2, or 2 to 14, or 2 to 12, or 2 to 10, or 2 to 8, or 2 to 6, or 2 to 5, or 2 to 4, or 2 to 3, or 3 to 14, or 3 to 12, or 3 to 10, or 3 to 8, or 3 to 6, or 3 to 5, or 3 to 4, or 4 to 14, or 4 to 12, or 4 to 10, or 4 to 8, or 4 to 6, or 4 to 5, or 5 to 14, or 5 to 12, or 5 to 10, or 5 to 8, or 5 to 6, or 6 to 14, or 6 to 12, or 6 to 10, or 6 to 8% by weight based on the total weight of the polyester composition.

[0084] In embodiments, the polyester composition comprises 0.1 to 5% by weight of component (b) and 1 to 10% by weight of component (c), or 0.5 to 4% by weight of component (b) and 2 to 8% by weight of component (c), or 0.5 to 2.5% by weight of component (b) and 3 to 6% by weight of component (c), or 1 to 2% by weight of component (b) and 3.5 to 5.5% by weight of component (c) based on the total weight of the polyester composition. In embodiments, component (b) comprises siloxane and component (b) comprises an ethylene acrylate terpolymer. In embodiments, component (b) comprises siloxane and component (b) comprises a terpolymer of ethylene, acrylic acid, and glycidyl (meth)acrylate. In one embodiment, component (b) comprises Genioplast S and component (b) comprises Lotader 8900. In one embodiment, the polyester composition comprises DX4000 or DX4001 in an amount of 93 to 95% by weight, Genioplast S in an amount of 1 to 2% by weight, and Lotader 8900 in an amount of 4 to 5% by weight.

[0085] The present invention can be further explained by way of examples of the following preferred embodiments, which are included for illustrative purposes only and are understood not to limit the scope of the present invention unless otherwise specified.

[0086] Experimental Section Section 1. Testing of Base Resins Several commercially available resins were subjected to a series of tests. This test was designed to set a baseline for the performance of the copolyester composition from the perspective of physical properties and frictional performance.

[0087] Using established test methods defined by ASTM, physical properties typically reported in technical data sheets (TDS) were evaluated using injection-molded tensile test specimens or flexural test specimens. For commercially available resins, the drying conditions and processing conditions reported in the technical data sheets were utilized for processing. In the case of modified resins, the processing conditions to be used were selected based on those of the base resin.

[0088] Multiple tests were completed for all samples, and the modified resins are detailed in Section 3 below. These test methods are classified as follows: ● Specific physical properties commonly found in technical data sheets. The specific tests included tensile properties (ASTM D638), flexural properties (ASTM D790), notched Izod impact properties (ASTM D256), and heat deflection properties (ASTM D648). In all cases, both commercially available resins and modified resins were subjected to standard conditioning and test protocols. ● The coefficient of static friction and the coefficient of kinetic friction (μ s and μ k) The friction profiles of the base resins reported as such. These values were measured using a Bruker tribometer by intentionally contacting the surfaces of pairs of 4-inch × 4-inch × 1 / 8-inch plaques manufactured using injection molding. To avoid contamination of the friction data measurements, gloves were always worn to avoid direct contact with the test pieces. After molding, a pair of plaques was used to measure the coefficient of friction according to the following definitions. ○ Static COF (μ s ) is measured at the limit where both the contact force (F z ) between the two plaques and the relative velocity (v x ) between the two contacting plaques approach zero. For example: ■ F z = 0.05 N, v x = 0.01 mm / sec ○ Kinetic COF (μ k ) is defined as the friction measured at a constant force and relative velocity between two contacting plaques. For example: ■ F z = 3.00 N, v x = 10.0 mm / sec

[0089] An overview of the commercially available resins evaluated as examples of "controls" or "comparisons" is shown in Table 1 below.

Table 1

[0090] An overview of the physical properties of the control / comparison materials is shown in Table 2 below.

[0091]

Table 2

[0092] An overview of the physical property data in Table 2 reveals that resins C-01 and C-02 (ABS and polycarbonate (PC), respectively) exhibit higher rigidity in both tensile modulus and flexural modulus than all other materials evaluated. Resin C-03 (a cellulose material) shows similar tensile properties as C-01, except for modulus, and similar levels of impact toughness when measured by the notched Izod test. The notch sensitivity of resins C-06, C-07, C-09, and C-10 is significantly higher than that of C-01, while the rigidity of resins C-04, C-05, and C-08 is the lowest among the commercial resins evaluated.

[0093] The frictional performance of the materials in Table 1 was evaluated to quantify the coefficient of static friction and the coefficient of kinetic friction (μ s and μ k ), respectively. The coefficient of friction (COF) values are listed in Table 3 below.

Table 3

[0094] An overview of Table 3 shows that C-01 (ABS) and C-02 (PC) have similar friction profiles indicating the coefficient of static and kinetic friction when measured according to the slide thread type test (Table 3). Furthermore, resin C-01 shows lower frictional performance compared to all resins evaluated. Therefore, in order to enable functionality in applications that previously utilized ABS materials and require similar frictional behavior, it would be necessary to modify the frictional performance of other resins (e.g., C-03 to C-10) to match that of C-01 in the friction test while maintaining (or not significantly reducing) their physical properties (particularly rigidity and impact toughness) compared to the unmodified base resin.

[0095] Section 2. Modification By incorporating various additives, twin-screw mixing and various additives (plural possible) were used to generate modified development samples in order to modify performance, particularly the friction profile. These additives can vary in chemical nature, including, for example, ranging from short-chain molecules (such as waxes) to high molecular weight or ultra-high molecular weight organosiloxanes (such as PDMS). In the mixed formulations, it was found that the additives can function as internal lubricants and / or external lubricants depending on the specific additive chemistry, molecular weight, loading level, and functionality. The additives utilized are listed in Table 4 below.

Table 4

[0096] In addition to the above additives, additional additives that can be incorporated into potential formulations are additives specifically designed to modify impact toughness. Additives utilized for impact modification are typically incorporated at loading levels of less than 15 wt%, and span multiple chemical natures and morphologies (such as core-shell, branched, reactive, MBS, acrylic, EGMA, etc.). Impact modifiers tested alone or in combination with additives (from Table 4) are shown in Table 5 below.

Table 5

[0097] Section 3. Examples Modification using friction additives and / or impact modifiers generated multiple samples of TMCD and EG-containing copolyesters (such as Eastman GMX201 (Sample C-06), Tritan™ DX4001 (Sample C-07, and Tritan™ DX4000 (Sample C-10)). Physical properties were measured before and after the thermal aging protocol. The friction performance of some formulations was also evaluated using a tribometer (as described above). The results are reported in the following table summarizing the performance of the modified formulations compared to the control examples.

[0098] Table 6 summarizes the formulations evaluated in this study (GX-01 to GX-35 using Sample C-06 as the base resin, DX-01 to DX-21 using Sample C-07 as the base resin, and DX-22 to DX-30 using Sample C-10 as the base resin). The specific compositions of the friction additives are described in comparison to control or comparative examples. The "base resins" utilized in the modified Tritan™ samples were Tritan™ GMX201 (C-06), Tritan™ DX4001 (C-07), and Tritan™ DX4000 (C-10), but it should be noted that the findings from this study provide insights into the use of other TMCD and EG base resins (e.g., Tritan™ GMX200).

[0099]

Table 6-1

Table 6-2

Table 6-3

[0100] The physical properties and performance of the resins for all examples were measured according to the same procedures and test methods described above for all control, comparative, and / or commercially available resins. An overview of the physical properties (particularly tensile properties, notched Izod impact toughness, flexural modulus, and heat deflection temperature) of the resins for all examples is shown in Table 7.

[0101]

Table 7-1

Table 7-2

Table 7-3

Table 7-4

Table 7-5

Table 7-6

[0102] Physical properties were also evaluated after a simple accelerated aging protocol. All samples were subjected to a thermal aging protocol and then this was completed by performing physical property tests on the thermally aged test specimens according to the standard ASTM test methods as described above. The purpose of performing the tests both before and after thermal exposure was to determine whether any substantial changes in performance and physical properties were observed in the examples of the modified copolyesters resulting from friction modification and additives. Table 8 summarizes the tensile properties as measured after standard conditioning (72 hours at 23 °C, 50% RH) and after the thermal aging protocol (200 hours at 60 °C).

[0103]

Table 8-1

Table 8-2

Table 8-3

[0104] The summary in Table 8 reveals that, generally, there is a minimal shift in tensile properties when compared to Sample C-01 and unmodified copolyester Sample C-06, except for GX-33, GX-34, GX-35, GX-36, and unmodified copolyester sample C-07. GX-33 and GX-34 contain T-01, while GX-35 and GX-36 contained T-01 and I-06. Inclusion of T-01 unexpectedly accelerates aging significantly, and further addition of I-06 seems to further accelerate the aging of GX copolyesters. As seen in Samples DX-17, DX-18, DX-19, and DX-20, the same behavior was not observed when DX4001 was used as the copolyester. The modified copolyester samples showed a reduction in impact toughness across all samples evaluated after aging, but the performance in both fracture mode and impact energy of the modified samples, except for GX-33, GX-34, GX-35, and GX-36, still far exceeded the performance of the unmodified copolyesters (C-06, C-07). Not all combinations of copolyester, friction modifier, and impact modifier result in a minimal reduction in performance.

[0105] Finally, the friction performance of specific modified samples of GMX201 and DX4001 was compared to control samples C-06 and C-07. The results are presented in Table 9 below. Table 9 also includes data on the haze % of specific DX4001 samples.

[0106]

Table 9-1

Table 9-2

[0107] The overview of Table 9 reveals that when the impact modifier I-06 is included, in samples GX-17 and GX-18, compared to C-06, and in samples DX-11 and DX-12, compared to C-07, the static and dynamic friction increase. The same behavior is also seen when I-06 is used in addition to the friction modifier T-02, with an increase in static and dynamic friction in samples GX-38 and GX-39 compared to GX-36 and GX-37, and in samples DX-23 and DX-24 compared to DX-21 and DX-22. However, in samples DX-25, DX-26, DX-27, and DX-28, an unexpected synergistic effect was observed between the friction modifier T-03 and the impact modifier I-06. In these samples, when the impact modifier I-6 was added, a further decrease in static and dynamic friction was observed compared to the case of using only the friction modifier T-03. As shown in samples GX-40, GX-41, GX-42, and GX-43, when GMX201 was used as the copolyester, the same effect was not observed. Furthermore, as shown in samples GX-34 and GX-35 compared to GX-32 and GX-33, and in DX-19 and DX-20 compared to DX-17 and DX-18, including the impact modifier I-06 together with the friction modifier T-1 had no effect on friction. This unexpected behavior may provide a way to create / construct materials with adjustable friction and impact performance, specifically providing low friction and high impact performance exceeding C-01. A further overview of Table 9 reveals that the haze values of the samples using T-1, T-7, T-8, and T-9 are unexpectedly low, resulting in highly transparent materials with the same friction as C-01.

[0108] Although the invention has been described in detail with reference to its specific embodiments, it will be understood that changes and modifications may affect the spirit and scope of the invention.

Claims

1. A polymer composition, (a) (i) diacid residues comprising about 90 to 100 mole percent of terephthalic acid residues and 0 to about 10 mole percent of isophthalic acid residues, and (ii) diol residues comprising 58 to 95 mole percent of ethylene glycol residues and 5 to 42 mole percent of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, wherein the copolyester comprises a total of 100 mole percent of diacid residues and a total of 100 mole percent of diol residues, (b) A friction additive selected from waxes and siloxanes in an amount of about 0.1 to about 12 weight percent; and (c) At least one impact modifier in an amount of approximately 0.5 to approximately 15 weight percent, The polymer composition comprising the above.

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

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

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

5. The composition according to claim 4, wherein the friction additive is present in an amount of about 0.1 to about 7 weight percent.

6. The composition according to claim 4, wherein the friction additive is a polyester-modified siloxane.

7. The composition according to claim 4, wherein the friction additive is a non-reactive siloxane.

8. The composition according to claim 4, wherein the friction additive is an aryl-modified siloxane.

9. The composition according to claim 1, wherein the polyester composition is a copolyester comprising a diol residue containing 10 to 42 mole percent of TMCD residues and 58 to 90 mole percent of EG residues.

10. The composition according to claim 9, wherein the polyester composition is a copolyester containing 20 to 30 mole percent of TMCD residues and 70 to 80 mole percent of diol residues including EG residues.

11. The composition according to claim 9, wherein the polyester composition is a copolyester containing a diol residue comprising 30 to 40 mole percent of TMCD residues and 60 to 70 mole percent of EG residues.

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

13. The composition according to claim 12, wherein (d) is selected from polyamide; polystyrene; styrene acrylonitrile; acrylonitrile butadiene styrene; poly(methyl methacrylate); acrylic; poly(etherimide); polyamide; polystyrene; polystyrene copolymer; styrene acrylonitrile copolymer; acrylonitrile butadiene styrene copolymer; poly(methyl methacrylate); acrylic copolymer; poly(etherimide); polyphenylene oxide; poly(phenylene oxide) / polystyrene blend; polycarbonate; poly(ester carbonate); polyphenylene sulfide / sulfone; polysulfone; polysulfone ether; and poly(ether ketone), or a mixture thereof.

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

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

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

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

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

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

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