KR20090079211A - Polyester compositions which comprise tetramethylcyclobutanediol, cyclohexanedimethanol and ethylene glycol, and manufacturing processes therefor - Google Patents

Abstract

Described as one aspect of the invention are polyester compositions comprising at least one polyester which comprises: (a) a dicarboxylic acid component comprising: (i) about 90 to about 100 mole % of terephthalic acid residues; (ii) 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) about 20 to about 40 mole % 2,2,4,4-tetramethy-1,3-cyclobutanediol residues; and (ii) about 20 to about 40 mole % cyclohexanedimethanol residues; (iii) ethylene glycol residues, and (iv) less than about 2 mole % of a modifying glycol having from 3 to 16 carbon atoms; wherein the total mole % of the dicarboxylic acid component is 100 mole %, and wherein the total mole % of the glycol component is 100 mole %; and wherein the inherent viscosity of the polyester is from 0.50 to 1.2 dL/g as determined in 60/40 (wt/wt) phenol/ tetrachloroethane at a concentration of 0.25 g/50 ml at 25°C. The polyesters may be manufactured into articles.

Description

POLYETSTER COMPOSITIONS WHICH COMPRISE TETRAMETHYLCYCLOBUTANEDIOL, CYCLOHEXANEDIMETHANOL AND ETHYLENE GLYCOL, AND MANUFACTURORING PROCESSES

The present invention generally has a particular combination of two or more of high notched Izod impact strength, specific glass transition temperature (Tg), specific flexural modulus, good transparency, and good color, and is suitable for use in products, such as thermoformed sheets and films. Easily molded, terephthalic acid, esters thereof or mixtures thereof, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, cyclohexanedimethanol, and ethylene glycol, Or to polyester compositions prepared from chemical equivalents.

Certain commercially available polymers, such as bisphenol A polycarbonate, have desirable glass transition temperatures and notched Izod impact strengths for thermoformed films and sheets, but are known to require a drying process prior to thermoforming. Other commercially available polymers, such as acrylic compounds and certain impact modified acrylic compounds, are known to have desirable glass transition temperatures for thermoformed films and sheets, but do not appear to require a drying process prior to thermoforming. However, they are typically less than 2 feet-lbs / inch in ambient notch Izod impact strength, and are often not suitable for certain end uses. Thus, having a combination of properties suitable for thermoformed film and sheet applications, including combinations of two or more of high notched Izod impact strength, specific intrinsic viscosity, specific glass transition temperature (Tg), specific flexural modulus, good transparency, and good color There is a continuing commercial need for polymeric materials.

Also for polymer materials having a combination of properties desirable for thermoformed film and sheet applications, including combinations of three or more of high notch Izod impact strength, specific glass transition temperature (Tg), specific flexural modulus, good transparency, and good color. Commercial demands continue.

In addition, polymeric materials having a combination of properties desirable for thermoformed film and sheet applications, including combinations of all properties of high notch Izod impact strength, specific glass transition temperature (Tg), specific flexural modulus, good transparency, and good color. There is a continuing commercial demand for.

Additionally, in one embodiment, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, ethylene glycol, and cyclohexane have good color and / or good transparency There is a continuing need for polyesters comprising methanol and methods of making such polyesters.

In addition, as one embodiment, in the art, bubbling, splay formation, color formation, foaming, by-product gas generation, and erratic melt levels (ie, pulsation of polyester or polyester production and processing systems) There is a continuing need for a method for easily producing the polyester of the present invention without at least one of pulsating). There is also a need in the art for a method of easily producing the polyesters of the present invention on a large scale (eg, laboratory scale and / or commercial production) without one or more of the above-mentioned difficulties occurring.

Summary of the Invention

Formed from terephthalic acid, its esters and / or mixtures thereof, ethylene glycol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and cyclohexanedimethanol, with specific thermal stability Certain polyester compositions, including agents, reaction products thereof, and mixtures thereof, have aspects of one or more of high notched Izod impact strength, specific intrinsic viscosity, specific glass transition temperature (Tg), specific flexural modulus, good transparency, and good color It is believed to be superior to certain commercial polymers at.

In other embodiments of the invention, for example, thermoformed films, including combinations of two or more of high notch Izod impact strength, specific intrinsic viscosity, specific glass transition temperature (Tg), specific flexural modulus, good transparency, and good color; There is a continuing commercial need for polymeric materials having a combination of properties desirable for certain applications, such as sheet applications.

In other embodiments of the present invention, certain applications, such as thermoformed film and sheet applications, including combinations of three or more of high notched Izod impact strength, specific glass ion ionicity (Tg) and specific flexural modulus, good transparency, and good color There is a continuing commercial need for polymeric materials having a combination of desirable properties.

In another embodiment of the invention, a polymer having a combination of properties that are desirable for certain applications, such as thermoformed film and sheet applications, including combinations of two or more of high notched Izod impact strength, specific glass transition temperature (Tg), and specific flexural modulus. There is a continuing commercial need for materials.

In one embodiment, when one or more of the phosphorus compounds described herein are used in the process for preparing the polyesters according to the invention, bubbling, flaring formation, color formation, foaming, byproduct gas evolution, and erratic melting levels (ie It is believed that the polyester can be readily produced without at least one of polyester or polyester pulsation and pulsation of the processing system). In a further embodiment, one or more methods according to the invention facilitate polyesters useful in the present invention on a large scale (e.g., on a laboratory scale and / or on a commercial production scale) without causing one or more of the problems described above. It is believed to provide a means that can be manufactured easily.

As used herein, the term "bulk" includes the amount of polyester (s) useful in the present invention that is produced in an amount greater than 100 pounds. In one embodiment, the term “bulk” as used herein includes the amount of polyester (s) useful in the present invention that is produced in an amount greater than 1000 pounds.

In one embodiment, methods of making polyesters useful in the present invention may include batch or continuous processes.

In one embodiment, methods of making polyesters useful in the present invention may include a continuous method.

In one aspect, the invention is a polyester composition comprising at least one polyester,

a dicarboxylic acid component comprising (a) from about 90 to about 100 mole percent of terephthalic acid residues, and (ii) from about 0 to about 10 mole percent of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; And

(b) about 20 to about 40 mole percent of (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and (ii) about 20 to about 40 mole percent of cyclohexanedimethanol residues. a glycol component comprising (iii) less than about 2 mole percent of a modified glycol having from 3 to 16 carbon atoms, and (iv) an ethylene glycol moiety,

The total mole% of the dicarboxylic acid component is 100 mole% and the total mole% of the glycol component is 100 mole%,

The sum of the mole% of 2,2,4,4-tetramethyl-1,3-cyclobutadiethanol and cyclohexanedimethanol is less than 40 to 70 mole% of the total mole% of the glycol component,

A polyester composition, wherein the polyester has an inherent viscosity of 0.50 to 1.2 dL / g when measured in a 60/40 (weight / weight) phenol / tetrachloroethane solution at a concentration of 0.25 g / 50 ml at 25 ° C.

In one aspect, the present invention provides a polyester composition comprising at least one polyester,

a dicarboxylic acid component comprising (a) from about 90 to about 100 mole percent of terephthalic acid residues, and (ii) from about 0 to about 10 mole percent of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; And

(b) about 20 to about 40 mole percent of (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and (ii) about 20 to about 40 mole of cyclohexanedimethanol residues. %, (iii) an ethylene glycol moiety, and (iv) a glycol component comprising less than about 2 mole% of modified glycol having 3 to 16 carbon atoms,

The total mole% of the dicarboxylic acid component is 100 mole% and the total mole% of the glycol component is 100 mole%,

The sum of the mole% of 2,2,4,4-tetramethyl-1,3-cyclobutadiethanol and cyclohexanedimethanol is less than 40 to 70 mole% of the total mole% of the glycol component,

When measured in a 60/40 (weight / weight) phenol / tetrachloroethane solution at a concentration of 0.25 g / 50 ml at 25 ° C., the inherent viscosity of the polyester is 0.50 to 1.2 dL / g,

Optionally, at least one branching agent is added prior to and / or during the polymerization of the polyester.

In one aspect, the invention is a polyester composition comprising at least one polyester,

a dicarboxylic acid component comprising (a) from about 90 to about 100 mole percent of terephthalic acid residues, and (ii) from about 0 to about 10 mole percent of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms. ; And

(b) about 20 to about 40 mole percent of (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and (ii) about 20 to about 40 mole of cyclohexanedimethanol residues. %, (iii) an ethylene glycol moiety, and (iv) a glycol component comprising less than about 2 mole% of modified glycol having 3 to 16 carbon atoms,

The total mole% of the dicarboxylic acid component is 100 mole% and the total mole% of the glycol component is 100 mole%,

The sum of the mole% of 2,2,4,4-tetramethyl-1,3-cyclobutadiethanol and cyclohexanedimethanol is less than 40 to 70 mole% of the total mole% of the glycol component,

When measured in a 60/40 (weight / weight) phenol / tetrachloroethane solution at a concentration of 0.25 g / 50 ml at 25 ° C., the inherent viscosity of the polyester is 0.50 to 1.2 dL / g,

Polyester has a Tg of about 100 to about 110 ° C., a flexural modulus of 23 ° C. of at least 290,000 psi according to ASTM D790, as measured by TA 2100 (Thermal Analyst Instrument) at a scan rate of 20 ° C./min. And a notched Izod impact strength of at least 10 feet-lbs / inch or more as measured according to ASTM D256 at 10 mil notches using a 1/8 inch thick bar at 23 ° C.

In one aspect, the invention

(I) a die comprising (a) from about 90 to about 100 mole percent of (e) terephthalic acid residues, and (ii) from about 0 to about 10 mole percent of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms. Carboxylic acid components; And (b) from about 20 to about 40 mole percent of (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and (ii) from about 20 to about 40 cyclohexanedimethanol residues. At least one polyester comprising a mole%, (iii) an ethylene glycol moiety, and (iv) less than about 2 mole% modified glycol having 3 to 16 carbon atoms; And

(II) one or more phosphorus compounds selected from alkyl phosphate esters, aryl phosphate esters, mixed alkyl aryl phosphate esters, reaction products thereof, and mixtures thereof,

The total mole% of the dicarboxylic acid component is 100 mole% and the total mole% of the glycol component is 100 mole%,

The sum of the mole% of 2,2,4,4-tetramethyl-1,3-cyclobutadiethanol and cyclohexanedimethanol is less than 40 to 70 mole% of the total mole% of the glycol component,

When measured in a 60/40 (weight / weight) phenol / tetrachloroethane solution at a concentration of 0.25 g / 50 ml at 25 ° C., the inherent viscosity of the polyester is 0.50 to 1.2 dL / g,

Polyester has a Tg of about 100 to about 110 ° C., a flexural modulus of at least 230,000 psi according to ASTM D790, and a 23 ° C. at 23 ° C., measured by TA 2100 (Thermal Analyst Instruments) at a scan rate of 20 ° C./min. And a notched Izod impact strength of at least 10 feet-lbs / inch or more as measured according to ASTM D256 with a 10 mil notch using a 8 inch thick bar.

In one aspect, the invention

(I) a die comprising (a) from about 90 to about 100 mole percent of (e) terephthalic acid residues, and (ii) from about 0 to about 10 mole percent of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms. Carboxylic acid components; (b) about 20 to about 40 mole percent of (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and (ii) about 20 to about 40 mole of cyclohexanedimethanol residues. a glycol component comprising%, (iii) ethylene glycol residues, and (iv) less than about 2 mole percent of modified glycols having 3 to 16 carbon atoms; And c) optionally, at least one polyester comprising at least one branching agent; And

(II) one or more phosphorus compounds selected from alkyl phosphate esters, aryl phosphate esters, mixed alkyl aryl phosphate esters,

The total mole% of the dicarboxylic acid component is 100 mole% and the total mole% of the glycol component is 100 mole%,

The sum of the mole% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and cyclohexanedimethanol is less than 40 to 70 mole% of the total mole% of the glycol component ,

A polyester composition, wherein the polyester has an inherent viscosity of 0.50 to 1.2 dL / g when measured in a 60/40 (weight / weight) phenol / tetrachloroethane solution at a concentration of 0.25 g / 50 ml at 25 ° C.

In one aspect, the invention

(I) (a) (i) about 90 to about 100 mole percent terephthalic acid residues; And (ii) about 0 to about 10 mole percent of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; And (b) about 20 to about 40 mole percent of (i) 2,2,4,4-tetramethyl-1,3-cyclobutyene indiol residues, and (ii) about 20 to about 40 mole of cyclohexanedimethanol residues. a mixture comprising:%, (iii) an ethylene glycol moiety, and a glycol component comprising (iv) less than about 2 mole percent of modified glycols having from 3 to 16 carbon atoms in the range of 0 psig to 75 psig Heating at one or more temperatures selected from 150 to 250 ° C. under one or more pressures selected from; And (II) the product of step (I) is heated to a final poly by heating at a temperature of 230 to 320 ° C. under one or more pressures selected from the final pressure of step (I) to 0.02 Torr (absolute pressure). Generating an ester,

The molar ratio of glycol component / dicarboxylic acid component added in step (I) is 1.01 to 3.0 / 1.0,

The mixture in step (I) comprises (i) at least one catalyst comprising at least one tin compound, and optionally titanium, gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium, aluminum compounds, and lithium hydroxide Or at least one catalyst selected from sodium hydroxide and aluminum compounds; And (ii) heating in the presence of one or more phosphorus compounds,

The total mole% of the dicarboxylic acid component in the final polyester is 100 mol%, the total mole% of the glycol component in the final polyester is 100 mol%,

The sum of the mole% of 2,2,4,4-tetramethyl-1,3-cyclobutadiethanol and cyclohexanedimethanol is less than 40 to 70 mole% of the total mole% of the glycol component,

Regarding the method for producing a polyester, the inherent viscosity of the polyester is 0.50 to less than 1.2 dL / g when measured in a 60/40 (weight / weight) phenol / tetrachloroethane solution at a concentration of 0.25 g / 50 ml at 25 ° C. will be.

In one aspect, the invention

(I) a die comprising (a) from about 90 to about 100 mole percent of (e) terephthalic acid residues, and (ii) from about 0 to about 10 mole percent of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms. Carboxylic acid components; And (b) from about 20 to about 40 mole percent of (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and (ii) from about 20 to about 40 cyclohexanedimethanol residues. 0 psig-75 psig, a mixture comprising a mole percent, (iii) an ethylene glycol moiety, and a glycol component comprising (iv) less than about 2 mole% of modified glycols having from 3 to 16 carbon atoms, Heating at one or more temperatures selected from 150 to 250 ° C. under one or more pressures selected from the range; And (II) the product of step (I) is heated to a final poly by heating at a temperature of 230 to 320 ° C. under one or more pressures selected from the final pressure of step (I) to 0.02 Torr (absolute pressure). Generating an ester,

The molar ratio of glycol component / dicarboxylic acid component added in step (I) is 1.01 to 3.0 / 1.0,

The mixture in step (I) comprises (i) one or more catalysts comprising one or more titanium compounds, and optionally tin, gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium, aluminum compounds, and lithium hydroxide Or in the presence of at least one catalyst selected from sodium hydroxide and an aluminum compound, and (ii) at least one phosphorus compound,

The total mole% of the dicarboxylic acid component in the final polyester is 100 mol%, the total mole% of the glycol component in the final polyester is 100 mol%,

The sum of the mole% of 2,2,4,4-tetramethyl-1,3-cyclobutadiethanol and cyclohexanedimethanol is less than 40 to 70 mole% of the total mole% of the glycol component,

Regarding a method for producing a polyester, the inherent viscosity of the polyester is 0.50 to 1.2 dL / g, as measured in a 60/40 (weight / weight) phenol / tetrachloroethane solution at a concentration of 0.25 g / 50 ml at 25 ° C. will be.

In one aspect, the invention

(I) a die comprising (a) from about 90 to about 100 mole percent of (e) terephthalic acid residues, and (ii) from about 0 to about 10 mole percent of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms. Carboxylic acid component, and (b) from about 20 to about 40 mole percent of (i) 2,2,4,4-tetramethyl-1,3-cyclobutadienol residues; (ii) about 20 to about 40 mole% cyclohexanedimethanol residues; selecting from a range of 0 psig to 75 psig, a mixture comprising (iii) an ethylene glycol moiety and a glycol component comprising (iv) less than about 2 mole percent of modified glycols having from 3 to 16 carbon atoms Heating at one or more temperatures selected from 150 to 250 ° C. under one or more pressures; And (II) the product of step (I) is heated to a final poly by heating at a temperature of 230 to 320 ° C. under one or more pressures selected from the final pressure of step (I) to 0.02 Torr (absolute pressure). Generating an ester,

The molar ratio of glycol component / dicarboxylic acid component added in step (I) is 1.01 to 3.0 / 1.0,

The mixture in step (I) comprises (i) at least one catalyst comprising at least one titanium compound and at least one tin compound, and optionally gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium, aluminum compound, And at least one catalyst selected from lithium hydroxide or sodium hydroxide and an aluminum compound, and (ii) in the presence of at least one phosphorus compound,

The total mole% of the dicarboxylic acid component in the final polyester is 100 mol% and the total mole% of the glycol component in the final polyester is 100 mol%,

The sum of the mole% of 2,2,4,4-tetramethyl-1,3-cyclobutadiethanol and cyclohexanedimethanol is less than 40 to 70 mole% of the total mole% of the glycol component,

Regarding a method for producing a polyester, the inherent viscosity of the polyester is 0.50 to 1.2 dL / g, as measured in a 60/40 (weight / weight) phenol / tetrachloroethane solution at a concentration of 0.25 g / 50 ml at 25 ° C. will be.

In one embodiment, in the polyesters useful in the present invention and / or in the methods useful in the present invention, the b ^* color values for the polyesters useful in the present invention indicate that L ^* represents lightness coordinates and a ^* represents red / Measured by the L ^* a ^* b ^* color system of the CIE (International Illumination Commission), which represents green coordinates and b ^* represents yellow / blue coordinates, in one embodiment, in the presence and / or absence of toner It may be less than -12 to 12. In one embodiment, the b ^* color value of the polyesters useful in the present invention may be 0 to 10 [in one embodiment, in the presence and / or absence of toner]. In one embodiment, the b ^* color value for the polyesters useful in the present invention may be 0 to 5 [in one embodiment, in the presence and / or absence of toner].

In one embodiment, the present invention includes a thermoset sheet that may include any polyester composition of the present invention.

In one embodiment, the polyesters useful in the present invention may comprise one or more phosphate esters in the presence or absence of a heat stabilizer.

In one embodiment, the polyesters useful in the present invention may include one or more phosphate esters described herein as being as heat stabilizers.

In one embodiment, the polyesters useful in the present invention do not contain any branching agents or optionally one or more branching agents are added before or during the polymerization of the polyester.

In one embodiment, the polyesters useful in the present invention contain one or more branching agents, regardless of the method or order in which they are added.

In one embodiment, certain polyesters useful in the present invention may be amorphous or semicrystalline. In one embodiment, certain polyesters useful in the present invention may have a relatively low degree of crystallinity. Therefore, certain polyesters useful in the present invention may have a substantially amorphous form, which means that the polyester comprises substantially unordered regions of the polymer.

In one embodiment, the polyesters, polyester compositions and / or methods of the invention may comprise one or more phosphorus compounds.

In one embodiment, the polyesters, polyester compositions and / or methods of the invention may comprise phosphorus atoms.

In one embodiment, the polyesters and / or polyester compositions useful in the present invention may comprise tin atoms.

In one embodiment, the polyesters and / or polyester compositions useful in the present invention may comprise titanium atoms.

In one embodiment, the polyesters and / or polyester compositions useful in the present invention may comprise titanium atoms and tin atoms.

In one embodiment, the polyesters, polyester compositions and / or methods of the invention may comprise phosphorus atoms and tin atoms.

In one embodiment, the polyester composition, polyester composition and / or method of the invention may comprise phosphorus atoms and titanium atoms.

In one embodiment, the polyesters, polyester compositions and methods according to the invention may comprise phosphorus atoms, tin atoms, and titanium atoms.

In one embodiment, any of the polyesters, polyester compositions, and / or methods according to the invention may comprise one or more phosphorus compounds.

In one embodiment, any of the polyesters, polyester compositions and / or methods according to the invention may comprise one or more tin compounds.

In one embodiment, any of the polyesters, polyester compositions, and / or methods according to the invention may comprise one or more tin compounds and one or more phosphorus compounds.

In one embodiment, any polyester, polyester composition and / or method useful in the present invention may comprise one or more titanium compounds.

In one embodiment, any of the polyesters, polyester compositions and / or methods useful in the present invention may include one or more titanium compounds and one or more phosphorus compounds.

In one embodiment, any polyester, polyester composition and / or method useful in the present invention comprises one or more tin compounds and optionally titanium, gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium, aluminum compounds, And one or more catalysts selected from lithium hydroxide or sodium hydroxide and aluminum compounds.

In one embodiment, any polyester, polyester composition, and / or method of making polyesters useful in the present invention may include one or more tin compounds and one or more titanium compounds.

In one embodiment, any polyester, polyester composition, and / or method of preparing the polyesters useful in the present invention may include one or more tin compounds, one or more titanium compounds, and one or more phosphorus compounds.

In one embodiment, one or more phosphorus compounds useful in the present invention include phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphonic acid, and various esters and salts thereof. The ester can be alkyl, branched alkyl, substituted alkyl, difunctional alkyl, alkyl ethers, aryl and substituted aryl.

In one embodiment, one or more phosphorus compounds useful in the present invention are substituted or unsubstituted alkyl phosphate esters, substituted or unsubstituted aryl phosphate esters, substituted or unsubstituted mixed alkyl aryl phosphate esters, diphosphites, phosphoric acid One or more phosphorus compounds selected from one or more of salts, phosphine oxides and mixed alkyl aryl phosphites, reaction products thereof, and mixtures thereof. Phosphate esters include esters in which phosphoric acid is fully esterified or only partially esterified.

In one embodiment, one or more phosphorus compounds useful in the present invention are substituted or unsubstituted alkyl phosphate esters, substituted or unsubstituted aryl phosphate esters, mixed substituted or unsubstituted alkyl aryl phosphate esters, reaction products thereof, and these One or more phosphorus compounds selected from one or more of the mixtures thereof. Phosphate esters include esters in which phosphoric acid is fully esterified or only partially esterified.

In one embodiment, the one or more phosphorus compounds useful in the present invention are selected from one or more of alkyl phosphate esters, aryl phosphate esters, mixed alkyl aryl phosphate esters, reaction products thereof and mixtures thereof.

In one embodiment, one or more phosphorus compounds useful in the present invention may include one or more aryl phosphate esters.

In one embodiment, one or more phosphorus compounds useful in the present invention may include one or more unsubstituted aryl phosphate esters.

In one embodiment, one or more phosphorus compounds useful in the present invention may include one or more aryl phosphate esters that are not substituted with benzyl groups.

In one embodiment, one or more phosphorus compounds useful in the present invention may include one or more triaryl phosphate esters.

In one embodiment, one or more phosphorus compounds useful in the present invention may include one or more triaryl phosphate esters that are not substituted with benzyl groups.

In one embodiment, one or more phosphorus compounds useful in the present invention may include one or more alkyl phosphate esters.

In one embodiment, the one or more phosphorus compounds useful in the present invention may include triphenyl phosphate and / or Merpol A. In one embodiment, any polyester composition of the present invention may comprise triphenyl phosphate.

In one embodiment, any of the methods described herein for preparing any polyester composition and / or polyester may comprise one or more mixed alkyl aryl phosphites, such as Doverphos S-9228 ( Bis (2,4-dicumylphenyl) pentaerythritol diphosphite, also known as Dover Chemicals, CAS # 154862-43-8.

In one embodiment, any polyester composition and / or any method described for the preparation of the polyester may comprise one or more phosphine oxides.

In one embodiment, any polyester composition and / or any method described for the preparation of the polyester can include one or more salts of phosphoric acid, such as KH ₂ PO ₄ and Zn ₃ (PO ₄ ) ₂ .

It is believed that any of the polyesters useful in the present invention can be made using any method of making polyesters useful in the present invention.

In one embodiment, the pressure used in step (I) of any of the methods of the present invention consists of one or more pressures selected from 0 psi to 75 psig. In one embodiment, the pressure used in step (I) of any of the methods of the present invention consists of one or more pressures selected from 0 psig to 50 psig.

In one embodiment, the pressure used in step (II) of any method of the present invention consists of one or more pressures selected from the range of 20 to 0.02 Torr (absolute pressure); In one embodiment, the pressure used in step (II) of any of the methods of the present invention consists of one or more pressures selected from the range of 10 to 0.02 Torr (absolute pressure); In one embodiment, the pressure used in step (II) of any method of the present invention consists of one or more pressures selected from the range of 5 to 0.02 Torr (absolute pressure); In one embodiment, the pressure used in step (II) of any of the methods of the present invention is at least one pressure selected from the range of 3 to 0.02 Torr (absolute pressure); In one embodiment, the pressure used in step (II) of any method of the present invention consists of one or more pressures selected from the range of 20 to 0.1 Torr (absolute pressure); In one embodiment, the pressure used in step (II) of any of the methods of the present invention consists of one or more pressures selected from the range of 10 to 0.1 Torr (absolute pressure); In one embodiment, the pressure used in step (II) of any method of the present invention consists of one or more pressures selected from the range of 5 to 0.1 Torr (absolute pressure); In one embodiment, the pressure used in step (II) of any method of the present invention consists of one or more pressures selected from the range of 3 to 0.1 Torr (absolute pressure).

In one embodiment, the molar ratio of glycol component / dicarboxylic acid component added in step (I) of any of the methods of the present invention is 1.0 to 3.0 / 1.0; In one embodiment, the molar ratio of glycol component / dicarboxylic acid component added in step (I) of any of the methods of the invention is 1.0 to 2.5 / 1.0; In one embodiment, the molar ratio of glycol component / dicarboxylic acid component added in step (I) of any of the methods of the present invention is 1.0 to 2.0 / 1.0; In one embodiment, the molar ratio of glycol component / dicarboxylic acid component added in step (I) of any of the methods of the present invention is 1.0 to 1.75 / 1.0; In one embodiment, the molar ratio of glycol component / dicarboxylic acid component added in step (I) of any of the methods of the invention is 1.0 to 1.15 / 1.0.

In one embodiment, the molar ratio of glycol component / dicarboxylic acid component added in step (I) of any of the methods of the present invention is 1.01 to 3.0 / 1.0; In one embodiment, the molar ratio of glycol component / dicarboxylic acid component added in step (I) of any of the methods of the present invention is 1.01 to 2.5 / 1.0; In one embodiment, the molar ratio of glycol component / dicarboxylic acid component added in step (I) of any of the methods of the present invention is 1.01 to 2.0 / 1.0; In one embodiment, the molar ratio of glycol component / dicarboxylic acid component added in step (I) of any of the methods of the invention is 1.01 to 1.75 / 1.0; In one embodiment, the molar ratio of glycol component / dicarboxylic acid component added in step (I) of any of the methods of the invention is 1.01 to 1.15 / 1.0.

In any method embodiment for preparing the polyesters useful in the present invention, the heating time of step (II) may be 1 to 5 hours. In any method embodiment for preparing the polyesters useful in the present invention, the heating time of step (II) can be 1 to 4 hours. In any method embodiment for preparing the polyesters useful in the present invention, the heating time of step (II) may be 1 to 3 hours. In any method embodiment for preparing the polyesters useful in the present invention, the heating time of step (II) may be 1.5 to 3 hours. In any method embodiment for preparing the polyesters useful in the present invention, the heating time of step (II) may be 1 to 2 hours.

In one embodiment, the addition of phosphorus compound (s) to the method (s) of the present invention can result in a weight ratio of total phosphorus atoms to total tin atoms in the final polyester from 0 to 20: 1. In one embodiment, the addition of phosphorus compound (s) to the method (s) of the present invention can result in a weight ratio of total phosphorus atoms to total tin atoms in the final polyester of 1 to 20: 1.

In one embodiment, the addition of phosphorus compound (s) to the method (s) of the present invention can result in a weight ratio of total phosphorus atoms to total tin atoms in the final polyester from 0 to 15: 1. In one embodiment, the addition of phosphorus compound (s) to the method (s) of the present invention can result in a weight ratio of total phosphorus atoms to total tin atoms in the final polyester of 1 to 15: 1.

In one embodiment, the addition of phosphorus compound (s) to the method (s) of the present invention can result in a weight ratio of total phosphorus atoms to total tin atoms in the final polyester from 0 to 10: 1. In one embodiment, the addition of phosphorus compound (s) to the method (s) of the present invention can result in a weight ratio of total phosphorus atoms to total tin atoms in the final polyester of 1 to 10: 1.

In one embodiment, adding phosphorus compound (s) to the method (s) of the present invention can result in a weight ratio of total phosphorus atoms to total tin atoms in the final polyester from 0 to 5: 1. In one embodiment, the addition of phosphorus compound (s) to the method (s) of the present invention can result in a weight ratio of total phosphorus atoms to total tin atoms in the final polyester of 1 to 5: 1.

In one embodiment, adding phosphorus compound (s) to the method (s) of the present invention can result in a weight ratio of total phosphorus atoms to total tin atoms in the final polyester from 0 to 3: 1. In one embodiment, the addition of phosphorus compound (s) to the process (s) of the present invention may result in a weight ratio of total phosphorus atoms to total tin atoms in the final polyester of 1 to 3: 1.

For example, the weight of tin atoms and phosphorus atoms present in the final polyester can be measured in ppm and consequently will have a weight ratio of total phosphorus atoms to total tin atoms in the final polyester of any of the aforementioned weight ratios. Can be.

In one embodiment, the addition of phosphorus compound (s) to the method (s) of the present invention can result in a weight ratio of total phosphorus atoms to total titanium atoms in the final polyester from 0 to 20: 1. In one embodiment, the addition of phosphorus compound (s) to the method (s) of the present invention can result in a weight ratio of total phosphorus atoms to total titanium atoms in the final polyester of 1 to 20: 1.

In one embodiment, adding phosphorus compound (s) to the method (s) of the present invention can result in a weight ratio of total phosphorus atoms to total titanium atoms in the final polyester from 0 to 15: 1. In one embodiment, the addition of phosphorus compound (s) to the method (s) of the present invention can result in a weight ratio of total phosphorus atoms to total titanium atoms in the final polyester of 1 to 15: 1.

In one embodiment, adding phosphorus compound (s) to the method (s) of the present invention can result in a weight ratio of total phosphorus atoms to total titanium atoms in the final polyester from 0 to 10: 1. In one embodiment, the addition of phosphorus compound (s) to the method (s) of the present invention may result in a weight ratio of total phosphorus atoms to total titanium atoms in the final polyester of 1 to 10: 1.

In one embodiment, adding phosphorus compound (s) to the method (s) of the present invention can result in a weight ratio of total phosphorus atoms to total titanium atoms in the final polyester from 0 to 5: 1. In one embodiment, the addition of phosphorus compound (s) to the method (s) of the present invention can result in a weight ratio of total phosphorus atoms to total titanium atoms in the final polyester of 1 to 5: 1.

In one embodiment, adding phosphorus compound (s) to the method (s) of the present invention can result in a weight ratio of total phosphorus atoms to total titanium atoms in the final polyester from 0 to 3: 1. In one embodiment, the addition of phosphorus compound (s) to the method (s) of the present invention can result in a weight ratio of total phosphorus atoms to total titanium atoms in the final polyester of 1 to 3: 1.

For example, the weight of titanium atoms and phosphorus atoms present in the final polyester can be measured in ppm and consequently the weight ratio of total phosphorus atoms to total titanium atoms in the final polyester of any of the weight ratios described above. It can have

In one embodiment, the amount of tin atoms in the polyesters useful in the present invention may be from 0 to 400 ppm tin atoms based on the weight of the final polyester.

In one embodiment, the amount of tin atoms in the polyesters useful in the present invention may be from 15 to 400 ppm tin atoms based on the weight of the final polyester.

In one embodiment, the amount of titanium atoms in the polyesters useful in the present invention may be from 0 to 400 ppm titanium atoms, based on the weight of the final polyester.

In one embodiment, the amount of titanium atoms in the polyesters useful in the present invention may be 15 to 400 ppm titanium atoms, based on the weight of the final polyester.

In one embodiment, the amount of phosphorus atoms in the polyesters useful in the present invention may be from 1 to 500 ppm of phosphorus atoms based on the weight of the final polyester.

In one embodiment, the amount of phosphorus atoms in the polyesters useful in the present invention can be from 1 to 500 ppm of phosphorus atoms based on the weight of the final polyester, and the amount of titanium atoms in the polyester is based on the weight of the final polyester It may be 1 to 100 ppm of the atom.

In one embodiment, the amount of phosphorus atoms in the polyesters useful in the present invention can be from 1 to 500 ppm of phosphorus atoms based on the weight of the final polyester, and the amount of titanium atoms in the polyester is based on the weight of the final polyester It may be 1 to 400 ppm of the atom.

In one embodiment, the amount of phosphorus atoms in the polyesters useful in the present invention is from 1 to 500 ppm of phosphorus atoms based on the weight of the final polyester, and the amount of titanium atoms in the polyester is based on the weight of the final polyester of titanium atoms 1 To 100 ppm.

In one embodiment, the amount of phosphorus atoms in the polyesters useful in the present invention is from 1 to 500 ppm phosphorus atoms based on the weight of the final polyester, and the amount of tin atoms in the polyesters useful in the present invention is based on the weight of the final polyester Tin atoms are 1 to 400 ppm, and the amount of titanium atoms in the polyester may be 1 to 100 ppm titanium based on the weight of the final polyester.

In one embodiment, the polyester composition may comprise an injection molded product, an extruded product, a cast extruded product, a profile extruded product, a melt spun product, a thermoformed product, an extrusion molded product, an injection blow molded product, an injection stretch blow molded product, an extrusion It is useful in articles including, but not limited to, extrusion, calendering and / or molded articles including, but not limited to, blow molded articles and extrusion stretch blow molded articles. These products may include, but are not limited to, films, bottles, containers, sheets, and / or fibers.

In one embodiment, the polyester compositions useful in the present invention include extruded film (s) and / or sheet (s), calendering film (s) and / or sheet (s), compression molded film (s) and / or sheets. (S), solution casting film (s) and / or sheet (s) can be used in various types of films and / or sheets, including but not limited to. Methods of making films and / or sheets include, but are not limited to, extrusion, calendering, compression molding, and solution casting.

In one aspect, the invention relates to thermoformed film (s) and / or sheet (s) comprising the polyester (s) and / or polyester compositions of the invention.

In one embodiment, the present invention relates to an article incorporating the thermoformed film and / or sheet of the present invention.

In addition, in one embodiment, a method of making a thermoformed film and / or sheet is provided, which excludes the drying step of the film and / or sheet prior to thermoforming.

In one embodiment, the present invention provides improved color and / or transparency while containing ethylene glycol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol and cyclohexanedimethanol It provides a method for producing a polyester having.

In one embodiment, the polyesters useful in the present invention may be amorphous or semicrystalline. In one embodiment, certain polyesters useful in the present invention may have a relatively low crystallinity. Certain polyesters useful in the present invention have a substantially amorphous form, meaning that the polyester comprises substantially non-oriented regions of the polymer.

The invention may be more readily understood by reference to the following detailed description and working examples of certain embodiments of the invention. For the purposes of the present invention, certain embodiments of the invention are described in the Summary of the Invention and are further described herein below. In addition, other embodiments of the invention are described herein.

Terephthalic acid, esters and / or mixtures thereof, ethylene glycol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, cyclohexanediol, and specific heat stabilizers, Certain polyesters and / or polyester compositions according to the invention, including their reaction products and mixtures thereof, have high notched izod impact strength, specific intrinsic viscosity, specific glass transition temperature (Tg), specific flexural modulus, good transparency And excellent combinations of two or more of the best colors. In certain embodiments of the present invention, certain polyesters and / or polyester compositions according to the present invention are characterized by high notch Izod impact strength, specific intrinsic viscosity, specific glass transition temperature (Tg), specific flexural modulus, good transparency and good color. It is believed that it can have three or more unique combinations.

In certain embodiments of the present invention, certain polyesters and / or polyester compositions according to the present invention are characterized by high notch Izod impact strength, specific intrinsic viscosity, specific glass transition temperature (Tg), specific flexural modulus, good transparency and good color. It is believed that it can have a unique combination of four or more.

In another embodiment of the present invention, certain polyesters and / or polyester compositions according to the present invention have a high notch Izod impact strength, a specific intrinsic viscosity, a specific glass transition temperature (Tg), a specific flexural modulus, good transparency and good color It is believed to have the only total combination.

If polyesters and / or polyester compositions containing some or all of the aforementioned properties are useful in many applications, these properties are particularly useful in thermoformed sheet applications.

In one embodiment, copolyesters containing 2,2,4,4-tetramethyl-1,3-cyclobutanediol and ethylene glycol can be prepared using a titanium based catalyst. In other embodiments, the introduction of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and / or color can be further improved by the use of tin-based catalysts in addition to titanium-based catalysts. Is considered. It is believed that the color of such copolyesters can be improved by adding certain levels of phosphorus containing compounds during polymerization.

In one embodiment, when at least the phosphorus compounds described above are used in the process for the preparation of the polyesters according to the invention, the polyesters are bubbling, flaring, color forming, foaming, by-product gas evolution, and erratic melt levels ( That is, it is believed that the polyester of the present invention can be easily produced without one or more of polyester or pulsation of the processing system). In other embodiments, one or more methods of the present invention provide a means for more easily producing large quantities of polyesters useful in the present invention (eg, pilot run scale and / or commercial production) while avoiding one or more of the foregoing difficulties. It is believed to provide. As used herein, the term “bulk” includes the amount of polyester (s) useful in the present invention produced in an amount greater than 100 pounds. In one embodiment, the term “bulk” as used herein includes the amount of polyester (s) useful in the present invention that is produced in an amount greater than 1000 pounds.

In one embodiment, methods of making polyesters useful in the present invention may include batch or continuous processes.

In one embodiment, methods of making polyesters useful in the present invention include continuous processes.

When tin is added to the polyester and / or polyester composition and / or the method for producing the polyester according to the invention, it is added to the method for producing the polyester in the form of a tin compound. The amount of tin added to the polyesters of the invention and / or the polyester compositions of the invention and / or the process of the invention can be measured in the form of tin atoms present in the final polyester, for example in weight ppm. .

When titanium is added to the polyester and / or polyester composition and / or the method for producing the polyester according to the invention, it is added to the method for producing the polyester in the form of a titanium compound. The amount of titanium compound added to the polyester according to the invention and / or to the polyester composition according to the invention and / or to the process according to the invention is in the form of titanium present in the final polyester, for example in units of weight ppm. It can be measured.

When phosphorus is added to the polyester and / or polyester composition and / or the process for producing the polyester according to the invention, it is added to the process for producing the polyester in the form of a phosphorus compound. In one embodiment, such phosphorus compounds may comprise one or more phosphate ester (s). The amount of phosphorus compound added to the polyester according to the invention and / or to the polyester composition according to the invention and / or to the process according to the invention is in the form of phosphorus atoms present in the final polyester, for example by weight ppm Can be measured.

As used herein, the term “polyester” is intended to include “copolyester” and includes one or more difunctional carboxylic acids and / or polyfunctional carboxylic acids and one or more difunctional hydroxyl compounds and / or polyfunctional hydroxyl compounds, eg For example, it is understood to mean a synthetic polymer prepared by the reaction of a branching agent. Typically, the difunctional carboxylic acid may be a dicarboxylic acid and the difunctional hydroxyl compound may be a dihydric alcohol such as, for example, glycols and diols. The term "glycol" as used herein includes, but is not limited to, diols, glycols and / or polyfunctional hydroxyl compounds, such as branching agents. Alternatively, the bifunctional carboxylic acid can be, for example, a hydroxy carboxylic acid such as p-hydroxybenzoic acid, and the bifunctional hydroxyl compound can be an aromatic nucleus (eg hydroquinone) having two hydroxyl substituents. As used herein, the term “residue” means any organic structure that is incorporated into a polymer via polycondensation and / or esterification reactions from the corresponding monomers. The term "repeating unit" as used herein refers to an organic structure having dicarboxylic acid residues and diol residues bonded through carbonyloxy groups. Thus, for example, the dicarboxylic acid residues may be derived from dicarboxylic acid monomers or their associated acid halides, esters, salts, anhydrides and / or mixtures thereof. In addition, the term “diacid” as used herein includes polyfunctional acids, such as branching agents. As used herein, the term “dicarboxylic acid” refers to dicarboxylic acids useful in the course of reaction with diols to make polyesters and their associated acid halides, esters, semi-esters, salts, semi-salts, anhydrides, mixed anhydrides Or any derivative of dicarboxylic acids, including mixtures thereof. As used herein, the term “terephthalic acid” refers to terephthalic acid itself and residues thereof, as well as acid halides, esters, semi-esters, salts, semi-salts, and the like, which are useful in the reaction with diols to prepare polyesters. It is intended to include any derivative of terephthalic acid, including anhydrides, mixed anhydrides, and / or mixtures or residues thereof.

Typically, the polyesters used in the present invention can be prepared from dicarboxylic acids and diols which react in substantially equal amounts and are incorporated into the polyester polymer as corresponding residues. Therefore, the polyesters of the present invention contain substantially equimolar amounts of acid residues (100 mol%) and diol (and / or polyfunctional hydroxyl compound) residues (100 mol%) such that the total moles of repeating units are 100 mol%. It may contain. Thus, the mole percentages provided herein can be based on the total moles of acid residues, the total moles of diol residues, or the total moles of repeat units. For example, polyesters containing 10 mol% isophthalic acid based on total acid residues means that the polyester contains 10 mol% isophthalic acid residues in a total of 100 mol% acid residues. Therefore, there are 10 moles of isophthalic acid residues for every 100 moles of acid residues. In another example, a polyester containing 30 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol based on the total diol residues has a total of 100 mol% of die It is meant to contain 30 mole% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues in all residues. Thus, there are 30 moles of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues for every 100 moles of diol residues.

In another aspect of the invention, the Tg of the polyester composition useful in the present invention may be one or more of the following ranges: 90 to 120 ° C; 95 to 120 ° C; 100 to 120 ° C; 105 to 120 ° C; 110 to 120 ° C; 90 to 115 ° C; 95 to 115 ° C; 100 to 115 ° C; 105 to 115 ° C; 90 to 110 ° C; 95 to 110 ° C; 100 to 110 ° C; 90 to 100 ° C; 90 to 105 ° C; 95 to 105 ° C; And 90 to 100 ° C.

In another embodiment according to the present invention, the glycol component of the polyester composition useful in the present invention may be included in one or more of the following combinations, but is not limited to: 2,2,4,4-tetramethyl-1, 20 to 40 mol% of 3-cyclobutadiethanol, 20 to 40 mol% of cyclohexanedimethanol, and 30 to 60 mol% of ethylene glycol; 20 to less than 35 mol% of 2,2,4,4-tetramethyl-1, 3-cyclobutanediol, 20 to 40 mol% of cyclohexanedimethanol, and 30 to 60 mol% of ethylene glycol; 20 to 30 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 20 to 40 mol% of cyclohexanedimethanol, and 30 to 60 mol% of ethylene glycol; And 20 to 25 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 20 to 40 mol% of cyclohexanedimethanol, and 30 to 60 mol% of ethylene glycol.

In another embodiment according to the present invention, the glycol component of the polyester composition useful in the present invention may be included in one or more of the following combinations, but is not limited to: 2,2,4,4-tetramethyl-1, 25 to 40 mol% of 3-cyclobutenediol, 20 to 40 mol% of cyclohexanedimethanol, and 30 to 55 mol% of ethylene glycol; 25 to 35 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 20 to 40 mol% of cyclohexanedimethanol, and 30 to 55 mol% of ethylene glycol; And 25 to 30 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 20 to 40 mol% of cyclohexanedimethanol, and 30 to 55 mol% of ethylene glycol.

In another embodiment according to the present invention, the glycol component of the polyester composition useful in the present invention may be included in one or more of the following combinations, but is not limited to: 2,2,4,4-tetramethyl-1, 30 to 40 mol% of 3-cyclobutadiethanol, 20 to 40 mol% of cyclohexanedimethanol, and 30 to 50 mol% of ethylene glycol; And 30 to 35 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 20 to 40 mol% of cyclohexanedimethanol, and 30 to 50 mol% of ethylene glycol.

In another embodiment according to the present invention, the glycol component of the polyester composition useful in the present invention may be included in one or more of the following combinations, but is not limited to: 2,2,4,4-tetramethyl-1, 20 to 40 mol% of 3-cyclobutadiethanol, 20 to 35 mol% of cyclohexanedimethanol, and 30 to 60 mol% of ethylene glycol; 20 to 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 20 to 30 mol% of cyclohexanedimethanol, and 30 to 60 mol% of ethylene glycol; And 20 to 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 20 to 25 mol% of cyclohexanedimethanol, and 30 to 60 mol% of ethylene glycol.

In another embodiment according to the present invention, the glycol component of the polyesters useful in the present invention may be included in one or more of the following combinations, but is not limited to: 2,2,4,4-tetramethyl-1,3 20-40 mol% cyclobutadiethanol, 25-40 mol% cyclohexanedimethanol, and 30-55 mol% ethylene glycol; 20 to 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 25 to 35 mol% of cyclohexanedimethanol, and 30 to 55 mol% of ethylene glycol; And 20 to 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 25 to 30 mol% of cyclohexanedimethanol, and 30 to 50 mol% of ethylene glycol.

In one embodiment, the glycol component of the polyesters useful in the present invention may be included in one or more of the following combinations, but are not limited to: 2,2,4,4-tetramethyl-1,3-cyclo 20-40 mol% butanediol, 30-40 mol% cyclohexanedimethanol, and 30-50 mol% ethylene glycol; And 20 to 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 30 to 35 mol% of cyclohexanedimethanol, and 30 to 55 mol% of ethylene glycol.

In another embodiment according to the present invention, the glycol component of the polyester composition useful in the present invention comprises 2,2,4,4-tetramethyl-1,3-cyclobutanediol and cyclohexanedimethanol The sum of the mole% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and cyclohexanedimethanol is less than 40 to 70 mole% of the total mole% of the total glycol component. .

In embodiments of the present invention, polyesters useful in the present invention may exhibit one or more of the following inherent viscosities as measured in 60/40 (weight / weight) phenol / tetrachloroethane at a concentration of 0.25 g / 50 ml at 25 ° C. There is: 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; 0.58 to less than 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; 0.60 to less than 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; 0.60 to less than 0.75 dL / g; 0.60 to 0.72 dL / g; 0.60 to 0.70 dL / g; 0.60 to less than 0.70 dL / g; 0.60 to 0.68 dL / 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; 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; And 0.68 to 0.72 dL / g.

It is contemplated that compositions useful in the present invention may have one or more of the intrinsic viscosity ranges described herein and one or more of the monomer ranges of the compositions described herein, unless stated otherwise. It is also contemplated that compositions useful in the present invention may have one or more of the Tg ranges described herein and one or more of the monomer ranges of the compositions described herein, unless stated otherwise. It is also contemplated that compositions useful in the present invention may have one or more of the Tg ranges described herein, one or more of the inherent viscosity ranges described herein, and one or more of the monomer ranges of the compositions described herein, unless otherwise noted.

In one embodiment, terephthalic acid can be used as starting material. In other embodiments, dimethyl terephthalate may be used as starting material. In other embodiments, a mixture of terephthalic acid and dimethyl terephthalate may be used as starting material and / or intermediate material.

In certain embodiments, terephthalic acid or its esters, such as, for example, dimethyl terephthalate or a mixture of terephthalic acid residues and esters thereof, may constitute most or all of the dicarboxylic acid component used to prepare the polyesters useful in the present invention. In certain embodiments, terephthalic acid residues may constitute some or all of the dicarboxylic acid component used to form the polyesters useful in the present invention. In certain embodiments, higher amounts of terephthalic acid can be used to produce higher impact strength properties. As used herein, the terms "terephthalic acid" and "dimethyl terephthalate" are used interchangeably herein. In one embodiment, dimethyl terephthalate is some or all of the dicarboxylic acid component used to prepare the polyesters useful in the present invention. In all embodiments, 70-100 mole%; Alternatively 80 to 100 mole%; Alternatively 90 to 100 mole%; Alternatively 99 to 100 mole%; Or 100 mol% terephthalic acid and / or dimethyl terephthalate and / or mixtures thereof.

In addition to terephthalic acid, the dicarboxylic acid component of the polyesters useful in the present invention may comprise 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% modified aromatic dicarboxylic acid. Therefore, when present, the amount of one or more modified aromatic dicarboxylic acids may range from these any preceding endpoint values, including, for example, 0.01 to 10 mol%, 0.01 to 5 mol%, and 0.01 to 1 mol%. have. In one embodiment, modified aromatic dicarboxylic acids that can be used in the present invention include, but are not limited to, having up to 20 carbon atoms and can be linear, para-oriented or symmetric. Examples of modified aromatic dicarboxylic acids that can be used in the present invention are isophthalic acid, 4,4'-biphenyldicarboxylic acid, 1,4-, 1,5-, 2,6-, 2,7-naphthalenedicarboxylic acid and trans -4,4'- stilbendicarboxylic acid, and esters thereof, including, but not limited to. In one embodiment, the modified aromatic dicarboxylic acid is isophthalic acid.

Carboxylic acid components of the polyesters useful in the present invention include one or more aliphatic dicarboxylic acids containing 2 to 16 carbon atoms, such as cyclohexanedicarboxylic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid And, further, up to 10 mol%, such as up to 5 mol% or up to 1 mol%, suberic acid, azelaic acid and dodecanedio dicarboxylic acid. Certain embodiments may also include 0.01 to 10 mol%, for example 0.1 to 10 mol%, 1 to 10 mol%, 5 to 10 mol% of one or more modified aliphatic dicarboxylic acids. Another embodiment contains 0 mol% modified aliphatic dicarboxylic acid. The total mole% of the dicarboxylic acid component is 100 mole%. In one embodiment, adipic acid and / or glutaric acid are provided to modify the aliphatic dicarboxylic acid component of the present invention.

Modified dicarboxylic acids of the present invention may include indan dicarboxylic acids such as indan-1,3-dicarboxylic acid and / or phenylindan dicarboxylic acid. In one embodiment, the dicarboxylic acid is 1,2,3-trimethyl-3-phenylindane-4 ', 5-dicarboxylic acid and 1,1,3-trimethyl-5-carboxy-3- (4-carboxy Phenyl) indan dicarboxylic acid. For the purposes of the present invention, US Patent Publication No. 2006 / 0004151A1 of Shaikh et al., Assigned to General Electric Company, entitled “Copolymer Containing Indan Residues and Any indane dicarboxylic acid described in "Copolymers Containing Indan Moieties and Blends Thereof" can be used as one or more modified dicarboxylic acids within the scope of the present invention and described in US Patent Publication No. 2006 / 0004151A1. Is incorporated herein by reference in connection with any indane dicarboxylic acid described herein.

Esters of terephthalic acid and other modified dicarboxylic acids or their corresponding esters and / or salts may be used in place of dicarboxylic acids. 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 one or more of methyl, ethyl, propyl, isopropyl and phenyl esters.

For the desired polyester, the molar ratio of cis / trans 2,2,4,4-tetramethyl-1,3-cyclobutanediol can vary from their respective pure forms and mixtures thereof. In certain embodiments, the mole percent of cis and / or trans 2,2,4,4, -tetramethyl-1,3-cyclobutanediol is greater than 50 mol% cis and less than 50 mol% trans Or more than 55 mol% cis form and less than 45 mol% trans form; Or 30 to 70 mol% cis form and 70 to 30 mol% trans form; Or 40 to 60 mol% cis form and 60 to 40 mol% trans form; Or 50 to 70 mol% of the trans form and 50 to 30 mol% of the cis form, or 50 to 70 mol% of the cis form and 50 to 30 mol% of the trans form; Or 60 to 70 mol% cis form and 30 to 40 mol% trans form; Or more than 70 mole% cis and less than 30 mole% trans, wherein the total mole% of cis- and trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol is 100 Molar%. In further embodiments, the molar ratio of cis / trans 2,2,4,4, -tetramethyl-1,3-cyclobutanediol is 50/50 to 0/100, for example 40/60 to 20 / It can vary in the range of 80.

Cyclohexanedimethanol may be cis, trans or a mixture thereof (such as a cis / trans ratio of 60:40 to 40:60, or a cis / trans ratio of 70:30 to 30:70). In other embodiments, trans-cyclohexanedimethanol can be present in an amount of from 60 to 80 mole percent, and cis-cyclohexanedimethanol can be present in an amount of from 20 to 40 mole percent, with cis-cyclo The total percentage of hexanedimethanol and trans-cyclohexanedimethanol is 100 mol%. In certain embodiments, trans-cyclohexanedimethanol can be present in an amount of 60 mol% and cis-cyclohexanedimethanol can be present in an amount of 40 mol%. In certain embodiments, trans-cyclohexanedimethanol can be present in an amount of 70 mol% and cis-cyclohexanedimethanol can be present in an amount of 30 mol%. Any 1,1-, 1,2-, 1,3-, 1,4-isomer or mixtures thereof of cyclohexanedimethanol may be present in the glycol component of the present invention. Cis and trans isomers are not present for 1,1-cyclohexanedimethanol.

In one embodiment, the polyesters useful in the present invention include 1,4-cyclohexanedimethanol. In other embodiments, polyesters useful in the present invention include 1,4-cyclohexanedimethanol and 1,3-cyclohexanedimethanol. The molar ratio of cis / trans 1,4-cyclohexanedimethanol can vary from 50/50 to 0/100, for example from 40/60 to 20/80.

In one embodiment, the glycol component of the polyester portion of the polyester composition useful in the present invention is 2,2,4,4-tetramethyl-1,3-cyclobutanediol or cyclohexanedimethanol Or 30 mol% or less of one or more modified glycols other than ethylene glycol; In one embodiment, the glycol component of the polyester portion of the polyester composition useful in the present invention is 2,2,4,4-tetramethyl-1,3-cyclobutanediol or cyclohexanedimethanol Or 25 mol% or less of one or more modified glycols other than ethylene glycol; In one embodiment, the glycol component of the polyester portion of the polyester composition useful in the present invention is 2,2,4,4-tetramethyl-1,3-cyclobutanediol or cyclohexanedimethanol Or up to 20 mol% of one or more modified glycols other than ethylene glycol, and in one embodiment, polyesters useful in the present invention may contain less than 15 mol% of one or more modified glycols. have. In another embodiment, the polyesters useful in the present invention may contain up to 10 mol% of one or more modified glycols. In other embodiments, polyesters useful in the present invention may contain up to 5 mol% of one or more modified glycols. In other embodiments, polyesters useful in the present invention may contain up to 3 mole percent of one or more modified glycols. In other embodiments, polyesters useful in the present invention may contain up to 2 mole percent of one or more modified glycols. In other embodiments, polyesters useful in the present invention may contain 0 mol% modified glycols.

Modified glycols useful for the polyesters useful in the present invention refer to diols other than 2,2,4,4-tetramethyl-1,3-cyclobutanediol, cyclohexanedimethanol and ethylene glycol And may contain 2 to 16 carbon atoms. Examples of suitable modified glycols are diethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1, 5-pentanediol, 1,6-hexanediol, p-xylene glycol, polytetramethylene glycol or mixtures thereof, but is not limited thereto. In other embodiments, the modified glycols include, but are not limited to, one or more of 1,3-propanediol and / or 1,4-butanediol. In one embodiment, the at least one modified glycol is diethylene glycol. In one embodiment, diethylene glycol is not added as individual monomers and is formed during the polymerization.

Polyesters useful in the polyester composition according to the present invention may be selected from the group consisting of three or more carboxyl substituents, hydroxyl substituents, or a combination thereof, wherein at least one residue of a branching monomer (also referred to herein as a branching agent) 0 to 10 mol%, for example, 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 mole% of. In certain embodiments, branching monomers or branching agents may be added before and / or during and / or after polymerization of the polyester. Therefore, the polyester (s) useful in the present invention may be linear or branched.

Examples of branched monomers are polyfunctional such as trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, glycerol, pentaerythritol, citric acid, tartaric acid, 3-hydroxyglutaric acid, and the like. Include, but are not limited to, acids or polyfunctional alcohols. In one embodiment, the branched monomer residues are trimellitic anhydride, pyromellitic dianhydride, glycerol, sorbitol, 1,2,6-hexanetriol, pentaerythritol, trimethylolethane and / or And 0.1 to 0.7 mole percent of one or more residues selected from one or more of trimesic acids. Branched monomers may be added to the polyester reaction mixture in the form of concentrates, such as those described in US Pat. Nos. 5,654,347 and 5,696,176, the disclosures of which are incorporated herein by reference. Or blend with polyester.

The polyesters of the present invention may comprise one or more chain extenders. Suitable chain extenders include, but are not limited to, polyfunctional (including but not limited to) polyisocyanates such as polyfunctional epoxides including epoxylated novolacs, and phenoxy resins. In certain embodiments, chain extenders may be added at the end of the polymerization process or after the polymerization process. When added after the polymerization process, the chain extender may be incorporated by compounding or adding during conversion processes such as injection molding or extrusion. The amount of chain extender used may vary depending on the particular monomer composition used and the physical properties required, but is generally from about 0.1 to about 10 weight percent, such as from about 0.1 to about 5 weight percent, based on the total weight of the polyester to be.

The glass transition temperature (Tg) of the polyesters useful in the present invention was measured using TA DSC 2920, a Thermal Analyst Instrument, at a scanning rate of 20 ° C./min.

Due to the long crystallization half life at 170 ° C. (e.g., greater than 5 minutes) exhibited by certain polyesters useful in the present invention, injection molding parts, injection blow molded articles, injection stretch blow molded articles, It is possible to produce articles comprising extruded films, extruded sheets, extrusion blow molded articles, extrusion stretch blow molded articles and fibers. The thermoformable sheet is an example of a product provided by the present invention. The polyesters according to the invention can be amorphous or semicrystalline. In one embodiment, certain polyesters useful in the present invention may have a relatively low crystallinity. Thus, certain polyesters useful in the present invention may have a substantially amorphous form, meaning that the polyester comprises regions of substantially irregular polymers.

In one embodiment, an “amorphous” polyester may have a crystal half life 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. have. In one embodiment of the invention, the crystallization half life may be greater than 1,000 minutes at 170 ° C. In another embodiment of the present invention, the crystallization half life of the polyesters useful in the present invention may be greater than 10,000 minutes at 170 ° C. The crystallization half-life of the polyesters used in the present invention can be measured using methods known to those skilled in the art. The light transmission of a sample via a laser and photo-detector temperature - by measuring, as a function of time on a temperature controlled stage, it is possible to measure the crystallization half-life of t _1/2 of the polyester. This measurement was performed by exposing the polymer to the temperature T _max and then cooling it to the desired temperature. The sample was then maintained at the desired temperature by the high temperature stage while measuring the transmittance as a function of time. Initially, the sample was visually transparent with high light transmittance and began to become opaque as the sample crystallized. The crystallization half-life was recorded as the time at which the light transmittance was approximately half the initial and final transmittances. T _max is defined as the temperature required to melt the crystalline domains of the sample (if crystalline domains are present). Samples were conditioned by heating each sample to T _max before crystallization half-life measurement. T _{max The} absolute temperature depends on the composition. For example, it may be necessary to heat the PCT to some temperature above 290 ° C. to melt the crystalline domains.

In one embodiment, certain polyesters useful in the present invention may be visually transparent. The term “visually transparent” is defined herein as a state where no blur, haze, and / or blur is present when it is visually examined. In other embodiments, when blending polyesters with polycarbonates, including but not limited to bisphenol A polycarbonate, the blend may be visually transparent.

In one embodiment, polyesters useful in the present invention and / or polyester compositions of the present invention [with or without toner] are Hunter Labs Ultra, a product of Hunter Associates Labs (Reston, VA). It may have color values L ^* , a ^* and b ^* that can be measured using the Hunter Lab Ultrascan Spectra Colorimeter. Color determination is the average of the values measured on pellets of polyester, or plaques or other items injection molded or extruded therefrom. L ^* represents the lightness coordinate, a ^* represents the red / green coordinate, b ^* are measured by them to the yellow / blue coordinate representing the L ^* of the CIE (International Commission on Illumination) a ^* b ^* color system. In certain embodiments, the b ^* value of the polyesters useful in the present invention [in one embodiment, in the absence and / or presence of toner] may be between −12 and less than 12, and the L ^* value may be between 50 and 90. . In other embodiments, the b ^* values of the polyesters useful in the present invention [in one embodiment, in the presence and / or absence of toner (s)] can be represented by one of the following ranges: -10 to 10; -10 to less than 10; -10 to 9; -10 to 8; -10 to 7; -10 to 6; -10 to 5; -10 to 4; -10 to 3; -10 to 2; -5 to 9; -5 to 8; -5 to 7; -5 to 6; -5 to 5; -5 to 4; -5 to 3; -5 to 2; 0 to 9; 0 to 8; 0 to 7; 0 to 6; 0 to 5; 0 to 4; 0 to 3; 0 to 2; 1 to 10; 1 to 9; 1 to 8; 1 to 7; 1 to 6; 1 to 5; 1 to 4; 1 to 3; And 1 to 2. In other embodiments, the L ^* values of the polyesters useful in the present invention may be represented by one of the following ranges: 50 to 60; 50 to 70; 50 to 80; 50 to 90; 60 to 70; 60 to 80; 60 to 90; 70 to 80; 79 to 90.

It is believed that deleterious color interactions occur due to the titanium catalyst or tin catalyst used to prepare polyesters containing ethylene glycol. In one embodiment of the invention, the b ^* color values for the polyesters useful in the present invention prepared using at least one titanium compound and at least one tin compound in combination with the at least one phosphorus compound described above, It is believed that the use of the cit tin catalyst alone significantly improved. The use of one or more titanium catalysts in combination with one or more phosphorus compounds to produce polyesters useful in the present invention is believed to be significantly improved over the use of titanium catalysts alone in the preparation of such polyesters.

Notch Izod impact strength as described in ASTM D256 is a common method of measuring toughness. Notched Izod impact strength is measured at 23 ° C. with a 10 mil notch of 3.2 mm (1/8 inch) thick as measured according to ASTM D256. In one embodiment, certain polyesters useful in the present invention are 500 J / m (10 feet-pounds / inch) at 23 ° C. with a notched 10 mil notch of 3.2 mm (1/8 inch) thick as measured according to ASTM D256. The above notched Izod impact strength can be exhibited. In one embodiment, certain polyesters useful in the present invention are about 10 feet-lbs / inch to about 35 feet- at 23 ° C. with just 10 mils notch of 3.2 mm (1/8 inch) thick as measured according to ASTM D256. Notch Izod impact strength in pounds per inch. In another embodiment, certain polyesters useful in the present invention are notched Izod perimeters that do not break more than about 10 feet-lbs / inch at 23 ° C. with 3.2 mm (1/8 inch) thick 10-mill notches measured according to ASTM D256. It can indicate strength.

In one embodiment, certain polyesters useful in the present invention may exhibit a density greater than 1.2 g / ml at 23 ° C.

In one embodiment, certain polyesters useful in the present invention may exhibit a flexural modulus of at least 290,000 ° C. as defined in ASTM D790. In other embodiments, certain polyesters useful in the present invention may exhibit flexural modulus at 23 ° C. from about 290,000 psi to about 370,000 psi, as defined by ASTM D790. In other embodiments, certain polyesters useful in the present invention may exhibit flexural modulus at 23 ° C. from about 290,000 psi to about 350,000 psi, as defined by ASTM D790.

Certain polyesters useful in the present invention have a Tg of about 100 to about 110 ° C., as defined by ASTM D790, as determined by ASTM D790, as measured by TA 2100 (Thermal Analyst Instruments) at a scan rate of 20 ° C./min, according to 290,000 psi. Flexural modulus of at least 23 ° C. and at least 10 feet-lbs / inch of notched Izod impact strength as measured according to ASTM D256 at 10 mil notches using a 1/8 inch thick bar at 23 ° C. .

Other polyesters useful in the present invention have a Tg of about 100 to about 110 ° C., as defined by ASTM D790, as defined by ASTM D790, as measured by TA 2100 (Thermal Analyst Instruments) at a scan rate of 20 ° C./min. one or more of a flexural modulus of 23 ° C. of psi, and notch Izod impact strength until not breaking more than 10 feet-lbs / inch, measured according to ASTM D256, with a 10 mil notch using a 1/8 inch thick bar at 23 ° C. May contain properties.

Other polyesters useful in the present invention have a Tg of about 100 to about 110 ° C., as defined by ASTM D790, as defined by ASTM D790, as measured by TA 2100 (Thermal Analyst Instruments) at a scan rate of 20 ° C./min. flexural modulus of 23 ° C. in psi, and notched Izod impact strength of greater than 10 feet-lbs / inch to 35 feet-lbs / inch, measured according to ASTM D256, with 10 mil notches using a 1/8 inch thick bar at 23 ° C. It may include one or more of the properties.

In some embodiments, the use of polyester compositions useful in the present invention can minimize and / or reduce the drying step prior to melt processing and / or thermoforming.

As used herein, the term "phosphorus compound" is intended to include their reaction products.

In one embodiment, the phosphorus compounds useful in the present invention may be organic compounds, such as phosphorous acid esters containing, for example, halogenated or non-halogenated organic substituents. Phosphorus compounds useful in the present invention include a wide variety of phosphorus compounds that are well known in the art such as, for example, phosphine, phosphite, phosphinite, phosphonite, phosphinate, phosphonate, phosphine oxide and phosphate. It may include.

Examples of phosphorus compounds useful in the present invention include tributyl phosphate, triethyl phosphate, tributoxyethyl phosphate, tert-butylphenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, ethyl dimethyl phosphate, isodecyl diphenyl phosphate , Trilauryl phosphate, triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, tert-butylphenyl diphenyl phosphate, resorcinol bis (diphenyl phosphate), tribenzyl phosphate, phenyl ethyl phosphate, trimethyl thio Onophosphate, phenyl ethyl thionophosphate, dimethyl methylphosphonate, diethyl methylphosphonate, diethyl pentylphosphonate, dilauryl methylphosphonate, diphenyl methylphosphonate, dibenzyl methylphospho Nate, diphenyl cresylphosphone Citrate, dimethyl cresylphosphonate, dimethyl methylthiophosphonate, phenyl diphenylphosphinate, benzyl diphenylphosphinate, methyl diphenylphosphinate, trimethyl phosphine oxide, triphenyl phosphine Oxide, tribenzyl phosphine oxide, 4-methyl diphenyl phosphine oxide, triethyl phosphite, tributyl phosphite, trilauryl phosphite, triphenyl phosphite, tribenzyl phosphite, phenyl diethyl phosphite, phenyl Dimethyl phosphite, benzyl dimethyl phosphite, dimethyl methyl phosphite, diethyl pentyl phosphonite, diphenyl methyl phosphonite, dibenzyl methyl phosphonite, dimethyl cresyl phosphonite, methyl dimethyl phosphate Pinite, Methyl Diethyl Phosphite, Phenyl Diphenyl Phosphite, Methyl Diphenyl Phosphite Nitrite, benzyl diphenylphosphinite, triphenyl phosphine, tribenzyl phosphine, and methyl diphenyl phosphine. In one embodiment, triphenyl phosphine oxide is excluded as a heat stabilizer in the process (s) of making polyesters useful in the present invention and / or in the polyester composition (s) of the present invention.

In one embodiment, phosphorus compounds useful in the present invention are those wherein at least one of the hydrogen atoms (bonded to oxygen or phosphorus atoms) of the acid compound is alkyl, branched alkyl, substituted alkyl, alkyl ether, substituted alkyl ether, alkyl Any of the phosphorus-based acids described above replaced by -aryl, alkyl-substituted aryl, aryl, substituted aryl and mixtures thereof. In other embodiments, phosphorus compounds useful in the present invention include, but are not limited to, the aforementioned compounds wherein at least one of the hydrogen atoms bonded to the oxygen atoms of the compound is replaced with metal ions or ammonium ions.

The ester may contain alkyl, branched alkyl, substituted alkyl, alkyl ether, aryl and / or substituted aryl groups. The ester may also have one or more alkyl groups and one or more aryl groups. The number of ester groups present in a particular phosphorus compound can vary from zero up to the maximum allowable based on the number of hydroxyl groups present in the phosphorus compound used. For example, alkyl phosphate esters can include one or more mono-, di- and tri-alkyl phosphate esters; Aryl phosphate esters include one or more mono-, di- and tri-aryl phosphate esters; Alkyl phosphate esters and / or aryl phosphate esters also include, but are not limited to, mixed alkyl aryl phosphate esters having one or more alkyl and one aryl group.

In one embodiment, heat stabilizers useful in the present invention include, but are not limited to, alkyl, aryl or mixed alkyl aryl esters or partial esters of phosphoric acid, phosphorous acid, phosphinic acid, phosphonic acid or phosphonic acid. Alkyl or aryl groups may contain one or more substituents.

In one embodiment, phosphorus compounds useful in the present invention are substituted or unsubstituted alkyl phosphate esters, substituted or unsubstituted aryl phosphate esters, substituted or unsubstituted mixed alkyl aryl phosphate esters, diphosphites, salts of phosphoric acid, Phosphine oxide, and one or more heat stabilizers selected from one or more of mixed aryl alkyl phosphites, reaction products thereof, and mixtures thereof. Phosphate esters include esters in which phosphoric acid is fully esterified or only partially esterified.

In one embodiment, for example, phosphorus compounds useful in the present invention may include one or more phosphate esters.

In one embodiment, the phosphorus compounds useful in the present invention are substituted or unsubstituted alkyl phosphate esters, substituted or unsubstituted aryl phosphate esters, mixed substituted or unsubstituted alkyl aryl phosphate esters, reaction products thereof, and mixtures thereof One or more heat stabilizers selected from one or more of. Phosphate esters include esters in which phosphoric acid is fully esterified or only partially esterified.

In one embodiment, for example, phosphorus compounds useful in the present invention may include one or more phosphate esters.

In other embodiments, phosphate esters useful in the present invention may include, but are not limited to, alkyl phosphate esters, aryl phosphate esters, mixed alkyl aryl phosphate esters, and / or mixtures thereof.

In certain embodiments, phosphate esters useful in the present invention are those in which the groups on the phosphate esters comprise alkyl, alkoxyalkyl, phenyl or substituted phenyl groups. These phosphate esters are generally referred to herein as alkyl and / or aryl phosphate esters. Certain preferred embodiments include trialkyl phosphates, triaryl phosphates, alkyl diaryl phosphates, dialkyl aryl phosphates and mixtures of such phosphates, wherein the alkyl group preferably has 2 to 12 carbon atoms, and aryl The group is preferably phenyl.

Representative alkyl and branched alkyl groups preferably contain 1-12 carbon atoms, including but not limited to ethyl, propyl, isopropyl, butyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl, decyl and dodecyl It is to contain. Substituted alkyl groups include, but are not limited to, those containing one or more of carboxylic acid groups and their esters, hydroxyl groups, amino groups, keto groups, and the like.

Representative of alkyl-aryl and substituted alkyl-aryl groups are those wherein the alkyl moiety contains 1 to 12 carbon atoms and the aryl group is phenyl or substituted phenyl (hydrogen at any carbon position on the phenyl ring is alkyl, branched alkyl) , Aryl, hydroxyl, and the like). Preferred aryl groups include phenyl or substituted phenyl, where hydrogen at any position on the phenyl ring is substituted with groups such as alkyl, branched alkyl, aryl, hydroxyl, and the like.

In one embodiment, the phosphate esters useful in the present invention are dibutylphenyl phosphate, triphenyl phosphate, tricresyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, trioctyl phosphate, and / or tributyl phosphate in particular. And mixtures thereof, including but not limited to mixtures of tricresyl phosphate and mixtures of isocetyl diphenyl phosphate and 2-ethylhexyl diphenyl phosphate.

In one embodiment, one or more phosphorus compounds useful in the present invention include one or more aryl phosphate esters.

In one embodiment, one or more phosphorus compounds useful in the present invention comprise one or more unsubstituted aryl phosphate esters.

In one embodiment, one or more phosphorus compounds useful in the present invention include one or more aryl phosphate esters that are not substituted with benzyl groups.

In one embodiment, any phosphorus compound useful in the present invention may comprise one or more alkyl phosphate esters.

In one embodiment, phosphate esters useful in the present invention as heat stabilizers and / or color stabilizers include, but are not limited to, one or more of trialkyl phosphates, triaryl phosphates, alkyl diaryl phosphates, and mixed alkyl aryl phosphates Do not.

In one embodiment, phosphate esters useful herein as heat stabilizers and / or color stabilizers include, but are not limited to, one or more of triaryl phosphates, alkyl diaryl phosphates, and mixed alkyl aryl phosphates.

In one embodiment, phosphate esters useful herein as heat stabilizers and / or color stabilizers include, but are not limited to, triaryl phosphates and mixed alkyl aryl phosphates.

In one embodiment, one or more phosphorus compounds useful in the present invention include, but are not limited to, triaryl phosphates such as, for example, triphenyl phosphate. In one embodiment, the one or more heat stabilizers include, but are not limited to, Murpole A. In one embodiment, one or more heat stabilizers useful in the present invention include, but are not limited to, triphenyl phosphate and Murpole A. Murpole A is Stepan Chemical Co and / or E.I. Phosphate ester commercially available from E.I. duPont de Nemours & Co. The CAS registry number for Murpol A is believed to be CAS registry number 37208-27-8.

In one embodiment, any phosphorus compound useful in the present invention may include one or more triaryl phosphate esters that are not substituted with benzyl groups.

In one embodiment, the polyester composition and / or process of the invention may comprise 2-ethylhexyl diphenyl phosphate.

In one embodiment, any of the methods described herein for preparing any polyester composition and / or polyester may comprise one or more mixed alkyl aryl phosphites, such as Doverforce S-9228 (Dover Chemicals, One or more mixed alkyl aryl phosphites, such as bis (2,4-dicumylphenyl) pentaerythritol diphosphite, also known as CAS # 154862-43-8).

In one embodiment, any polyester composition and / or any method described for the preparation of the polyester may comprise one or more phosphine oxides.

In one embodiment, any polyester composition and / or any method for the preparation of polyester may comprise salts of one or more phosphoric acids, for example KH ₂ PO ₄ and Zn ₃ (PO ₄ ) ₂ . .

The term "heat stabilizer" is intended to include its reaction products. The term "reaction product" used with the heat stabilizer of the present invention refers to any product of the catalyst as well as any product of polycondensation or esterification between any monomer and heat stabilizer used to prepare the polyester. Refers to the product of a polycondensation or ester reaction between

In one embodiment of the invention, phosphorus compounds useful in the present invention may act as heat stabilizers. In one embodiment of the present invention, phosphorus compounds useful in the present invention may act as heat stabilizers but may also act as color stabilizers. In one embodiment of the present invention, phosphorus compounds useful in the present invention may act as heat stabilizers and color stabilizers.

When phosphorus is added to the polyester and / or polyester composition and / or polyester process of the invention, it is added in the form of a phosphorus compound, for example one or more phosphate esters. The amount of the phosphorus compound (for example at least one phosphate ester) added to the polyester according to the invention and / or to the polyester composition according to the invention and / or to the method according to the invention is for example final as measured in weight ppm. It can be measured in the form of phosphorus atoms present in the polyester.

The amount of phosphorus compound added during or after polymerization may include, but is not limited to, the following: 1 to 5000 ppm, 1 to 1000 ppm, 1 to 900 ppm, 1 to 800 ppm, 1 based on the total weight of the polyester composition To 700ppm, 1 to 600ppm, 1 to 500ppm, 1 to 400ppm, 1 to 350ppm, 1 to 300ppm, 1 to 250ppm, 1 to 200ppm, 1 to 150ppm, 1 to 100ppm, 10 to 5000ppm, 10 to 1000ppm, 10 to 900ppm , 10 to 800ppm, 10 to 700ppm, 10 to 600ppm, 10 to 500ppm, 10 to 400ppm, 10 to 350ppm, 10 to 300ppm, 10 to 250ppm, 10 to 200ppm, 10 to 150ppm, 10 to 100ppm.

In one embodiment, the amount of phosphorus compound of the invention added during the polymerization is selected from the following: 1 to 5000 ppm, based on the total weight of the polyester composition, as measured in the form of phosphorus atoms in the final polyester , 1 to 1000ppm, 1 to 900ppm, 1 to 800ppm, 1 to 700ppm, 1 to 600ppm, 1 to 500ppm, 1 to 400ppm, 1 to 350ppm, 1 to 300ppm, 1 to 250ppm, 1 to 200ppm, 1 to 150ppm, 1 To 100 ppm; 1-60ppm, 2-5000ppm, 2-1000ppm, 2-900ppm, 2-800ppm, 2-700ppm, 2-600ppm, 2-500ppm, 2-400ppm, 2-350ppm, 2-300ppm, 2-250ppm 200 ppm, 2 to 150ppm, 2 to 100ppm, 2 to 60ppm, 2 to 20ppm, 3 to 5000ppm, 3 to 1000ppm, 3 to 900ppm, 3 to 800ppm, 3 to 700ppm, 3 to 600ppm, 3 to 500ppm, 3 to 400ppm, 3 to 350ppm, 3 to 300ppm, 3 to 250ppm, 3 to 200ppm, 3 to 150ppm, 3 to 100ppm, 3 to 60ppm, 3 to 20ppm, 4 to 5000ppm, 4 to 1000ppm, 4 to 900ppm, 4 to 800ppm, 4 to 4ppm 700ppm, 4 to 600ppm, 4 to 500ppm, 4 to 400ppm, 4 to 350ppm, 4 to 300ppm, 4 to 250ppm, 4 to 200ppm, 4 to 150ppm, 4 to 100ppm, 4 to 60ppm, 4 to 20ppm, 5 to 5000ppm, 5-1000ppm, 5-900ppm, 5-800ppm, 5-700ppm, 5-600ppm, 5-500ppm, 5-400ppm, 5-350ppm, 5-300p pm, 5 to 250ppm, 5 to 200ppm, 5 to 150ppm, 5 to 100ppm, 5 to 60ppm, 5 to 20ppm, 6 to 5000ppm, 6 to 1000ppm, 6 to 900ppm, 6 to 800ppm, 6 to 700ppm, 6 to 600ppm, 6 to 500ppm, 6 to 400ppm, 6 to 350ppm, 6 to 300ppm, 6 to 250ppm, 6 to 200ppm, 6 to 150ppm, 6 to 100ppm, 6 to 60ppm, 6 to 20ppm, 7 to 5000ppm, 7 to 1000ppm, 7 to 7ppm 900ppm, 7-800ppm, 7-700ppm, 7-600ppm, 7-500ppm, 7-400ppm, 7-350ppm, 7-300ppm, 7-250ppm, 7-200ppm, 7-150ppm, 7-100ppm, 7-60ppm, 7 to 20ppm, 8 to 5000ppm, 8 to 1000ppm, 8 to 900ppm, 8 to 800ppm, 8 to 700ppm, 8 to 600ppm, 8 to 500ppm, 8 to 400ppm, 8 to 350ppm, 8 to 300ppm, 8 to 250ppm, 8 to 8ppm 200ppm, 8-150ppm, 8-100ppm, 8-60ppm, 8-20ppm, 9-5000ppm, 9-1000ppm, 9-900ppm, 9-800ppm, 9-7 00ppm, 9-600ppm, 9-500ppm, 9-400ppm, 9-350ppm, 9-300ppm, 9-250ppm, 9-200ppm, 9-150ppm, 9-100ppm, 9-60ppm, 9-20ppm, 10-5000ppm, 10 to 1000ppm, 10 to 900ppm, 10 to 800ppm, 10 to 700ppm, 10 to 600ppm, 10 to 500ppm, 10 to 400ppm, 10 to 350ppm, 10 to 300ppm, 10 to 250ppm, 10 to 200ppm, 10 to 150ppm, 10 to 10ppm 100 ppm, 10 to 60 ppm, 10 to 20 ppm, 50 to 5000 ppm, 50 to 1000 ppm, 50 to 900 ppm, 50 to 800 ppm, 50 to 700 ppm, 50 to 600 ppm, 50 to 500 ppm, 50 to 400 ppm, 50 to 350 ppm, 50 to 300 ppm, 50 to 250ppm, 50 to 200ppm, 50 to 150ppm, 50 to 100ppm, 50 to 80ppm, 100 to 5000ppm, 100 to 1000ppm, 100 to 900ppm, 100 to 800ppm, 100 to 700ppm, 100 to 600ppm, 100 to 500ppm, 100 to 100ppm 400ppm, 100-350ppm, 100-300ppm, 100-250ppm, 100-200ppm, 100-150ppm, 150 to 5000ppm, 150 to 1000ppm, 150 to 900ppm, 150 to 800ppm, 150 to 700ppm, 150 to 600ppm, 150 to 500ppm, 150 to 400ppm, 150 to 350ppm, 150 to 300ppm, 150 to 250ppm, 150 to 200ppm, 200 to 200ppm 5000ppm, 200-1000ppm, 200-900ppm, 200-800ppm, 200-700ppm, 200-600ppm, 200-500ppm, 200-400ppm, 200-350ppm, 200-300ppm, 200-250ppm, 250-5000ppm, 250-1000ppm, 250-900 ppm, 250-800 ppm, 250-700 ppm, 250-600 ppm, 250-500 ppm, 250-400 ppm, 250-350 ppm, 250-300 ppm, 500-5000 ppm, 300-1000 ppm, 300-900 ppm, 300-800 ppm, 300-800 700ppm, 300-600ppm, 300-500ppm, 300-400ppm, 300-350ppm, 350-5000ppm, 350-1000ppm, 350-900ppm, 350-800ppm, 350-700ppm, 350-600ppm, 350-500ppm, 350-400ppm.

The amount of catalyst is 10 to 20,000 ppm, or 10 to 10,000 ppm, or 10 to 10,000 ppm, or 10 to 1000 ppm, or 10 to 500 ppm, or 10 to 300 ppm, or 10 to 10 based on the weight of the final polymer based on the catalyst metal. 250 ppm. The process can be carried out in a batch or continuous process. In one embodiment, the method is carried out in a continuous process.

In one embodiment, a catalyst suitable for use in the process of the present invention for producing polyesters useful in the present invention comprises one or more titanium compounds. The polyester composition of the present invention may also comprise one or more of the tin compounds useful in the method of the present invention. In one embodiment, the catalyst may comprise a combination of one or more tin compounds and one or more titanium compounds. Other catalysts may be used in the present invention with one or more titanium compounds and / or one or more tin compounds. Other catalysts may include, but are not limited to, gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium, aluminum compounds, and lithium hydroxide or sodium hydroxide and aluminum compounds.

The method can be carried out in a batch or continuous manner. In one embodiment, the catalyst consists essentially of one or more tin compounds. In one embodiment, the catalyst consists essentially of one or more titanium compounds. In one embodiment, the catalyst consists essentially of one or more titanium compounds and one or more tin compounds. In one embodiment, tin compounds and / or titanium compounds can be used in ester reactions or polycondensation reactions or both. In one embodiment, the catalyst comprises a titanium compound used in the ester reaction. Generally, in one embodiment, the titanium compound is used in an amount of about 0.005 to about 0.2% by weight of the dicarboxylic acid or dicarboxylic acid ester. Typically, in one embodiment, less than about 700 ppm titanium element, based on the total weight of the polyester, may be present as a residue in the polyester.

When tin is added to the polyester and / or polyester composition of the present invention and / or the method for producing the polyester, it is added to the polyester production method in the form of a tin compound. The amount of tin compound added to the polyester of the invention and / or the polyester composition of the invention and / or the process of the invention can be measured in the form of tin atoms present in the final polyester, for example in weight ppm. .

When titanium is added to the polyester and / or polyester composition and / or polyester production method of the present invention, it is added to the polyester production method in the form of a titanium compound. The amount of titanium compound added to the polyester of the invention and / or the polyester composition of the invention and / or the method of the invention can be measured in the form of titanium atoms present in the final polyester, for example in weight ppm. .

In another embodiment, the catalyst essentially comprises a titanium compound used in the esterification reaction in the following amounts: 10 ppm to 20,000 ppm, based on the weight of the final polyester, as measured in the form of titanium atoms in the final polyester. Or 10 to 10,000 ppm, or 10 to 5000 ppm, or 10 to 4500 ppm, or 10 to 4000 ppm, or 10 to 3500 ppm, or 10 to 3000 ppm, or 10 to 2500 ppm, or 10 to 2000 ppm, or 10 to 1500 ppm, or 10 to 1000 ppm, or 10 to 500 ppm, or 10 to 300 ppm, or 10 to 250 ppm, or 15 ppm to 20,000 ppm, or 15 to 10,000 ppm, or 15 to 5000 ppm, or 15 to 4500 ppm, or 15 to 4000 ppm, or 15 to 3500 ppm, or 15 to 3000ppm, or 15 to 2500ppm, or 15 to 2000ppm, or 15 to 1500ppm, or 15 to 1000ppm, or 15 to 500ppm, or 15 to 400ppm, or 15 to 300ppm, or 15 to 250ppm, or 20ppm to 20,000ppm, or 20 to 10,000ppm, or 20 to 5000ppm, or 20 to 4500ppm, or 20 to 4000ppm, or 20 to 3500ppm, or 20 to 3000ppm, or 20 to 2500ppm, or 20 to 2000ppm Or 20 to 1500 ppm, or 20 to 1000 ppm, or 20 to 500 ppm, or 20 to 300 ppm, or 20 to 250 ppm, or 25 to 20,000 ppm, or 25 to 10,000 ppm, or 25 to 5000 ppm, or 25 to 4500 ppm, or 25 To 4000 ppm, or 25 to 3500 ppm, or 25 to 3000 ppm, or 25 to 2500 ppm, or 25 to 2000 ppm, or 25 to 1500 ppm, or 25 to 1000 ppm, or 25 to 500 ppm, or 25 to 400 ppm, or 25 to 300 ppm, or 25 To 250 ppm, or 30 ppm to 20,000 ppm, or 30 to 10,000 ppm, or 30 to 5000 ppm, or 30 to 4500 ppm, or 30 to 4000 ppm, or 30 to 3500 ppm, or 30 to 3000 ppm, or 30 to 2500 ppm, and 30 to 2000ppm, or 30 to 1500ppm, or 30 to 1000ppm, or 30 to 500ppm, or 30 to 300ppm, or 30 to 250ppm, or 35ppm to 20,000ppm, or 35 to 10,000ppm, or 35 to 5000ppm, or 35 to 4500ppm Or 35 to 4000 ppm, or 35 to 3500 ppm, or 35 to 3000 ppm, or 35 to 2500 ppm, or 35 to 2000 ppm, or 35 to 1500 ppm, or 35 to 1000 ppm, or 35 to 500 ppm, or 35 to 300 ppm, or 35 to 250 ppm Or 40 ppm to 20,000 ppm, or 40 to 10,000 ppm, or 40 to 5000 ppm, or 40 to 4500 ppm, or 40 to 4000 ppm, or 40 to 3500 ppm, or 40 to 3000 ppm, or 40 to 2500 ppm, or 40 to 2000 ppm, or 40 To 1500 ppm, or 40 to 1000 ppm, or 40 to 500 ppm, or 40 to 300 ppm, or 40 to 250 ppm, or 40 to 200 ppm, or 45 ppm to 20,000 ppm, or 45 to 10,000 ppm, or 45 to 5000 ppm, or 45 to 4500ppm, or 45 to 4000ppm, or 45 to 3500ppm, or 45 to 3000ppm, or 45 to 2500ppm, or 45 to 2000ppm, or 45 to 1500ppm, or 45 to 1000ppm, or 45 to 500ppm, or 45 to 300ppm, or 45 to 250ppm, or 50ppm to 20,000ppm, or 50 to 10,000ppm, or 50 to 5000ppm, or 50 to 4500ppm, or 50 to 4000ppm, or 50 to 3500ppm, or 50 to 3000ppm, or 50 to 2500ppm, or 50 to 2000ppm Or 50 to 1500 ppm, or 50 to 1000 ppm, or 50 to 500 ppm, or 50 to 300 ppm, or 50 to 250 ppm, or 50 to 200 ppm, or 50 to 150 ppm, or 50 to 125 ppm.

In other embodiments, the polyesters of the present invention may be prepared using one or more tin compounds in addition to titanium compounds as catalysts. For example, reference is made to US Pat. No. 2,720,507, which is incorporated herein by reference in the context of tin catalysts. These catalysts are tin compounds containing one or more organic radicals. These catalysts include compounds of divalent or tetravalent tin having the formula described below:

A. M ₂ (Sn (OR) ₄ )

B. MH (Sn (OR) ₄ )

C. M '(Sn (OR) ₄ )

D. M '(HSn (OR) ₄ ) ₂

E. M ₂ (Sn (OR) ₆ )

F. MH (Sn (OR) ₆ )

G. M '(Sn (OR) ₆ )

H. M '(HSn (OR) ₆ ) ₂

I. Sn (OR) ₂

J. Sn (OR) ₄

K. SnR ' ₂

L. SnR ' ₄

M. R ' ₂ SnO

N.

O.

P.

Q.

Where

M is an alkali metal such as lithium, sodium or potassium,

M 'is an alkaline earth metal such as Mg, Ca or Sr,

Each R is an alkyl radical containing 1 to 8 carbon atoms,

Each R 'radical is an alkyl radical containing 1 to 8 carbon atoms (i.e., an R radical) and an aryl radical of benzene series containing 6 to 9 carbon atoms (e.g., phenyl, tolyl, benzyl, phenyl Radicals such as ethyl), and a substituent selected from the group consisting of

Ac is an acyl radical derived from an organic acid containing 2 to 18 carbon atoms (eg, acetyl, butyryl, lauroyl, benzoyl, stearoyl, etc.).

Meerwein, Ann. 476, 113 (1929), can be used to prepare novel bimetallic alkoxide catalysts. As seen in the literature of Meyerbine, these catalysts are not simply mixtures of two metal alkoxides. These are confirmed compounds having a salt-like structure. These are the compounds described above by the formulas A to H. Those not specifically described by Meyervine can be prepared by procedures similar to the working examples and methods described by Meyervine.

Other tin compounds can also be prepared by various methods such as those described in the following: For the preparation of diaryl tin dihalides (formula P), see Ber. 62, 996 (1929); J. Am. Chem. Soc. 49, 1369 (1927). For the preparation of dialkyl tin dihalides (formula P) see J. Am. Chem. Soc. 47, 2568 (1925); C.A. 41, 90 (1947). For the preparation of diaryl tin oxide (Formula M), see J. Am. Chem. Soc. 48, 1054 (1926). For the preparation of tetraaryl tin compounds (Formula K), see C.A. 32, 5387 (1938). For the preparation of tin alkoxides (Formula J), see C.A. 24, 586 (1930). For the preparation of alkyl tin salts (Formula Q), see C.A. 31, 4290. For the preparation of alkyl tin compounds (formula K and L), see C.A. 35, 2470 (1941); C.A. 33, 5357 (1939). For the preparation of mixed alkyl aryl tins (Formulas K and L), see C.A. 31, 4290 (1937); C.A. 38, 331 (1944). For the preparation of other tin compounds not covered by these citations, see Krause and V. Grosse, "Die Chemie der Metal-Organischen Verbindungen", published in Berlin, 1937, Gebroder-Borntrager. .

Tin alkoxides (Formulas I and J) and bimetallic alkoxides (Formulas A through H) are straight and branched chain alkyl radicals such as diethoxide, tetramethoxide, tetrabutoxide, tetra-tert-butoxide, tetrahex It contains the R substituent which can represent a side etc.

Alkyl derivatives (formula K and L) contain one or more alkyl radicals attached to the tin atom via a direct C-Sn linkage (eg, dibutyl tin, dihexyl tin, tetra-butyl tin, tetraethyl tin, tetramethyl Tin, dioctyl tin, etc.). Two of the tetraalkyl radicals may be replaced with oxygen atoms to form compounds having the formula M such as dimethyl tin oxide, diethyl tin oxide, dibutyl tin oxide, diheptyl tin oxide, and the like. In one embodiment, the tin catalyst comprises dimethyl tin oxide.

The complex can be produced by reacting dialkyl tin oxide with an alkali metal alkoxide (e.g., by reacting dibutyl tin oxide with sodium ethoxide, etc.) in an alcohol solution to produce a compound having the formula N, i.e. a compound which is a particularly useful catalyst. Can be. This formula is intended to represent the reaction products described. Tin compounds containing alkyl and alkoxy radicals, such as diethyl tin dietoside, dibutyl tin dibutoxide, dihexyl tin dimethoxide and the like are also useful catalysts (see Formula O).

Salts derived from dialkyl tin oxides reacted with carboxylic acids or hydrochloric acid are also of particular value as catalysts (see formulas P and Q). Examples of these catalytic condensing agents are dibutyl tin diacetate, diethyl tin dibutyrate, dibutyl tin dilauroate, dimethyl tin dibenzoate, dibutyl tin dichloride, diethyl tin dichloride, dioctyl Tin dichloride, dihexyl tin distearate, and the like.

Tin compounds having the formulas K, L and M, wherein at least one of the R ′ radicals represent aryl radicals of benzene series, such as phenyl, tolyl, benzyl, and the like, can be prepared. Examples are diphenyl tin, tetraphenyl tin, diphenyl dibutyl tin, dietolyl diethyl tin, diphenyl tin oxide, dibenzyl tin, tetrabenzyl tin, di ([B-phenylethyl) tin oxide, dibenzyl tin oxide And the like.

Examples of catalysts useful in the present invention include, but are not limited to, one or more of butyltin tris-2-ethylhexanoate, dibutyltin diacetate, dibutyltin oxide, and dimethyl tin oxide.

In one embodiment, catalysts useful in the present invention include, but are not limited to, one or more of butyltin tris-2-ethylhexanoate, dibutyltin diacetate, dibutyltin oxide and dimethyl tin tin tin tin.

Processes for preparing polyesters using tin-based catalysts are well known and described in the aforementioned US Pat. No. 2,720,507.

Titanium-containing compounds useful in the present invention include tetraethyl titanate, acetyltripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, polybutyl titanate, 2-ethylhexyl titanate, octylene glycol titanate, Lactate titanate, triethanolamine titanate, acetylacetonate titanate, ethylacetoacetic acid ester titanate, isostearyl titanate, acetyl triisopropyl titanate, titanium tetraisopropoxide titanium glycolate, titanium butock Said, hexylene glycol titanate, and any tee including but not limited to tetraisooctyl titanate, titanium dioxide, titanium dioxide / silicon dioxide coprecipitation, and titanium dioxide zirconium dioxide coprecipitation There may be mentioned titanium-containing compounds.

The polyester portion of the polyester composition useful in the present invention, for example, by a method in a homogeneous solution, by an ester exchange method in a melt, and by a method known in the literature such as by a two-phase interfacial method. It can manufacture. Suitable methods include, but are not limited to, reacting one or more dicarboxylic acids with one or more glycols for a time sufficient to produce a polyester at 100 to 315 ° C. and 0.1 to 760 mmHg. See US Pat. No. 3,772,405 for methods of making polyesters (the disclosure of which is incorporated herein by reference).

Generally polyesters are titanium catalysts described herein in an inert atmosphere at elevated temperatures during the condensation process from about 225 to 310 ° C., as described in detail in US Pat. No. 2,720,507, which is incorporated herein by reference. And / or by condensing the dicarboxylic acid or dicarboxylic acid ester with glycol in the presence of titanium and tin catalyst and then performing condensation at low pressure during the second half of the condensation.

In another aspect, the present invention relates to a method of making the copolyester of the present invention. In one embodiment, the method is directed to the preparation of copolyesters comprising terephthalic acid, 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol It is about. The method comprises the steps of (A) heating a mixture comprising monomers useful for the polyesters of the invention in the presence of at least one tin catalyst and at least one phosphate ester for a time sufficient to produce an initial polyester at 150-250 ° C .; (b) polycondensing it by heating the product of step (A) at a temperature of 230 to 320 ° C. for 1 to 6 hours; And (C) removing any unreacted glycols.

The reaction time of the esterification step (A) depends on the temperature, pressure selected and the feed molar ratio of glycol to dicarboxylic acid.

In one embodiment, step (A) may be carried out until at least 50% by weight of 2,2,4,4-tetramethyl-1,3-cyclobutanediol has reacted. Step (A) can be carried out under a pressure of 0 to 100 psig. The term “reaction product” as used in connection with any catalyst useful in the present invention refers to any product of a polycondensation or esterification reaction of any monomer and catalyst used to make the polyester and to any other type of catalyst Refers to the product of a polycondensation or esterification reaction in between.

Typically, step (B) and step (C) can be carried out simultaneously. These steps can be carried out by methods known in the art, such as placing the reaction mixture at a pressure below 0.002 psig and below atmospheric pressure or blowing hot nitrogen gas over the mixture.

In one embodiment, the present invention provides a pharmaceutical composition comprising (I) about (a) (i) about 90 to about 100 mole percent terephthalic acid residues, and (ii) aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms. Dicarboxylic acid components, including 0 to about 10 mole percent; And (b) from about 20 to about 40 mole percent of (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and (ii) from about 20 to about 40 cyclohexanedimethanol residues. 0 psig-75 psig, a mixture comprising a mole percent, (iii) an ethylene glycol moiety, and a glycol component comprising (iv) less than about 2 mole% of modified glycols having from 3 to 16 carbon atoms, Heating at one or more temperatures selected from 150 to 250 ° C. under one or more pressures selected from the range; And (II) the product of step (I) is heated to a final poly by heating at a temperature of 230 to 320 ° C. under one or more pressures selected from the final pressure of step (I) to 0.02 Torr (absolute pressure). Generating an ester,

The molar ratio of glycol component / dicarboxylic acid component added in step (I) is 1.01 to 3.0 / 1.0,

(i) at least one catalyst comprising at least one titanium compound, and optionally tin, gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium, aluminum compounds, and lithium hydroxide or sodium hydroxide and aluminum compounds Heating the mixture in step (I) in the presence of at least one catalyst and (ii) a phosphorus compound,

The total mole% of the dicarboxylic acid component in the final polyester is 100 mol%, the total mole% of the glycol component in the final polyester is 100 mol%,

The sum of the mole% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and cyclohexanedimethanol of the final polyester is 40 to 70 mole% of the total mole% of the glycol component. Less than,

For preparing a polyester having a intrinsic viscosity of 0.50 to 1.2 dL / g of the polyester as measured in a 60/40 (weight / weight) phenol / tetrachloroethane solution at a concentration of 0.25 g / 50 ml at 25 ° C., It relates to a method referred to herein as a "method comprising titanium".

In one embodiment, the present invention provides a pharmaceutical composition comprising (I) about (a) (i) about 90 to about 100 mole percent terephthalic acid residues, and (ii) aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms. Dicarboxylic acid components, including 0 to about 10 mole percent; And (b) from about 20 to about 40 mole percent of (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and (ii) from about 20 to about 40 cyclohexanedimethanol residues. 0 psig-75 psig, a mixture comprising a mole percent, (iii) an ethylene glycol moiety, and a glycol component comprising (iv) less than about 2 mole% of modified glycols having from 3 to 16 carbon atoms, Heating at one or more temperatures selected from 150 to 250 ° C. under one or more pressures selected from the range; And (II) the product of step (I) is heated to a final poly by heating at a temperature of 230 to 320 ° C. under one or more pressures selected from the final pressure of step (I) to 0.02 Torr (absolute pressure). Generating an ester,

The molar ratio of glycol component / dicarboxylic acid component added in step (I) is 1.01 to 3.0 / 1.0,

At least one catalyst comprising at least one tin compound and at least one titanium compound, and optionally gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium, aluminum compounds, and lithium hydroxide and sodium hydroxide and aluminum compounds Heating the mixture of step (I) in the presence of at least one catalyst and (ii) a phosphorus compound,

The total mole% of the dicarboxylic acid component in the final polyester is 100 mol%, the total mole% of the glycol component in the final polyester is 100 mol%,

The sum of the mole% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and cyclohexanedimethanol of the final polyester is 40 to 70 mole% of the total mole% of the glycol component. Less than,

For preparing a polyester having a intrinsic viscosity of 0.50 to 1.2 dL / g of the polyester as measured in a 60/40 (weight / weight) phenol / tetrachloroethane solution at a concentration of 0.25 g / 50 ml at 25 ° C., And methods referred to as “methods including tin and titanium”.

In the process of the invention referred to as "methods comprising titanium" and "methods comprising titanium and tin", one or more phosphorus compounds, for example one or more phosphate esters, are added in steps (I), (II) and / Or in both steps (I) and (II).

In any method of the present invention useful for preparing polyesters useful in the present invention, one or more phosphorus compounds, reaction products thereof and mixtures thereof may be added during esterification, polycondensation or both and / or after polymerization Can be added. In one embodiment, phosphorus compounds useful in any of the methods of the present invention may be added during esterification. In one embodiment, when the phosphorus compound is added after both esterification and polycondensation, it is added in an amount of 0.01 to 2% by weight based on the total weight of the final polyester. In one embodiment, the phosphorus compound may comprise one or more phosphate esters. In one embodiment, the phosphorus compound may comprise, for example, one or more phosphate esters. In one embodiment, the phosphorus compound may comprise one or more phosphorus compounds added in the ester step. In one embodiment, for example, it may include one or more phosphate esters added in the ester step.

It is contemplated that any of the polyesters useful in the present invention may be made using any method of making polyesters useful in the present invention.

The reaction time of the esterification step (I) depends on the temperature, pressure selected and the feed molar ratio of glycol to dicarboxylic acid.

In one embodiment, the pressure used in step (II) of any of the methods of the present invention consists of one or more pressures selected from the range of 20 to 0.02 Torr (absolute pressure); In one embodiment, the pressure used in step (II) of any method of the present invention consists of one or more pressures selected from the range of 10 to 0.02 Torr (absolute pressure); In one embodiment, the pressure used in step (II) of any method of the present invention consists of one or more pressures selected from the range of 5 to 0.02 Torr (absolute pressure); In one embodiment, the pressure used in step (II) of any method of the present invention consists of one or more pressures selected from the range of 3 to 0.02 Torr (absolute pressure); In one embodiment, the pressure used in step (II) of any method of the present invention consists of one or more pressures selected from the range of 20 to 0.1 Torr (absolute pressure); In one embodiment, the pressure used in step (II) of any method of the present invention consists of one or more pressures selected from the range of 10 to 0.1 Torr (absolute pressure); In one embodiment, the pressure used in step (II) of any method of the present invention consists of one or more pressures selected from the range of 5 to 0.1 Torr (absolute pressure); In one embodiment, the pressure used in step (II) of any of the methods of the present invention consists of one or more pressures selected from the range of 3 to 0.1 Torr (absolute pressure).

In one embodiment, the molar ratio of glycol component / dicarboxylic acid component added in step (I) of any of the methods of the present invention is 1.0 to 3.0 / 1.0; In one embodiment, the molar ratio of glycol component / dicarboxylic acid component added in step (I) of any of the methods of the present invention is 1.0 to 2.5 / 1.0; In one embodiment, the molar ratio of glycol component / dicarboxylic acid component added in step (I) of any of the methods of the present invention is 1.0 to 2.0 / 1.0; In one embodiment, the molar ratio of glycol component / dicarboxylic acid component added in step (I) of any of the methods of the present invention is 1.0 to 1.75 / 1.0; In one embodiment, the molar ratio of glycol component / dicarboxylic acid component added in step (I) of any of the methods of the invention is 1.0 to 1.5 / 1.0.

In one embodiment, the molar ratio of glycol component / dicarboxylic acid component added in step (I) of any of the methods of the present invention is 1.01 to 3.0 / 1.0; In one embodiment, the molar ratio of glycol component / dicarboxylic acid component added in step (I) of any of the methods of the present invention is 1.01 to 2.5 / 1.0; In one embodiment, the molar ratio of glycol component / dicarboxylic acid component added in step (I) of any of the methods of the present invention is 1.01 to 2.0 / 1.0; In one embodiment, the molar ratio of glycol component / dicarboxylic acid component added in step (I) of any of the methods of the present invention is 1.01 to 1.75 / 1.0; In one embodiment, the molar ratio of glycol component / dicarboxylic acid component added in step (I) of any of the methods of the invention is 1.01 to 1.5 / 1.0.

In any method embodiment for preparing the polyesters useful in the present invention, the heating time of step (II) is 1 to 5 hours, or 1 to 4 hours, or 1 to 3 hours, or 1.5 to 3 hours, or 1 To 2 hours. In one embodiment, the heating time of step (II) may be 1.5 to 3 hours.

In one embodiment, the polyesters, polyester compositions and / or methods of the invention may comprise phosphorus atoms.

In one embodiment, the polyesters, polyester compositions and / or methods of the invention may comprise tin atoms.

In one embodiment, the polyesters, polyester compositions and / or methods of the invention may comprise titanium atoms and tin atoms.

In one embodiment, the polyesters, polyester compositions and / or methods of the invention useful in the present invention may comprise phosphorus atoms and titanium atoms.

In one embodiment, the polyesters, polyester compositions and / or methods of the invention useful in the present invention may comprise phosphorus atoms and tin atoms.

In one embodiment, the polyesters, polyester compositions and / or methods of the invention useful in the present invention may include phosphorus atoms, tin atoms and titanium atoms.

In one embodiment, any of the polyesters, polyester compositions, and / or methods of the present invention may comprise one or more phosphorus compounds.

In one embodiment, any of the polyesters, polyester compositions and / or methods of the invention may comprise one or more titanium compounds.

In one embodiment, any of the polyesters, polyester compositions, and / or methods of the invention may comprise one or more tin compounds.

In one embodiment, the polyesters, polyester compositions and / or methods of the invention may comprise one or more titanium compounds and one or more phosphorus compounds.

In one embodiment, any of the polyesters, polyester compositions, and / or methods of making polyesters useful in the present invention may include one or more tin compounds and one or more titanium compounds.

In one embodiment, any of the polyesters, polyester compositions, and / or methods of making polyesters useful in the present invention may include one or more tin compounds, one or more titanium compounds, and one or more phosphorus compounds.

In one embodiment, the weight ratio of total phosphorus atoms to total tin atoms in the final polyester can be from 0 to 20: 1 by adding phosphorus compound (s) to the method (s) of the present invention. In one embodiment, the weight ratio of total phosphorus atoms to total tin atoms in the final polyester can be from 1 to 20: 1 by adding phosphorus compound (s) to the method (s) of the present invention. In one embodiment, the weight ratio of total phosphorus atoms to total tin atoms in the final polyester may be from 0 to 15: 1 by adding phosphorus compound (s) to the method (s) of the present invention. In one embodiment, the weight ratio of total phosphorus atoms to total tin atoms in the final polyester can be from 1 to 15: 1 by adding phosphorus compound (s) to the method (s) of the present invention. In one embodiment, the weight ratio of total phosphorus atoms to total tin atoms in the final polyester can be from 0 to 10: 1 by adding phosphorus compound (s) to the method (s). In one embodiment, the weight ratio of total phosphorus atoms to total tin atoms in the final polyester can be from 1 to 10: 1 by adding phosphorus compound (s) to the method (s). In one embodiment, the weight ratio of total phosphorus atoms to total tin atoms in the final polyester may be from 0 to 5: 1 by adding phosphorus compound (s) to the method (s). In one embodiment, the weight ratio of total phosphorus atoms to total tin atoms in the final polyester can be from 1 to 5: 1 by adding phosphorus compound (s) to the method (s) of the present invention. In one embodiment, the weight ratio of total phosphorus atoms to total tin atoms in the final polyester can be from 0 to 3: 1 by adding phosphorus compound (s) to the method (s). In one embodiment, the weight ratio of total phosphorus atoms to total tin atoms in the final polyester may be between 1 and 3: 1 by adding phosphorus compound (s) to the method (s). For example, the weight of tin atoms and phosphorus atoms present in the final polyester can be measured in ppm, and the weight ratio of total phosphorus atoms to total tin atoms in the final polyester can be any of the above weight ratios.

In one embodiment, the amount of tin atoms in the polyesters useful in the present invention may be from 0 to 400 ppm tin atoms based on the weight of the final polyester.

In one embodiment, the amount of tin atoms in the polyesters useful in the present invention may be from 15 to 400 ppm tin atoms based on the weight of the final polyester.

In one embodiment, the amount of titanium atoms in the polyesters useful in the present invention may be from 0 to 400 ppm titanium atoms, based on the weight of the final polyester.

In one embodiment, the amount of titanium atoms in the polyesters useful in the present invention may be from 15 to 400 ppm titanium atoms, based on the weight of the final polyester.

In one embodiment, the amount of phosphorus atoms in the polyesters useful in the present invention may be from 1 to 500 ppm phosphorus atoms based on the weight of the final polyester.

In one embodiment, the amount of tin atoms in the polyesters useful in the present invention may be from 1 to 400 ppm tin atoms based on the weight of the final polyester, and the amount of phosphorus atoms in the final polyester useful in the present invention may be the final polyester. It may be from 1 to 500 ppm based on the weight of.

In one embodiment, the amount of phosphorus atoms in the polyesters useful in the present invention can be from 1 to 500 ppm phosphorus atoms based on the weight of the final polyester, and the amount of titanium atoms in the polyester is based on the weight of the final polyester It may be 1 to 400 ppm titanium atoms.

In one embodiment, the amount of phosphorus atoms in the polyesters useful in the present invention can be from 1 to 500 ppm phosphorus atoms based on the weight of the final polyester, and the amount of titanium atoms in the polyester is based on the weight of the final polyester It may be 1 to 100 ppm of titanium atoms.

In one embodiment, the amount of phosphorus atoms in the polyesters useful in the present invention may be from 1 to 500 ppm phosphorus atoms based on the weight of the final polyester and the amount of tin atoms in the polyester based on the weight of the final polyester It may be 1 to 400 ppm tin atoms, and the amount of titanium atoms in the polyester may be 1 to 100 ppm titanium atoms based on the weight of the final polyester.

The invention also relates to a polyester composition prepared by the method (s) described above.

The invention also relates to a polymer blend. The blend comprises (a) from 5 to 95% by weight of one or more of the aforementioned polyesters; And (b) 5 to 95 weight percent of the polymer component.

Suitable examples of polymer components include nylon; Polyesters other than those described herein; Polyamides such as DuPont ZYTEL®; Polystyrene; Polystyrene copolymers; Styrene acrylonitrile copolymers; Acrylonitrile butadiene styrene copolymer; Poly (methyl methacrylate); Acrylic copolymers; Poly (ether-imide) such as ULTEM® (poly (ether-imide) from General Electric); Polyphenylene oxide, such as poly (2,6-dimethylphenylene oxide), or Noryl 1000® (a blend of poly (2,6-dimethylphenylene oxide) and polystyrene resin, a general electric product) Poly (phenylene oxide) / polystyrene blends; Polyphenylene sulfide; Polyphenylene sulfide / sulfone; Poly (ester-carbonate); Polycarbonates such as LEXAN® (polycarbonate from General Electric); Polysulfones; Polysulfone ethers; And poly (ether-ketones) of aromatic dihydroxy compounds; Or mixtures of any of the above polymers. The blend can be prepared by conventional processing techniques known in the art, such as melt blending or solution blending. In one embodiment, no polycarbonate is present in the polyester composition. When polycarbonate is used in the blend of the polyester composition of the present invention, the blend may be visually transparent. However, polyester compositions useful in the present invention also contemplate the exclusion of polycarbonates and the inclusion of polycarbonates.

Polycarbonates useful in the present invention are prepared according to known processes, for example by reacting a carbonate precursor (e.g., phosgene, haloformate or carbonate ester), molecular weight modifier, acid acceptor and catalyst with a dihydroxy aromatic compound. can do. Methods of making polycarbonates are known in the art and are described, for example, in US Pat. No. 4,452,933, the disclosures relating to the production of polycarbonates being incorporated herein by reference.

Examples of suitable carbonate precursors include carbonyl bromide, carbonyl chloride or mixtures thereof; Diphenyl carbonate; Di (halophenyl) carbonates such as di (trichlorophenyl) carbonate, di (tribromophenyl) carbonate and the like; Di (alkylphenyl) carbonates such as di (tolyl) carbonate; Di (naphthyl) carbonate; Di (chloronaphthyl) carbonate or mixtures thereof; And bis-haloformates of dihydric phenols.

Examples of suitable molecular weight modifiers include, but are not limited to, phenol, cyclohexanol, methanol, alkylated phenols such as octylphenol, para-tert-butyl-phenol, and the like. In one embodiment, the molecular weight modifier is phenol or alkylated phenol.

Acid acceptors can be organic or inorganic acid acceptors. Suitable organic acid acceptors may be tertiary amines and include but are not limited to materials such as pyridine, triethylamine, dimethylaniline, tributylamine and the like. The inorganic acid acceptor may be hydroxide, carbonate, bicarbonate or phosphate of alkali or alkaline earth metals.

Catalysts used in the preparation of the polycarbonates useful in the present invention that can be used typically include, but are not limited to, helping to polymerize monomers and phosgene. Suitable catalysts include tertiary amines such as triethylamine, tripropylamine, N, N-dimethylaniline; Such as tetraethylammonium bromide, cetyl triethyl ammonium bromide, tetra-n-heptylammonium iodide, tetra-n-propyl ammonium bromide, tetramethyl ammonium chloride, tetra-methyl ammonium hydroxide, tetra-n-butyl ammonium eye Quaternary ammonium compounds such as odide, benzyltrimethyl ammonium chloride; And quaternary phosphonium compounds such as, for example, n-butyltriphenyl phosphonium bromide and methyltriphenyl phosphonium bromide.

Polycarbonates useful in the polyester blends of the present invention are also described in US Pat. No. 3,169,121; 3,207,814; 3,498,499; No. 4,194,038; No. 4,156,069; Copolyestercarbonates such as those described in US Pat. Nos. 4,430,484, 4,465,820 and 4,981,898, the disclosures relating to copolyestercarbonates from each of these US patents are incorporated herein by reference.

Copolyestercarbonates useful in the present invention may be purchased commercially and / or prepared by methods known in the art. For example, they can typically be obtained by reacting one or more dihydroxy aromatic compounds with a mixture of phosgene and one or more dicarboxylic acid chlorides (especially isophthaloyl chloride, terephthaloyl chloride or both).

In addition, polyester compositions, and polymer blend compositions useful in the present invention may also be used as colorants, toners, dyes, mold release agents, flame retardants, plasticizers, nucleating agents, stabilizers (UV stabilizers other than the phosphorus compounds described herein, thermal stability Conventional additives such as, but not limited to, agents and / or reaction products thereof), fillers and impact modifiers, may be contained from 0.01 to 25% by weight, based on the weight of the total composition. Examples of typical commercial impact modifiers that are well known in the art and useful in the present invention are ethylene / propylene terpolymers, functionalized polyolefins such as those containing methyl acrylate and / or glycidyl methacrylate. , Styrene-based block copolymer impact modifiers and impact modifiers of various acrylic core / shell types. Residues of such additives are also considered as part of the polyester composition.

In addition, certain reagents that color the polymer may be added to the melt. In one embodiment, a clearing toner is added to the melt to reduce b ^* of the melt phase product of the resulting polyester polymer. Such cleaning agents include inorganic and organic toners. In addition, red toner may also be used to adjust a ^* color. Organic toners such as blue and red organic toners can be used, such as the toners described in US Pat. No. 5,372,864 and US Pat. No. 5,384,377, which are incorporated herein in their entirety. The organic toner can be supplied as a premix composition. The premix composition may be a pure blend of red and blue compounds or the composition may be pre-dissolved or slurried in one of the raw materials of the polyester, for example ethylene glycol.

The total amount of toner component added depends, of course, on the efficiency of the toner and the amount of yellow inherent in the base polyester. Generally, a concentration of up to about 15 ppm and a minimum concentration of about 0.5 ppm of the combined organic toner components are used. The total amount of the refreshing additive is typically from 0.5 to 10 ppm.

The toner may be added to the esterification zone or the polycondensation zone. Preferably, the toner is added to the initial stage of the ester zone or the polycondensation zone, such as a prepolymerization reactor.

Reinforcing materials may be useful in the compositions of the present invention. Reinforcing materials may include, but are not limited to, carbon filaments, silicates, mica, clays, talc, titanium dioxide, wollastonite, glass flakes, glass beads and fibers, and polymeric fibers and combinations thereof. In one embodiment, the reinforcing material is glass, such as fibrous glass filaments, mixtures of glass and talc, mixtures of glass and mica, and mixtures of glass and polymer fibers.

The invention also relates to film (s) and / or sheet (s) comprising the polyester compositions and / or polymer blends of the invention. Methods of molding polyester and / or blends into film (s) and / or sheet (s) are well known in the art. Examples of film (s) and / or sheet (s) of the invention include extruded film (s) and / or sheet (s), calendered film (s) and / or sheet (s), compression molded films (S) and / or sheet (s), solution casted film (s) and / or sheet (s). Methods of making films and / or sheets include, but are not limited to, extrusion, calendering, compression molding, and solution casting.

Examples of possible products made from films and / or sheets useful in the present invention include uniaxially stretched films, biaxially stretched films, shrink films (whether uniaxially or biaxially stretched), liquid crystal display films ( Including but not limited to diffuser sheets, compensation films or protective films), thermoformed sheets, graphic art films, outdoor signs, skylights, coating (s), coated products, painted products, laminates, laminated products And / or multiwall films and / or sheets.

As used herein, a “graphic art film” refers to a heat-curable ink (eg, a heat-curable ink or an air-curable ink) or a radiation-curable ink (eg, an ultraviolet-curable ink) printed thereon or in it. It is a film which has. "Curable" refers to polymerizable and / or crosslinked. In addition to the inks, the graphic art film may optionally also include varnishes, coatings, laminates and adhesives.

Examples of thermoformed or air-cured inks include pigment (s) dispersed in one or more standard carrier resins. Pigments include 4B Toner (PR57), 2B Toner (PR48), Lake Red C (PR53), Ritol Red (PR49), Iron Oxide (PR101), Permanent Red R (PR4), Permanent Red 2G (PO5), Pirazolone Orange ( PO13), diaryl yellow (PY12, 13, 14), monoazo yellow (PY3, 5, 98), phthalocyanine green (PG7), phthalocyanine blue, β form (PB15), ultra Marine (PB62), permanent violet (PV23), titanium dioxide (PW6), carbon black (furnace / channel) (PB7), PMTA pink, green, blue, violet (PR81, PG1, PB1, PV3), copper Ferrocyanide dye complexes (PR169, PG45, PB62, PV27) and the like. [The above designations in parentheses refer to the general color index created by the Society of Dyers and Colourists.] Using these pigments and combinations thereof, white, black, blue, purple, red, green, yellow, cyan Various colors can be obtained, including but not limited to magenta or scarlet.

Other exemplary inks, including radiation-cured inks, are disclosed in US Pat. No. 5,382,292, the disclosure of which is incorporated herein by reference.

Examples of typical carrier resins used in standard inks include resins having nitrocellulose, amides, urethanes, epoxides, acrylates and / or ester functional groups. Standard carrier resins include nitrocellulose, polyamide, polyurethane, ethyl cellulose, cellulose acetate propionate, (meth) acrylate, poly (vinyl butyral), poly (vinyl acetate), poly (vinyl chloride), and the like. It includes one or more. These resins can be blended with widely used blends, including nitrocellulose / polyamides and nitrocellulose / polyurethanes.

The ink resin (s) can typically be solvated or dispersed in one or more solvents. Typical solvents used include, but are not limited to, water, alcohols (eg ethanol, 1-propanol, isopropanol, etc.), acetates (eg n-propyl acetate), aliphatic hydrocarbons, aromatic hydrocarbons (eg toluene) and ketones It is not limited. Such solvents are typically in an amount sufficient to provide an ink having a viscosity of at least 15 seconds, such as at least 20 seconds, at least 25 seconds or 25 to 35 seconds, as measured on a # 2 Zahn cup known in the art. Can be incorporated.

In one embodiment, the polyester has a Tg value sufficient to be thermoformed and also to be easily printed.

In one embodiment, the graphic art film has one or more properties selected from thermoformability, toughness, transparency, chemical resistance, Tg and flexibility.

Graphic art films can be used in a variety of applications, such as, for example, decorated products in molds, embossed products, hard-coated products. The graphic art film can be smooth or textured.

Examples of graphic art films include nameplates; Membrane switch overlay (eg, for electrical appliances); Point of purchase display; Flat or in-mold decorative panels of the washing machine; Flat panel touch panels (eg, capacitive touch pad array); Flat panel of oven; Automotive decorative trims (such as polyester laminates); Automotive instrument panel; Cell phone covers; Heating and ventilation control display; Automotive console panel; Automotive gear shift panel; Control displays or warning signals for automotive instrument panels; A facing, dial or display of a household appliance; Outer shell, dial or display of the washing machine; Outer shell, dial or display of the dishwasher; Keypads for electronic products; Keypads for mobile telephones, personal digital assistants (PDAs or portable computers) or remote controls; Displays for electronics; Displays of portable electronic products such as telephones and PDAs; Panels and housings of mobile or standard telephones; Logo of electronic products; And logos of mobile phones.

Multiwall film or sheet refers to an extruded sheet as a profile consisting of multiple layers that are connected to each other by vertical ribs. Examples of multiwall films or sheets include, but are not limited to, outdoor shields (eg, greenhouses and commercial canopies).

Examples of extruded articles comprising polyester compositions useful in the present invention include thermoformed sheets, films for graphic arts, outdoor signs, skylights, multiwall films, plastic films for plastic glass laminates, and liquid crystal displays (LCDs). LCD films including, but not limited to, diffuser sheets, compensation films, and protective films.

In one embodiment, the present invention encompasses thermoplastic articles, typically in the form of sheets, embedded with a decorative material, comprising any of the compositions described above.

As used herein, an “outdoor sign” contains symbols (eg, numbers, letters, words, pictures, etc.), patterns, or designs made from the polyesters described herein or coated with the polyesters or polyester films described herein. Refers to the surface. In one embodiment, the outdoor sign includes a polyester containing printed symbols, patterns or designs. In one embodiment, the sine can withstand typical climatic conditions, such as rain, snow, ice, sleet, high humidity, heat, wind, sunlight, or a combination thereof, for a sufficient time, for example from one day to several years or more.

Exemplary outdoor signs include, but are not limited to, advertising signs, neon signs, electroluminescent signs, electric signs, fluorescent signs, and light emitting diode (LED) displays. Other exemplary signs include, but are not limited to, painted signs, vinyl decorated signs, thermoformed signs, and hard coated signs.

In one embodiment, the outdoor sign has one or more properties selected from thermoformability, toughness, transparency, chemical resistance and Tg.

As used herein, “vending machine display panel” refers to the front or side panel of a vending machine, through which a customer can view items sold or advertisements for these items. In one embodiment, the vending machine display panel may be a visually transparent panel of the vending machine, where the customer can see the item being sold. In other embodiments, the vending machine display panel may have sufficient rigidity to contain content in the machine and / or to abrogate destruction and / or theft.

In one embodiment, vending machine display panels are widely used in the art, such as flat display panels for snacks, beverages, popcorn or sticker / ticket vending machines, and capsule display panels such as in rounded gum vending machines or bulk candy vending machines. It may have a known dimension.

In one embodiment, the vending machine display panel may optionally contain advertising media or product identification marks. This information can be applied by methods well known in the art, such as silk screens.

In one embodiment, the vending machine display panel may be resistant to temperatures of −100 to 120 ° C. In other embodiments, the vending machine display panel may be UV resistant, for example by adding one or more UV additives as disclosed herein.

In one embodiment, the vending machine display panel has one or more properties selected from thermoformability, toughness, transparency, chemical resistance and Tg.

As used herein, a "purchase point of view display" refers to a fully or partially closed case having one or more visually transparent panels for displaying an item. Point-of-purchase displays are often used in retail stores to catch the eye of the customer. Examples of point-of-purchase displays include closed wall mounts, countertops, closed poster stands, display cases (eg, trophy display cases), sign frames, and cases for computer disks such as CDs and DVDs. The point of purchase display may include a shelf, additional containers (eg, magazine or brochure holders). One skilled in the art can easily plan the shape and dimensions of the point-of-purchase display depending on the item being displayed. For example, the display may be small, such as a jewel case, or may be a larger closed cabinet for displaying several trophies.

In one embodiment, the point of purchase display has one or more properties selected from toughness, transparency, chemical resistance, Tg and hydrolysis stability.

As used herein, “electrical product component” refers to a rigid component used in connection with an electrical product. In one embodiment, the electrical appliance part may be partially or wholly separated from the electrical appliance. In other embodiments, the electrical appliance component is typically made from a polymer. In one embodiment, the electrical appliance part is visually transparent.

Examples of electrical appliance parts include those requiring toughness and durability, such as cups and bowls used in food processors, mixers, blenders, and choppers; Refrigerator and freezer temperatures such as refrigerators and freezer trays, reservoirs, and shelves (eg, refrigerator temperatures above 0 ° C. (eg 2 ° C.) to 5 ° C., or freezer temperatures such as −20 to 0 ° C., eg −18). Temperature capable of withstanding a temperature below 0 ° C. such as ° C .; Parts having sufficient hydrolysis stability at temperatures below 90 ° C. such as washing machine doors, steam cleaner boxes, tea kettles and coffee pots; And a vacuum cleaner box and a dirt cup.

In one embodiment, such electrical appliance parts have one or more properties selected from toughness, transparency, chemical resistance, Tg, hydrolysis stability, and dishwasher stability. The electrical appliance part may also be selected from a steam cleaner box which may in one embodiment have one or more properties selected from toughness, transparency, chemical resistance, Tg and hydrolysis stability.

In one embodiment, polyesters useful in electrical appliance parts have a Tg of 105 to 140 ° C.

As used herein, the term “skylight” refers to a light transmissive panel fixed to the roof surface such that the panel forms part of the ceiling. In one embodiment, the panel is rigid, such as having dimensions sufficient to achieve stability and durability, which dimensions can be readily determined by one skilled in the art. In one embodiment, the skylight panel has a thickness greater than 3/16 inches, such as 1/2 inch or more.

In one embodiment, the skylight panel is visually transparent. In one embodiment, the skylight panel can transmit at least 35%, at least 50%, at least 75%, at least 80%, at least 90% or even at least 95% of visible light. In other embodiments, the skylight panel comprises one or more UV additives that allow the skylight panel to block up to 80%, 90% or 95% of the UV light.

In one embodiment, the skylight has one or more properties selected from thermoformability, toughness, transparency, chemical resistance and Tg.

As used herein, “outdoor shield” refers to a structure having one or more rigid panels, having a roof and / or walls that can at least slightly protect from natural forces such as sunlight, rain, snow, wind, cold, and the like. In one embodiment, the outdoor shield has at least a roof and / or one or more walls. In one embodiment, the outdoor shield has dimensions sufficient to achieve stability and durability, which dimensions can be readily determined by one skilled in the art. In one embodiment, the outdoor shield panel has a thickness greater than 3/16 inches.

In one embodiment, the outdoor shield panel is visually transparent. In one embodiment, the outdoor shield panel can transmit at least 35%, at least 50%, at least 75%, at least 80%, at least 90% or even at least 95% of visible light. In other embodiments, the outdoor shield panel includes one or more UV additives that allow the outdoor shield to block UV light by 80%, 90% or 95%.

Examples of outdoor shields include safety panes, traffic waiting rooms (eg, bus waiting rooms), telephone booths, and smoking rooms. In one embodiment, where the shield is a traffic waiting room, telephone booth or smoking room, the shield has one or more properties selected from thermoformability, toughness, transparency, chemical resistance and Tg. In one embodiment, where the shield is a safety pane, the shield has one or more properties selected from toughness, transparency, chemical resistance, and Tg.

As used herein, the term “canopy” refers to a structure with a roof that can at least slightly protect it from natural forces such as sunlight, rain, snow, wind, cold, and the like. In one embodiment, the roofed structure has one or more rigid panels, in whole or in part, such as having dimensions sufficient to achieve stability and durability, which dimensions can be readily determined by one skilled in the art. In one embodiment, the canopy panel has a thickness greater than 3/16 inches, such as 1/2 inch or more.

In one embodiment, the canopy panel is visually transparent. In one embodiment, the canopy panel can transmit at least 35%, at least 50%, at least 75%, at least 80%, at least 90% or even at least 95% of visible light. In other embodiments, the canopy panel includes one or more UV additives that allow the canopy to block UV light by 80%, 90% or 95%.

Examples of canopies include shielded passageways, roof lights, solariums, aircraft canopies, and awnings. In one embodiment, the canopy has one or more properties selected from toughness, transparency, chemical resistance, Tg and flexibility.

As used herein, "soundproof wall" refers to a rigid structure that can reduce the amount of noise transmission at two points of the same distance as compared to the amount of noise transmission from one point on one side of the structure without the sound barrier to the other on the other side. . Noise transfer reduction efficiency can be assessed by methods known in the art. In one embodiment, the amount of noise transmission reduced is 25 to 90%.

In other embodiments, the sound barrier is a standard test method for laboratory measurement of airborne sound transmission loss of building partitions and elements, for example, ASTM E90 "loss of noise transmission generated in the air of building partitions and components. And may be rated as a noise transfer class value as described in ASTM E413 "Classification of Rating Sound Insulation." The STC 55 barrier can reduce the noise of a jet engine of about 130 dBA to 60 dBA, the noise level in a typical office. The soundproof room may have a noise level of 0 to 20 dBA. One skilled in the art can construct and arrange sound barriers to achieve the desired STC rating. In one embodiment, the sound barrier has a grade of STC of at least 20, such as 20 to 60.

In one embodiment, the sound barrier comprises a plurality of panels connected and arranged to achieve a desired barrier profile. Sound barriers can be used along streets and highways to dampen vehicle noise. Alternatively, sound barriers may be used as separate panels or panels in a home or office, or inserted into structures of walls, floors, ceilings, doors and / or windows.

In one embodiment, the sound barrier is visually transparent. In one embodiment, the sound barrier can transmit at least 35%, at least 50%, at least 75%, at least 80%, at least 90% or even at least 95% of visible light. In other embodiments, the sound barrier comprises one or more UV additives that enable the sound barrier to block up to 80%, 90% or 95% of UV light.

In one embodiment, the sound barrier has one or more properties selected from toughness, transparency, chemical resistance and Tg.

As used herein, "greenhouse" refers to a closed structure used for the cultivation and / or protection of plants. In one embodiment, the greenhouse can maintain a desirable humidity and / or gas (oxygen, carbon dioxide, nitrogen, etc.) content for cultivating the plant while at least some protection from natural forces such as sunlight, rain, snow, wind, cold, and the like. have. In one embodiment, the roof of the greenhouse comprises one or more rigid panels, in whole or in part, such as having dimensions sufficient to achieve stability and durability, which dimensions can be readily determined by one skilled in the art. In one embodiment, the greenhouse panel has a thickness greater than 3/16 inches, such as 1/2 inch or more.

In one embodiment, the greenhouse panel is visually transparent. In other embodiments, the roof and walls of the greenhouse are substantially all visually transparent. In one embodiment, the greenhouse panel may transmit at least 35%, at least 50%, at least 75%, at least 80%, at least 90% or even at least 95% of visible light. In other embodiments, the greenhouse panel includes one or more UV additives that allow the greenhouse to block UV light by 80%, 90% or 95%.

In one embodiment, the greenhouse panel has one or more properties selected from toughness, transparency, chemical resistance and Tg.

As used herein, “optical medium” refers to an information storage medium on which information is recorded by irradiating a laser beam, such as light in the visible light wavelength range (eg, light having a wavelength of 600 to 700 nm). By irradiating the laser beam, the irradiated area of the recording layer is locally heated to change its physical or chemical characteristics, and a pit is created in the irradiated area of the recording layer. Since the optical characteristics of the generated pits are different from those of the unirradiated zone, digital information is optically recorded. The recorded information can generally be read by a reproducing procedure comprising irradiating the recording layer with a laser beam having the same wavelength as used in the recording procedure and detecting the light-reflective difference between the pits and their periphery. have.

In one embodiment, the optical medium includes a transparent disk having a helical pregroove, a recording dye layer located in the pregroove where information is recorded by irradiating a laser beam, and a light-reflective layer. The optical medium may optionally be recorded by the customer. In one embodiment, the optical medium is selected from compact discs (CDs) and digital video discs (DVDs). The optical medium may be sold with prerecorded information or sold as a disc that can be recorded.

In one embodiment, at least one of the following comprises a polyester of the present invention: a substrate, at least one protective layer of the optical medium and a recording layer of the optical medium.

In one embodiment, the optical medium has one or more properties selected from toughness, transparency, chemical resistance, Tg and hydrolysis stability.

As used herein, “glass laminate” refers to one or more coatings on glass, where one or more of the coatings comprise polyester. The coating can be a film or a sheet. The glass may be transparent, colored or reflective. In one embodiment, the laminate is permanently bonded to the glass, such as by applying the laminate under heating and pressurization to produce a single solid laminated glass article. One or both sides of the glass can be laminated. In certain embodiments, the glass laminate contains more than one coating comprising the polyester composition of the present invention. In other embodiments, the organic laminate comprises multiple glass substrates and more than one coating comprising the polyester composition of the present invention.

Exemplary glass laminates include windows (e.g., skyscrapers, windows for building porches), safety glass, windshields for vehicles (e.g. cars, buses, jets, armed vehicles), bulletproof glass, security glass (e.g., for banks). ), Typhoon protective glass, aircraft canopies, mirrors, solar glass panels, flat panel displays, and storm resistant windows. The glass laminate may be visually transparent, frosted, etched, or patterned.

In one embodiment, the glass laminate may be resistant to temperatures of -100 to 120 ° C. In other embodiments, the glass laminate may be UV resistant, such as by adding one or more UV additives as disclosed herein.

Methods of laminating the films and / or sheets of the invention on glass are well known to those skilled in the art. By lamination by vacuum, it can be laminated without using an adhesive layer. In order to obtain an effective bond between the glass layer and the laminate, in one embodiment, the glass has a low surface roughness.

Alternatively, the laminate of the present invention can be bonded to the glass using, for example, double-sided adhesive tapes, adhesive layers or gelatin layers obtained by applying hot melt, pressure sensitive or thermosensitive adhesives or UV or electron-beam curable adhesives. . The adhesive layer can be applied to the glass sheet, the laminate or both, and can be protected by a stripping layer that can be removed immediately before lamination.

In one embodiment, the glass laminate has one or more properties selected from toughness, transparency, chemical resistance, hydrolysis stability and Tg.

As used herein, the term "wt" means "weight".

The following examples further illustrate the methods by which the polyesters of the present invention can be made and evaluated, and are purely intended to illustrate the invention and are not intended to limit the scope of the invention. Unless indicated otherwise, parts are parts by weight, temperature is in ° C or is room temperature, and pressure is at or near atmospheric.

The following examples generally describe the glass transition temperature, notched Izod impact strength as compared to methods for preparing polyester and other high polyesters based on 2,2,4,4-tetramethyl-1,3-cyclobutanediol. And 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-cyclohexanedimethanol and ethylene glycol for the properties of various copolyesters such as flexural modulus. Illustrate the effect of use. In addition, based on the examples below, those skilled in the art will know how certain catalyst systems and thermal stabilizers are used to prepare the polyesters of the present invention.

How to measure

The intrinsic viscosity of the polyester was measured in 60/40 (weight / weight) phenol / tetrachloroethane at a concentration of 0.5 g / 50 ml at 25 ° C. and reported in dL / g.

Unless stated otherwise, the glass transition temperature (T _g ) was measured using a Thermal Analyst Instruments TA DSC 2920 instrument at a scanning rate of 20 ° C./min according to ASTM D3418.

The glycol content and cis / trans ratio of the composition were determined by proton nuclear magnetic resonance (NMR) spectroscopy. 60/40 (w / w) phenol / tetrachloro using chloroform-trifluoroacetic acid (70-30 vol / vol) for polymers or with deuterated chloroform for immobilization for oligomer samples Using ethane, all NMR spectra were recorded on a Zeol Eclipse Plus 600 MHz nuclear magnetic resonance spectrometer. By comparing with the mono- and dibenzoate esters of the model 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 2,2,4,4-tetramethyl-1,3-cyclo The peak of butanediol resonance was determined. These model compounds are very similar to the resonance sites found in polymers and oligomers.

Unless otherwise stated, the polymer was dried overnight at 80 ° C. in a dryer and injection molded in a Boy 22S molding machine to produce flex bars of 1/8 × 1/2 × 5 inches. These bars were cut to a length of 2.5 inches and the 10 mil notches were engraved 1/2 inch wide. The average Izod impact strength was determined from measurements on five specimens according to ASTM D256. Flexural modulus was measured according to the method of ASTM D790.

Color values reported herein are determined using ASTM D 6290-98 and measurements from Hunter Labs Ultrascan XE Spectrophotometer (Hunter Associates Laboratories Inc .; Reston, VA) with the following parameters: CIELAB L ^* , a ^* and b ^* values measured according to ASTM E308-99: (1) D65 light source, (2) 10 ° observer, (3) reflection mode with specular reflection angle, (4) wide field of view, (5) 1 "pot size. Unless otherwise noted, measurements were made on polymer granules milled through a 6 mm sieve. Haze was measured on 4 × 4 × 1/8 inch test specimens in accordance with ASTM D-1003.

In the examples below the amounts of tin (Sn) and titanium (Ti) are reported in ppm of metal and measured by a Pananalytical Axios Advanced wavelength dispersive x-ray fluorescence spectrometer (XRF). The amount of phosphorus was similarly reported in ppm of elemental phosphorus and was also measured by XRF using the same instrument. The values reported in the paragraph of the "P measurement" in the following examples are those obtained using phosphorus as described above.

Unless stated otherwise, the cis / trans ratio of 1,4-cyclohexanedimethanol used in the examples below was about 30/70 and may be between 35/65 and 25/75. Unless stated otherwise, the cis / trans ratio of 2,2,4,4-tetramethyl-1,3-cyclobutane diol used in the examples below is about 50/50 and 45/55 to 50/50 It was.

The following abbreviations apply throughout the working embodiments and the drawings:

CHDM: 1,4-cyclohexanedimethanol

DBTO: Dibutyltin Oxide

DMT: dimethyl terephthalate

DEG: Diethylene Glycol

DMTO: Dimethyl Tin Oxide

EG: ethylene glycol

IV: intrinsic viscosity

Tg: glass transition temperature

TIIP: titanium isopropoxide

TMCD: 2,2,4,4-tetramethyl-1,3-cyclobutanediol

TPA: terephthalic acid

TPP: Triphenyl Phosphate

Example  One

This example shows dimethyl terephthalate (DMT), 1,4-cyclohexanedimethanol (CHDM), 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) and ethylene The manufacturing method of the polyester containing glycol (EG) is illustrated.

DMT is commercially available from Cape Industries, CHDM (min. 98%), EG and TMCD (min. 98%) were obtained from Eastman Chemical Company. The tin compound was dibutyltin (IV) oxide (Fascat 4201; available from Adrich). The titanium compound was titanium (IV) isopropoxide (obtained from Aldrich). Phosphorus compound was triphenyl phosphate (TPP, Aldrich (98%) or Ferro Corporation (FERRO, Corp.)). Unless stated otherwise below, a source of phosphorus was added first with the rest of the polyester reagent. The cis / trans ratio of CHDM and TMCD is as described above.

Example  1A

This example shows 100 mole% of dimethyl terephthalate residue, 30 mole% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol moiety and 30 mole% of 1,4-cyclohexane. The preparation of copolyesters having the desired compositional ratios of ceindadimethanol residues and remaining ethylene glycol residues is described.

In a 500 milliliter flask equipped with a nitrogen inlet, a metal stirrer and a short distillation column, 99.71 g of dimethyl terephthalate, 21.63 g of 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclo A mixture of 37.86 g butanediol and 20.95 g ethylene glycol was added. In addition, 0.0077 g of dibutyltin (IV) oxide, 0.0218 g of titanium (IV) isopropoxide, and 0.50 g of triphenyl phosphate were added to the 500 milliliter flask. The flask was placed in a Wood's metal bath preheated to 200 ° C. Stirring speed was set to 200 RPM at the beginning of the experiment. The contents of the flask were heated at 200 ° C. for 60 minutes and then the temperature was gradually raised to 210 ° C. over 5 minutes. The reaction mixture was maintained at 210 ° C. for 60 minutes and then heated to 275 ° C. for 90 minutes. Once at 275 ° C., vacuum was applied over an additional 10 minutes to the set point of 100 mmHg and the stirring speed was reduced to 100 RPM. The pressure inside the flask was further reduced to a set point of 0.3 mm Hg over the next 5 minutes and the stirring speed was reduced to 50 RPM. This pressure was maintained for a total of 220 minutes to remove excess unreacted diol. This resulted in a polymer having a high melt viscosity, visually transparent, colorless to light yellow with a glass transition temperature of 107 ° C. and an intrinsic viscosity of 0.67 dl / g. NMR analysis showed that the copolyester had 30 mol% of 1,4-cyclohexanedimethanol residues, 30 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and ethylene glycol It showed that it consists of 40 mol% of lycol residues.

Example  1B to Example  1K

Various polyesters were prepared as described above from 100 mol% dimethyl terephthalate. However, different amounts of triphenyl phosphate were added to the initial reaction mixture as shown in Table 1. The mole percent of TMCD and CHDM for the execution of this example is shown in Table 1, with the remainder of the glycol being EG. The glycol / acid ratio is 1.5 / 1 and the glycol feed comprises 20 mol% CHDM, 35 mol% TMCD and 45 mol% EG. The Camille process control system facilitated the set point and data collection. Once the reaction dissolved, stirring was started and slowly increased. The following Camille sequence was used to make this copolyester.

Camille Order of Examples 1B-1K

The stirring speed was lowered to 25 rpm in step 10 and lowered to 10 rpm if the viscosity was too high. The retention time in step 10 for Examples G and H was 130 minutes.

Example  2

This example illustrates the effect of a heat stabilizer on the intrinsic viscosity and polymer color of the cocolister, wherein the target composition uses tin and a titanium catalyst, 100 mole% of dimethyl terephthalate residue, 30 mole. % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, 30 mole% 1,4-cyclohexanedimethanol residues, and 40 mole% ethylene glycol residues It is composed. Unless otherwise noted, the sources of monomers, catalysts, and heat stabilizers are the same as in Example 1.

Example  2A

In a 500 milliliter flask equipped with a nitrogen inlet, a metal stirrer and a short distillation column, 99.71 g of dimethyl terephthalate, 21.63 g of 1,4-cyclohexanedimethanol, 37.86 g of 2,2,4,4-tetramethyl- A mixture of 1,3-cyclobutanediol and 20.95 g of ethylene glycol was added. In addition, 0.0077 g of dibutyltin (IV) oxide and 0.0218 g of titanium (IV) isopropoxide were added to the 500 milliliter flask. The flask was placed in a Wood's metal bath preheated to 200 ° C. Stirring speed was set to 200 RPM at the beginning of the experiment. The contents of the flask were heated at 200 ° C. for 60 minutes and then the temperature was gradually raised to 210 ° C. over 5 minutes. The reaction mixture was held at 210 ° C. for 60 minutes and then heated to 275 ° C. for 90 minutes. Once at 275 ° C., vacuum was gradually applied over an additional 10 minutes to a set point of 100 mm Hg and the stirring speed was reduced to 100 RPM. The pressure inside the flask was further reduced to a set point of 0.3 mm Hg over an additional 5 minutes and the stirring speed was reduced to 50 RPM. This pressure was maintained for a total of 220 minutes to remove excess unreacted diol. This resulted in a polymer having a glass transition temperature of 117.7 ° C. and an intrinsic viscosity of 1.011 dl / g. NMR analysis showed that the copolyester had 29 mol% of 1,4-cyclohexanedimethanol residues, 37 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and ethylene glycol It showed that it consists of 34 mol% of lycol residues.

Example  2B to Example  2E

Various polyesters were prepared as described above from 100 mol% dimethyl terephthalate. However, different amounts of triphenyl phosphate were added to the initial reaction mixture as shown in Table 2. The molar percentages of TMCD and CHDM for the execution of this example are shown in Table 2 and the rest of the glycol is EG. The glycol / acid ratio is 1.5 / 1 and the glycol feed comprises 20 mol% CHDM, 35 mol% TMCD and 45 mol% EG. The Camille process control system facilitated the set point and data collection. Once the reaction dissolved, stirring was started and slowly increased. The following Camille sequence was used to prepare this high polyester.

Camille Order of Examples 2B-E

In step 10, the stirring speed was lowered to 25 rpm and, if the viscosity was too high, to 10 rpm.

Example  3

This example comprises dimethyl terephthalate (DMT), 1,4-cyclohexanedimethanol (CHDM), 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), and The manufacturing method of the copolyester containing ethylene glycol (EG) is demonstrated. These polyesters were made on a laboratory run scale. In addition, this example illustrates the properties of the polyester according to the invention compared to TMCD-based other polyesters.

Example  3A

The polyesters of this example were prepared from the target composition for 30 mol% TMCD, 20 mol% CHDM and 50 mol% EG diol components and 100 mol% DMT. The TMCD used in this preparation was the result of 40 pounds of various TMCD glycol samples by manual. The sample was ground and mixed to give a batch of TMCD containing 55% of the sheet isomer and 45% of the trans isomer. The sources of CHCM, DMT, catalyst and heat stabilizer are the same as in Example 1. The amount of each component loaded into the reaction vessel is shown in Table 3 below. This amount of raw material provided a molar ratio of glycol: acid of 2: 1, TMCD was charged in 50 mol% excess and CHDM in 7 mol% excess. The target catalyst for this batch was 200 ppm Sn from dibutyltin oxide. The transesterification step was carried out at 200 ° C. for a residual time of 2 hours and then at 220 ° C. for a residual time of 1 hour, where the pressure was atmospheric pressure and the stirring speed was 25 RPM. Then the temperature was raised to 280 ° C. Once the temperature reached 240 ° C., the shaker was run for 6 minutes on the contrary and then at 25 RPM for an additional 6 minutes. The temperature was then increased to 280 ° C. while applying a vacuum at a rate of 13 mmHg / min. The polycondensation step was carried out at 280 ° C. and under vacuum of 0.2 to 0.3 mmHg. After 45 minutes under these conditions, the shaker speed was set to 10 rpm and the mixture was held for an additional 45 minutes, after which the polyester was extruded into dry ice. The cooled extruded polymer was ground to pass through a 6 mm screen. The resulting copolyester has an IV of 0.667 dL / g, which means the average of the intrinsic viscosity of the polyester at the beginning and end of the extrusion. This polyester was molded and tested on a test bar on a TOYO 90A molding machine. The NMR composition and test results of the final polyesters are shown in Table 4 below.

Example  3B

The polyester of this example was prepared in the same manner as the polyester of Example 3A, except that there was no CHDM. Polyester was made from a target composition of 20 mol% TMCD and 80 mol% EG diol component and 100 mol% DMT. The amounts of raw materials used in the production of this polyester are shown in Table 3 above, and the NMR compositions and their properties of the final polyesters are shown in Table 4 below.

Example  3C

The polyester of this example was prepared from 20 mol% TMCD and 80 mol% of the target composition of the diol component of CHDM and 100 mol% DMT. This copolyester was prepared in the same manner as in Example 3B except that CHDM was used instead of EG. The properties of the material are reported in Table 4 below.

The above results indicate that the copolyesters according to the present invention exhibit superior combinations of flexural modulus (stiffness) and impact strength (toughness) compared to DMT and TMCD-based copolyesters containing CHDM or EG at the same glass transition temperature. It has a presence. For example, the copolyesters according to the present invention have an impact strength of more than 1000% compared to TMCD and EG based copolyesters, with only a 8% reduction in elastic modulus. In addition, the copolyesters of the present invention have about 25% higher flexural modulus compared to TMCD and CHDM based copolyesters (Example C), while still maintaining acceptable notched Izod impact strength.

The results in Table 4 show that polyesters with desirable properties of toughness and stiffness retain good haze properties. Those skilled in the art will understand that the catalyst system and / or heat stabilizer used in the preparation of the copolyesters of Table 4 is not expected to have a significant impact on flexural modulus or notched Izod impact strength.

Example  4

This example illustrates the effect of the amount of heat stabilizer and catalyst selection on the intrinsic viscosity and final color of the copolyester, wherein the target composition comprises 100 mol% of dimethyl terephthalate residue, 30 mol% of 2, 2,4,4-tetramethyl-1,3-cyclobutanediol residues, 30 mole% 1,4-cyclohexanedimethanol residues, and 40 mole% ethylene glycol residues.

In a 500 milliliter flask equipped with a nitrogen inlet, a metal stirrer and a short distillation column, 99.71 g of dimethyl terephthalate, 21.63 g of 1,4-cyclohexanedimethanol, 37.86 g of 2,2,4,4-tetramethyl- A mixture of 1,3-cyclobutanediol and 20.95 g of ethylene glycol was added. Various amounts of dibutyltin (IV) oxide, titanium (IV) isopropoxide, and triphenyl phosphate were added to the 500 milliliter flask. The flask was placed in a wood metal bath preheated to 200 ° C. Stirring speed was set to 200 RPM at the beginning of the experiment. The contents of the flask were heated at 200 ° C. for 60 minutes and then the temperature was gradually raised to 210 ° C. over 5 minutes. The reaction mixture was held at 210 ° C. for 60 minutes and then heated to 275 ° C. for 90 minutes. Once at 275 ° C., vacuum was gradually applied over an additional 10 minutes to a set point of 100 mm Hg and the stirring speed was reduced to 100 RPM. The pressure inside the flask was further reduced to 0.3 mm Hg over the next 5 minutes and the stirring speed was reduced to 50 RPM. This pressure was maintained for a total of 220 minutes to remove excess unreacted diol. All samples were prepared in the same manner using the triphenyl phosphate content and catalyst reported in Table 5. The mole percent of final TMCD and CHDM for this copolyester is also reported in Table 5, with the remaining amount of diol being EG. The effects of the catalyst system and the heat stabilizer on the introduction of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, copolyester color and intrinsic viscosity are reported in Table 5. Examples G, H, and I in Table 5, below, correspond to Examples 2A, 2D, and 1A, respectively, for ease of comparison between polyesters prepared using different catalyst systems and different contents of phosphorus. It is included in Table 5 below.

Examples B and C are included herein to illustrate the effect of catalyst systems and heat stabilizers on TMCD introduction, color, and intrinsic viscosity, although not within the scope of the originally filed claims.

While the invention has been described in detail with reference to the embodiments disclosed herein, it will be understood that modifications or variations can be made within the spirit and scope of the invention.

Claims (76)

A polyester composition comprising at least one polyester, a dicarboxylic acid component comprising (a) from about 90 to about 100 mole percent of terephthalic acid residues, and (ii) from about 0 to about 10 mole percent of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; And (b) about 20 to about 40 mole percent of (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and (ii) about 20 to about 40 mole of cyclohexanedimethanol residues. %, (iii) an ethylene glycol moiety, and (iv) a glycol component comprising less than about 2 mole% of a modifying glycol having 3 to 16 carbon atoms, The total mole% of the dicarboxylic acid component is 100 mole% and the total mole% of the glycol component is 100 mole%, The sum of the mole% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and cyclohexanedimethanol is less than 40 to 70 mole% of the total mole% of the glycol component , When measured in a 60/40 (weight / weight) phenol / tetrachloroethane solution at a concentration of 0.25 g / 50 ml at 25 ° C., the inherent viscosity of the polyester is from 0.50 to 1.2 dL / g, Polyester composition. The method of claim 1, The polyester composition, wherein ethylene glycol is present in an amount of about 30 to about 60 mol%. The method of claim 1, The polyester composition, wherein ethylene glycol is present in an amount of about 30 to about 50 mole%. The method of claim 1, The polyester composition, wherein ethylene glycol is present in an amount of about 35 to about 45 mol%. The method of claim 1, The polyester composition, wherein the intrinsic viscosity of the polyester is 0.5 to 1 dL / g. The method of claim 1, The polyester composition, wherein the inherent viscosity of the polyester is 0.5 to 0.75 dL / g. The method of claim 1, The polyester composition, wherein the inherent viscosity of the polyester is 0.60 to 0.75 dL / g. The method according to any one of claims 1, 2 and 6, The polyester composition, wherein the polyester has a Tg of 100 to 110 ° C. The method of claim 1, The polyester composition, wherein the polyester has a Tg of 102 to 108 ° C. The method according to any one of claims 1, 2 and 6, A polyester composition comprising one or more phosphorus compounds selected from one or more of alkyl phosphate esters, aryl phosphate esters, mixed alkyl aryl phosphate esters, reaction products thereof and mixtures thereof. The method of claim 1, A polyester composition comprising one or more phosphorus compounds selected from one or more of trialkyl phosphates, triaryl phosphates, alkyl diaryl phosphates, and mixed alkyl aryl phosphates. The method of claim 1, A polyester composition comprising one or more phosphorus compounds selected from one or more of triaryl phosphates, alkyl diaryl phosphates, and mixed alkyl aryl phosphates. The method of claim 1, Selected from one or more of dibutylphenyl phosphate, triphenyl phosphate, tricresyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, trioctyl phosphate, isocetyl diphenyl phosphate, and 2-ethylhexyl diphenyl phosphate A polyester composition comprising at least one phosphorus compound. The method of claim 1, A polyester composition comprising at least one phosphorus compound selected from dibutylphenyl phosphate, triphenyl phosphate, isocetyl diphenyl phosphate, and 2-ethylhexyl diphenyl phosphate. The method of claim 1, A polyester composition comprising at least one phosphorus compound selected from triphenyl phosphate, Merpol A, and 2-ethylhexyl diphenyl phosphate. The method of claim 1, And at least one heat stabilizer in an amount of about 1 ppm to about 500 ppm based on the total weight of the polyester. The method of claim 1, A polyester composition comprising one or more phosphorus compounds in an amount of about 1 ppm to about 300 ppm based on the total weight of the polyester. The method of claim 1, A polyester composition comprising one or more phosphorus compounds in an amount of about 1 ppm to about 100 ppm based on the total weight of the polyester. The method of claim 1, Polyester is diethylene glycol, 1,2-propanediol, neopentyl glycol, polytetramethylene glycol, 1,5-pentanediol, 1,6-hexanediol, p A polyester composition comprising at least one modified glycol selected from xylene glycol, 1,3-propanediol and 1,4-butanediol or mixtures thereof. The method of claim 1, The polyester composition, wherein the polyester comprises diethylene glycol. The method of claim 1, 40-60 mole% cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol having 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues A polyester composition comprising a residue and from 40 to 60 mole% of a trans-2,2,4,4-tetramethyl-1,3-cyclobutadiinol residue. A polyester composition according to claim 1, and Poly (etherimide), polyphenylene oxide, poly (phenylene oxide) / polystyrene blend, polystyrene resin, polyphenylene sulfide, polyphenylene sulfide / sulfone, poly (ester-carbonate), polycarbonate, polysulfone, At least one polymer of polysulfone ether, poly (ether-ketone), polyester other than the polyester according to claim 1, and mixtures thereof Blend comprising. A blend comprising the polyester composition according to claim 1, and at least one polycarbonate. The method of claim 1, A polyester composition comprising a branching agent for polyester. The method of claim 1, A polyester composition, wherein the flexural modulus of the polyester is at least 290,000 psi. The method of claim 1, The polyester composition, wherein the polyester is amorphous. The method of claim 1, The polyester composition, wherein the polyester has a crystallization half life of greater than 5 minutes at 170 ° C. The method of claim 1, The polyester composition, wherein the polyester has a density of greater than 1.2 g / ml at 23 ° C. The method of claim 1, The polyester composition is at least one selected from colorants, mold release agents, phosphorus compounds other than the phosphorus compounds described in claim 1, plasticizers, nucleating agents, UV stabilizers, glass fibers, carbon fibers, fillers, impact modifiers or mixtures thereof A polyester composition comprising an additive. The method of claim 1, Wherein the polyester has a notched Izod impact strength of at least 3 feet-lbs / inch as measured according to ASTM D256 at 10 mil notches using a 1/8 inch thick bar at 23 ° C. The method of claim 1, The polyester composition having a notched Izod impact strength of at least 10 feet-lbs / inch as measured according to ASTM D256 with 10 mil notches using a 1/8 inch thick bar at 23 ° C. The method of claim 1, The pulleyster has a Tg of about 100 to about 110 ° C as measured by TA 2100 (Thermal Analyst Instrument) at a scan rate of 20 ° C / min, 23 ° C above 290,000 psi, defined according to ASTM D790. A flexural modulus of and a notched Izod impact strength of more than 10 feet-lbs / inch as measured according to ASTM D256 with a 10 mil notch using a 1/8 inch thick bar at 23 ° C., Polyester composition. The method of claim 1, A polyester composition, wherein the b ^* color value of the polyesters useful in the present invention is -12 to less than 12 as measured by the L ^* a ^* b ^* color system. An article comprising the polyester composition according to claim 1 comprising a film or sheet. An article comprising the polyester composition of claim 1 comprising a thermoformed film or sheet. A polyester composition comprising at least one polyester, a dicarboxylic acid component comprising (a) from about 90 to about 100 mole percent of terephthalic acid residues, and (ii) from about 0 to about 10 mole percent of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; And (b) about 20 to about 40 mole percent of (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and (ii) about 20 to about 40 mole of cyclohexanedimethanol residues. %, (iii) an ethylene glycol moiety, and (iv) a glycol component comprising less than about 2 mole% of modified glycol having 3 to 16 carbon atoms, The total mole% of the dicarboxylic acid component is 100 mole% and the total mole% of the glycol component is 100 mole%, The sum of the mole% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and cyclohexanedimethanol is less than 40 to 70 mole% of the total mole% of the glycol component , When measured in a 60/40 (weight / weight) phenol / tetrachloroethane solution at a concentration of 0.25 g / 50 ml at 25 ° C., the inherent viscosity of the polyester is 0.50 to 1.2 dL / g, The polyester comprises at least one branching agent, Polyester composition. The method of claim 1, The polyester composition, wherein the polyester comprises a branching agent in an amount of 0.01 to 5% by weight based on the total weight of the polyester. The method of claim 1, The polyester composition, wherein the polyester comprises a branching agent in an amount of 0.01 to 1% by weight based on the total weight of the polyester. The method of claim 1, At least one phosphorus compound is present in an amount from about 1 ppm to about 500 ppm based on the total weight of the polyester. The method of claim 1, Polyester composition comprising at least one titanium compound in an amount of from about 1 ppm to about 100 ppm based on the total weight of the polyester. (I) a die comprising (a) from about 90 to about 100 mole percent of (e) terephthalic acid residues, and (ii) from about 0 to about 10 mole percent of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms. Carboxylic acid components; And (b) from about 20 to about 40 mole percent of (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and (ii) from about 20 to about 40 cyclohexanedimethanol residues. 0 psig-75 psig, a mixture comprising a mole percent, (iii) an ethylene glycol moiety, and a glycol component comprising (vi) less than about 2 mole% of modified glycols having from 3 to 16 carbon atoms, Heating at one or more temperatures selected from 150 to 250 ° C. under one or more pressures selected from the range; And (II) the product of step (I) is heated to a final polyester at a temperature of 230 to 320 ° C. for one to six hours under one or more pressures selected from the final pressure of step (I) to 0.02 Torr (absolute pressure). Including the steps of: The molar ratio of glycol component / dicarboxylic acid component added in step (I) is 1.01 to 3.0 / 1.0, The mixture in step (I) comprises (i) one or more catalysts comprising one or more titanium compounds, and optionally tin, gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium, aluminum compounds, and hydroxides Heating in the presence of at least one catalyst selected from lithium or sodium hydroxide and aluminum compounds, and (ii) at least one phosphorus compound, The total mole% of the dicarboxylic acid component in the final polyester is 100 mol%, the total mole% of the glycol component in the final polyester is 100 mol%, The sum of the mole% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and cyclohexanedimethanol of the final polyester is 40 to 70 mole% of the total mole% of the glycol component. Less than, The polyester has a inherent viscosity of 0.50 to 1.2 dL / g as measured in a 60/40 (weight / weight) phenol / tetrachloroethane solution at a concentration of 0.25 g / 50 ml at 25 ° C. 42. The method of claim 41 wherein The molar ratio of glycol component / dicarboxylic acid component added in step (I) is 1.01 to 2 / 1.0. 42. The method of claim 41 wherein The molar ratio of glycol component / dicarboxylic acid component added in step (I) is 1.01 to 1.5 / 1.0. 42. The method of claim 41 wherein The heating time in step (II) is 1 to 4 hours. 42. The method of claim 41 wherein Wherein the weight ratio of total phosphorus atoms to total titanium atoms in the final polyester is from 0 to 20: 1. 42. The method of claim 41 wherein Wherein the weight ratio of total phosphorus atoms to total titanium atoms in the final polyester is from 1 to 10: 1. 42. The method of claim 41 wherein Wherein the weight ratio of total phosphorus atoms to total titanium atoms in the final polyester is from 0 to 5: 1. 42. The method of claim 41 wherein Wherein the weight ratio of total phosphorus atoms to total titanium atoms in the final polyester is from 1 to 5: 1. 42. The method of claim 41 wherein Wherein the weight ratio of total phosphorus atoms to total titanium atoms in the final polyester is 1 to 3: 1. 42. The method of claim 41 wherein Wherein the amount of titanium atoms present in the final polyester can be from 1 to 100 ppm titanium atoms, based on the weight of the final polyester. 42. The method of claim 41 wherein Ethylene glycol is present in the final polyester in an amount of about 30 mol% to about 60 mol%. 42. The method of claim 41 wherein The catalyst (s) used in step (I) comprise at least one titanium compound and at least one tin compound. 42. The method of claim 41 wherein The catalyst used in step (I) consists essentially of at least one titanium compound. 42. The method of claim 41 wherein A polyester composition, wherein the b ^* color value of the polyesters useful in the present invention is -12 to less than 12 as measured by the L ^* a ^* b ^* color system. 42. The method of claim 41 wherein A polyester composition, wherein the b ^* color value of the polyesters useful in the present invention is -10 to less than 10 as measured by the L ^* a ^* b ^* color system. (I) a die comprising (a) from about 90 to about 100 mole percent of (e) terephthalic acid residues, and (ii) from about 0 to about 10 mole percent of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms. Carboxylic acid components; And (b) from about 20 to about 40 mole percent of (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and (ii) from about 20 to about 40 cyclohexanedimethanol residues. 0 psig-75 psig, a mixture comprising a mole percent, (iii) an ethylene glycol moiety, and a glycol component comprising (iv) less than about 2 mole% of modified glycols having from 3 to 16 carbon atoms, Heating at one or more temperatures selected from 150 to 250 ° C. under one or more pressures selected from the range; And (II) the product of step (I) is heated by heating at a temperature of 230 to 320 ° C. for 1 to 6 hours under one or more pressures selected from the final pressure of step (I) to 0.02 Torr (absolute pressure). Generating a polyester, The molar ratio of glycol component / dicarboxylic acid component added in step (I) is 1.01 to 3.0 / 1.0, The mixture in step (I) comprises (i) one or more catalysts comprising one or more titanium compounds and one or more tin compounds, and optionally gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium, aluminum compounds And at least one catalyst selected from lithium hydroxide or sodium hydroxide and an aluminum compound; And (ii) heating in the presence of one or more phosphorus compounds, The total mole% of the dicarboxylic acid component in the final polyester is 100 mol%, the total mole% of the glycol component in the final polyester is 100 mol%, The polyester has a inherent viscosity of 0.50 to 1.2 dL / g as measured in a 60/40 (weight / weight) phenol / tetrachloroethane solution at a concentration of 0.25 g / 50 ml at 25 ° C. The method of claim 56, wherein The molar ratio of glycol component / dicarboxylic acid component added in step (I) is 1.01 to 2 / 1.0. The method of claim 56, wherein The molar ratio of glycol component / dicarboxylic acid component added in step (I) is 1.01 to 1.5 / 1.0. The method of claim 56, wherein The heating time in step (II) is 1 to 4 hours. The method of claim 56, wherein The sum of the mole% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and cyclohexanedimethanol of the final polyester is from 40 mole% to 70 of the total mole% of the glycol component Less than mole%. The method of claim 56, wherein The weight ratio of total phosphorus atoms to total titanium atoms to total tin atoms in the final polyester is from 0 to 20: 0 to 10: 1. The method of claim 56, wherein Wherein the weight ratio of total phosphorus atoms to total titanium atoms to total tin atoms in the final polyester is from 1 to 10: 1 to 10: 1. The method of claim 56, wherein The weight ratio of total phosphorus atoms to total titanium atoms to total tin atoms in the final polyester is from 1 to 10: 1 to 5: 1. The method of claim 56, wherein And wherein the weight ratio of total phosphorus atoms to total titanium atoms to total tin atoms in the final polyester is 1 to 5: 1 to 4: 1. The method of claim 56, wherein Wherein the weight ratio of total phosphorus atoms to total titanium atoms in the final polyester is from 0 to 4: 1. The method of claim 56, wherein Wherein the weight ratio of total phosphorus atoms to total titanium atoms in the final polyester is from 1 to 10: 1. The method of claim 56, wherein Wherein the weight ratio of total phosphorus atoms to total titanium atoms in the final polyester is from 0 to 5: 1. The method of claim 56, wherein Wherein the weight ratio of total phosphorus atoms to total titanium atoms in the final polyester is from 1 to 5: 1. The method of claim 56, wherein Wherein the amount of titanium atoms present in the final polyester can be from 1 to 100 ppm titanium atoms, based on the weight of the final polyester. The method of claim 56, wherein Wherein the amount of tin atoms present in the final polyester can be from 1 to 400 ppm tin atoms based on the weight of the final polyester. The method of claim 56, wherein Wherein the amount of phosphorus atoms present in the final polyester can be from 1 to 500 ppm phosphorus atoms based on the weight of the final polyester. The method of claim 56, wherein The amount of titanium atoms present in the final polyester can be from 1 to 100 ppm titanium atoms based on the weight of the final polyester and the amount of tin atoms present in the final polyester is 1 based on the weight of the final polyester And from 400 ppm tin atoms and the amount of phosphorus atoms present in the final polyester can be from 1 to 500 ppm phosphorus atoms based on the weight of the final polyester. The method of claim 56, wherein Ethylene glycol is present in the final polyester in an amount of about 30 mol% to about 60 mol%. The method of claim 56, wherein The catalyst (s) used in step (I) consist essentially of at least one titanium compound and at least one tin compound. The method of claim 56, wherein A polyester composition, wherein the b ^* color value of the polyesters useful in the present invention is -12 to less than 12 as measured by the L ^* a ^* b ^* color system. The method of claim 56, wherein A polyester composition, wherein the b ^* color value of the polyesters useful in the present invention is -10 to less than 10 as measured by the L ^* a ^* b ^* color system.