CN116897176A

CN116897176A - Polyester composition comprising tetramethylcyclobutanediol and 1, 4-cyclohexanedimethanol with improved catalyst system comprising titanium and zinc

Info

Publication number: CN116897176A
Application number: CN202180094175.1A
Authority: CN
Inventors: B·A·谢弗; K·E·艾伦
Original assignee: Eastman Chemical Co
Current assignee: Eastman Chemical Co
Priority date: 2020-12-18
Filing date: 2021-12-16
Publication date: 2023-10-17

Abstract

A polyester composition comprising: (1) at least one polyester comprising: (a) a dicarboxylic acid component comprising: (i) About 70 to about 100 mole% of the residues of terephthalic acid or an ester thereof; (ii) About 0 to about 30 mole% of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; (b) a glycol component comprising: (i) About 10 to about 60 mole% of 2, 4-tetramethyl-1, 3-cyclobutanediol residues; (ii) About 40 to about 90 mole% of 1, 4-cyclohexanedimethanol residues; (iii) optionally, residues of at least one modifying diol; wherein the total mole% of dicarboxylic acid component in the final polyester is 100 mole%, wherein the total mole% of diol component in the final polyester is 100 mole%; and (2) a residue comprising titanium atoms and zinc atoms and less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of tin atoms.

Description

Polyester composition comprising tetramethylcyclobutanediol and 1, 4-cyclohexanedimethanol with improved catalyst system comprising titanium and zinc

Technical Field

The present invention relates to polyester compositions made from residues of terephthalic acid or one or more esters thereof, 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD), and 1, 4-cyclohexanedimethanol. The polyester composition can be catalyzed by a catalyst system comprising titanium and zinc atoms, which results in good TMCD incorporation, improved color, and achievement of the desired IV reactivity over a range of compositions.

Background

Tin (Sn) -based catalysts are generally most effective in incorporating TMCD into polyesters (Caldwell et al, CA 740050, and Kelsey et al, macromolecules 2000, 33, 581). However, tin-based catalysts generally produce yellow to amber copolyesters in the presence of EG, see, e.g., kelsey, U.S. patent 5,705,575; and Morris et al, U.S. Pat. No. 5,955,565.

Titanium (Ti) based catalysts have been reported to be ineffective in incorporating 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) into polyesters (Caldwell et al, CA 740050, kelsey et al, macromolecules 2000, 33, 5810).

U.S. patent application No. 2007/0142511 discloses that polyesters having a glycol component comprising TMCD and EG, optionally at levels of CHDM, can be prepared with titanium-based catalysts. It has been shown that the incorporation of TMCD can be improved by using tin-based catalysts in combination with titanium-based catalysts. It also shows that the color of these copolyesters can be improved by adding a certain level of phosphorus-containing compounds. The publication discloses a broad compositional range, wherein the glycol component comprises: (i) about 1 to about 90 mole% TMCD residues; and (ii) about 99 to about 10 mole% of EG residues. However, this catalyst system requires increasingly significant amounts of Sn whenever relatively high levels of EG are present.

There is a commercial need for polymeric materials having a combination of properties that make them desirable for injection molding, blow molding, extrusion, and thermoforming film and sheet applications, including one, two, or a combination of three or more of the following properties: good notched Izod impact strength, good intrinsic viscosity, good glass transition temperature (Tg), good flexural modulus, good tensile strength, good clarity, good color, good dishwasher washability (dishwash), good TMCD incorporation, and good/improved melt stability.

Summary of The Invention

It has been found that when DMT, TMCD and CHDM are catalyzed with at least one titanium catalyst and at least one zinc catalyst, significant amounts of TMCD can be incorporated into the polymer. It has also been found that a catalyst system comprising a combination of titanium and zinc catalysts can provide one or more, two or more, or a combination of three or more of the following properties: good notched Izod impact strength, good intrinsic viscosity, good glass transition temperature (Tg), good flexural modulus, good tensile strength, good clarity, good color, good dishwasher washability, good TMCD incorporation, and good/improved melt and/or thermal stability.

In certain aspects, the combination of titanium and zinc catalysts can produce reactive copolyesters having good TMCD incorporation and achieving the desired intrinsic viscosity over a broad compositional range including, but not limited to: (a) a dicarboxylic acid component comprising: (i) 70 to 100 mole% of terephthalic acid and/or dimethyl terephthalate residues; and (ii) from about 0 to about 30 mole% of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a glycol component comprising about 10 to about 50 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) residues and about 50 to about 90 mole% 1, 4-cyclohexanedimethanol residues (CHDM), based on the total of the glycol components, 100 mole%, and the dicarboxylic acid component total 100 mole%.

It is unpredictable that the polyesters and/or polyester compositions of the invention will possess these properties when they are prepared using catalyst systems that do not require the use of tin catalysts.

In one aspect, the polyesters and/or polyester compositions of the invention may comprise residues of TMCD in an amount of about 10 to about 55 mole%, or about 10 to about 50 mole%, or about 10 to about 45 mole%, or about 10 to about 40 mole%, or about 15 to about 55 mole%, or about 15 to about 50 mole%, or about 15 to about 45 mole%, or about 15 to about 40 mole%, or about 20 to about 55 mole%, or about 20 to about 50 mole%, or about 20 to about 45 mole%, or about 20 to about 40 mole%, or about 20 to about 35 mole%, or about 20 to about 30 mole%, or about 25 to about 55 mole%, or about 25 to about 50 mole%, or about 25 to about 45 mole%, or about 25 to about 40 mole%, or about 30 to about 55 mole%, or about 30 to about 50 mole%, or about 30 to about 45 mole%, or about 30 to about 40 mole%, or about 30 to about 35 mole%, or about 35% based on the total of the polyester as a percent to about 100 mole% of the total residues.

In one aspect, the polyesters and/or polyester compositions of the invention can comprise from about 10 to about 50 mole%, or from about 20 to about 40 mole%, or from about 25 to about 50 mole%, or from about 30 to about 45 mole% of TMCD residues, based on a total mole percent of diol residues in the final polyester equal to 100 mole%.

In one aspect, the polyesters and/or polyester compositions of the invention can comprise CHDM residues in an amount of about 45 to about 90 mole%, or about 50 to about 90 mole%, or about 55 to about 90 mole%, or about 60 to about 90 mole%, or about 45 to about 85 mole%, or about 50 to about 85 mole%, or about 55 to about 85 mole%, or about 60 to about 85 mole%, or about 45 to about 80 mole%, or about 50 to about 80 mole%, or about 55 to about 80 mole%, or about 60 to about 80 mole%, or about 65 to about 80 mole%, or about 70 to about 80 mole%, or about 45 to about 75 mole%, or about 50 to about 75 mole%, or about 55 to about 75 mole%, or about 60 to about 75 mole%, or about 45 to about 70 mole%, or about 50 to about 70 mole%, or about 55 to about 70 mole%, or about 60 to about 70 mole%, or about 45 to about 65 mole%, or about 50 to about 65 mole%, or about 55 to about 80 mole%, based on the total of the polyester residues as a hundred mole% of the total of the polyester residues.

In one aspect, the polyesters and/or polyester compositions of the invention can comprise from about 50 to about 80 mole%, or from about 60 to about 80 mole%, or from about 50 to about 75 mole%, or from about 50 to about 70 mole%, or from about 55 to about 70 mole% CHDM residues, based on a total mole percent of diol residues in the final polyester equal to 100 mole%.

In one aspect, in one embodiment, the polyesters and/or polyester compositions of the invention may comprise from 10 to 50 mole% TMCD residues and from 50 to 90 mole% CHDM residues; or 10 to 45 mole% TMCD residues and 55 to 90 mole% CHDM residues; or 10 to 40 mole% TMCD residues and 60 to 90 mole% CHDM residues; or 10 to 35 mole% TMCD residues and 65 to 90 mole% CHDM residues; or 15 to 50 mole% TMCD residues and 50 to 85 mole% CHDM residues; or 15 to 45 mole% TMCD residues and 55 to 85 mole% CHDM residues; or 15 to 40 mole% TMCD residues and 60 to 85 mole% CHDM residues; or 15 to 35 mole% TMCD residues and 65 to 85 mole% CHDM residues; or 20 to 45 mole% TMCD residues and 55 to 80 mole% CHDM residues; or 20 to 40 mole% TMCD residues and 60 to 80 mole% CHDM residues; or 20 to 35 mole% TMCD residues and 65 to 80 mole% CHDM residues; or 25 to 45 mole% TMCD residues and 55 to 75 mole% CHDM residues; or 25 to 40 mole% TMCD residues and 60 to 75 mole% CHDM residues; or 25 to 35 mole% TMCD residues and 65 to 75 mole% CHDM residues; or 30 to 35 mole% TMCD residues and 65 to 70 mole% CHDM residues, based on a total mole percent of diol residues in the final polyester equal to 100 mole%.

In one aspect, the polyesters and/or polyester compositions of the invention wherein TMCD: CHDM is 1:9 to 1:1, or 1:4 to 1:1, or 1:3 to 1:1.5, or 1:3 to 1:1, or 1:2 to 1:1, or 1:1.5 to 1:1.

Optionally, the polyesters of the invention may contain modified diols, which may be present in the remaining mole percent.

In one aspect, these modifying diols may include diethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, ethylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, terephthalyl alcohol, neopentyl glycol, isosorbide, polytetramethylene glycol, or mixtures thereof.

In one aspect, the polyesters and/or polyester compositions of the invention may comprise residues of ethylene glycol.

In one aspect, the polyesters and/or polyester compositions of the invention can comprise less than 55 mole%, or less than 50 mole%, or less than 40 mole%, or less than 35 mole%, or less than 30 mole%, or less than 25 mole%, or less than 20 mole%, or less than 15 mole%, or less than 10 mole%, or 0 mole% of ethylene glycol residues, based on a total mole percent of glycol residues in the final polyester equal to 100 mole%.

In one aspect, the polyesters and/or polyester compositions of the invention may comprise residues of at least one of 1, 3-propanediol, 1, 4-butanediol, and neopentyl glycol, or residues of a mixture of two or more.

In one aspect, the polyester composition may not comprise hexylene glycol, and/or not comprise propylene glycol, and/or not comprise butylene glycol.

In one aspect, the polyester and/or polyester composition can comprise less than 10 mole%, or less than 5 mole%, or less than 2 mole%, or 0 mole% trimethylolpropane.

In certain aspects of the invention, the polyester may contain less than about 2 mole%, or less than about 3 mole%, or less than about 4 mole%, or less than about 5 mole% of a second modified diol having 3 to 16 carbon atoms. In certain embodiments, the polyester contains only the second modifying diol. It should be understood that some other diol residues (e.g., diethylene glycol) may be formed in situ during processing.

In one aspect, the polyester and/or polyester composition can comprise less than 10 mole%, or less than 5 mole%, or less than 2 mole%, or 0 mole% of a polyol.

In one aspect, the polyester and/or polyester composition can comprise less than 10 mole%, or less than 5 mole%, or less than 2 mole%, or 0 mole% of 1, 4-bis (2-hydroxyethyl) terephthalate.

In one aspect, the polyester and/or polyester composition can comprise less than 10 mole%, or less than 5 mole%, or less than 2 mole%, or 0 mole% butanediol.

In one aspect, the diacid component of the polyesters of the invention can include modified aromatic and/or aliphatic dicarboxylic acid ester residues.

In one aspect, the diacid component of the polyesters of the invention can comprise the residues of dimethyl terephthalate.

In one aspect, the polyester composition of the present invention may comprise:

(1) At least one polyester comprising:

(a) A dicarboxylic acid component comprising:

(i) About 70 to about 100 mole% of the residues of terephthalic acid or an ester thereof;

(ii) About 0 to about 30 mole% of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms;

(b) A glycol component comprising:

(i) About 10 to about 50 mole% of 2, 4-tetramethyl-1, 3-cyclobutanediol residues;

(ii) About 50 to about 80 mole% 1, 4-cyclohexanedimethanol residues;

wherein the total mole% of dicarboxylic acid component of the final polyester is 100 mole% and

wherein the total mole% of the glycol component of the final polyester is 100 mole%; and

(2) A residue comprising titanium atoms and zinc atoms, and less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or 0 to 30ppm, or 0 to 20ppm, or 0 to 10ppm, or 0ppm of tin atoms;

wherein the intrinsic viscosity is from 0.35 to 0.80dL/g, or from 0.35 to 0.75dL/g, or from 0.40 to 0.75, or from 0.45 to 0.75dL/g, or from 0.50 to 0.75dL/g, as measured in 60/40 (weight/weight) phenol/tetrachloroethane at a concentration of 0.5g/100ml at 25 ℃; and having a b-x value of less than 20, less than 15, or less than 14, or less than 13, or less than 12, or less than 11, or less than 10, or less than 9, or less than 8.5, or less than 8, or less than 7, or less than 6, or less than 5, or 1 to 10, or 1 to 9, or 1 to 8, or 1 to 7, or 1 to 6, or 1 to 5, or 2 to 6; and L values of 70 to 95 or 75 to 90, as determined by the L x a x b x color system of CIE (International Commission on Illumination). In some embodiments, a may also have a value of less than 7, or less than 4, or less than 3, or less than 2, or less than 1, or less than 0, or less than-1, or less than-1.5, or less than-2.

In one aspect, the intrinsic viscosity may be from 0.35 to 1.2dL/g, or from 0.35 to 0.80dL/g, or from 0.35 to 0.75dL/g, or from 0.35 to 0.70dL/g, or from 0.35 to 0.60dL/g, or from 0.40 to 0.75dL/g, or from 0.40 to 0.70dL/g, or from 0.40 to 0.65dL/g, or from 0.40 to 0.60dL/g, or from 0.45 to 0.75dL/g, or from 0.45 to 0.70dL/g, or from 0.45 to 0.65dL/g, or from 0.45 to 0.60dL/g, or from 0.50 to 1.2dL/g, or from 0.50 to 0.80dL/g, or from 0.50 to 0.75dL/g, or from 0.50 to 0.70dL/g, or from 0.45 to 0.75dL/g, or from 0.45 to 0.70dL/g, or from 0.65dL/g, or from 0.55 to 0.60dL/g, or from 0.45 to 0.60dL/g, as measured in 60/40 (weight/weight) phenol/tetrachloroethane at a concentration of 0.5g/100ml at 25 ℃.

In one aspect, the polyester and/or polyester composition of the invention may have a Tg of 85 to 130 ℃, or 100 to 125 ℃, or 100 to 120 ℃, or 85 to 120 ℃.

In one aspect, the polyesters and/or polyester compositions of the invention comprise at least one titanium source that is at least one of: titanium carbonate, titanium acetate, titanium benzoate, titanium succinate, titanium isopropoxide, titanium methoxide, titanium oxalate, titanium nitrate, titanium ethoxide, titanium hydroxide, titanium hydride, titanium ethoxide, titanium alkyl, titanium zinc hydride, titanium borohydride, lithium oxide, titanium acetylacetonate, titanium triisopropoxide chloride, titanium bis (acetylacetonate), titanium n-butoxide, titanium t-butoxide.

In one embodiment, the polyesters and/or polyester compositions of the present invention comprise at least one titanium source selected from titanium dioxide, titanium isopropoxide, titanium acetylacetonate oxide, titanium bis (acetylacetonate) diisopropoxide, and/or combinations thereof.

In one aspect, the polyester composition can comprise at least one catalytically active zinc source. These zinc compounds may include zinc compounds having at least one organic substituent.

Suitable examples of zinc compounds may include at least one carboxylate salt of zinc. Examples of zinc may include at least one zinc source selected from zinc borate, zinc oxide, zinc naphthenate, zinc tert-butoxide, zinc methoxide, zinc hydroxide, zinc acetate, zinc diacetate, zinc dihydrate, zinc octoate, zinc carbonate, dialkyl zinc, dimethyl zinc, diaryl zinc (e.g., diphenyl zinc), isopropyl alcohol zinc phosphate, and/or zinc acetylacetonate.

In one aspect, the polyesters and/or polyester compositions of the invention may contain zinc acetylacetonate and zinc isopropoxide. In one aspect, zinc acetate and/or zinc acetate dihydrate and/or zinc naphthenate and/or zinc carbonate and/or residues thereof or combinations thereof are absent.

In one aspect, the polyesters and/or polyester compositions of the invention may comprise zinc acetylacetonate.

In one aspect of the present invention, the polyesters and/or polyester compositions of the invention may comprise 20 to 750ppm, or 20 to 500ppm, or 20 to 450ppm, or 20 to 400ppm, or 20 to 350ppm, or 20 to 300ppm, or 20 to 275ppm, or 20 to 250ppm, or 20 to 200ppm, or 50 to 1000ppm, or 50 to 750ppm, or 50 to 500ppm, or 50 to 450ppm, or 50 to 400ppm, or 50 to 300ppm, or 50 to 275ppm, or 50 to 250ppm, or 50 to 200ppm, or 60 to 1000ppm, or 60 to 750ppm, or 60 to 500ppm, or 60 to 450ppm, or 60 to 400ppm, or 60 to 350ppm, or 60 to 300ppm, or 60 to 275ppm, or 60 to 250ppm, or 60 to 200ppm, or 60 to 150ppm, or 60 to 100ppm, or 75 to 1000ppm, or 75 to 750ppm, or 75 to 500ppm, or 75 to 450ppm, or 75 to 400ppm, or 75 to 350ppm, or 75 to 300ppm, or 75 to 250ppm, or 250ppm or 70 to 100ppm, or 70 to 90ppm, or 65 to 100ppm, or 65 to 90ppm, or 80 to 1000ppm, or 80 to 750ppm, or 80 to 500ppm, or 80 to 450ppm, or 80 to 400ppm, or 80 to 350ppm, or 80 to 300ppm, or 80 to 275ppm, or 80 to 250ppm, or 80 to 200ppm, or 100 to 1000ppm, or 100 to 750ppm, or 100 to 500ppm, or 100 to 450ppm, or 100 to 400ppm, or 100 to 350ppm, or 100 to 300ppm, or 100 to 275ppm, or 100 to 250ppm, or 100 to 200, or 150 to 1000ppm, or 150 to 750ppm, or 150 to 500ppm, or 150 to 450ppm, or 150 to 400ppm, or 150 to 350ppm, or 150 to 300ppm, or 150 to 250ppm, or 200 to 1000ppm, or 200 to 500ppm, or 200 to 450ppm, or 200 to 400ppm, or 200 to 350ppm, or 200 to 300ppm, or 200 to 250ppm, relative to the mass of the final polyester produced.

In one aspect, the polyesters and/or polyester compositions of the invention may contain zinc atoms, the amount is 50 to 1000ppm, or 50 to 750ppm, or 50 to 500ppm, or 50 to 450ppm, or 50 to 400ppm, or 50 to 300ppm, or 50 to 275ppm, or 50 to 250ppm, or 50 to 200ppm, or 60 to 1000ppm, or 60 to 750ppm, or 60 to 500ppm, or 60 to 450ppm, or 60 to 400ppm, or 60 to 350ppm, or 60 to 300ppm, or 60 to 275ppm, or 60 to 250ppm, or 60 to 200ppm, or 60 to 150ppm, or 60 to 100ppm, or 75 to 1000ppm, or 75 to 750ppm, or 75 to 500ppm, or 75 to 450ppm, or 75 to 400ppm, or 75 to 350ppm, or 75 to 300ppm, or 75 to 250ppm, or 75 to 200ppm, or 70 to 100ppm, or 70 to 90ppm, or 65 to 100ppm, or 65 to 90ppm, or from 80 to 1000ppm or 80 to 750ppm, or 80 to 500ppm, or 80 to 450ppm, or 80 to 400ppm, or 80 to 350ppm, or 80 to 300ppm, or 80 to 275ppm, or 80 to 250ppm, or 80 to 200ppm, or 100 to 1000ppm, or 100 to 750ppm, or 100 to 500ppm, or 100 to 450ppm, or 100 to 400ppm, or 100 to 350ppm, or 100 to 300ppm, or 100 to 275ppm, or 100 to 250ppm, or 100 to 200, or 150 to 1000ppm, or 150 to 750ppm, or 150 to 500ppm, or 150 to 450ppm, or 150 to 400ppm, or 150 to 350ppm, or 150 to 300ppm, or 150 to 250ppm, or 200 to 1000ppm, or 200 to 750ppm, or 200 to 500ppm, or 200 to 450ppm, or 200 to 400ppm, or 200 to 350ppm, or 200 to 300ppm, or 200 to 250ppm, relative to the mass of the final polyester produced.

In one aspect, the polyesters and/or polyester compositions of the invention are provided, wherein the ratio of titanium atoms to zinc atoms may be 0.50-1:5 to 5:1, or 0.50-1:4 to 4:1, or 0.50-1:3 to 3:1, or 0.50:1 to 1:5, or 0.50-1 to 1:4, or 0.60-1:5 to 5:1, or 0.60-1:4 to 4:1, or 0.60-1:3 to 3:1, or 0.60:1 to 1:5, or 0.60-1 to 1:4, or 0.70-1:5 to 5:1, or 0.70-1:4 to 4:1, or 0.70-1:3 to 3:1, or 0.70-1:2 to 2:1, or 0.70-1:1 or 0.70-1.2 to 1:4, or 0.75-1:5 to 5:1, or 0.75-1.2 to 1:4 to 4:1, or 0.75-1:3 to 3:1, or 0.75-1:2 to 2:1, or 0.75-1.0 to 1:4, or 0.80:1.2 to 1:4, or 1.0 to 1.5:1.0 to 1:7.1, or 1.0 to 1.5:1.0 to 3, or 1.0 to 1.5:1.0 to 2, or 1.0 to 1.5:1.0 to 2.5, or 0.80-1:5 to 5:1, or 0.80-1.2 to 4:1, or 0.80-1:3 to 3:1, or 0.80-1:2 to 2:1, or 0.80-1:1 to 2:1, or 0.80-1:1.0 to 2:1.

In one aspect, the polyesters and/or polyester compositions of the invention may have the following total catalyst metal atoms present in the composition: 150 to 800ppm, or 150 to 725ppm, or 150 to 700ppm, or 150 to 500ppm, or 150 to 450ppm, or 150 to 400ppm, or 150 to 300ppm,200 to 800ppm, or 200 to 725ppm, or 200 to 700ppm, or 200 to 600ppm, or 200 to 500ppm, or 200 to 450ppm, or 200 to 400ppm, or 200 to 300ppm, or 250 to 800ppm, or 250 to 725ppm, or 250 to 700ppm, or 250 to 500ppm, or 250 to 450ppm, or 250 to 400ppm, or 300 to 800ppm, or 300 to 725ppm, or 300 to 700ppm, or 300 to 500ppm, or 300 to 450ppm, or 300 to 400ppm, or 350 to 800ppm, or 350 to 725ppm, or 350 to 700ppm, or 350 to 500ppm, or 350 to 450ppm relative to the mass of the final polyester produced.

In one aspect, the polyesters and/or polyester compositions of the invention may include polyesters having a degree of polymerization of: 0.01 to 300, or 0.01 to 250, or 0.01 to 200, or 0.01 to 150, or 0.01 to 130, or 0.01 to 120, or 0.10 to 300, or 0.10 to 250, or 0.10 to 200, or 0.10 to 150, or 0.10 to 130, or 0.10 to 120, or 0.20 to 300, or 0.20 to 250, or 0.20 to 200, or 0.20 to 150, or 0.20 to 130, or 0.20 to 120, or 0.15 to 300, or 0.15 to 250, or 0.15 to 200, or 0.15 to 150, or 0.15 to 130, or 0.15 to 120.

In one aspect, the polyesters and/or polyester compositions of the invention can have a number average molecular weight of from 4,800 to 16,000.

In one aspect, the polyesters and/or polyester compositions of the invention may have the following b-values: -10 to less than 20; or-10 to less than 18; or-10 to less than 15; or-10 to less than 14; or-10 to less than 10; or 1 to less than 20; or 1 to less than 18; or 5 to less than 20; or 5 to less than 18; or 8 to less than 20; or 8 to less than 18; or 8 to less than 15; or-3 to 10; or-5 to 5; or-5 to 4; or-5 to 3; or 1 to 20; or 1 to 18; or 1 to 15; or 1 to 14; or 1 to less than 10; or 1 to 10; or 1 to 9; or 1 to 8;1 to 7; or 1 to 6; or 1 to 5; or 2 to 25; or 2 to 20; or 2 to 18; or 2 to 15; or 2 to 14; or 2 to less than 10; or 2 to 9; or 2 to 8; or 2 to 7; or 2 to 6; or 2 to 5; or 3 to 20; or 3 to 18; or 3 to 15; or 3 to 14; or 3 to less than 10; or 3 to 8; or 3 to less than 20; or less than 15; or less than 14; or less than 13; or less than 12; or less than 11; or less than 10; or less than 9; or less than 8.5; or less than 8; or less than 7; or less than 6; or less than 5; or less than 4; or less than 3, as determined by the color system of L x a x b x CIE (International Commission on Illumination).

In one aspect, the polyesters and/or polyester compositions of the invention may have an L value of 50 to 99, or 50 to 90, or 60 to 99, or 60 to 90, or 60 to 85, or 60 to 80, or 60 to 75, or 60 to 70, or 65 to 99, or 65 to 90, or 65 to 85, or 65 to 80, or 65 to 75, or 70 to 90, or 70 to 99, or 70 to 90, or 70 to 85, or 70 to 80, or 75 to 95, or 77 to 90, or 75 to 85, or 80 to 95 as determined by the L x a b color system of CIE (International Commission on Illumination).

In one aspect, b and/or L and/or a values may be obtained in the presence and/or absence of one or more toners.

In one aspect, the polyesters and/or polyester compositions of the invention may comprise residues of at least one branching agent in an amount of 0.01 to 10 mole%, or 0.01 to 5 mole%, based on the total mole percent of diacid or diol residues.

In one aspect, the polyesters and/or polyester compositions of the invention can have a melt viscosity of less than 30,000, or less than 20,000, or less than 12,000, or less than 10,000, or less than 7,000, or less than 5,000 poise, or less than 3,000 poise measured at 290 ℃ on a rotary melt rheometer at 1 rad/sec.

In one aspect, the polyesters and/or polyester compositions of the invention can have a notched Izod impact strength of at least 1ft-lbs/in, or at least 2ft-lbs/in, or at least 3ft-lbs/in, or 7.5ft-lbs/in, or 10ft-lbs/in measured in a 1/8 inch thick test stick at 23℃with a 10 mil notch according to ASTM D256.

In one aspect, the polyester composition may comprise methyl groups in an amount of 5.0 mole% or less, or 4.5 mole% or less, or 4 mole% or less, or 3.5 mole% or less, or 3 mole% or less, or 2.5 mole% or less, or 2.0 mole% or less, or 1.5 mole% or less, or 1.0 mole% or less, in the final polyester and/or polyester composition of the present invention.

In one aspect of the present invention, the polyesters and/or polyester compositions of the invention may comprise greater than 50 mole% of cis-2, 4-tetramethyl-1, 3-cyclobutanediol and less than 50 mole% of trans-2, 4-tetramethyl-1, 3-cyclobutanediol or greater than 70 mole% cis-2, 4-tetramethyl-1, 3-cyclobutanediol and less than 30 mole% trans-2, 4-tetramethyl-1, 3-cyclobutanediol, or greater than 75 mole% trans-TMCD and less than 25 mole% cis-TMCD; or greater than 80 mole% trans-TMCD and less than 20 mole% cis-TMCD; or greater than 85 mole% trans-TMCD and less than 15 mole% cis-TMCD; or more than 90 mole% cis-2, 4-tetramethyl-1, 3-cyclobutanediol and less than 10 mole% trans-2, 4-tetramethyl-1, 3-cyclobutanediol or more than 95 mole% cis-2, 4-tetramethyl-1, 3-cyclobutanediol and less than 5 mole% trans-2, 4-tetramethyl-1, 3-cyclobutanediol.

In one aspect, the polyester composition of the invention may comprise a blend of at least one polyester useful in the invention and at least one polymer selected from at least one of the following: other polyesters (e.g., polyethylene terephthalate (PET) (including recycled PET, i.e., rPET), polycyclohexylene terephthalate (e.g., PCT), modified PET, or PET modified with 1, 4-cyclohexanedimethanol CHDM (e.g., PETG), poly (etherimide), polyphenylene ether/polystyrene blends, polystyrene resins, polyphenylene sulfide/polysulfones, poly (ester-carbonates), polycarbonates, polysulfones, polysulfone ethers, and poly (ether-ketones).

In one aspect, the polyester compositions of the present invention may comprise at least one polycarbonate, or no carbonate groups.

In one aspect, the polyester compositions of the present invention may be free of crosslinking agents.

In one aspect, the polyester compositions of the present invention may comprise residues of at least one phosphorus compound.

In one aspect, the polyester compositions of the present invention may comprise residues of phosphoric acid, phosphorous acid, phosphonic acid, hypophosphorous acid, phosphinic acid, and/or various esters and/or salts thereof. These esters may be alkyl, branched alkyl, substituted alkyl, difunctional alkyl, alkyl ether, aryl, and substituted aryl.

In one aspect, the polyester compositions of the present invention may comprise substituted or unsubstituted alkyl phosphates, substituted or unsubstituted aryl phosphates, substituted or unsubstituted mixed alkyl aryl phosphates, bisphosphites, phosphates, phosphine oxides, and mixed arylalkyl phosphites, reaction products thereof, and/or mixtures thereof.

In one aspect, the polyester composition of the present invention may comprise at least one of a substituted or unsubstituted alkyl phosphate, a substituted or unsubstituted aryl phosphate, a mixed substituted or unsubstituted alkylaryl phosphate, a reaction product thereof, and mixtures thereof.

In one aspect, the polyester composition of the present invention may not comprise a phosphorus compound.

In one aspect, the polyesters and/or polyester compositions of the invention can comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm tin atoms.

In one aspect, the polyesters and/or polyester compositions of the invention can comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm manganese atoms.

In one aspect, the polyesters and/or polyester compositions of the invention can comprise less than 30ppm, or less than 20ppm, or less than 1 ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm cobalt atoms.

In one aspect, the polyesters and/or polyester compositions of the invention can comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of any of tin atoms and germanium atoms.

In one aspect, the polyesters and/or polyester compositions of the invention can comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of any of antimony atoms and/or germanium atoms.

In one aspect, the polyesters and/or polyester compositions of the invention can comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of any of tin atoms and manganese atoms.

In one aspect, the polyesters and/or polyester compositions of the invention can comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of any of tin atoms and/or aluminum atoms.

In one aspect, the polyesters and/or polyester compositions of the invention can comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of any of lithium atoms and/or aluminum atoms.

In one aspect, the polyesters and/or polyester compositions of the invention can comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of any of tin atoms, lithium atoms, and/or aluminum atoms.

In one aspect, the polyesters and/or polyester compositions of the invention can comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of any of the following: tin and/or manganese and/or magnesium and/or germanium and/or antimony, cobalt and/or cadmium and/or calcium and/or sodium and/or gallium atoms, and may not include any combination of these atoms or may not include all of these atoms.

In one aspect, the polyesters and/or polyester compositions of the invention can comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of any of the following: tin atoms, manganese atoms, magnesium atoms, germanium atoms, antimony atoms, cobalt atoms, and/or calcium atoms, and any combination of these atoms may be excluded or all of these atoms may be excluded.

In one aspect, the polyesters and/or polyester compositions of the invention can comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of any of the following: tin atoms, manganese atoms, lithium atoms, germanium atoms, and cobalt atoms, and any combination of these atoms may be excluded or all of these atoms may be excluded.

In one aspect, the polyesters and/or polyester compositions of the invention can comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of gallium atoms.

In one aspect, the polyesters and/or polyester compositions of the invention can comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of any sodium and/or potassium atoms.

In one aspect, a method of making any of the polyester compositions herein is provided, comprising the steps of:

(I) Heating the mixture to at least one temperature selected from 150 ℃ to 300 ℃ at least one pressure selected from 0psig to 100psig, wherein the mixture comprises:

(a) A dicarboxylic acid component comprising:

(i) 70 to 100 mole% of terephthalic acid residues;

(ii) 0 to 30 mole% of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

(iii) 0 to 10 mole% of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

(b) A glycol component comprising:

(i) 10 to 50 mole% of 2, 4-tetramethyl-l, 3-cyclobutanediol residues; and

(ii) 50 to 90 mole% of modified 1, 4-cyclohexanedimethanol residues;

wherein the molar ratio of diol component/dicarboxylic acid component added in step (I) is 1.0 to 1.5/1.0;

(II) heating the product of step (I) at a temperature of 230 ℃ to 320 ℃ for 1 to 6 hours at least one pressure selected from the final pressure of step (I) to 0.22 torr absolute;

wherein the mixture in step (I) or (II) is heated, respectively, in the presence of at least one catalyst selected from the group consisting of at least one zinc compound and one titanium compound, when heated; and is also provided with

Wherein the final product after step (II) comprises titanium atoms and zinc atoms;

wherein the total mole% of dicarboxylic acid component of the final polyester is 100 mole%;

wherein the total mole% of the glycol component of the final polyester is 100 mole%;

wherein the final polyester has an intrinsic viscosity of 0.35 to 1.2dL/g measured in 60/40 (weight/weight) phenol/tetrachloroethane at a concentration of 0.25g/50ml at 25 ℃; and

Wherein the final polyester has a Tg of 85 ℃ to 200 ℃.

In one aspect, there is provided the above process, except that the titanium catalyst source is added in step (I) and the zinc catalyst source is added in step (II).

In one aspect, the process for making polyesters useful in the present invention can comprise a batch process or a continuous process.

In one aspect, the process for making polyesters useful in the present invention comprises a continuous process.

In one aspect, the present invention relates to a process for making a polyester comprising the steps of:

(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 10 to about 50 mole% 2, 4-tetramethyl-l, 3-cyclobutanediol residues; and

(ii) About 50 to about 90 mole% of 1, 4-cyclohexanedimethanol residues;

wherein the molar ratio of diol component/dicarboxylic acid component added in step (I) is 1.01-3.0/1.0, and wherein TMCD is added in an amount of about 10 to 50 mole%, optionally allowing at least 30% conversion of TMCD in the reaction, and obtaining a final polymer having about 10 to 50 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol residues and about 50 to about 90 mole% 1, 4-cyclohexanedimethanol residues;

Wherein the mixture in step (I) is heated in the presence of:

(i) At least two catalysts comprising Li and Al; and (ii) and optionally to

At least one phosphorus compound;

(II) heating the product of step (I) at a temperature of 230 ℃ to 320 ℃ for 1 to 6 hours at least one pressure selected from the final pressure of step (I) to 0.02 torr absolute to form a final polyester;

wherein the total mole% of dicarboxylic acid component of the final polyester is 100 mole%; and wherein the total mole% of the glycol component of the final polyester is 100 mole%; and is also provided with

Wherein the intrinsic viscosity of the polyester, measured at 25℃in 60/40 (weight/weight) phenol/tetrachloroethane at a concentration of 0.25g/50ml, is from 0.35 to 0.80dL/g; and wherein the polyester has an L color value of 75 or greater, or greater than 75, as determined by the L x a x b color system measured according to ASTM D6290-98 and ASTM E308-99 on polymer particles ground to pass a 1mm screen. In certain aspects, the catalyst is free of tin. In one aspect, the polyesters useful in the present invention may comprise at least one phosphate ester, whether present as a heat stabilizer or not.

In one aspect, the polyesters useful in the present invention are free of branching agents or at least one branching agent is added prior to or during polymerization of the polyester.

In one aspect, the polyesters useful in the present invention contain at least one branching agent regardless of the method or sequence of their addition.

In one aspect, certain polyesters useful in the present invention may be amorphous or semi-crystalline. In one aspect, certain polyesters useful in the present invention may have relatively low crystallinity. Certain polyesters useful in the present invention can thus have a substantially amorphous morphology, meaning that the polyesters contain substantially disordered polymer regions.

The at least one phosphorus compound useful in the present invention is selected from at least one of alkyl phosphates, aryl phosphates, mixed alkyl aryl phosphates, reaction products thereof, and mixtures thereof.

In one aspect, the at least one phosphorus compound useful in the present invention may comprise at least one aryl phosphate.

In one aspect, the at least one phosphorus compound useful in the present invention may comprise at least one unsubstituted aryl phosphate.

In one aspect, the at least one phosphorus compound useful in the present invention may comprise at least one aryl phosphate ester that is not substituted with a benzyl group.

In one aspect, the at least one phosphorus compound useful in the present invention may comprise at least one triaryl phosphate ester.

In one aspect, the at least one phosphorus compound useful in the present invention may comprise at least one triaryl phosphate ester that is not substituted with a benzyl group.

In one aspect, the at least one phosphorus compound useful in the present invention may comprise at least one alkyl phosphate.

In one aspect, the at least one phosphorus compound useful in the present invention may comprise triphenyl phosphate and/or Merpol a. In one aspect, any of the polyester compositions of the present invention can comprise triphenyl phosphate.

In one aspect, any of the methods described herein for making any of the polyester compositions and/or polyesters may comprise at least one mixed alkylaryl phosphite, such as bis (2, 4-dicumyl benzene) pentaerythritol diphosphite, also known as dovephos S-9228 (Dover Chemicals, CAS # 154862-43-8).

In one aspect, any of the methods described herein for making any of the polyester compositions and/or polyesters may comprise at least one phosphine oxide.

In one aspect, any of the methods described herein for making any of the polyester compositions and/or polyesters may comprise at least one phosphate salt, such as KH2PO4 and Zn3 (PO 4) 2.

It is believed that any process that can be used to make the polyesters and/or polyester compositions of the invention can be used to make any polyester useful in the invention.

In one aspect, the pressure used in step (I) of any of the methods of the present invention consists of at least one pressure selected from the group consisting of 0psig to 75 psig. In one aspect, the pressure used in step (I) of any of the methods of the present invention consists of at least one pressure selected from the group consisting of 0psig to 50 psig.

In one aspect, the pressure used in step (II) of any of the methods of the present invention consists of at least one pressure selected from the group consisting of 20 torr absolute to 0.02 torr absolute; in one aspect, the pressure used in step (II) of any of the methods of the invention consists of at least one pressure selected from the group consisting of 10 torr absolute to 0.02 torr absolute; in one aspect, the pressure used in step (II) of any of the methods of the invention consists of at least one pressure selected from the group consisting of 5 torr absolute to 0.02 torr absolute; in one aspect, the pressure used in step (II) of any of the methods of the invention consists of at least one pressure selected from the group consisting of 3 torr absolute to 0.02 torr absolute; in one aspect, the pressure used in step (II) of any of the methods of the invention consists of at least one pressure selected from the group consisting of 20 torr absolute to 0.1 torr absolute; in one aspect, the pressure used in step (II) of any of the methods of the invention consists of at least one pressure selected from the group consisting of 10 torr absolute to 0.1 torr absolute; in one aspect, the pressure used in step (II) of any of the methods of the invention consists of at least one pressure selected from the group consisting of 5 torr absolute to 0.1 torr absolute; in one aspect, the pressure used in step (II) of any of the methods of the present invention consists of at least one pressure selected from the group consisting of 3 torr absolute to 0.1 torr absolute.

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

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

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

The weight (ppm) of zinc atoms and titanium atoms present in the final polyester can be measured, for example, in any of the foregoing weight ratios of the final polyester.

In one aspect, the polyesters and/or polyester compositions of the invention can be used in non-coating compositions, non-adhesive compositions. Thermoplastic polyester compositions, articles of manufacture, shaped articles, thermoplastic shaped articles, molded articles, extruded articles, injection molded articles, blow molded articles, films and/or sheets (e.g., calendered, cast or extruded), thermoformed films or sheets, containers and/or bottles (e.g., baby bottles or sports bottles or water bottles).

In one aspect, the polyester composition can be used in shaped articles, including but not limited to extruded and/or molded articles, including but not limited to injection molded articles, extruded articles, cast extruded articles, profile extruded articles, melt spun articles, thermoformed articles, extrusion molded articles, injection blow molded articles, injection stretch blow molded articles, extrusion blow molded articles, and extrusion stretch blow molded articles. Such articles may include, but are not limited to, films, bottles, containers, drinking tools, medical accessories, sheets, and/or fibers.

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

In one aspect, the present invention relates to one or more thermoformed films and/or sheets comprising one or more polyesters and/or polyester compositions of the present invention.

In one aspect, the present invention relates to articles of manufacture incorporating the thermoformed films and/or sheets of the present invention.

In one aspect, any method of making polyesters useful in the present invention and described herein or known to one of ordinary skill in the art can be used to make any polyester and/or polyester composition of the present invention.

In one aspect, any polyester and/or polyester composition described herein is also considered to be within the scope of the invention, regardless of the method of its manufacture, and any product made thereby.

In one aspect, the present invention relates to articles of manufacture, such as shaped articles, comprising any of the polyesters and/or polyester compositions of the invention.

Detailed Description

The present invention may be understood more readily by reference to the following detailed description of certain embodiments of the invention and the working examples. Certain embodiments of the invention are described in the summary of the invention and are further described below, in accordance with one or more objects of the invention. Further, other embodiments of the invention are described herein.

It is believed that certain polyesters and/or one or more polyester compositions of the present invention formed from terephthalic acid, esters and/or mixtures thereof, 2, 4-tetramethyl-1, 3-cyclobutanediol, and at least one modified diol and further comprising certain titanium and zinc catalysts and optionally stabilizers, reaction products thereof, and mixtures thereof may have one or more, two or more, or unique combinations of three or more of the following properties: good notched Izod impact strength, good intrinsic viscosity, good glass transition temperature (Tg), good flexural modulus, good tensile strength, good clarity, good color, good dishwasher washability, good TMCD incorporation, and good/improved melt stability.

In one aspect, copolyesters containing a range of compositions of 2, 4-tetramethyl-l, 3-cyclobutanediol, 1, 4-cyclohexanedimethanol, and optionally at least one modified diol can be prepared using at least one titanium catalyst and at least one zinc catalyst.

The present invention relates to polyesters based on terephthalic acid or esters thereof, 2, 4-tetramethyl-l, 3-cyclobutanediol, 1, 4-cyclohexanedimethanol, and optionally at least one modified diol, catalyzed by certain catalyst types and/or amounts, which provide improved properties (as described herein), and in certain embodiments, at least one titanium catalyst and at least one zinc catalyst result in good TMCD incorporation, improved color (higher brightness and/or less yellow), and achieving the desired Intrinsic Viscosity (IV) reactivity within the compositional ranges described herein.

When titanium is added to the polyester and/or polyester composition and/or the process for producing a polyester of the present invention, it is added to the process for producing a polyester 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 process of the invention may be measured in terms of titanium atoms present in the final polyester, for example in ppm by weight.

When zinc is added to the polyester and/or polyester composition of the invention and/or the process for making the polyester, zinc is added to the process for making the polyester as a zinc compound. The amount of zinc compound added to the polyester of the invention and/or the polyester composition of the invention and/or the process of the invention may be measured in terms of zinc atoms present in the final polyester, for example in ppm by weight.

When phosphorus is added to the polyester and/or the polyester composition and/or the process for producing a polyester of the present invention, it is added to the process for producing a polyester in the form of a phosphorus compound. In one aspect, the phosphorus compound may include at least one phosphate ester. The amount of phosphorus compound [ e.g., one or more phosphate esters ] 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 terms of phosphorus atoms present in the final polyester, e.g., in ppm by weight.

The term "polyester" as used herein is intended to include "copolyesters" and is understood to mean a synthetic polymer prepared by the reaction of one or more difunctional carboxylic acids and/or polyfunctional carboxylic acids with one or more difunctional hydroxyl compounds and/or polyfunctional hydroxyl compounds (e.g., branching agents). Typically, the difunctional carboxylic acid may be a dicarboxylic acid and the difunctional hydroxyl compound may be a diol, such as a glycol or diol. The term "glycol" as used herein includes, but is not limited to, diols, and/or polyfunctional hydroxy compounds, such as branching agents. Alternatively, the difunctional carboxylic acid may be a hydroxycarboxylic acid, such as parahydroxybenzoic acid, and the difunctional hydroxyl compound may be an aromatic nucleus bearing 2 hydroxyl substituents, such as hydroquinone. The term "residue" as used herein refers to any organic structure incorporated into a polymer by polycondensation and/or esterification of the corresponding monomers. The term "repeat unit" as used herein refers to an organic structure having dicarboxylic acid residues and diol residues bonded through a carbonyloxy group. Thus, for example, the dicarboxylic acid residues may be derived from dicarboxylic acid monomers or related acid halides, esters, salts, anhydrides, and/or mixtures thereof. Furthermore, the term "diacid" as used herein includes polyfunctional acids, such as branching agents. Thus, the term "dicarboxylic acid" as used herein is intended to include dicarboxylic acids and any derivatives of dicarboxylic acids, including their related acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, and/or mixtures thereof, which can be used in a reaction process with a glycol to make a polyester. The term "terephthalic acid" as used herein is intended to include terephthalic acid itself and its residues as well as any derivatives of terephthalic acid, including its related acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides and/or mixtures thereof or residues thereof, which can be used in a reaction process with a glycol to produce a polyester.

The polyesters useful in the present invention can generally be prepared from dicarboxylic acids and diols which are reacted in substantially equal proportions and incorporated into the polyester polymer in the form of their corresponding residues. Thus, the polyesters of the invention may contain substantially equimolar proportions of acid residues (100 mole%) and glycol (and/or polyfunctional hydroxy compound) residues (100 mole%) such that the total moles of repeating units is equal to 100 mole%. Thus, the mole percentages provided in the present disclosure may be based on the total moles of acid residues, the total moles of glycol residues, or the total moles of repeat units. For example, a polyester containing 10 mole% isophthalic acid based on total acid residues means that the polyester contains 10 mole% isophthalic acid residues in a total of 100 mole% acid residues. Thus, 10 moles of isophthalic acid residues are present per 100 moles of acid residues. In another example, a polyester containing 25 mole% 2, 4-tetramethyl-l, 3-cyclobutanediol based on total diol residues means that the polyester contains 25 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol residues in a total of 100 mole% diol residues. Thus, 25 moles of 2, 4-tetramethyl-1, 3-cyclobutanediol residues are present per 100 moles.

In one embodiment, there is provided a copolyester composition comprising a copolyester, optionally having good color, good TMCD incorporation and/or reactivity to achieve a desired intrinsic viscosity throughout the entire composition range, the composition comprising: (a) A dicarboxylic acid component comprising from about 10 to about 50 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) residues and from about 50 to about 90 mole% 1, 4-Cyclohexanedimethanol (CHDM) residues; wherein the total mole% of the dicarboxylic acid component of the final polyester is 100 mole%, and wherein the total mole% of the glycol component of the final polyester is 100 mole%.

In one embodiment, the polyesters and/or polyester compositions of the invention may comprise residues of 2, 4-tetramethyl-1, 3-cyclobutanediol in an amount from about 10 to about 55 mole%, or from about 10 to about 50 mole%, or from about 10 to about 45 mole%, or from about 10 to about 40 mole%, or from about 15 to about 55 mole%, or from about 15 to about 50 mole%, or from about 15 to about 45 mole%, or from about 15 to about 40 mole%, or from about 20 to about 55 mole%, or from about 20 to about 50 mole%, or from about 20 to about 45 mole%, or from about 20 to about 40 mole%, or from about 20 to about 35 mole%, or from about 20 to about 30 mole%, or from about 25 to about 55 mole%, or from about 25 to about 50 mole%, or from about 25 to about 45 mole%, or from about 25 to about 40 mole%, or from about 30 to about 55 mole%, or from about 30 to about 50 mole%, or from about 30 to about 45 mole%, or from about 30 to about 40 mole%, or from about 40 to about 35 mole%, or from about 35 mole%.

In one embodiment, the polyesters and/or polyester compositions of the invention may comprise residues of 2, 4-tetramethyl-1, 3-cyclobutanediol in an amount from about 20 to about 50 mole%, or from about 20 to about 40 mole%, or from about 25 to about 50 mole%, or from about 30 to about 45 mole%.

In one embodiment, the polyesters and/or polyester compositions of the invention may comprise 1, 4-cyclohexanedimethanol residues in an amount of about 45 to about 90 mole%, or about 50 to about 90 mole%, or about 55 to about 90 mole%, or about 60 to about 90 mole%, or about 45 to about 85 mole%, or about 50 to about 85 mole%, or about 55 to about 85 mole%, or about 60 to about 85 mole%, or about 45 to about 80 mole%, or about 50 to about 80 mole%, or about 55 to about 80 mole%, or about 60 to about 80 mole%, or about 65 to about 80 mole%, or about 70 to about 80 mole%, or about 45 to about 75 mole%, or about 50 to about 75 mole%, or about 55 to about 75 mole%, or about 60 to about 75 mole%, or about 45 to about 70 mole%, or about 50 to about 70 mole%, or about 55 to about 70 mole%, or about 60 to about 70 mole%, or about 45 to about 65 mole%, or about 65 to about 50 to about 55 mole%, or about 55 to about 55 mole%.

In one embodiment, the polyesters and/or polyester compositions of the invention may comprise 1, 4-cyclohexanedimethanol residues in an amount of about 50 to about 80 mole%, or about 60 to about 80 mole%, or about 50 to about 75 mole%, or about 50 to about 70 mole%, or about 55 to about 70 mole%.

In one embodiment, the polyesters and/or polyester compositions of the invention may comprise 2, 4-tetramethyl-1, 3-cyclobutanediol residues in an amount of from 20 to 45 mole% and 1, 4-cyclohexanedimethanol residues in an amount of from 55 to 80 mole%, or 2, 4-tetramethyl-1, 3-cyclobutanediol residues in an amount of from 20 to 40% by mole and 1, 4-cyclohexanedimethanol residues in an amount of from 60 to 80% by mole, or 2, 4-tetramethyl-1, 3-cyclobutanediol residues in an amount of from 20 to 35% by mole and 1, 4-cyclohexanedimethanol residues in an amount of from 65 to 80% by mole, or 2, 4-tetramethyl-1, 3-cyclobutanediol residues in an amount of from 25 to 45% by mole and 1, 4-cyclohexanedimethanol residues in an amount of from 55 to 75% by mole, or 2, 4-tetramethyl-1, 3-cyclobutanediol residues in an amount of from 25 to 40% by mole and 1, 4-cyclohexanedimethanol residues in an amount of from 60 to 75% by mole, or 2, 4-tetramethyl-1, 3-cyclobutanediol residues in an amount of from 25 to 35% by mole and 1, 4-cyclohexanedimethanol residues in an amount of from 65 to 75% by mole; or 2, 4-tetramethyl-1, 3-cyclobutanediol residues in an amount of from 30 to 35% by mole and 1, 4-cyclohexanedimethanol residues in an amount of from 65 to 70% by mole.

In one embodiment, the polyesters and/or polyester compositions of the invention wherein TMCD: CHDM is from 1:9 to 1:1, or from 1:4 to 1:1, or from 1:3 to 1:1.5, or from 1:3 to 1:1, or from 1:2 to 1:1, or from 1:1.5 to 1:1.

In one embodiment, the polyesters useful in the polyester compositions of the invention may optionally comprise modified diol residues.

In one embodiment, these modified diols may include at least one of diethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, 1, 4-cyclohexanedimethanol, ethylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, terephthalyl alcohol, neopentyl glycol, isosorbide, polytetramethylene glycol, or mixtures thereof.

In one embodiment, the polyesters and/or polyester compositions of the invention may or may not contain residues of ethylene glycol.

In one embodiment, the polyesters and/or polyester compositions of the invention may comprise less than 55 mole%, or less than 50 mole%, or less than 40 mole%, or less than 35 mole%, or less than 30 mole%, or less than 25 mole%, or less than 20 mole%, or less than 15 mole%, or less than 10 mole%, or 0 mole% of ethylene glycol residues.

In one embodiment, the polyesters and/or polyester compositions of the invention may comprise less than 20 mole%, or less than 15 mole%, or less than 10 mole%, or less than 5 mole%, or less than 2 mole%, or 0 mole% of 1, 3-propanediol, 1, 4-butanediol, and/or neopentyl glycol.

In one embodiment, the polyesters and/or polyester compositions of the invention may comprise less than 20 mole%, or less than 15 mole%, or less than 10 mole%, or less than 5 mole%, or less than 2 mole%, or 0 mole% neopentyl glycol residues and/or 1, 4-butanediol residues.

In one embodiment, the polyester and/or polyester composition can comprise less than 20 mole%, or less than 15 mole%, or less than 10 mole%, or less than 5 mole%, or less than 2 mole%, or 0 mole% trimethylolpropane.

In one embodiment, the polyester and/or polyester composition may comprise less than 20 mole%, or less than 15 mole%, or less than 10 mole%, or less than 5 mole%, or less than 2 mole%, or 0 mole% of a polyol.

In one embodiment, the polyester and/or polyester composition can comprise less than 20 mole%, or less than 15 mole%, or less than 10 mole%, or less than 5 mole%, or less than 2 mole%, or 0 mole% of 1, 4-bis (2-hydroxyethyl) terephthalate.

In one embodiment, the polyester and/or polyester composition can comprise less than 20 mole%, or less than 15 mole%, or less than 10 mole%, or less than 5 mole%, or less than 2 mole%, or 0 mole% butanediol.

In one embodiment, the polyesters and/or polyester compositions of the invention may comprise residues of at least one of 1, 3-propanediol, 1, 4-butanediol, and neopentyl glycol, or mixtures of two or more.

In one embodiment, the extent of TMCD incorporation or conversion in the final polymer may be greater than 50 mole% cis-2, 4-tetramethyl-1, 3-cyclobutanediol and less than 50 mole% trans-2, 4-tetramethyl-1, 3-cyclobutanediol, or greater than 70 mole% cis-2, 4-tetramethyl-1, 3-cyclobutanediol and less than 30 mole% trans-2, 4-tetramethyl-1, 3-cyclobutanediol, or greater than 75 mole% cis-TMCD and less than 25 mole% trans-TMCD; or greater than 80 mole% cis-TMCD and less than 20 mole% trans-TMCD; or greater than 85 mole% cis-TMCD and less than 15 mole% trans-TMCD; or more than 90 mole% of cis-2, 4-tetramethyl-1, 3-cyclobutanediol and less than 10 mole% of trans-2, 4-tetramethyl-1, 3-cyclobutanediol, or more than 95 mole% of cis-2, 4-tetramethyl-1, 3-cyclobutanediol and less than 5 mole% of trans-2, 4-tetramethyl-1, 3-cyclobutanediol.

In one embodiment, terephthalic acid can be used as a starting material. In another embodiment, dimethyl terephthalate may be used as a raw material. In yet another embodiment, a mixture of terephthalic acid and dimethyl terephthalate may be used as a raw material and/or as an intermediate material.

In certain embodiments, terephthalic acid or an ester thereof, such as dimethyl terephthalate or a mixture of terephthalic acid residues and esters thereof, may constitute part or all of the dicarboxylic acid component used to form the polyesters useful in the present invention. In certain embodiments, the terephthalic acid residues may comprise part 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 polyesters with higher impact strengths. For the purposes of this disclosure, the terms "terephthalic acid" and "dimethyl terephthalate" are used interchangeably herein. In one embodiment, dimethyl terephthalate is part or all of the dicarboxylic acid component used to make the polyesters useful in the present invention. In certain embodiments, 70 to 100 mole% may be used; or 80 to 100 mole%; or 90 to 100 mole%; or 99 to 100 mole%; or 100 mole% terephthalic acid and/or dimethyl terephthalate and/or mixtures thereof.

In addition to terephthalic acid, the dicarboxylic acid component of the polyesters of the invention may comprise less than 30 mole%, or less than 20 mole%, or less than 10 mole%, or less than 5 mole%, or from 0 to 30 mole%, or from 0 to 20 mole%, or from 0 to 10 mole%, or from 0 to 5 mole%, or from 0 to 1 mole%, or from 0.01 to 10 mole%, or from 0.1 to 10 mole%, or from 1 or 10 mole%, or from 5 to 10 mole%, or 0 mole% of one or more modified aromatic dicarboxylic acids. Yet another embodiment contains 0 mole% of the modified aromatic dicarboxylic acid. Thus, it is contemplated that the amount of the one or more modified aromatic dicarboxylic acids, if present, may be within any of these aforementioned endpoints, including, for example, 0.01 to 10 mole%, 0.01 to 5 mole%, and 0.01 to 1 mole. In one embodiment, the modified aromatic dicarboxylic acids useful in the present invention include, but are not limited to, those having up to 20 carbon atoms, and which may be linear, para-oriented, or symmetrical. Modified aromatic dicarboxylic acids useful in the present invention include, but are not limited to, isophthalic acid, 4 '-biphthalic acid, 1,4-, 1,5-, 2,6-, 2, 7-naphthalenedicarboxylic acid, and trans-4, 4' -stilbenedicarboxylic acid and esters thereof. In one embodiment, the modified aromatic dicarboxylic acid is isophthalic acid.

The carboxylic acid component of the polyesters of the invention may be further modified with less than 30 mole%, or less than 20 mole%, or less than 10 mole%, or less than 5 mole%, or 0 to 30 mole%, or 0 to 20 mole%, or 0 to 10 mole%, or 0 to 5 mole%, or 0 to 1 mole%, or 0.01 to 10 mole%, or 0.1 to 10 mole%, or 1 or 10 mole%, or 5 to 10 mole%, or 0 mole% of one or more aliphatic dicarboxylic acids containing 2-16 carbon atoms, such as cyclohexane dicarboxylic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and dodecanedicarboxylic acid. Yet another embodiment contains 0 mole% of the modified aliphatic dicarboxylic acid. The total mole% of the dicarboxylic acid component was 100 mole%. In one embodiment, adipic acid and/or glutaric acid is provided in the modified aliphatic dicarboxylic acid component of the present invention.

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

In one embodiment, the diacid component of the polyester and/or polyester composition of the invention may comprise residues of dimethyl terephthalate. In one embodiment, the diacid component comprises 0 to 30 mole percent, or 0 to 20 mole percent, or 0 to 10 mole percent aliphatic diacid residues, including but not limited to 1, 4-cyclohexanedicarboxylic acid (CHDA), based on the total mole percent of diacid residues in the final polyester equal to 100 mole percent.

In one embodiment, the polyesters and/or polyester compositions of the invention can comprise CHDA in an amount of less than 30 mole%, or less than 20 mole%, or less than 10 mole%, or less than 5 mole%, or from 0 to 30 mole%, or from 0 to 20 mole%, or from 0 to 10 mole%, or from 0 to 5 mole%, or from 0 to 1 mole%, or from 0.01 to 10 mole%, or from 0.1 to 10 mole%, or from 1 or 10 mole%, or from 5 to 10 mole%, or 0 mole%, based on a total mole percent of diacid residues in the final polyester equal to 100 mole%.

In one embodiment, the polyesters and/or polyester compositions of the invention can comprise less than 30 mole%, or less than 20 mole%, or less than 10 mole%, or less than 5 mole%, or from 0 to 30 mole%, or from 0 to 20 mole%, or from 0 to 10 mole%, or from 0 to 5 mole%, or from 0 to 1 mole%, or from 0.01 to 10 mole%, or from 0.1 to 10 mole%, or from 1 or 10 mole%, or from 5 to 10 mole%, or 0 mole% trans-CHDA based on a total mole percent of diacid residues in the final polyester equal to 100 mole%.

In one embodiment, the number average molecular weight of the polyesters and/or polyester compositions of the invention may be from 4,800 to 16,000.

In one embodiment, the polyesters and/or polyester compositions of the invention may comprise:

(1) At least one polyester comprising:

(a) A dicarboxylic acid component comprising:

(b) A glycol component comprising:

(ii) About 50 to about 90 mole% of 1, 4-cyclohexanedimethanol residues;

wherein the total mole% of dicarboxylic acid component of the final polyester is 100 mole%, and

(2) A residue containing titanium atoms and zinc atoms, and less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or 0 to 30ppm, or 0 to 20ppm, or 0 to 10ppm, or 0ppm of tin atoms;

wherein the intrinsic viscosity is from 0.35 to 0.75dL/g, or from 0.40 to 0.75, or from 0.45 to 0.75dL/g, as measured at 25 ℃ in 60/40 (weight/weight) phenol/tetrachloroethane at a concentration of 0.5g/100ml, and has a b value of less than 20, less than 15, or less than 14, or less than 13, or less than 1 2, or less than 11, or less than 10, or less than 9, or less than 8.5, or less than 8, or less than 7, or less than 6, or less than 5, or from 1 to 10, or from 1 to 9, or from 1 to 8, or from 1 to 7, or from 1 to 6, or from 1 to 5, or from 2 to 6, as measured by the L x a b color system of CIE (International Commission on Illumination), and a L value of 70 to 95, or 75 to 90. In some embodiments, a may also have a value of less than 7, or less than 4, or less than 3, or less than 2, or less than 1, or less than 0, or less than-1, or less than-1.5, or less than-2.

In one embodiment, the inherent viscosity of the polyester and/or polyester composition of the invention, as measured at 25℃in 60/40 (weight/weight) phenol/tetrachloroethane at a concentration of 0.5g/100ml, may be 0.35 to 1.2dL/g, or 0.35 to 0.80dL/g, or 0.35 to 0.75dL/g, or 0.35 to 0.70dL/g, or 0.35 to 0.60dL/g, or 0.40 to 0.75dL/g, or 0.40 to 0.70dL/g, or 0.40 to 0.65dL/g, or 0.40 to 0.60dL/g, or 0.45 to 0.75dL/g, or 0.45 to 0.70dL/g, or 0.45 to 0.65dL/g, or 0.45 to 0.60dL/g, or 0.50 to 1.2dL/g, or 0.50 to 0.70dL/g, or 0.80 to 0.70dL/g, or 0.40 to 0.65dL/g, or 0.75dL/g, or 0.55 to 0.75dL/g, or 0.50 to 0.60 dL/g.

The molar ratio of cis/trans 2, 4-tetramethyl-1, 3-cyclobutanediol may vary from the pure form of each and mixtures thereof for the desired polyester. In some embodiments of the present invention, in some embodiments, the mole percentage of cis and/or trans 2, 4-tetramethyl-1, 3-cyclobutanediol is greater than 50 mole% of cis 2, 4-tetramethyl-1, 3-cyclobutanediol and less than 50 mole% of trans-2, 4-tetramethyl-1, 3-cyclobutanediol, or greater than 70 mole% of cis 2, 4-tetramethyl-1, 3-cyclobutanediol and less than 30 mole% of trans 2, 4-tetramethyl-1, 3-cyclobutanediol, or greater than 75 mole% of cis TMCD and less than 25 mole% of trans TMCD; or greater than 80 mole% cis-TMCD and less than 20 mole% trans-TMCD; or greater than 85 mole% cis-TMCD and less than 15 mole% trans-TMCD; or more than 90 mole% of cis-2, 4-tetramethyl-1, 3-cyclobutanediol and less than 10 mole% of trans-2, 4-tetramethyl-1, 3-cyclobutanediol, or more than 95 mole% of cis-2, 4-tetramethyl-1, 3-cyclobutanediol and less than 5 mole% of trans-2, 4-tetramethyl-1, 3-cyclobutanediol.

In other embodiments, the molar ratio of cis/trans 2, 4-tetramethyl-1, 3-cyclobutanediol may vary from 50/50 to 0/100, for example from 40/60 to 20/80.

In one embodiment, the polyesters and/or polyester compositions of the invention may comprise 1, 4-cyclohexanedimethanol. In another embodiment, the polyesters and/or polyester compositions of the invention may comprise 1, 4-cyclohexanedimethanol and 1, 3-cyclohexanedimethanol. The molar ratio of cis/trans 1, 4-cyclohexanedimethanol may vary from 50/50 to 0/100, for example between 40/60 and 20/80.

In some embodiments, the polyesters and/or polyester compositions of the invention may comprise 0 to 10 mole%, such as 0.01 to 5 mole%, 0.01 to 1 mole%, 0.05 to 5 mole%, 0.05 to 1 mole%, or 0.1 to 0.7 mole% of a branching monomer (also referred to herein as branching agent) having 3 and more carboxyl substituents, hydroxyl substituents, or combinations thereof, based on the total mole percentage of diol or diacid residues, respectively. In certain embodiments, the branching monomer or branching agent may be added before and/or during and/or after polymerization of the polyester. In embodiments, one or polyesters useful in the present invention may thus be linear or branched.

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

The polyesters and/or polyester compositions of the invention may comprise at least one chain extender. Suitable chain extenders include, but are not limited to, polyfunctional (including, but not limited to difunctional) isocyanates, polyfunctional epoxides (including, for example, epoxidized novolac resins), and phenoxy resins. In certain embodiments, the chain extender may be added at the end of the polymerization process, or after the polymerization process. If added after the polymerization process, the chain extender may be incorporated by compounding or by addition during the conversion process (e.g., injection molding or extrusion). The amount of chain extender used may vary depending on the particular monomer composition used and the physical properties desired, but is generally from about 0.1% to about 10% by weight, such as from about 0.1 to about 5% by weight, relative to the mass of the polyester.

In one embodiment, certain polyesters and/or polyester compositions useful in the present invention may be visually clear. The term "visually transparent" is defined herein as the absence of perceptible cloudiness, blurriness and/or turbidity when visually inspected.

In one embodiment, the polyesters useful in the present invention and/or the polyester compositions of the present invention [ in one embodiment, in the presence and/or absence of one or more toners ] can have color values L, a, and b, which can be determined using Hunter Lab Ultrascan Spectra Colorimeter manufactured by Hunter Associates Lab inc., reston, va. Color determination is the average of the values measured on polyester pellets or panels or other articles injection molded or extruded from them. They were determined by the color system of L x a x b x CIE (International Commission on Illumination) (translation), where L x represents the luminance coordinates, a x values represent the red/green coordinates, and b x represents the yellow/blue coordinates.

In one embodiment, the one or more phosphorus compounds may be organic compounds, such as phosphate esters containing halogenated or non-halogenated organic substituents. In certain embodiments, the one or more phosphorus compounds may comprise a wide range of phosphorus compounds, such as phosphines, phosphites, phosphinites, phosphonites, phosphine oxides, and phosphates.

Examples of phosphorus compounds useful in the present invention may include tributyl phosphate, triethyl phosphate, tributoxyethyl phosphate, t-butylphenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, ethyldimethyl phosphate, isodecyl diphenyl phosphate, trilauryl phosphate, triphenyl phosphate, tricresyl phosphate, tris (xylyl) phosphate, t-butylphenyl diphenyl phosphate, resorcinol tetraphenyl diphenyl phosphate, tribenzyl phosphate, phenylethyl phosphate, trimethyl thiophosphate, phenylethyl thiophosphate, dimethyl methylphosphonate, diethyl pentylphosphonate, dilauryl methylphosphonate, diphenyl methylphosphonate, dibenzyl methylphosphonate, diphenyl methylphosphonate, dimethyl methylphosphonate, phenyl diphenylphosphinate, benzyl diphenylphosphinate, methyl diphenylphosphinate, trimethylphosphine oxide, triphenylphosphine oxide, tricresylphosphine, 4-methylphosphine, tricresylphosphine, trimethylphosphorous acid, dimethylbenzyl phosphite, dibenzyl phosphate, dibenzyl phosphite, benzyl phosphite, dibenzyl phosphate, dibenzyl phosphite, benzyl phosphite, dibenzyl phosphite, diphenyl phosphine. In one embodiment, triphenylphosphine oxide is excluded as a heat stabilizer in one or more of the methods of the present invention for making polyesters and/or in one or more of the polyester compositions of the present invention.

In one embodiment, the phosphorus compounds useful in the present invention can be any of the foregoing phosphorus-based acids in which one or more hydrogen atoms of the acid compound (bonded to oxygen or phosphorus atoms) are substituted with an alkyl group, branched alkyl group, substituted alkyl group, alkyl ether, substituted alkyl ether, alkyl-aryl group, alkyl substituted aryl group, substituted aryl group, and mixtures thereof. In another embodiment, phosphorus compounds useful in the present invention include, but are not limited to, the compounds described above in which at least one hydrogen atom bonded to an oxygen atom of the compound is replaced with a metal ion or an ammonium ion.

The esters may contain alkyl groups, branched alkyl groups, substituted alkyl groups, alkyl ethers, aryl groups and/or substituted aryl groups. The esters may also have at least one alkyl group and at least one aryl group. The number of ester groups present in a particular phosphorus compound may vary from zero to the maximum allowed based on the number of hydroxyl groups present on the phosphorus compound used. For example, the alkyl phosphate may include one or more of a mono-alkyl phosphate, a di-alkyl phosphate, and a tri-alkyl phosphate; aryl phosphates include one or more of monoaryl phosphates, diaryl phosphates, and triaryl phosphates; and alkyl and/or aryl phosphates also include, but are not limited to, mixed alkyl aryl phosphates having at least one alkyl group and one aryl group.

In one embodiment, phosphorus compounds useful in the present invention include, but are not limited to, phosphoric acid, phosphorous acid, hypophosphorous acid, phosphonic acids or alkyl esters, aryl esters or mixed alkylaryl or partial esters of phosphonic acids. The alkyl or aryl groups may contain one or more substituents.

In one embodiment, the phosphorus compounds useful in the present invention comprise at least one phosphorus compound selected from at least one of substituted or unsubstituted alkyl phosphates, substituted or unsubstituted aryl phosphates, substituted or unsubstituted mixed alkyl aryl phosphates, bisphosphites, salts of phosphoric acid, phosphine oxides and mixed aryl alkyl phosphites, reaction products thereof, and mixtures thereof. Phosphate esters include esters in which the phosphoric acid is fully esterified or only partially esterified.

In one embodiment, for example, the phosphorus compounds useful in the present invention may include at least one phosphate ester.

In one embodiment, the phosphorus compound useful in the present invention comprises at least one phosphorus compound selected from at least one of substituted or unsubstituted alkyl phosphates, substituted or unsubstituted aryl phosphates, substituted or unsubstituted mixed alkyl aryl phosphates, reaction products thereof, and mixtures thereof. Phosphate esters include esters in which the phosphoric acid is fully esterified or only partially esterified.

In another embodiment, the 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, the phosphates useful in the present invention are those wherein the group on the phosphate is alkyl, alkoxy-alkyl, phenyl or substituted phenyl. These phosphates are generally referred to herein as alkyl and/or aryl phosphates. Certain preferred embodiments include trialkyl phosphates, triaryl phosphates, alkyl diaryl phosphates, dialkyl aryl phosphates and mixtures of such phosphates, wherein alkyl groups are preferably those containing from 2 to 12 carbon atoms, and the aryl groups are preferably phenyl groups.

Representative alkyl and branched alkyl groups are preferably those containing from 1 to 12 carbon atoms including, but not limited to, ethyl, propyl, isopropyl, butyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl, decyl and dodecyl. Substituted alkyl groups include, but are not limited to, those containing at least one of carboxylic acid groups and esters thereof, hydroxyl groups, amino groups, ketone groups, and the like.

Representative alkyl-aryl and substituted alkyl-aryl groups are those wherein the alkyl moiety contains from 1 to 12 carbon atoms and aryl is phenyl or substituted phenyl, wherein groups such as alkyl, branched alkyl, aryl, hydroxy, and the like, replace a hydrogen at any carbon position on the phenyl ring. Preferred aryl groups include phenyl or substituted phenyl wherein groups such as alkyl, branched alkyl, aryl, hydroxy, and the like replace a hydrogen at any carbon position on the phenyl ring.

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

In one embodiment, at least one phosphorus compound useful in the present invention comprises at least one aryl phosphate.

In one embodiment, at least one phosphorus compound useful in the present invention comprises at least one unsubstituted aryl phosphate.

In one embodiment, at least one phosphorus compound useful in the present invention comprises at least one aryl phosphate ester that is not substituted with a benzyl group.

In one embodiment, any phosphorus compound useful in the present invention may comprise at least one alkyl phosphate.

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

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

In one embodiment, the phosphate esters useful as heat stabilizers and/or color stabilizers in the present invention include, but are not limited to, at least one of the following: triaryl phosphates and mixed alkylaryl phosphates.

In one embodiment, the at least one phosphorus compound useful in the present invention may include, but is not limited to, triaryl phosphates, such as triphenyl phosphate. In one embodiment, the at least one heat stabilizer includes, but is not limited to, merpol a. In one embodiment, at least one heat stabilizer useful in the present invention includes, but is not limited to, at least one of triphenyl phosphate and Merpol a. Merpol A is a phosphate ester available from Stepan Chemical Co and/or E.I.duPont de Nemours & Co. The CAS Registry number for Merpol A is believed to be CAS Registry #37208-27-8.

In one embodiment, any phosphorus compound useful in the present invention may comprise at least one triaryl phosphate ester that is not substituted with a benzyl group.

In one embodiment, the polyester compositions and/or methods of the present invention can comprise 2-ethylhexyl diphenyl phosphate.

In one embodiment, any of the methods described herein for making any polyester composition and/or polyester may comprise at least one mixed alkylaryl phosphite, such as bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, also known as dovephos S-9228 (Dover Chemicals, CAS # 15486243-8).

In one embodiment, any of the methods described herein for making any of the polyester compositions and/or polyesters may comprise at least one phosphine oxide.

In one embodiment, any of the methods described herein for making any of the polyester compositions and/or polyesters may comprise at least one phosphate salt, such as KH2PO4 and Zn3 (PO 4) 2.

The term "heat stabilizer" is intended to include one or more reaction products thereof. The term "reaction product" used in connection with the heat stabilizer of the present invention is any product of a polycondensation or esterification reaction between the heat stabilizer and any monomer used to make a polyester, and a polycondensation or esterification reaction between a catalyst and any other type of additive.

In one embodiment of the present invention, the phosphorus compounds useful in the present invention may act as heat stabilizers. In one embodiment of the present invention, the phosphorus compounds useful in the present invention may not act as heat stabilizers, but may act as color stabilizers. In one embodiment of the present invention, the phosphorus compounds useful in the present invention can act as both a heat stabilizer and a color stabilizer.

In one embodiment, the amount of phosphate of the present invention added during polymerization is selected from the following: 10 to 200ppm, calculated relative to the mass of the final polyester composition and measured as phosphorus atoms in the final polyester. In embodiments of the invention, phosphorus may be present in an amount of 10 to 100, or 10 to 80, or 10 to 60, or 10 to 55, or 15 to 55, or 18 to 52, or 20 to 50ppm relative to the mass of the final polyester composition and measured as phosphorus atoms in the final polyester.

In one embodiment, the catalyst system comprises at least one titanium compound. In one embodiment, the titanium compound may be used in an esterification reaction or a polycondensation reaction or both. In one embodiment, the catalyst system comprises at least one titanium compound for the esterification reaction. In one embodiment, the catalyst system contains at least one titanium compound residue for the polycondensation reaction.

Titanium-containing compounds useful in the present invention include any titanium-containing compound including, but not limited to, at least one of titanium carbonate, titanium acetate, titanium benzoate, titanium succinate, titanium isopropoxide, titanium methoxide, titanium oxalate, titanium nitrate, titanium ethoxide, titanium hydroxide, titanium hydride, titanium ethoxide, titanium alkyl, titanium zinc hydride, titanium borohydride, lithium oxide, titanium acetylacetonate, titanium triisopropoxide chloride, titanium bis (acetylacetonate), titanium n-butoxide, titanium tert-butoxide.

In one embodiment, the catalyst mixture contains at least one zinc compound. In one embodiment, the zinc compound may be used in an esterification reaction or a polycondensation reaction, or both. In one embodiment, the catalyst system comprises at least one zinc compound for the esterification reaction. In one embodiment, the catalyst mixture contains at least one zinc compound for the polycondensation reaction.

In one embodiment, the polyester composition may comprise at least one catalytically active zinc source. These zinc compounds may include zinc compounds having at least one organic substituent.

Suitable examples of zinc compounds may comprise at least one carboxylate salt of zinc. Examples of zinc may include at least one zinc source selected from zinc borate, zinc oxide, zinc naphthenate, zinc tert-butoxide, zinc methoxide, zinc hydroxide, zinc acetate, zinc diacetate, zinc dihydrate, zinc octoate, zinc carbonate, dialkyl zinc, dimethyl zinc, diaryl zinc (diphenyl zinc), zinc isopropoxide, zinc phosphate and/or zinc acetylacetonate.

In one embodiment, the polyesters and/or polyester compositions of the invention may comprise at least one zinc source selected from zinc acetylacetonate and zinc isopropoxide.

In one embodiment, the polyesters and/or polyester compositions of the invention may comprise at least one zinc source selected from zinc acetylacetonate.

In one aspect, zinc acetate and/or zinc acetate dihydrate and/or zinc naphthenate and/or zinc carbonate and/or residues thereof are absent.

In one embodiment, the polyesters and/or polyester compositions of the invention may contain the following amounts of titanium atoms: 20 to 750ppm, or 20 to 500ppm, or 20 to 450ppm, or 20 to 400ppm, or 20 to 350ppm, or 20 to 300ppm, or 20 to 275ppm, or 20 to 250ppm, or 20 to 200ppm, or 50 to 1000ppm, or 50 to 750ppm, or 50 to 500ppm, or 50 to 450ppm, or 50 to 400ppm, or 50 to 300ppm, or 50 to 275ppm, or 50 to 250ppm, or 50 to 200ppm, or 60 to 1000ppm, or 60 to 750ppm, or 60 to 500ppm, or 60 to 450ppm, or 60 to 400ppm, or 60 to 350ppm, or 60 to 300ppm, or 60 to 275ppm, or 60 to 250ppm, or 60 to 200ppm, or 60 to 150ppm, or 60 to 100ppm, or 75 to 1000ppm, or 75 to 750ppm, or 75 to 500ppm, or 75 to 450ppm, or 75 to 400ppm, or 75 to 350ppm, or 75 to 300ppm, or 75 to 250ppm, or 70 to 200ppm, or 100 to 100 ppm. Or 70 to 90ppm, or 65 to 100ppm, or 80 to 1000ppm, or 80 to 750ppm, or 80 to 500ppm, or 80 to 450ppm, or 80 to 400ppm, or 80 to 350ppm, or 80 to 300ppm, or 80 to 275ppm, or 80 to 250ppm, or 80 to 200ppm, or 100 to 1000ppm, or 100 to 750ppm, or 100 to 500ppm, or 100 to 450ppm, or 100 to 400ppm, or 100 to 350ppm, or 100 to 300ppm, or 100 to 275ppm, or 100 to 250ppm, or 100 to 200, or 150 to 1000ppm, or 150 to 750ppm, or 150 to 500ppm, or 150 to 450ppm, or 150 to 400ppm, or 150 to 350ppm, or 150 to 300ppm, or 150 to 250ppm, or 200 to 1000ppm, or 200 to 750ppm, or 200 to 500ppm, or 200 to 450ppm, or 200 to 400ppm, or 200 to 300ppm, or 200 to 250ppm, relative to the mass of the final polyester produced.

In one embodiment, the polyesters and/or polyester compositions of the invention may contain zinc atoms, the amount is 50 to 1000ppm, or 50 to 750ppm, or 50 to 500ppm, or 50 to 450ppm, or 50 to 400ppm, or 50 to 300ppm, or 50 to 275ppm, or 50 to 250ppm, or 50 to 200ppm, or 60 to 1000ppm, or 60 to 750ppm, or 60 to 500ppm, or 60 to 450ppm, or 60 to 400ppm, or 60 to 350ppm, or 60 to 300ppm, or 60 to 275ppm, or 60 to 250ppm, or 60 to 200ppm, or 60 to 150ppm, or 60 to 100ppm, or 75 to 1000ppm, or 75 to 750ppm, or 75 to 500ppm, or 75 to 450ppm, or 75 to 400ppm, or 75 to 300ppm, or 75 to 250ppm, or 75 to 200ppm, or 70 to 100ppm, or 70 to 90ppm, or 65 to 100ppm, or 65 to 90ppm, or 80 to 1000ppm or 80 to 750ppm, or 80 to 500ppm, or 80 to 450ppm, or 80 to 400ppm, or 80 to 350ppm, or 80 to 300ppm, or 80 to 275ppm, or 80 to 250ppm, or 80 to 200ppm, or 100 to 1000ppm, or 100 to 750ppm, or 100 to 500ppm, or 100 to 450ppm, or 100 to 400ppm, or 100 to 350ppm, or 100 to 300ppm, or 100 to 275ppm, or 100 to 250ppm, or 100 to 200, or 150 to 1000ppm, or 150 to 750ppm, or 150 to 500ppm, or 150 to 450pprn, or 150 to 400ppm, or 150 to 350ppm, or 150 to 300ppm, or 150 to 250ppm, or 200 to 1000ppm, or 200 to 750ppm, or 200 to 500ppm, or 200 to 450ppm, or 200 to 400ppm, or 200 to 350ppm, or 200 to 300ppm, or 200 to 250ppm, relative to the mass of the final polyester produced.

In one embodiment, the polyesters and/or polyester compositions of the invention are provided wherein the total catalyst metal atoms present in the composition are 150 to 800ppm, or 150 to 725ppm, or 150 to 700ppm, or 150 to 500ppm, or 150 to 450ppm, or 150 to 400ppm, or 150 to 300ppm,200 to 800ppm, or 200 to 725ppm, or 200 to 700ppm, or 200 to 600ppm, or 200 to 500ppm, or 200 to 450ppm, or 200 to 400ppm, or 200 to 300ppm, or 250 to 800ppm, or 250 to 725ppm, or 250 to 700ppm, or 250 to 500ppm, or 250 to 450ppm, or 250 to 400ppm, or 300 to 800ppm, or 300 to 725ppm, or 300 to 700ppm, or 300 to 500ppm, or 300 to 450ppm, or 300 to 400ppm, or 350 to 800ppm, or 350 to 700ppm, or 350 to 500ppm, or 350 to 450ppm relative to the mass of the final polyester.

In one embodiment, the polyesters and/or polyester compositions of the invention are provided, wherein the ratio of titanium atoms to zinc atoms, in ppm, may be 0.50-1:5 to 5:1, or 0.50-1:4 to 4:1, or 0.50-1:3 to 3:1, or 0.50:1 to 1:5, or 0.50-1 to 1:4, or 0.60-1:5 to 5:1, or 0.60-1:4 to 4:1, or 0.60-1:3 to 3:1, or 0.60:1 to 1:5, or 0.60-1 to 1:4, or 0.70-1:5 to 5:1, or 0.70-1:4 to 4:1, relative to the mass of the final polyester produced or 0.70-1:3 to 3:1, or 0.70-1:2 to 2:1, or 0.70-1.2 to 1:4, or 0.75-1:5 to 5:1, or 0.75-1.2 to 1:4 to 4:1, or 0.75-1:3 to 3:1, or 1:3 to 3:1, or 0.75-1:2 to 2:1, or 0.75-1.0 to 1:4, or 0.80:1.2 to 1:4, or 1.0 to 1.5:1.0 to 1:7.1, or 1.0 to 1.5:1.0 to 3, or 1.0 to 1.5:1.0 to 2, or 1.0 to 1.5:1.0 to 2.5, or (0.80-1): 5 to 5:1, or 1:5 to 5:1, or (0.80-1.2) to 4:1, or 1:4 to 4:1, or (0.80-1) to 3 to 3:1, or 1:3 to 3:1, or (0.80-1) to 2 to 2:1, 1:2 to 2:1, or (1-1.3) to (1-1.3), or (1-1.25) to (1-1.25).

In one embodiment, the polyesters and/or polyester compositions of the invention are provided wherein the ratio of titanium atoms to zinc atoms (in ppm relative to the mass of the final polyester produced) may be from 1:5 to 5:1, from 1:4 to 4:1, or from 1:3 to 3:1, or from 1:2 to 2:1.

In one embodiment, suitable catalysts for use in the process of the present invention to prepare polyesters useful in the present invention include at least one titanium compound and one zinc compound. In certain embodiments, other catalysts may be used in the present invention in combination with at least one titanium compound and at least one zinc compound. Other catalysts may include, but are not limited to, those based on antimony, cobalt, magnesium, germanium.

In one embodiment, the polyesters and/or polyester compositions of the invention can comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of tin atoms.

In one embodiment, the polyesters and/or polyester compositions of the invention can contain less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of branchatoms.

In one embodiment, the polyesters and/or polyester compositions of the invention can comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm cobalt atoms.

In one embodiment, the polyesters and/or polyester compositions of the invention can comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm tin and no germanium atoms.

In one embodiment, the polyesters and/or polyester compositions of the invention can comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of antimony atoms and/or germanium atoms.

In one embodiment, the polyesters and/or polyester compositions of the invention can comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of any of tin atoms and manganese atoms.

In one embodiment, the polyesters and/or polyester compositions of the invention can comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of any of tin atoms and/or aluminum atoms.

In one embodiment, the polyesters and/or polyester compositions of the invention can comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of any of lithium atoms and/or aluminum atoms.

In one embodiment, the polyesters and/or polyester compositions of the invention can comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of any of tin atoms, lithium atoms, and/or aluminum atoms.

In one embodiment, the polyesters and/or polyester compositions of the invention can comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of any of the following: tin and/or manganese and/or magnesium and/or germanium and/or antimony, cobalt and/or cadmium and/or calcium and/or sodium and/or gallium atoms, and may not include any combination of these atoms or may not include all of these atoms.

In one embodiment, the polyesters and/or polyester compositions of the invention can comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of any of the following: tin atoms, manganese atoms, magnesium atoms, germanium atoms, antimony atoms, cobalt atoms, and/or calcium atoms, and any combination of these atoms may be excluded or all of these atoms may be excluded.

In one embodiment, the polyesters and/or polyester compositions of the invention can comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of any of the following: tin atoms, manganese atoms, lithium atoms, germanium atoms, and cobalt atoms, and any combination of these atoms may be excluded or all of these atoms may be excluded.

In one embodiment, the polyesters and/or polyester compositions of the invention can comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of gallium atoms.

In one embodiment, the polyesters and/or polyester compositions of the invention can comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of any sodium and/or potassium atoms.

In certain embodiments of the invention, the Tg of the polyester and/or polyester composition may be selected from one of the following ranges: tg of 85 to 130 ℃, or 100 to 125 ℃, or 100 to 120 ℃. Using TA DSC 2920 from Thermal Analyst Instrument in The glass transition temperature (T) of the polyester was measured at a scan rate of 20℃per minute _g )。

In one embodiment, the polyesters and/or polyester compositions of the invention may have a degree of polymerization of 0.01 to 300, or 0.01 to 250, or 0.01 to 200, or 0.01 to 150, or 0.01 to 130, or 0.01 to 120, or 0.10 to 300, or 0.10 to 250, or 0.10 to 200, or 0.10 to 150, or 0.10 to 130, or 0.10 to 120, or 0.20 to 300, or 0.20 to 250, or 0.20 to 200, or 0.20 to 150, or 0.20 to 130, or 0.20 to 120, or 0.15 to 300, or 0.15 to 250, or 0.15 to 200, or 0.15 to 150, or 0.15 to 130, or 0.15 to 120.

It is contemplated that the compositions useful in the present invention may have at least one of the intrinsic viscosity ranges described herein and at least one of the monomer ranges of the compositions described herein, unless otherwise indicated. It is also contemplated that, unless otherwise indicated, the compositions useful in the present invention may have T as described herein _g At least one of the ranges and at least one of the monomer ranges of the compositions described herein. It is also contemplated that, unless otherwise indicated, the compositions useful in the present invention may have at least one of the intrinsic viscosity ranges described herein, T described herein _g At least one of the ranges and at least one of the monomer ranges of the compositions described herein.

The polyester fraction useful in the polyester compositions of the invention can be produced by methods known in the literature, for example by methods in homogeneous solutions, by transesterification processes in the melt, and by two-phase interfacial processes. Suitable methods include, but are not limited to, the step of reacting one or more dicarboxylic acids with one or more diols at a temperature of 100 ℃ to 315 ℃ at a pressure of 0.1 to 760mmHg for a time sufficient to form a polyester. Methods of making polyesters are described in U.S. Pat. No. 3,772,405, the disclosure of which is incorporated herein by reference.

As described in further detail in U.S. patent No. 2,720,507, incorporated herein by reference, polyesters can generally be prepared by condensing a dicarboxylic acid or dicarboxylic ester with a glycol at elevated temperatures (which are gradually increased during the condensation process up to about 225-310 ℃) in an inert atmosphere in the presence of one or more titanium catalysts and one or more zinc (and optionally other catalysts) as described herein and at low pressure at a later stage of the condensation.

In one embodiment, the present invention relates to a process for making a polyester comprising the steps of:

(a) A dicarboxylic acid component comprising:

(i) About 90 to about 100 mole% of terephthalic acid residues;

(b) A glycol component comprising:

(i) About 10 to about 50 mole% of 2, 4-tetramethyl-1, 3-cyclobutanediol residues; and

(ii) About 50 to about 90 mole% of 1, 4-cyclohexanedimethanol residues;

wherein the molar ratio of diol component/dicarboxylic acid component added in step (I) is from 1.01 to 3.0/1.0, and wherein TMCD is added in an amount of about 10 to 50 mole%, optionally allowing for at least 30% conversion of TMCD in the reaction and obtaining a final polymer having about 10 to 50 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol residues;

wherein the mixture in step (I) is heated in the presence of:

(i) At least two catalysts comprising Ti and Zn; and (ii) optionally at least one of

A phosphorus compound;

wherein the total mole% of dicarboxylic acid component of the final polyester is 100 mole%; and wherein the total mole% of the glycol component of the final polyester is 100 mole%;

wherein the intrinsic viscosity of the polyester is from 0.35 to 0.80dL/g as measured in 60/40 (weight/weight) phenol/tetrachloroethane at a concentration of 0.25g/50ml at 25 ℃; and wherein the L color value is 75 or greater, or greater than 75, as determined by the L x a x b color system measured according to ASTM D6290-98 and ASTM E308-99 on polymer particles milled to pass a 1mm screen.

In certain embodiments, the catalyst may comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of tin atoms.

In one embodiment, the polyesters useful in the present invention may comprise at least one phosphate ester, whether present as a heat stabilizer or not.

In the process of the invention, at least one phosphorus compound, for example at least one phosphate, may be added to step (I), step (II) and/or steps (I) and (II) and/or after step (I) and/or after step (II). In certain embodiments, the at least one phosphorus compound may be added to only step (I) or to only step (II).

In embodiments of the present invention, at least one phosphorus compound, reaction products thereof, and mixtures thereof may be added during esterification, polycondensation, or both, and/or it may be added after polymerization. In one embodiment, the phosphorus compounds useful in any of the methods of the present invention may be added during the esterification process. In one embodiment, if the phosphorus compound is added after esterification and polycondensation, it is added in an amount of 0 to 2 wt% based on the total weight of the final polyester. In one embodiment, if the phosphorus compound is added after both esterification and polycondensation, it is added in an amount of 0.01 to 2 weight percent based on the total weight of the final polyester. In one embodiment, the phosphorus compound may comprise at least one phosphate ester. In one embodiment, the phosphorus compound may comprise at least one phosphorus compound added during the esterification step. In one embodiment, the phosphorus compound may comprise at least one phosphate ester, for example, which is added during the esterification step.

It is believed that the methods of making polyesters described herein can be used to make polyesters useful in the present invention.

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

In one embodiment, the pressure used in step (II) of any of the methods of the present invention consists of at least one pressure selected from the group consisting of 20 torr absolute to 0.02 torr absolute; in one embodiment, the pressure used in step (II) of any of the methods of the present invention consists of at least one pressure selected from the group consisting of 10 torr absolute to 0.02 torr absolute; in one embodiment, the pressure used in step (II) of any of the methods of the present invention consists of at least one pressure selected from the group consisting of 5 torr absolute to 0.02 torr absolute; in one embodiment, the pressure used in step (II) of any of the methods of the present invention consists of at least one pressure selected from the group consisting of 3 torr absolute to 0.02 torr absolute; in one embodiment, the pressure used in step (II) of any of the methods of the invention consists of at least one pressure selected from the group consisting of 20 torr absolute to 0.1 torr absolute; in one embodiment, the pressure used in step (II) of any of the methods of the present invention consists of at least one pressure selected from the group consisting of 10 torr absolute to 0.1 torr absolute; in one embodiment, the pressure used in step (II) of any of the methods of the invention consists of at least one pressure selected from the group consisting of 5 torr absolute to 0.1 torr absolute; in one embodiment, the pressure used in step (II) of any of the methods of the present invention consists of at least one pressure selected from the group consisting of 3 torr absolute to 0.1 torr absolute.

In one embodiment, the molar ratio of diol component/dicarboxylic acid component added in step (I) of the process of the present invention is from 1.0 to 2.0/1.0; in one embodiment, the molar ratio of diol component/dicarboxylic acid component added in step (I) of the process of the present invention is from 1.01 to 2.0/1.0; in one embodiment, the molar ratio of diol component/dicarboxylic acid component added in step (I) of the process of the present invention is from 1.01 to 1.75/1.0; in one embodiment, the molar ratio of diol component/dicarboxylic acid component added in step (I) of the process of the present invention is from 1.01 to 1.7/1.0; in one embodiment, the molar ratio of diol component/dicarboxylic acid component added in step (I) of the process of the present invention is from 1.01 to 1.5/1.0; in one embodiment, the molar ratio of diol component/dicarboxylic acid component added in step (I) of the process of the present invention is from 1.01 to 1.2/1.0.

In embodiments of the present invention for the process for making polyesters, the heating time of step (II) may be from 1 to 5 hours or from 1 to 4 hours or from 1 to 3 hours or from 1.5 to 3 hours or from 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 useful in the present invention can comprise titanium atoms, zinc atoms, and optionally phosphorus atoms.

The invention further relates to polyester compositions prepared by one or more of the methods described above.

In embodiments of the present invention, certain agents that color the polymer may be added to the melt. In one embodiment, a bluing toner is added to the melt to reduce b-x of the resulting polyester polymer melt phase product. Such blue-dyeing agents include one or more blue inorganic and organic toners. In addition, one or more red toners may also be used to adjust the a-color. One or more organic toners, such as one or more of the blue and red organic toners, for example, one or more of those described in U.S. Pat. nos. 5,372,864 and 5,384,377, the entire contents of which are incorporated herein by reference, may be used. One or more toners may be fed 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 (e.g., ethylene glycol).

The total amount of added toner components may depend on the amount of yellow inherent in the base polyester and the efficacy of the toner. In one embodiment, a concentration of up to about 15ppm of the mixed toner component is employed with a minimum concentration of about 0.5 ppm. In one embodiment, the total amount of blue dye additives may be from 0.5 to 10ppm. In one embodiment, one or more toners may be added to the esterification or polycondensation zone. Preferably, the toner is added to the esterification zone, or to an early stage of the polycondensation zone, such as to a prepolymerization reactor.

The invention further relates to polymer blends. The blend comprises:

(a) 5 to 95 weight percent of at least one of the polyesters described above; and

(b) From 5 to 95% by weight of at least one polymer component, based on the total weight of the polymer blend equal to 100% by mole.

Suitable examples of polymer components include, but are not limited to, nylon; polyesters other than those described herein (e.g., PET); polyamides, e.g. from DuPontA polystyrene; a polystyrene copolymer; styrene acrylonitrile copolymer; acrylonitrile butadiene styrene copolymer; poly (methyl methacrylate); an acrylic copolymer; poly (ether-imide) s such as(poly (ether-imide) from General Electric); polyphenylene ethers, such as poly (2, 6-dimethyl-phenyl ether) or poly (phenyl ether)/polystyrene blends, such as NORYL +>(blend of poly (2, 6-dimethyl-phenyl ether) and polystyrene resin from General Electric); polyphenylene sulfide; polyphenylene sulfide/sulfone; poly (ester-carbonate); polycarbonates, e.g.

(polycarbonate from General Electric); polysulfone; polysulfone ether; and poly (ether-ketone) s of aromatic dihydroxy compounds; or a mixture of any of the foregoing polymers. The blend may be prepared by conventional processing techniques known in the art, such as melt blending or solution blending.

In one embodiment, the final polyesters and/or polyester compositions of the invention can be blended with recycled poly (ethylene terephthalate) (rPET).

In embodiments, the polyester compositions and polymer blend compositions may also contain from 0.01 to 25 weight percent, based on the total composition weight, of conventional additives such as one or more colorants, toners, dyes, mold release agents, flame retardants, plasticizers, nucleating agents, stabilizers (including but not limited to UV stabilizers, heat stabilizers other than the phosphorus compounds described herein, and/or reaction products thereof), fillers, and impact modifiers. Examples of commercially available impact modifiers include, but are not limited to, ethylene/propylene terpolymers, functionalized polyolefins such as those containing methyl acrylate and/or glycidyl methacrylate, styrene-based block copolymer impact modifiers, and various acrylic core/shell impact modifiers. Residues of such additives are also considered part of the polyester composition.

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

In one embodiment, the polyester composition can be used in shaped articles, including but not limited to extruded and/or molded articles, including but not limited to injection molded articles, extruded articles, cast extruded articles, profile extruded articles, melt spun articles, thermoformed articles, extrusion molded articles, injection blow molded articles, injection stretch blow molded articles, extrusion blow molded articles, and extrusion stretch blow molded articles. Such articles may include, but are not limited to, films, bottles, containers, drinking tools, medical accessories, sheets, and/or fibers.

In one embodiment, the present invention relates to one or more thermoformed films and/or one or more sheets comprising one or more polyesters and/or polyester compositions of the present invention.

In one embodiment, the present invention relates to articles of manufacture incorporating the thermoformed films and/or sheets of the present invention.

In one embodiment, the present invention relates to one or more films and/or one or more sheets comprising the polyester composition and/or polymer blend of the present invention. Methods of forming polyesters and/or blends into one or more films and/or one or more sheets are well known in the art. Examples of one or more films and/or one or more sheets of the present invention include, but are not limited to, one or more extruded films and/or sheets, compression molded films and/or sheets, solution cast films and/or sheets. Methods of making the film and/or sheet include, but are not limited to, extrusion, compression molding, and solution casting.

Examples of potential articles made from films and/or sheets useful in the present invention include, but are not limited to, thermoformed sheets, graphic arts films, outdoor signs, bullet-proof glass, skylights, one or more coatings, coated articles, painted articles, shoe stiffeners, laminates, laminated articles, medical packaging, general packaging, and/or multiwall films or sheets.

In one embodiment, the present invention relates to injection molded articles comprising the polyester compositions and/or polymer blends of the present invention. Injection molded articles may be intended to include injection stretch blow molded bottles, sunglass frames, lenses, sports water bottles, drinking vessels, food containers, medical devices and connectors, medical housings, electronics housings, cable assemblies, sound attenuating articles, cosmetic containers, wearable electronics, toys, promotional articles, appliance parts, automotive interior parts, and consumer household articles.

In embodiments of the present invention, certain polyesters and/or polyester compositions of the present invention may have a unique combination of all of the following properties: specific notched Izod impact strength, specific intrinsic viscosity, specific glass transition temperature (Tg), specific flexural modulus, good transparency and good color.

The process may be carried out as a batch or continuous process. In one embodiment, the process is conducted as a continuous process.

In one embodiment, the invention also relates to articles of manufacture made with any of the polyesters and/or polyester compositions described herein.

Because of the long crystallization half-time at 170 ℃ (e.g., greater than 5 minutes) exhibited by certain polyesters useful in the present invention, articles can be produced including, but not limited to, injection molded parts, injection blow molded articles, injection stretch blow molded articles, extruded films, extruded sheets, extrusion blow molded articles, extrusion stretch blow molded articles, and fibers. Thermoformable sheets are one example of articles of manufacture provided by the present invention. The polyesters of the invention may be amorphous or semi-crystalline. In one embodiment, certain polyesters useful in the present invention may have relatively low crystallinity. Certain polyesters useful in the present invention can thus have a substantially amorphous morphology, meaning that the polyesters contain substantially disordered polymer regions.

In any of the polyesters, polyester compositions, and/or methods of the invention, when additional zinc and/or titanium is added or present, the b-color of any given polyester of the invention may remain stable at a certain intrinsic viscosity, or decrease by less than 20%, or less than 15%, or less than 10%, or less than 5%, as determined by the L-a-b color system of CIE (International Commission on Illumination).

In certain embodiments, the b-value of the polyesters and/or polyester compositions of the invention may be from-10 to less than 20; or-10 to less than 18; or-10 to less than 15; or-10 to less than 14; or-10 to less than 10; or 1 to less than 20; or 1 to less than 18; or 5 to less than 20; or 5 to less than 18; or 8 to less than 20; or 8 to less than 18; or 8 to less than 15; or-3 to 10; or-5 to 5; or-5 to 4; or-5 to 3; or 1 to 20; or 1 to 18; or 1 to 15; or 1 to 14; or 1 to less than 10; or 1 to 10; or 1 to 9; or 1 to 8;1 to 7; or 1 to 6; or 1 to 5; or 2 to 25; or 2 to 20; or 2 to 18; or 2 to 15; or 2 to 14; or 2 to less than 10; or 2 to 9; or 2 to 8; or 2 to 7; or 2 to 6; or 2 to 5; or 3 to 20; or 3 to 18; or 3 to 15; or 3 to 14; or 3 to less than 10; or 3 to 8; or 3 to less than 20; or less than 15; or less than 14; or less than 13; or less than 12; or less than 11; or less than 10; or less than 9; or less than 8.5; or less than 8; or less than 7; or less than 6; or less than 5; or less than 4; or less than 3 as determined by the color system of L x a x b x CIE (International Commission on Illumination).

In certain embodiments, the L values of the polyesters and/or polyester compositions of the invention may be 50 to 99, or 50 to 90, or 60 to 99, or 60 to 90, or 60 to 85, or 60 to 80, or 60 to 75, or 60 to 70, or 65 to 99, or 65 to 90, or 65 to 85, or 65 to 80, or 65 to 75, or 70 to 90, or 70 to 99, or 70 to 90, or 70 to 85, or 70 to 80, or 75 to 95, or 77 to 90, or 75 to 85, or 80 to 95, or 80 to 90, as determined by the L x a b color system of CIE (International Commission on Illumination).

In one embodiment, values of b and/or L and/or a may be obtained in the presence of toner and/or in the absence of toner.

In any of the methods or polyesters or polyester compositions of the invention, the b-color of any given polyester of the invention may remain stable at a certain intrinsic viscosity when additional zinc is added and/or when additional titanium is added, or may be reduced by less than 20%, or less than 15%, or less than 10%, or less than 5%, as determined by the L-a-b color system of CIE (International Commission on Illumination).

Izod notched impact strength as described in ASTM D256 is a common method of measuring toughness. In one embodiment, the polyesters and/or polyester compositions of the invention can have a notched Izod impact strength of at least 1ft-lb/in, or at least 2ft-1bs/in, or at least 3ft-1bs/in, or 7.5ft-lbs/in, or 10ft-lbs/in measured at 23℃in a 1/8 inch thick test bar with a 10 mil notch according to ASTM D256.

The notched Izod impact strength is herein measured at 23℃in 3.2 millimeter (1/8 inch) thick bars using a 10 mil notched Izod according to ASTM D256. In one embodiment, certain polyesters and/or polyester compositions of the invention can exhibit a notched Izod impact strength of at least 25J/m (0.47 ft-lb/in) at 23℃in a 3.2 millimeter (1/8 inch) thick test bar with a 10 mil notch, as determined according to ASTM D256. In one embodiment, certain polyesters and/or polyester compositions of the invention may exhibit a notched Izod impact strength of about 25J/m (0.47 ft-lb/in) to about 75J/m (1.41 ft-lb/in) in a 3.2 millimeter (1/8 inch) thick bar at 23℃with a 10 mil notch, as determined according to ASTM D256. In another embodiment, certain polyesters and/or polyester compositions of the invention can exhibit a notched Izod impact strength of about 50J/m (0.94 ft-1 b/in) to about 75J/m (1.41 ft-1 b/in) in a 3.2 millimeter (1/8 inch) thick bar at 23℃with a 10 mil notch, as determined according to ASTM D256.

In one embodiment, certain polyesters and/or polyester compositions of the invention may exhibit at least one of the following densities: a density of greater than 1.2g/ml at 23 ℃.

In one embodiment, certain polyesters and/or polyester compositions of the invention useful in the present invention may exhibit useful thermal stability at 300 ℃ of no more than 0.20dL/g, or no more than 0.15dL/g, or no more than 0.12dL/g, or no more than 0.10dL/g, of an intrinsic viscosity measured in 60/40 (weight/weight) phenol/tetrachloroethane at a concentration of 0.5g/100ml at 25 ℃.

In one embodiment, certain polyesters and/or polyester compositions of the invention may exhibit a flexural modulus at 23 ℃ of equal to or greater than 2000MPa (290,000 psi) as determined by ASTM D790. In another embodiment, certain polyesters useful in the present invention may exhibit a tensile strength at 23 ℃ of about 2000MPa (290,000 psi) to about 2551MPa (370,000 psi) as determined by ASTM D638. In another embodiment, certain polyesters useful in the present invention may exhibit flexural modulus at 23 ℃ of about 2000MPa (290,000 psi) to about 2413MPa (350,000 psi) as determined by ASTM D790.

In one embodiment, certain polyesters and/or polyester compositions of the invention may exhibit a flexural modulus at 23 ℃ of equal to or greater than 2000MPa (290,000 psi) as determined by ASTM D790. In another embodiment, certain polyesters of the invention may exhibit a tensile strength at 23 ℃ of about 2000MPa (290,000 psi) to about 2551MPa (370,000 psi) as determined by ASTM D638. In another embodiment, certain polyesters of the invention may exhibit flexural modulus at 23 ℃ of about 2000MPa (290,000 psi) to about 2413MPa (350,000 psi) as determined by ASTM D790.

Certain polyesters and/or polyester compositions of the invention can have at least one of the following parameters: tg of about 85 to about 130 ℃ as measured by TA 2100Thermal Analyst Instrument at a scan rate of 20 ℃/min; flexural modulus at 23 ℃ equal to or greater than 2000MPa (290,000 psi) as determined by ASTM D790; and a notched Izod impact strength of 25J/m or greater (0.47 ft-lb/in) measured at 23℃with a 10 mil notched bar using a 1/8 inch thick test bar according to ASTM D256.

In certain embodiments, the final polyesters and/or polyester compositions of the invention can comprise methyl groups in an amount of 5.0 mole% or less, or 4.5 mole% or less, or 4 mole% or less, or 3 mole% or less, or 2.5 mole% or less, or 2.0 mole% or less, or 1.5 mole% or less, or 1.0 mole% or less.

It is believed that any of the methods of making polyesters described herein may be used to make polyester compositions useful in the present invention.

In one embodiment, the present invention also relates to a process for preparing any polyester useful in the present invention.

In one embodiment, the present invention also relates to a process for preparing any of the polyester compositions of the present invention.

In one embodiment, the invention also relates to a product prepared by any of the methods described herein.

In one embodiment, the polyesters and/or polyester compositions of the invention may be used in non-coating compositions, non-adhesive compositions, thermoplastic polyester compositions, articles of manufacture, shaped articles, thermoplastic shaped articles, molded articles, extruded articles, injection molded articles, blow molded articles, films and/or sheets (e.g., calendered, cast or extruded), thermoformed films or sheets, containers, or bottles (e.g., baby bottles or sports bottles or water bottles).

In one embodiment, the present invention comprises a thermoplastic article, typically in sheet form, having a decorative material embedded therein, the decorative material comprising any of the compositions described herein.

In one embodiment, the polyesters according to the invention may be used in appliance parts. As used herein, "implement component" refers to a rigid member that is used in conjunction with an implement. In one embodiment, the appliance component may be partially or completely separate from the appliance. In another embodiment, the appliance component is a component that is typically made of a polymer. In one embodiment, the appliance component is visually transparent.

In one embodiment, the polyesters according to the invention may be used for bottles and containers, including those injection molded, injection blow molded, injection stretch blow molded, blow molded or reheat blow molded. Articles made by these methods include double-walled cups, water bottles, sports bottles, bulk water containers, and baby bottles.

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

Examples

The following examples generally illustrate how the copolyesters of the invention are prepared and the effect of using 2, 4-tetramethyl-1, 3-cyclobutanediol and 1, 4-cyclohexanedimethanol with certain catalysts and stabilizers on various copolyester properties such as color and Intrinsic Viscosity (IV).

Measurement method

The intrinsic viscosity of the polyesters was measured in 60/40 (weight/weight) phenol/tetrachloroethane at a concentration of 0.5g/100ml at 25℃and reported in dL/g.

The diol content and cis/trans ratio of the composition were determined by proton Nuclear Magnetic Resonance (NMR) spectroscopy. All NMR spectra were recorded on a JEOL Eclipse Plus MHz NMR spectrometer using chloroform-trifluoroacetic acid (70-30 v/v) for the polymer or 60/40 (wt/wt) phenol/tetrachloroethane for the oligomer sample with deuterated chloroform added for locking. Peak assignment of 2, 4-tetramethyl-1, 3-cyclobutanediol resonance was performed by comparison with model monobenzoates and dibenzoates of 2, 4-tetramethyl-1, 3-cyclobutanediol. These model compounds are very close to the resonance sites found in polymers and oligomers.

Color values reported herein are CIELAB L, a, and b values measured following ASTM D6290-98 and ASTM E308-99 using measurements from a Hunter Lab Ultrascan XE spectrophotometer (Hunter Associates Laboratory inc., reston, va.) having the following parameters: (1) D65 light source, (2) 10 degree observer, (3) reflection mode including specular reflection angle, (4) large area field of view, (5) 1 "port size. Unless otherwise indicated, measurements were made on polymer particles ground to pass through a 1 mm screen.

The amounts of titanium (Ti) and zinc (Zn) in the following examples are reported in parts per million (ppm) of metal and are measured by inductively coupled plasma mass spectrometry (ICP). The amount of phosphorus is similarly reported as ppm of elemental phosphorus and is also measured by ICP using the same instrument. The values reported in the "P measured" column in the examples below are obtained by measuring phosphorus as described above.

Unless otherwise specified, the cis/trans ratio of 2, 4-tetramethyl-1, 3-cyclobutanediol used in the following examples is approximately 60/40, and may be 45/55 to 99/1.

IV or i.v. refer to the intrinsic viscosity measured as described herein unless otherwise indicated.

Preparation of copolyesters of examples 1-45

The preparation of the copolyesters of examples 1-45 as shown in Table 1 is illustrated by the preparation of the copolyester of example 38, with the target composition: preparation of copolyesters of 100 mole% dimethyl terephthalate residues, 35 mole% TMCD residues and 65 mole% CHDM residues. A mixture of 77.7 grams dimethyl terephthalate, 37.5 grams CHDM, 25.9 grams TMCD, 0.130 grams zinc acetylacetonate, and 0.077 grams titanium isopropoxide was placed in a 500 ml flask equipped with a nitrogen inlet, a metal stirrer, and a short distillation column. The flask was placed in a Wood's metal bath (Wood's metal) which had been heated to 220 ℃. The stirring speed was set at 175rpm and held for 15 minutes. The contents of the flask were heated to 230 ℃ over 5 minutes while stirring was simultaneously increased to 225 ℃ during this time. The contents were then slowly raised to 245 ℃ over 45 minutes. The contents were kept at 245 ℃ while the pressure was reduced to 250 torr over three minutes. The temperature was again raised to 265 ℃ over 15 minutes. The pressure was then reduced further to 3.5 torr over 8 minutes. Finally, the temperature was raised to 277 ℃, while the stirring rate was slowly reduced to 50rpm, and the pressure was reduced to 1 torr over the course of 20 minutes. The reaction was held at this final temperature, pressure and stirring rate for 35 minutes. A high melt viscosity, visually clear polymer was obtained with an intrinsic viscosity of 0.62dl/g. NMR analysis showed the polymer to consist of 31.47 mole% TMCD residues.

Table 1-contains TMCD, CHDM and 100 mole% DMT; copolyesters of Ti and Zn

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* Examples 18 and 19 were exposed to air; examples 41-48 are part of a molar ratio study, varying the excess diol throughout the process; example 20 water has been added; example 21 methanol has been added; examples 22-25, varying the final temperature and pressure; examples 26 and 27, varying the molar ratio; examples 36-39, 36 used 63.41 mole% cis TMCD,37 used 61.69 mole% cis TMCD,38 used 62.41 mole% cis TMCD, and 39 used 62.42 mole% cis TMCD.

Early experiments revealed that titanium and zinc in combination are capable of incorporating significant TMCD into polyesters, resulting in high intrinsic viscosity. Significant color improvement was observed with reduced total catalyst loading while TMCD incorporation and viscosity build were still very good. Together, these results also demonstrate a good range of TMCD incorporation, which can be controlled via the molar ratio of the diol charge.

Comparative series of polymers were prepared with tin and phosphorus catalyst packages as shown in table 2. Similar intrinsic viscosities and TMCD conversions were observed when compared to titanium and zinc, but it should be noted that phosphorus was believed to be required to reduce the color values to those observed with titanium and zinc.

Table 2: comprises TMCD; CHDM;100 mole% DMT; copolyesters of Sn (ppm) and phosphorus (P) (ppm); [ the Sn source is butyltin tris (2-ethylhexanoate) ]

It is unpredictable that Ti/Zn catalyst systems are advantageous compared to the use of tin catalyst systems in achieving similar good intrinsic viscosities and similar good colors (no phosphorus is required) as shown in table 2.

A comparative series of polymers was synthesized with a tin catalyst. Color, viscosity and TMCD incorporation were observed to be comparable to those provided by the Zn/Ti system described in this work.

Polymers prepared with zinc and titanium in combination and at various loadings were observed to be advantageous compared to polymers containing TMCD prepared with tin.

The present disclosure has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the disclosure.

Claims

1. A polyester composition comprising:

(1) At least one polyester comprising:

(a) A dicarboxylic acid component comprising:

(b) A glycol component comprising:

(i) About 10 to about 60 mole% of 2, 4-tetramethyl-1, 3-cyclobutanediol residues;

(ii) About 40 to about 90 mole% of 1, 4-cyclohexanedimethanol residues;

(iii) Optionally, residues of at least one modified diol;

wherein the total mole% of the dicarboxylic acid component of the final polyester is 100 mole%,

(2) A residue comprising titanium atoms and zinc atoms and less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or 0 to 30ppm, or 0 to 20ppm, or 0 to 10ppm, or 0ppm of tin atoms.

2. The polyester composition of claim 1, wherein the modified diol of the polyester comprises at least one of diethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, 1, 4-cyclohexanedimethanol, ethylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, terephthalyl alcohol, neopentyl glycol, isosorbide, polytetramethylene glycol, or mixtures thereof.

3. The polyester composition of claim 1 or 2 wherein the polyester comprises residues of 2, 4-tetramethyl-1, 3-cyclobutanediol in an amount of from about 10 to about 50 mole%, from 20 to about 50 mole%, or from about 20 to about 40 mole%, or from about 25 to about 50 mole%, or from about 30 to about 45 mole%.

4. The polyester composition of any of claims 1 to 3 wherein the polyester comprises 1, 4-cyclohexanedimethanol residues in an amount of about 40 to about 90%, or about 40 to about 80%, or about 40 to about 75%, or about 45 to about 70%, or about 50 to about 90%, or about 50 to about 80%, or about 60 to about 80%, or about 50 to about 75%, or about 50 to about 70%, or about 55 to about 70%.

5. The polyester composition of any of claims 1 to 4, wherein the diacid component of the polyester comprises aromatic and/or aliphatic dicarboxylic acid ester residues.

6. The polyester composition according to claim 1 to 5, wherein the polyester has an intrinsic viscosity of 0.25dL/g about 1.2dL/g, or 0.30dL/g about 1.2dL/g, or 0.35 about 1.2dL/g, or 0.40 about 1.2dL/g, or 0.45 about 1.2dL/g, or 0.50 about 1.2dL/g, or 0.55 about 1.2dL/g, or 0.60 about 1.2dL/g, or 0.25dL/g about 0.80dL/g, or 0.30dL/g about 0.80dL/g, or 0.35 about 0.80dL/g, or 0.40 about 0.80dL/g, or 0.45 about 0.80dL/g, or 0.50 about 0.80dL/g, or 0.55 about 1.2dL/g, or 0.30dL/g measured at 25 ℃ in 60/40 (weight/weight) phenol/tetrachloroethane at a concentration of 0.5g/100ml or 0.55 about 0.80dL/g, or 0.60 about 0.80dL/g, or 0.25dL/g about 0.75dL/g, or 0.30dL/g about 0.75dL/g, or 0.35 about 0.75dL/g, or 0.40 about 0.75dL/g, or 0.45 about 0.75dL/g, or 0.50 about 0.75dL/g, or 0.55 about 0.75dL/g, or 0.60 about 0.75dL/g, or 0.25dL/g about 0.70dL/g, or 0.30dL/g about 0.70dL/g, or 0.35 about 0.70dL/g, or 0.40 about 0.70dL/g, or 0.45 about 0.70dL/g, or 0.50 about 0.70dL/g, or 0.55 about 0.70dL/g, or 0.60 about 0.70dL/g, or 0.25 dL/g.

7. The polyester composition of any of claims 1 to 6, which does not comprise manganese atoms.

8. The polyester composition of any of claims 1 to 7, which does not comprise gallium atoms.

9. The polyester composition of any of claims 1 to 8 comprising the following amounts of titanium atoms: 20 to 750ppm, or 20 to 500ppm, or 20 to 450ppm, or 20 to 400ppm, or 20 to 350ppm, or 20 to 300ppm, or 20 to 275ppm, or 20 to 250ppm, or 20 to 200ppm, or 50 to 1000ppm, or 50 to 750ppm, or 50 to 500ppm, or 50 to 450ppm, or 50 to 400ppm, or 50 to 300ppm, or 50 to 275ppm, or 50 to 250ppm, or 50 to 200ppm, or 60 to 1000ppm, or 60 to 750ppm, or 60 to 500ppm, or 60 to 450ppm, or 60 to 400ppm, or 60 to 350ppm, or 60 to 300ppm, or 60 to 275ppm, or 60 to 250ppm, or 60 to 200ppm, or 60 to 150ppm, or 60 to 100ppm, or 75 to 1000ppm, or 75 to 750ppm, or 75 to 500ppm, or 75 to 450ppm, or 75 to 400ppm, or 75 to 350ppm, or 75 to 300ppm, or 75 to 250ppm, or 70 to 200ppm, or 100 to 100 ppm. Or 70 to 90ppm, or 65 to 100ppm, or 65 to 90ppm or 80 to 1000ppm, or 80 to 750ppm, or 80 to 500ppm, or 80 to 450ppm, or 80 to 400ppm, or 80 to 350ppm, or 80 to 300ppm, or 80 to 275ppm, or 80 to 250ppm, or 80 to 200ppm, or 100 to 1000ppm, or 100 to 750ppm, or 100 to 500ppm, or 100 to 450ppm, or 100 to 400ppm, or 100 to 350ppm, or 100 to 300ppm, or 100 to 275ppm, or 100 to 250ppm, or 100 to 200, or 150 to 1000ppm, or 150 to 750ppm, or 150 to 500ppm, or 150 to 450ppm, or 150 to 400ppm, or 150 to 350ppm, or 150 to 300ppm, or 150 to 250ppm, or 200 to 1000ppm, or 200 to 750ppm, or 200 to 500ppm, or 200 to 450ppm, or 200 to 400ppm, or 200 to 300ppm, or 200 to 250ppm, relative to the mass of the final polyester produced.

10. The polyester composition of any of claims 1 to 9 comprising the following amounts of zinc atoms: 50 to 1000ppm, or 50 to 750ppm, or 50 to 500ppm, or 50 to 300ppm, or 50 to 250ppm, or 50 to 200ppm, or 60 to 1000ppm, or 60 to 750ppm, or 60 to 500ppm, or 60 to 300ppm, or 60 to 250ppm, or 60 to 200ppm, or 75 to 1000ppm, or 75 to 750ppm, or 75 to 500ppm, or 75 to 300ppm, or 75 to 250ppm, or 75 to 200ppm, or 100 to 1000ppm, or 100 to 750ppm, or 100 to 500ppm, or 100 to 400ppm, or 100 to 300ppm, or 100 to 250ppm, or 100 to 200, or 150 to 1000ppm, or 150 to 750ppm, or 150 to 500ppm, or 150 to 400ppm, or 150 to 300ppm, or 150 to 250ppm, or 200 to 1000ppm, or 200 to 750ppm, or 200 to 500ppm, or 200 to 450ppm, or 200 to 400ppm, or 200 to 300ppm, or 200 to 250ppm relative to the mass of the final polyester produced.

11. The polyester composition of any of claim 1 to 10, wherein the ratio of titanium atoms to zinc atoms, in ppm relative to the mass of the final polyester produced, is from 0.50-1:5 to 5:1, or from 0.50-1:4 to 4:1, or from 0.50-1:3 to 3:1, or from 0.50:1 to 1:5, or from 0.50-1 to 1:4, or from 0.60-1:5 to 5:1, or from 0.60-1:4 to 4:1, or from 0.60-1:3 to 3:1, or from 0.60:1 to 1:5, or from 0.60-1 to 1:4, or from 0.70-1:5 to 5:1, or from 0.70-1:4 to 4:1, or from 0.70-1:3 to 3:1, or from 0.70-1:2 to 2:1, or from 0.70-1:2 to 1:4, or from 0.75-1:5 to 5:1 or 0.75-1.2 to 1:4 to 4:1, or 0.75-1:3 to 3:1, or 0.75-1:2 to 2:1, or 0.75-1.0 to 1:4, or 0.80:1.2 to 1:4, or 1.0 to 1.5:1.0 to 1:7.1, or 1.0 to 1.5:1.0 to 3, or 1.0 to 1.5:1.0 to 2, or 1.0 to 1.5:1.0 to 2.5, or (0.80-1) to 5:1, or (0.80-1.2) to 4:1, 1:4 to 4:1, or (0.80-1) to 3:1, 1:3 to 3:1, or (0.80-1) to 2.5:1, or (0.80-1) to 1.2:1, or (0.80-1.2) to 1.25-1.

12. The polyester composition of any of claims 1 to 11 wherein the total catalyst metal atoms present in the composition are in the following range: 150 to 800ppm, or 150 to 725ppm, or 150 to 700ppm, or 150 to 500ppm, or 150 to 450ppm, or 150 to 400ppm, or 150 to 300ppm,200 to 800ppm, or 200 to 725ppm, or 200 to 700ppm, or 200 to 600ppm, or 200 to 500ppm, or 200 to 450ppm, or 200 to 400ppm, or 200 to 300ppm, or 250 to 800ppm, or 250 to 725ppm, or 250 to 700ppm, or 250 to 500ppm, or 250 to 450ppm, or 250 to 400ppm, or 300 to 800ppm, or 300 to 725ppm, or 300 to 700ppm, or 300 to 500ppm, or 300 to 450ppm, or 300 to 400ppm, or 350 to 800ppm, or 350 to 725ppm, or 350 to 700ppm, or 350 to 500ppm, or 350 to 450ppm relative to the mass of the final polyester produced.

13. The polyester composition of any of claims 1 to 12, wherein at least one titanium source is selected from at least one of titanium carbonate, titanium acetate, titanium benzoate, titanium succinate, titanium isopropoxide, titanium methoxide, titanium oxalate, titanium nitrate, titanium ethoxide, titanium hydroxide, titanium hydride, titanium ethoxide, alkyl titanium, zinc titanium hydride, titanium borohydride, lithium oxide, titanium acetylacetonate, titanium triisopropoxide chloride, titanium bis (acetylacetonate) diisopropoxide, titanium n-butoxide, titanium tert-butoxide.

14. The polyester composition of any of claims 1 to 13 wherein at least one titanium source is selected from titanium dioxide, titanium isopropoxide, titanium acetylacetonate oxide, titanium bis (acetylacetonate) diisopropoxide, and/or combinations thereof.

15. The polyester composition of any of claims 1 to 14 wherein at least one zinc source is selected from zinc borate, zinc oxide, zinc naphthenate, zinc tert-butoxide, zinc methoxide, zinc hydroxide, zinc acetate, zinc diacetate, zinc dihydrate, zinc octoate, zinc carbonate, zinc dialkyl, zinc dimethyl, zinc diaryl, zinc isopropoxide, zinc phosphate, and/or zinc acetylacetonate; or wherein the at least one zinc source is selected from zinc acetylacetonate and zinc isopropoxide.

16. The polyester composition of any of claims 1 to 15 wherein the 2, 4-tetramethyl-1, 3-cyclobutanediol residues is a mixture comprising: more than 50 mole% of cis-2, 4-tetramethyl-1, 3-cyclobutanediol and less than 50 mole% of trans-2, 4-tetramethyl-1, 3-cyclobutanediol or greater than 70 mole% cis-2, 4-tetramethyl-1, 3-cyclobutanediol and less than 30 mole% trans-2, 4-tetramethyl-1, 3-cyclobutanediol, or greater than 75 mole% cis-TMCD and less than 25 mole% trans-TMCD; or greater than 80 mole% cis-TMCD and less than 20 mole% trans-TMCD; or greater than 85 mole% cis-TMCD and less than 15 mole% trans-TMCD; or more than 90 mole% of cis-2, 4-tetramethyl-1, 3-cyclobutanediol and less than 10 mole% of trans-2, 4-tetramethyl-1, 3-cyclobutanediol or more than 95 mole% of cis-2, 4-tetramethyl-1, 3-cyclobutanediol and less than 5 mole% of trans-2, 4-tetramethyl-1, 3-cyclobutanediol.

17. The polyester composition of any of claims 1 to 16, wherein the polyester composition comprises at least one polymer selected from at least one of the following: polyesters, polyetherimides, polyphenylene oxides, polyphenylene oxide/polystyrene blends, polystyrene resins, polyphenylene sulfides, polyphenylene sulfide/sulfones, poly (ester-carbonates), polycarbonates, polysulfones other than claim 1; polysulfone ethers and poly (ether-ketones); or wherein the polyester composition comprises a blend of the polyester with recycled poly (ethylene terephthalate) (rPET).

18. The polyester composition of any of claims 1 to 17 comprising residues of at least one phosphorus compound.

19. The polyester composition of any of claims 1 to 18 comprising methyl groups in an amount of 5.0 mole% or less, or 4.5 mole% or less, or 4 mole% or less, or 3.5 mole% or less, or 3 mole% or less, or 2.5 mole% or less, or 2.0 mole% or less, or 1.5 mole% or less, or 1.0 mole% or less in the final polyester and/or polyester composition of the invention.

20. The polyester composition of any of claims 1 to 19, wherein the polyester has a b x value of less than 6 as determined by the L x a x b x color system of CIE (International Commission on Illumination); and an intrinsic viscosity of 0.45-0.75dL/g, as measured in 60/40 (weight/weight) phenol/tetrachloroethane at a concentration of 0.5g/100ml at 25 ℃.

21. The polyester composition of claim 20 wherein the ratio of titanium atoms to zinc atoms is (0.80-1) to 3 to 3:1, 1:3 to 3:1 or (0.80-1) to 2:1, or (1-1.3) to (1-1.3), or (1-1.25) to (1-1.25) in ppm relative to the mass of the final polyester produced.

22. The polyester composition of any of claims 1 to 21 wherein the degree of incorporation or conversion of TMCD in the final polyester is greater than 55 mole%, or greater than 50 mole%, or greater than 45 mole%, or greater than 40 mole%, or greater than 35 mole%, or greater than 30 mole%.

23. An article of manufacture made from the polyester composition of claims 1-22.