CN116568725A

CN116568725A - Polyester compositions comprising tetramethylcyclobutanediol with improved catalyst systems comprising titanium and zinc atoms

Info

Publication number: CN116568725A
Application number: CN202180084612.1A
Authority: CN
Inventors: 布莱恩·艾伦·谢弗; 凯特·伊丽莎白·艾伦
Original assignee: Eastman Chemical Co
Current assignee: Eastman Chemical Co
Priority date: 2020-12-18
Filing date: 2021-12-16
Publication date: 2023-08-08
Also published as: CN116745339A; CN116917373A

Abstract

The present invention relates to 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 50 mole% of 2, 4-tetramethyl-1, 3-cyclobutanediol residues; (ii) about 50 to about 90 mole% of modified diol residues; 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 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.

Description

Polyester compositions comprising tetramethylcyclobutanediol with improved catalyst systems comprising titanium and zinc atoms

Technical Field

The present invention relates to polyester compositions made from terephthalic acid or an ester thereof, 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD), and residues of at least one modified diol. The polyester composition can be catalyzed by a catalyst system comprising titanium and zinc atoms to produce good TMCD binding and reactivity sufficient to achieve the desired inherent viscosity over a broad compositional range.

Background

Tin (Sn) based catalysts are generally the most effective for incorporating TMCD into polyesters (Caldwell et al, CA740050, and Kelsey et al, macromolcules2000, 33, 581). However, tin-based catalysts typically produce yellow to amber copolyesters in the presence of EG, see, for example, us patent 5,705,575 to Kelsey; 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, CA740050, kelsey et al, micromolels 2000, 33, 5810).

U.S. patent application No.2007/0142511 discloses that polyesters having glycol components comprising TMCD and EG and optionally a level of CHDM can be prepared with titanium-based catalysts. This publication discloses a broad compositional range with a glycol component comprising: (i) about 1 to about 90 mole% TMCD residues; and (ii) about 99 to about 10 mole% EG residues. However, when relatively high amounts of EG are present, such as polymers having TMCD and EG alone, the catalyst system requires a significant amount of Sn.

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

Disclosure of Invention

In one aspect, the present invention relates to novel polyesters and/or polyester compositions comprising TMCD, titanium atoms, and zinc atom residues, which may have one or more, two or more, or a combination of three or more of the following properties: good notched Izod impact strength, good inherent viscosity, good glass transition temperature (Tg), good flexural modulus, good tensile strength, good clarity, good color, good dishwasher performance, good TMCD bonding, good TMCD yield, and good/improved melt and/or thermal stability.

It is unexpected that they will have these properties when using catalyst systems that do not require the use of tin catalysts and/or titanium catalysts to prepare the polyesters and/or polyester compositions of the invention.

In one aspect, there is provided a polyester and/or polyester composition comprising a combination of titanium atoms and zinc atoms, further comprising: (a) a dicarboxylic acid component comprising: (i) 70-100 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: (i) 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) residues and at least one modified diol residue; or (ii) 10 to 50 mole% or 10 to 60 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) residues and 50 to 90 mole% or 40 to 90 mole% of modified diol residues; or (iii) 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; or (iv) about 10 to about 50 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) residues; about 50 to about 90 mole% Ethylene Glycol (EG) residues, and optionally, about 0.01 to about 5 mole% diethylene glycol residues; or (v) 10-50 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) residues and 50-90 mole% diethylene glycol (DEG) residues; or (vi) 10 to 60 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) residues and 40 to 90 mole% neopentyl glycol (NPG) residues, wherein the total mole% of the dicarboxylic acid component of the final polyester is 100 mole% and wherein the total mole% of the diol component of the final polyester is 100 mole%.

In one aspect, for diol components (b) (i) and (b) (ii) above, the modified diol may comprise at least one of diethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, 1, 4-cyclohexanedimethanol, EG, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, p-xylene glycol, neopentyl glycol, isosorbide, polytetramethylene glycol, or a combination thereof.

In one aspect, for diol component (b) (iii) above, the modifying diol may comprise diethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, EG, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, para-xylene glycol, neopentyl glycol, isosorbide, polytetramethylene glycol, or a combination thereof.

In one aspect, for diol component (b) (iv), the modified diol may comprise at least one of diethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, 1, 4-cyclohexanedimethanol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, p-xylene glycol, neopentyl glycol, isosorbide, polytetramethylene glycol, or a combination thereof.

In one aspect, for diol component (b) (v), the modified diol may comprise at least one of 1, 2-propanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, 1, 4-cyclohexanedimethanol, EG, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, p-xylene glycol, neopentyl glycol, isosorbide, polytetramethylene glycol, or a combination thereof.

In one aspect, for diol component (b) (vi), the modified diol may comprise at least one of 1, 2-propanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, 1, 4-cyclohexanedimethanol, EG, diethylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, p-xylene glycol, isosorbide, polytetramethylene glycol, or a combination thereof.

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 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% tetramethylene glycol.

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 55mol%, or about 10 to about 50mol%, or about 10 to about 45mol%, or about 10 to about 40mol%, or about 15 to about 55mol%, or about 15 to about 50mol%, or about 15 to about 45mol%, or about 15 to about 40mol%, or about 20 to about 55mol%, or about 20 to about 50mol%, or about 20 to about 45mol%, or about 20 to about 40mol%, or about 20 to about 35mol%, or about 20 to about 30mol%, or about 25 to about 55mol%, or about 25 to about 50mol%, or about 25 to about 45mol%, or about 25 to about 40mol%, or about 30 to about 55mol%, or about 30 to about 50mol%, or about 30 to about 45mol%, or about 30 to about 40mol%, or about 35 to about 55mol%, or about 35 to about 50mol%, or about 35 to about 45mol%. The modifying glycol may comprise the remaining mole percent.

In one aspect, the polyesters and/or polyester compositions of the invention can comprise residues of TMCD in an amount of about 10 to about 50 mole%, or about 15 to about 40 mole%, or about 20 to about 50 mole%, or about 20 to about 40 mole%, or about 25 to about 50 mole%, or about 25 to about 40 mole%. The modifying glycol may comprise the remaining mole percent.

In one aspect, 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 60 to about 70 mole%, or about 45 to about 65%, or about 50 to about 65 mole%, or about 55 to about 65% >.

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

In one aspect, the polyesters and/or polyester compositions of the invention may comprise 20 to 45 mole% TMCD residues and 55 to 80 mole% CHDM residues; or 20-40 mole% TMCD residues and 60-80 mole% CHDM residues; or 20-35 mole% TMCD residues and 65-80 mole% CHDM residues; or 25-45 mole% TMCD residues and 55-75 mole% CHDM residues; or 25-40 mole% TMCD residues and 60-75 mole% CHDM residues; or 25-35 mole% TMCD residues and 65-75 mole% CHDM residues; or 30 to 35 mole% TMCD residues and 65 to 70 mole% CHDM residues, based on the 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 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 aspect, the polyesters and/or polyester compositions of the invention may contain no 1, 4-cyclohexanedimethanol residues, or no more than 10 mole%, or no more than 5 mole% 1, 4-cyclohexanedimethanol residues.

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

In one aspect, the polyesters and/or polyester compositions of the invention may comprise EG residues in an amount of about 40 to about 90 mole%, or about 40 to about 80 mole%, or about 40 to about 70 mole%, or about 45 to about 75 mole%, or 50 to about 90 mole%, or about 50 to about 80 mole%, or about 50 to about 70 mole%, or about 60 to about 90 mole%, or about 60 to about 80 mole%, or about 65 to about 90 mole%, or about 65 to about 80 mole%, or about 70 to about 90 mole%.

In one aspect, the polyesters and/or polyester compositions of the invention may comprise EG residues in an amount of about 60 to about 90 mole%, or about 65 to about 90 mole%, or about 70 to about 90 mole%.

In one aspect, the polyesters and/or polyester compositions of the invention may comprise EG residues in an amount of 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 less than 5 mole%, or 0 mole%.

In one aspect, the polyesters and/or polyester compositions of the invention may comprise EG residues without 1, 4-cyclohexanedimethanol residues, or less than 10 mole% CHDM, or less than 5 mole% CHDM, wherein the remaining modified diols comprise at least one of diethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 2-methyl-1, 3-propanediol, 1, 5-pentanediol, 1, 6-hexanediol, p-xylene glycol, neopentyl glycol, isosorbide, polytetramethylene glycol, or combinations thereof.

In one aspect, the polyesters and/or polyester compositions of the invention may comprise 20 to 45 mole% TMCD residues, 20 to 45 mole% CHDM residues, and 10 to 60 mole% EG residues; or 20-40 mole% TMCD residues, 20-40 mole% CHDM residues, and 20-60 mole% EG residues; or 20-35 mole% TMCD residues, 20-35 mole% CHDM residues, and 30-60 mole% EG residues; or 25 to 45 mole% TMCD residues, or 25 to 45 mole% CHDM residues, and 10 to 50 mole% EG residues, based on the total mole% of diol residues in the final polyester, equal to 100 mole%.

In one aspect, the glycol component of the polyesters and/or polyester compositions used in the present invention include, but are not limited to, at least one of the following combinations of ranges: about 10 to about 27 mole% TMCD and about 90 to about 73 mole% ethylene glycol; about 15 to about 26 mole% TMCD and about 85 to about 74 mole% ethylene glycol; about 18 to about 26 mole percent TMCD and about 82 to about 77 mole percent ethylene glycol; about 20 to about 25 mole% TMCD and about 80 to about 75 mole% ethylene glycol; about 21 to about 24 mole% TMCD and about 79 to about 76 mole% ethylene glycol; or about 22 to about 24 mole% TMCD and about 78 to about 76 mole% ethylene glycol. In this embodiment, diethylene glycol may be present, either added or formed in situ. If formed in situ, diethylene glycol may be present in an amount of up to 2 mole%.

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

In one aspect, the polyesters and/or polyester compositions of the invention can comprise residues of diethylene glycol in an amount of from about 50 to about 90 mole%, or from about 50 to about 85 mole%, or from about 50 to about 80 mole%, or from about 50 to about 75 mole%, or from about 50 to about 65 mole%, or from about 55 to about 90 mole%, or from about 55 to about 85 mole%, or from about 55 to about 80 mole%, or from about 55 to about 75 mole%, or from about 55 to about 70 mole%, or from about 55 to about 65 mole%, or from about 60 to about 90 mole%, or from about 60 to about 85 mole%, or from about 60 to about 80 mole%, or from about 60 to about 75 mole%.

In one aspect, the polyesters and/or polyester compositions of the invention can comprise residues of diethylene glycol in an amount of from about 60 to about 90 mole%, or from about 60 to about 85 mole%, or from about 60 to about 80 mole%, or from about 60 to about 75 mole%, or from about 50 to about 90 mole%, or from about 50 to about 85 mole%, or from about 50 to about 80 mole%, or from about 50 to about 75 mole%.

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

In one aspect, the polyesters and/or polyester compositions of the invention may include cases where neopentyl glycol is not present, or residues of neopentyl glycol are present in an amount of less than 70 mole%, or less than 60 mole%, or less than 50 mole%, or less than 40 mole%, or less than 30 mole%, or less than 20 mole%, or less than 10 mole%, or from 25 to 80 mole%, or from 25 to 75 mole%, or from 25 to 70 mole%, or from 30 to 80 mole%, or from 30 to 75 mole%, or from 30 to 70 mole%, or from 35 to 80 mole%, or from 35 to 75 mole%, or from 35 to 70 mole%.

In one aspect, the polyesters and/or polyester compositions of the invention can comprise neopentyl glycol residues in an amount of from about 40 to about 90 mole%, or from about 40 to about 85 mole%, or from about 40 to about 80 mole%, or from about 40 to about 75 mole%, or from about 40 to about 70 mole%, or from about 45 to about 90 mole%, or from about 45 to about 85 mole%, or from about 45 to about 80 mole%, or from about 45 to about 75 mole%, or from about 45 to about 70 mole%, or from about 50 to about 90 mole%, or from about 50 to about 85 mole%, or from about 50 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 90 mole%, or from about 55 to about 85 mole%, or from about 55 to about 75 mole%, or from about 55 to about 70 mole%, or from about 60 to about 90 mole%, or from about 60 to about 85 mole%, or from about 60 to about 80 mole%, or from about 60 to about 75 mole%, or from about 60 to about 70 mole%, or from about 70 to about 90%.

In one aspect, the polyesters and/or polyester compositions of the invention may comprise: 10 to 45 mole% of TMCD residues and 55 to 90 mole% of NPG residues, or 10 to 40 mole% of TMCD residues and 60 to 90 mole% of NPG residues, or 10 to 35 mole% of TMCD residues and 65 to 90 mole% of NPG residues, or 20 to 45 mole% of TMCD residues and 55 to 80 mole% of NPG residues, or 20 to 40 mole% of TMCD residues and 60 to 80 mole% of NPG residues, or 20 to 35 mole% of TMCD residues and 65 to 80 mole% of NPG residues, or 25 to 45 mole% of TMCD residues and 55 to 75 mole% of NPG residues, or 25 to 40 mole% of TMCD residues and 60 to 75 mole% of NPG residues, or 25 to 35 mole% of TMCD residues and 65 to 75 mole% of NPG residues, or 30 to 35 mole% of TMCD residues and 65 to 70 mole% of NPG residues, based on the total polyester diol content being equal to 100 mole% based on the total polyester diol content.

In certain aspects of the invention, the polyester may comprise 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 diacid component of the polyesters of the invention can comprise 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 polyesters and/or polyester compositions of the 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% TMCD residues;

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

wherein the total mole% of the 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%; 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 inherent 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 determined at 25 ℃ in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5g/100 ml; 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 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 x b color system of CIE (international commission for illumination). In some embodiments, a may also have a value 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.

(1) At least one polyester comprising:

(a) A dicarboxylic acid component comprising:

(b) A glycol component comprising:

(i) About 20 to about 50 mole% TMCD residues;

(ii) About 50 to about 80 mole% EG residues;

wherein the inherent viscosity is from 0.35 to 1.0dL/g as determined at 25℃in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5g/100 ml; and has a b-x value of less than 25, or less than 20, or less than 18, or less than 15, or less than 10, or less than 5; and L values 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, or 80 to 90 as determined by the L x a x b color system of CIE (international commission for illumination).

(1) At least one polyester comprising:

(a) A dicarboxylic acid component comprising:

(b) A glycol component comprising:

(i) About 20 to about 50 mole% TMCD residues;

(ii) About 60 to about 80 mole% diethylene glycol residues;

wherein the inherent viscosity is from 0.55 to 0.85dL/g, or from 0.60 to 0.85dL/g, or from 0.55 to 0.80dL/g, or from 0.60 to 0.80dL/g, or from 0.55 to 0.78dL/g, or from 0.60 to 0.78dL/g, or from 0.55 to 0.75dL/g, or from 0.60 to 0.75dL/g, as determined at 25 ℃ in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5g/100 ml; and having a b-x value of less than 15, or less than 10, or from 1 to 15, or from 1 to 14, or from 1 to 13, or from 1 to 12, or from 1 to 10, 1 to 5; and L values of 70 to 95, or 75 to 90, or 70 to 85, or 75 to 85, as determined by the CIE (international commission on illumination) L x a x b x color system.

(1) At least one polyester comprising:

(a) A dicarboxylic acid component comprising:

(b) A glycol component comprising:

(i) About 15 to about 60 mole% TMCD residues;

(ii) About 40 to about 85 mole% neopentyl glycol residues;

(2) A residue comprising titanium atoms and zinc atoms, 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 inherent viscosity is from 0.25 to 0.75dL/g, or from 0.25 to 0.70dL/g, or from 0.25 to 0.60dL/g, or from 0.25 to 0.55dL/g, or from 0.25 to 0.50dL/g, or from 0.30 to 0.75dL/g, or from 0.30 to 0.70dL/g, or from 0.30 to 0.65dL/g, or from 0.30 to 0.60dL/g, or from 0.30 to 0.55dL/g, or from 0.30 to 0.50dL/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 0.35 to 0.55dL/g or 0.35 to 0.50dL/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 0.40 to 0.55dL/g, or 0.40 to 0.50dL/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 0.45 to 0.55dL/g, or 0.50 to 0.75dL/g, or 0.50 to 0.70dL/g, or 0.50 to 0.65dL/g, or 0.50 to 0.60dL/g, as determined at 25℃in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5g/100 ml; and having a b-x value of 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, or less than 7, or less than 6, or less than 5, or 1 to 15, or 1 to 10, or 1 to 9, 1 to 8, or 1 to 7, or 1 to 6, or 1 to 5, or 2 to 9, 2 to 8, or 2 to 7, or 2 to 6, or 2 to 5, or 3 to 9, 3 to 8, or 3 to 7, or 3 to 6; and L values of 75 to 100, or 80 to 100, or 75 to 95, or 80 to 95, as determined by the CIE (international commission on illumination) L x a x b x color system.

In one aspect, for any of the polyesters and/or polyester compositions of the invention, the inherent 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 0.75dL/g, or from 0.50 to 0.70dL/g, or from 0.50 to 0.60dL/g, or from 0.45 to 0.60dL/g, or from 0.55 to 0.70dL/g, as determined at 25℃in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5g/100 ml.

In one aspect, the Tg of the polyester and/or polyester composition of the invention can be 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 alkoxide, titanium alkyl hydride, titanium zinc hydride, titanium borohydride, titanium oxide, titanium acetylacetonate, titanium triisopropoxide chloride, titanium bis (acetylacetonate), titanium n-butoxide, titanium t-butoxide.

In one embodiment, the polyester and/or polyester composition of the present invention comprises 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 naphthalate, 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, 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 naphthalate and/or zinc carbonate and/or residues thereof or a combination thereof are absent.

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

In one aspect, the polyesters and/or polyester compositions of the invention may contain titanium atoms, the amount is 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 75 to 200ppm, or 70 to 100ppm, 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 aspect, the polyesters and/or polyester compositions of the invention may contain zinc atoms, titanium 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 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, wherein the ratio of titanium atoms to zinc atoms is 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 0.70-1.2 to 1:4, or 0.60-1:2 to 1:4, in ppm relative to the mass of the final polyester: 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 1:4 to 4:1, or 0.80-1:3 to 3:1, or 0.80-1:2 to 2:1, or 0.80-1.2 to 1:4.

In one aspect, the total amount of catalyst metal atoms present in the polyester and/or polyester composition of the invention may be 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 of the present invention, the polyesters and/or polyester compositions of the invention may have from-10 to less than 20, or from-10 to less than 18, or from-10 to less than 15, or from-10 to less than 14, or from-10 to less than 10, or from 1 to less than 20, or from 1 to less than 18, or from 5 to less than 20, or from 5 to less than 18, or from 8 to less than 20, or from 8 to less than 18, or from 8 to less than 15, or from-3 to 10, or from-5 to 5, or from-5 to 4, or from-5 to 3, or from 1 to 20, or from 1 to 18, or from 1 to 15, or from 1 to 14, or from 1 to less than 10, or from 1 to 9, or from 1 to 8, from 1 to 7, or from 1 to 6 or a b-value of 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 CIE (international commission on illumination) L x a x b x color system.

In one aspect, 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 CIE (international commission on illumination) L x a b color system.

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 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%, 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%; and

in one aspect, the melt viscosity of the polyesters and/or polyester compositions of the invention can be 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, or less than 3,000 poise, as measured on a rotary melt rheometer at 290 ℃ 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 1 ft-lbs/inch, or at least 2 ft-lbs/inch, or at least 3 ft-lbs/inch, or at least 7.5 ft-lbs/inch, or at least 10 ft-lbs/inch, in a 1/8 inch thick bar with a 10 mil cut according to ASTMD256 at 23 ℃.

In one aspect, the polyesters and/or polyester compositions of the invention may comprise TMCD residues that are a combination comprising: more than 50 mole% of cis-TMCD and less than 50 mole% of trans-TMCD, or more than 55 mole% of cis-TMCD and less than 45 mole% of trans-TMCD, or 50 to 70 mole% of cis-TMCD and 50 to 30 mole% of trans-TMCD, or 60 to 70 mole% of cis-TMCD and 30 to 40 mole% of trans-TMCD, or more than 70 mole% of cis-TMCD and less than 30 mole% of trans-TMCD, or more than 75 mole% of cis-TMCD and less than 25 mole% of trans-TMCD, or more than 80 mole% of cis-TMCD and less than 20 mole% of trans-TMCD, or more than 90 mole% of cis-TMCD and less than 10 mole% of trans-TMCD, or more than 95 mole% of cis-TMCD and less than 5 mole% of trans-TMCD, wherein the total mole percentage of cis-and trans-TMCD is equal to 100 mole%.

In one aspect, the polyester composition of the present invention may comprise a blend of at least one polyester of the present invention and at least one polymer selected from at least one of the following: other polyesters, such as polyethylene terephthalate (PET), including recycled PET, poly (cyclohexylene) 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/sulfone, poly (ester carbonate), polycarbonate, polysulfone ether, and poly (ether-ketone).

In one aspect, the final polyester composition of the invention can be blended with recycled poly (ethylene terephthalate) (rPET).

In one aspect, the polyesters and/or polyester compositions of the invention can comprise at least one polycarbonate, or be polycarbonate-free, or carbonate-free.

In one aspect, the polyesters and/or polyester compositions of the invention may be free of cross-linking agents.

In one aspect, the polyesters and/or polyester compositions of the invention can comprise residues of at least one phosphorus compound.

In one aspect, the polyesters and/or polyester compositions of the invention may comprise residues of phosphoric acid, phosphorous acid, phosphonic 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 polyesters and/or polyester compositions of the present invention can comprise substituted or unsubstituted alkyl phosphates, substituted or unsubstituted aryl phosphates, substituted or unsubstituted mixed alkyl aryl phosphates, bisphosphates, salts of phosphoric acid, phosphine oxides and mixed aryl alkyl phosphites, reaction products thereof, and/or combinations thereof.

In one aspect, the polyesters and/or polyester compositions of the present invention can comprise 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 combinations thereof.

In one aspect, the polyesters and/or polyester compositions of the invention may not contain phosphorus compounds.

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

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 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 of 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 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/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 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/or 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, less than 10ppm, or less than 5ppm, or less than 2ppm, or 0ppm of any of the lithium 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 may comprise any of the following: no tin atoms, and/or no manganese atoms, and/or no magnesium atoms, and/or no germanium atoms, and/or no antimony atoms, no cobalt atoms, and/or no cadmium atoms, and/or no sodium atoms, and/or no gallium atoms, and any combination of these or all of these may be excluded.

In one aspect, the polyesters and/or polyester compositions of the invention may comprise any of the following: no tin atoms, no manganese atoms, no magnesium atoms, no germanium atoms, no antimony atoms, no cobalt atoms, and/or no calcium atoms, and any combination of these or all of these may be excluded.

In one aspect, the polyesters and/or polyester compositions of the invention may comprise any of the following: no tin atoms, no manganese atoms, no lithium atoms, no germanium atoms, and no cobalt atoms, and any combination of these may be excluded or all of these 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 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 sodium atoms and/or potassium atoms.

In one aspect, a process for preparing any polyester and/or polyester composition is provided comprising the steps of:

(I) Heating a mixture at least one temperature selected from 150 ℃ to 300 ℃ at least one pressure selected from the range of 0psig to 75psig, 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) 10-50 mole% TMCD residues; and

(ii) 50 to 90 mole% of modified diol 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 0.02 torr absolute;

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

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

wherein the inherent viscosity of the final polyester is from 0.35 to 1.2dL/g as determined at 25℃in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.25g/50 ml; and

Wherein the Tg of the final polyester is from 85℃to 200 ℃.

In one aspect, the above process is provided, 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 extent of TMCD binding or conversion in the final polymer may be greater than 55mol%; or greater than 50 mole%; or greater than 45 mole%; or 45mol% or more; greater than 40mol%; or greater than 35 mole%; or greater than 30 mole%.

In one aspect, the process for preparing the polyesters of the invention can include batch or continuous processes.

In one aspect, the process for preparing the polyesters of the invention comprises a continuous process.

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

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

(a) A dicarboxylic acid component comprising:

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

(ii) About 0 to about 10 mole% of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and

(b) A glycol component comprising:

(i) About 10 to about 50 mole% TMCD residues; and

(ii) About 50 to about 90 mole% of at least one modified diol residue;

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 50mol%, and optionally, such that in the reaction TMCD is converted by at least 30% and a final polymer having about 10 to 50mol% TMCD residues is obtained;

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

(i) At least two catalysts comprising Li and Ga; and (ii) and optionally 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 the dicarboxylic acid component of the final polyester is 100 mole%; and is also provided with

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

wherein the inherent viscosity of the polyester is from 0.35 to 0.80dL/g as determined at 25℃in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.25g/50 ml; and wherein the polyester has an L color value of 75 or greater, or greater than 75 as determined by an L x a x b x color system as measured according to astm d6290-98 and astm e308-99 performed on polymer particles milled to pass a 1mm screen. In certain aspects, the catalyst is free of tin. In one aspect, the polyesters and/or polyester compositions of the invention may comprise at least one phosphate ester, whether present as a heat stabilizer or not.

In one aspect, the polyesters and/or polyester compositions of the invention may be free of branching agents or, alternatively, at least one branching agent may be added prior to or during polymerization of the polyester.

In one aspect, the polyesters and/or polyester compositions of the invention can comprise at least one branching agent, regardless of the method or sequence in which the branching agent is added.

In one aspect, certain polyesters and/or polyester compositions of the invention may be amorphous or semi-crystalline. In one aspect, certain polyesters and/or polyester compositions of the invention may have relatively low crystallinity. Thus, certain polyesters and/or polyester compositions of the invention can have a substantially amorphous morphology, meaning that the polyester comprises 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 used in the present invention may comprise at least one aryl phosphate.

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

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

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

In one aspect, the at least one phosphorus compound used 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 MerpolA. 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 preparing 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 dosverphoss-9228 (DoverChemicals, CAS # 154862-43-8).

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

In one aspect, the pressure used in step (I) of any of the methods of the present invention may consist of at least one pressure selected from the group consisting of 0psig to 100 psig. In one aspect, the pressure used in step (I) of any of the methods of the present invention may consist 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 may consist 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 may consist of a 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 present invention may consist of a 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 present invention may consist of a 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 present invention may consist of a 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 present invention may consist of at least one 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 present invention may consist of a 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 present invention may consist of at least one pressure selected from the group consisting of 5 torr to 0.1 torr absolute; in one aspect, the pressure used in step (II) of any of the methods of the present invention may consist 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 preparing the polyesters and/or polyester compositions of the invention, the heating time of step (II) may be from 1 to 5 hours. In any of the process embodiments for preparing the polyesters and/or polyester compositions of the invention, the heating time of step (II) may be from 1 to 4 hours. In any of the process embodiments for preparing the polyesters and/or polyester compositions of the invention, the heating time of step (II) may be from 1 to 3 hours. In any of the process embodiments for preparing the polyesters and/or polyester compositions of the invention, the heating time of step (II) may be from 1.5 to 3 hours. In any of the process embodiments for preparing the polyesters and/or polyester compositions of the invention, the heating time of step (II) may be from 1 to 2 hours.

In either method of the invention, the b-color of any given polyester of the invention may remain stable at a particular inherent viscosity when additional zinc and/or additional titanium is added, or may decrease by less than 20%, less than 15%, less than 10%, less than 5% as determined by the CIE (international commission on illumination) L-a-b-color system.

The weight (ppm) of zinc atoms and titanium atoms present in the final polyester can be measured, for example, in any of the above weight (ppm) 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 components, sheets, and/or fibers.

In one aspect, the polyesters and/or polyester compositions of the present invention can be used in various types of films and/or sheets, including but not limited to 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.

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

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

In one aspect, any polyesters and/or polyester compositions described herein are also considered to be within the scope of the invention, regardless of which method is used to make them, as well as any products made therefrom.

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

It is believed that certain polyesters and/or polyester compositions of the present invention formed from terephthalic acid, esters and/or mixtures thereof, TMCD, and at least one modified diol, and further comprising certain Ti and Zn catalysts and optionally stabilizers, reaction products thereof, and mixtures thereof, may have a unique combination of two or more, or three or more of the following properties: good notched Izod impact strength, good inherent viscosity, good glass transition temperature (Tg), good flexural modulus, good transparency, good color, good dishwasher durability, good TMCD bonding and good/improved melt and/or thermal stability.

In one embodiment, copolyesters containing 2, 4-tetramethyl-l, 3-cyclobutanediol and at least one modified diol in a composition range 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, TMCD and at least one modified diol, catalyzed by certain catalyst types and/or amounts that provide improved characteristics (as discussed herein), and in certain embodiments, catalyzed by at least one titanium catalyst and at least one zinc catalyst, resulting in good TMCD incorporation, improved color (higher brightness and/or less yellow) and reactivity to achieve a desired Inherent Viscosity (IV) within the compositional ranges described herein.

When titanium is added to the polyester and/or polyester composition and/or process for making a polyester of the present invention, it is added to the process for making 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 polyesters and/or polyester compositions and/or processes for making polyesters of the invention, it is added to the process for making polyesters in the form of 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 can be measured in terms of zinc atoms present in the final polyester, for example, in ppm by weight.

When phosphorus is added to the polyesters and/or polyester compositions and/or processes for making polyesters of the invention, it is added to the process for making polyesters in the form of a phosphorus compound. In one aspect, the phosphorus compound may comprise at least one phosphate ester. The amount of phosphorus compound [ e.g. phosphate ] 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, for example 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, such as branching agents. Typically, the difunctional carboxylic acid may be a dicarboxylic acid and the difunctional hydroxyl compound may be a diol, such as a diol and a diol. The term "glycol" as used herein includes, but is not limited to, glycols, 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 from the corresponding monomer by polycondensation and/or esterification reactions. As used herein, the term "repeat unit" 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, as used herein, the term "diacid" includes polyfunctional acids, such as branching agents. Thus, the term "dicarboxylic acid" as used herein includes 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 produce a polyester. As used herein, the term "terephthalic acid" is intended to include terephthalic acid itself and its residues as well as any derivatives of terephthalic acid, 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 that react in substantially equal proportions and are incorporated into the polyester polymer as their corresponding residues. Thus, the polyesters of the invention may contain substantially equal molar amounts 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 of the 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% TMCD based on total glycol residues means that the polyester contains 25 mole% TMCD residues of the total 100 mole% glycol residues. Thus, there are 25 moles of TMCD residues per 100 moles.

In one embodiment, a copolyester composition is provided comprising a copolyester, optionally having good color, good TMCD incorporation and/or reactivity to achieve a desired inherent viscosity over the entire composition range, the composition comprising: (a) a dicarboxylic acid component comprising: : (i) 70-100 mole% 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: (i) 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) residues and at least one modified diol residue; or (ii) 10 to 50 mole%, or 10 to 60 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) residues and 50 to 90 mole% or 40 to 90 mole% modified diol residues; or (iii) 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; or (iv) about 30 to about 50 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) residues; about 50 to about 70 mole% Ethylene Glycol (EG) residues, and optionally, about 0.01 to about 5 mole% diethylene glycol residues; or (v) 10-50 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) residues and 50-90 mole% diethylene glycol (DEG) residues; or (vi) 10 to 60 mole% or 20 to 60 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) residues and 40 to 90 mole% or 40 to 80 mole% neopentyl glycol (NPG) 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, for the above diol components (b) (i) and (b) (ii), the modified diol may comprise 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, p-xylene glycol, neopentyl glycol, isosorbide, polytetramethylene glycol, or mixtures thereof.

In one embodiment, for diol component (b) (iii) above, the modifying diol may comprise diethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, ethylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, p-xylene glycol, neopentyl glycol, isosorbide, polytetramethylene glycol, or mixtures thereof.

In one embodiment, for diol component (b) (iv), the modifying diol may comprise at least one of diethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, 1, 4-cyclohexanedimethanol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, p-xylene glycol, neopentyl glycol, isosorbide, polytetramethylene glycol, or mixtures thereof.

In one embodiment, for diol component (b) (v), the modified diol may comprise at least one of 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, p-xylene glycol, neopentyl glycol, isosorbide, polytetramethylene glycol, or mixtures thereof.

In one embodiment, for diol component (b) (vi), the modified diol may comprise at least one of 1, 2-propanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, 1, 4-cyclohexanedimethanol, ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, p-xylene glycol, isosorbide, polytetramethylene glycol, or mixtures thereof.

In one aspect, the polyesters and/or polyester compositions of the invention can comprise TMCD residues in an amount of about 10 to about 50 mole%, or about 10 to about 45 mole%, or about 10 to about 40 mole%, or about 10 to about 35 mole%, or about 15 to about 45 mole%, or about 15 to about 40 mole%, or about 15 to about 35 mole%, or about 20 to about 45 mole%, or about 20 to about 40 mole%, or about 20 to about 35 mole%, or about 25 to about 40 mole%, or about 25 to about 45 mole%, or about 25 to about 40 mole%, or about 30 to about 40 mole%, based on the total mole percent of glycol residues in the final polyester, equal to 100 mole%. Other modifying diols may include the remaining mole percent.

In one embodiment, the polyesters and/or polyester compositions of the invention may comprise from about 45 to about 90mol%, or from about 50 to about 90mol%, or from about 55 to about 90mol%, or from about 60 to about 90mol%, or from about 45 to about 85mol%, or from about 50 to about 85mol%, or from about 55 to about 85mol%, or from about 60 to about 85mol%, or from about 45 to about 80mol%, or from about 50 to about 80mol%, or from about 55 to about 80mol%, or from about 60 to about 80mol%, or from about 65 to about 80mol%, or from about 70 to about 80mol%, or from about 45 to about 75mol%, or from about 50 to about 75mol%, or from about 55 to about 75mol%, or from about 60 to about 75mol%, or from about 45 to about 70mol%, or from about 55 to about 70mol%, or from about 60 to about 70mol%, or from about 50 to about 65mol%, or from about 55 to about 65mol%, based on the total mole% of glycol residues in the final polyester is equal to 100%.

Other modifying diols may include the remaining mole percent.

In one embodiment, the polyesters and/or polyester compositions of the invention may be free of CHDM residues, or contain no more than 10 mole%, or no more than 5 mole% CHDM residues, based on the total mole% of glycol residues in the final polyester, equal to 100 mole%.

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

In one embodiment, 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.

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

In one embodiment, the polyesters and/or polyester compositions of the invention may comprise from about 60 to about 90 mole%, alternatively from about 65 to about 90 mole%, alternatively from about 70 to about 90 mole% of EG residues.

In one embodiment, the polyesters and/or polyester compositions of the invention may contain less than 70 mole%, or less than 60 mole%, or less than 50 mole%, or less than 40 mole%, or less than 30 mole%, or less than 20 mole%, or less than 10 mole% of EG residues.

In one embodiment, the polyesters and/or polyester compositions of the invention may comprise EG residues without 1, 4-cyclohexanedimethanol residues, or less than 10 mole% CHDM, wherein the remaining modified diols comprise at least one of diethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 2-methyl-1, 3-propanediol, 1, 5-pentanediol, 1, 6-hexanediol, p-xylene glycol, neopentyl glycol, isosorbide, polytetramethylene glycol, or mixtures thereof.

In one embodiment, the polyesters and/or polyester compositions of the invention may comprise the following ranges: 20-45 mole% TMCD residues, 20-45 mole% CHDM residues, and 10-60 mole% EG residues; or 20-40 mole% TMCD residues, 20-40 mole% CHDM residues, and 20-60 mole% EG residues; or 20-35 mole% TMCD residues, 20-35 mole% CHDM residues, and 30-60 mole% EG residues; or 25 to 45 mole% TMCD residues, or 25 to 45 mole% CHDM residues, and 10 to 50 mole% EG residues, based on the total mole% glycol residues in the final polyester, equal to 100 mole%.

In one embodiment, the glycol component used in the polyesters and/or polyester compositions of the invention includes, but is not limited to, at least one of the following combinations of ranges: about 10 to about 27 mole% TMCD and about 90 to about 73 mole% EG; about 15 to about 26 mole% TMCD and about 85 to about 74 mole% EG; about 18 to about 26 mole% TMCD and about 82 to about 77 mole% EG; about 20 to about 25 mole% TMCD and about 80 to about 75 mole% EG; about 21 to about 24 mole% TMCD and about 79 to about 76 mole% EG; or about 22 to about 24 mole% TMCD and about 78 to about 76 mole% EG. In this embodiment, the DEG may be present, either added or formed in situ. If formed in situ, DEG may be present in an amount of up to 2 mol%.

In one embodiment, the polyesters and/or polyester compositions of the invention may comprise EG residues without 1, 4-cyclohexanedimethanol residues, or less than 10 mole% CHDM, wherein the remaining modified diols comprise at least one of diethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 2-methyl-1, 3-propanediol, 1, 5-pentanediol, 1, 6-hexanediol, para-xylene glycol, neopentyl glycol, isosorbide, polytetramethylene glycol, or mixtures thereof.

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 a mixture of any two or more thereof.

In one embodiment, the polyesters and/or polyester compositions of the invention may not comprise hexanediol, and/or do not comprise propylene glycol and/or do not comprise butylene glycol.

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

In one embodiment, the polyesters and/or polyester compositions of the invention can comprise residues of diethylene glycol in an amount of from about 60 to about 90 mole%, or from about 60 to about 85 mole%, or from about 60 to about 80 mole%, or from about 60 to about 75 mole%, or from about 50 to about 90 mole%, or from about 50 to about 85 mole%.

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

In one embodiment, the polyesters and/or polyester compositions of the invention may include aspects in which no NPG is present, or in which NPG is present in an amount of less than 90 mole%, or less than 80 mole%, or less than 70 mole%, or less than 60 mole%, or less than 50 mole%, or less than 40 mole%, or less than 30 mole%, or less than 20 mole%, or less than 10 mole%, based on the total mole percent of diol residues in the final polyester equal to 100 mole%.

In one embodiment, the polyesters and/or polyester compositions of the invention may comprise residues of neopentyl glycol in an amount of from about 40 to about 90mol%, or from about 40 to about 85mol%, or from about 40 to about 80mol%, or from about 40 to about 75mol%, or from about 40 to about 70mol%, or from about 45 to about 90mol%, or from about 45 to about 85mol%, or from about 45 to about 80mol%, or from about 45 to about 75mol%, or from about 45 to about 70mol%, or from about 50 to about 90mol%, or from about 50 to about 85mol%, or from about 50 to about 80mol%, or from about 50 to about 75mol%, or from about 50 to about 70mol%, or from about 55 to about 90mol%, or from about 55 to about 85mol%, or from about 55 to about 75mol%, or from about 55 to about 70mol%, or from about 60 to about 90mol%, or from about 60 to about 85mol%, or from about 60 to about 80mol%, or from about 60 to about 75mol%, or from about 60 to about 70mol%, or from about 70%, or from about 50 to about 75mol%, or from about 50 to about 85mol%, or from about 50 to about 70mol%, or from about 55 to about 90mol%, or from about 55 to about 80mol%, or from about 55 to about 75mol%, or from about 30% or 30 mol%.

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

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 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% tetramethylene glycol.

The molar ratio of cis/trans TMCD may be different for the desired polyester than the respective pure forms and combinations thereof. In certain embodiments, the mole percent of cis and/or trans 2, 4-tetramethyl-1, 3-cyclobutanediol residues can be greater than 50 mole% cis-TMCD and less than 50 mole% trans-TMCD; or greater than 55 mole% cis-TMCD and less than 45 mole% trans-TMCD; or 50 to 70mol% cis-TMCD and 50 to 30mol% trans-TMCD; or 60 to 70mol% cis-TMCD and 30 to 40mol% trans-TMCD; or greater than 70 mole% cis-TMCD and less than 30 mole% trans-TMCD; 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 90 mole% cis-TMCD and less than 10 mole% trans-TMCD; or greater than 95 mole% cis-TMCD and less than 5 mole% trans-TMCD; wherein the total mole percent of cis-and trans-TMCD is equal to 100 mole percent. In other embodiments, the molar ratio of cis/trans-TMCD may vary from 50/50 to 0/100, for example between 40/60 and 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 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 certain embodiments, terephthalic acid or an ester thereof, such as dimethyl terephthalate, or a mixture of terephthalic acid residues and esters thereof, may comprise part or all of the dicarboxylic acid component used to form the polyesters and/or polyester compositions of the invention. In certain embodiments, the terephthalic acid residues may comprise part or all of the dicarboxylic acid component used to form the polyesters and/or polyester compositions of the present invention. In certain embodiments, higher amounts of terephthalic acid can be used to produce polyesters of higher impact strength. 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 of the invention. In certain embodiments, the range is 70 to 100mol%; or 80 to 100mol%; or 90 to 100mol%; or 99 to 100mol%; or 100mol% terephthalic acid and/or dimethyl terephthalate and/or mixtures thereof.

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

In addition to terephthalic acid or an ester thereof, such as dimethyl terephthalate, 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 0.01 to 5 mole%, or from 0.1 to 5 mole%, or from 1 or 5, or from 0.01 to 1 mole%, or from 0.1 to 1 mole%, or from 5 to 10 mole%, or 0 mole% of one or more modified aromatic dicarboxylic acids. Another embodiment contains 0 mole% of the modified aromatic dicarboxylic acid. Thus, if present, it is contemplated that the amount of the one or more modified aromatic dicarboxylic acids may be within the range of any of these aforementioned end points, 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. Examples of modified aromatic dicarboxylic acids useful in the present invention include, but are not limited to, isophthalic acid, 4 '-biphenyl dicarboxylic acid, 1,4-, 1,5-, 2,6-, 2, 7-naphthalene dicarboxylic 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 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 1 or 10 mole%, or from 5 to 10 mole%, or 0 mole% of one or more aliphatic dicarboxylic acids containing 2 to 16 carbon atoms, such as cyclohexane dicarboxylic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and dodecanedioic acid. Certain embodiments may also comprise less than 30mol%, or less than 20mol%, or less than 10mol%, or less than 5mol%, or from 0 to 30mol%, or from 0 to 20mol%, or from 0 to 10mol%, or from 0 to 5mol%, or from 0 to 1mol%, or from 0.01 to 10mol%, or from 0.1 to 10mol%, or 1 or 10mol%, or from 5 to 10mol%, or 0mol% of one or more modified aliphatic dicarboxylic acids. Yet another embodiment contains 0 mole% of the modified aliphatic dicarboxylic acid. The total mol% of the dicarboxylic acid component is 100mol%. In one embodiment, adipic acid and/or glutaric acid is provided in the modified aliphatic dicarboxylic acid component of the present invention.

Esters of terephthalic acid and other modified dicarboxylic acids or their corresponding esters and/or salts may be used in place of the dicarboxylic acids. Suitable examples of dicarboxylic acid esters include, but are not limited to, dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, and diphenyl esters. In one embodiment, the ester is selected from 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 the 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 is equal to 100 mole percent.

In one embodiment, the polyesters and/or polyester compositions of the invention may contain 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% CHDA based on the total mole percent of diacid residues in the final polyester equaling 100 mole%.

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

(1) At least one polyester comprising:

(a) A dicarboxylic acid component comprising:

(b) A glycol component comprising:

(i) About 10 to about 50 mole% TMCD residues;

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

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

wherein the total mole% of glycol 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 0 to 30ppm, or 0 to 20ppm, or 0 to 10ppm, or 0ppm of tin atoms;

wherein the inherent viscosity is from 0.35 to 0.75dL/g, or from 0.40 to 0.75dL/g, or from 0.45 to 0.70, as determined at 25 ℃ in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5g/100 ml; 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 CIE (international commission on illumination) L x a x b x color system. 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.

(1) At least one polyester comprising:

(a) A dicarboxylic acid component comprising:

(b) A glycol component comprising:

(i) About 10 to about 50 mole% TMCD residues;

(ii) About 50 to about 90 mole% of EG residues;

wherein the inherent viscosity is from 0.35 to 1.0dL/g as determined at 25℃in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5g/100 ml; and has a b-x value of less than 25, or less than 20, or less than 18, 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; and L values of 60 to 95, or 60 to 90, or 60 to 85, or 65 to 80, or 60 to 75, or 60 to 70, as determined by the CIE (international commission on illumination) L x a x b x color system.

(1) At least one polyester comprising:

(a) A dicarboxylic acid component comprising:

(b) A glycol component comprising:

(i) About 10 to about 50 mole% TMCD residues;

(ii) About 50 to about 90 mole% neopentyl glycol residues;

wherein the inherent viscosity is from 0.25 to 0.75dL/g, or from 0.25 to 0.70dL/g, or from 0.25 to 0.60dL/g, or from 0.25 to 0.55dL/g, or from 0.25 to 0.50dL/g, or from 0.30 to 0.75dL/g, or from 0.30 to 0.70dL/g, or from 0.30 to 0.60dL/g, or from 0.30 to 0.55dL/g, or from 0.30 to 0.50dL/g, or from 0.35 to 0.75dL/g, or from 0.35 to 0.70dL/g, or from 0.35 to 0.65dL/g, or from 0.35 to 0.60dL/g, or from 0.35 to 0.55dL/g or 0.35 to 0.50dL/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 0.40 to 0.55dL/g, or 0.40 to 0.50dL/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 0.45 to 0.55dL/g, or 0.50 to 0.75dL/g, or 0.50 to 0.70dL/g, or 0.50 to 0.65dL/g, or 0.50 to 0.60dL/g, as determined at 25℃in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5g/100 ml; and having a b-x value of 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, or less than 7, or less than 6, or less than 5, or 1 to 15, or 1 to 10, or 1 to 9, 1 to 8, or 1 to 7, or 1 to 6, or 1 to 5, or 2 to 9, 2 to 8, or 2 to 7, or 2 to 6, or 2 to 5, or 3 to 9, 3 to 8, or 3 to 7, or 3 to 6; and L values of 75 to 100, or 80 to 100, or 75 to 95, or 80 to 95, as determined by the CIE (international commission on illumination) L x a x b x color system.

(1) At least one polyester comprising:

(a) A dicarboxylic acid component comprising:

(b) A glycol component comprising:

(i) About 10 to about 50 mole% TMCD residues;

(ii) About 50 to about 90 mole% diethylene glycol residues;

wherein the inherent viscosity is from 0.55 to 0.85dL/g, or from 0.60 to 0.85dL/g, or from 0.55 to 0.80dL/g, or from 0.60 to 0.80dL/g, or from 0.55 to 0.78dL/g, or from 0.60 to 0.78dL/g, or from 0.55 to 0.75dL/g, or from 0.60 to 0.75dL/g, as determined at 25 ℃ in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5g/100 ml; and having a b-x value of 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, or 1 to 15, or 1 to 14, or 1 to 13, or 1 to 12, or 1 to 10, 1 to 5; and L values of 70 to 95, or 75 to 90, or 70 to 85, or 75 to 85, as determined by the CIE (international commission on illumination) L x a x b x color system. In some embodiments, a may have a value less than 0, or less than-1.0, or less than-1.5.

In one aspect, for any of the polyesters and/or polyester compositions of the invention, the inherent 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 0.75dL/g, or from 0.50 to 0.70dL/g, or from 0.50 to 0.60dL/g, or from 0.60dL/g, as determined at 25℃in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5g/100 ml.

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

In some embodiments, the polyesters 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%, based on the total mole% of diol or diacid residues; each is one or more residues of a branching monomer (also referred to herein as a branching agent) having 3 or more carboxyl substituents, hydroxyl substituents, or a combination thereof. In certain embodiments, the branching monomer or agent may be added before and/or during and/or after polymerization of the polyester. In embodiments, the polyesters used 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 the group consisting of: trimellitic anhydride, pyromellitic dianhydride, glycerol, sorbitol, 1,2, 6-hexanetriol, pentaerythritol, trimethylolethane and/or trimesic acid. The branching monomers may be added to the polyester reaction mixture or blended with the polyester in the form of a concentrate, such as described in U.S. Pat. nos. 5,654,347 and 5,696,176, the disclosures of which are incorporated herein by reference for branching monomers.

The polyesters 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 novolacs 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, such as injection molding or extrusion. The amount of chain extender used may vary depending on the particular monomer composition used and the physical properties desired, but is generally from about 0.1 to about 10 weight percent, for example from about 0.1 to about 5 weight percent, based on the total weight of the polyester.

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

Examples of the phosphorus compound usable in the present invention may include tributyl phosphate, triethyl phosphate, tributoxyethyl phosphate, t-butylbenzene diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, ethyldimethyl phosphate, isodecyl diphenyl phosphate, trilauryl phosphate, triphenyl phosphate, tricresyl phosphate, tri (xylene) phosphate, t-butylphenyl phosphate, resorcinol bis (diphenyl phosphate), tribenzyl phosphate, phenylethyl phosphate, trimethylthiophosphate, phenylethylthiophosphate, methylphosphonate, dimethyl methylphosphonate, diethyl pentylphonate, dilauryl methylphosphonate, diphenyl methylphosphonate, dibenzyl methylphosphonate, diphenyl methylphosphonate, dimethyl tolylphosphonate, dimethyl methylthiothiophosphonate, diphenyl phosphinate, methyl diphenylphosphinate, methyl tolylphosphinate trimethylphosphinic oxide, triphenylphosphine oxide, 4-methyldiphenylphosphinic oxide, triethyl phosphite, tributyl phosphite, triphenyl phosphite, tribenzyl phosphite, phenyl diethyl phosphite, phenyl dimethyl phosphite, benzyl dimethyl phosphite, diphenyl methylphosphonate, methyl benzylidene phosphonate diphenyl phosphinate, methyl phosphinate, diphenyl phosphinate methyl phosphinate, phenyl phosphinate, diphenyl phosphinate, phenyl phosphinate, methyl phosphinate, phenyl phosphinate, triphenyl phosphonate, methyl phosphinate, triphenylphosphine, phosphinate, methylphosphine, and phosphinate. In one embodiment, triphenylphosphine oxide is excluded as a heat stabilizer in the process for preparing the polyesters of the invention and/or in the polyester compositions of the 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, a branched alkyl group, a substituted alkyl group, an alkyl ether, a substituted alkyl ether, an alkyl-aryl group, an alkyl-substituted aryl group, a substituted aryl group, and combinations 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 esters 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, alkyl phosphates may include mono-, di-and trialkyl phosphates; aryl phosphates include one or more of mono-, di-and triaryl phosphates; and alkyl and/or aryl phosphates also include, but are not limited to, mixed alkylaryl 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, phosphinic acid, phosphonic acid, or alkyl esters, aryl esters, or mixed alkylaryl or partial esters of phosphinic acid. 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 alkylaryl phosphates, bisphosphites, phosphates, phosphine oxides, and mixed arylalkyl phosphites, reaction products thereof, and combinations thereof. Phosphate esters include esters in which the phosphoric acid is fully 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 alkylaryl phosphates, reaction products thereof, and combinations thereof. Phosphate esters include esters in which the phosphoric acid is fully 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 combinations thereof.

In certain embodiments, the phosphates useful in the present invention are those wherein the groups on the phosphate comprise alkyl, alkoxy-alkyl, phenyl or substituted phenyl. These phosphates are generally referred to herein as alkyl and/or aryl phosphates. Some preferred embodiments include trialkyl phosphates, triaryl phosphates, alkyl diaryl phosphates, dialkyl aryl phosphates, and combinations of these phosphates, wherein alkyl groups are preferably those containing 2-12 carbon atoms, and 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 of alkyl-aryl and substituted alkyl-aryl 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 are substituted with hydrogen at any carbon position on the benzene ring. Preferred aryl groups include phenyl or substituted phenyl wherein groups such as alkyl, branched alkyl, aryl, hydroxy, and the like are substituted with hydrogen at any 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 combinations thereof, including in particular, the combination of tributyl phosphate and tricresyl phosphate, and the combination of isocetyl diphenyl phosphate and 2-ethylhexyl diphenyl phosphate.

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

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

In one embodiment, at least one phosphorus compound for use 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 in the present invention as heat stabilizers and/or color stabilizers 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 in the present invention as heat stabilizers and/or color stabilizers 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 used as heat stabilizers and/or color stabilizers in the present invention may include, but are not limited to, at least one of the following: triaryl phosphates and mixed alkyl aryl 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, 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 commercially available from Stepan Chemical Co and/or E.I.DuPont de Nemours & Co. The CAS registry number for Merpol A is identified as 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 preparing 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 preparing any of the polyester compositions and/or polyesters can comprise at least one phosphine oxide.

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

The term "heat stabilizer" is intended to include the reaction products thereof. The term "reaction product" as used in connection with the heat stabilizer of the present invention refers to any product of a polycondensation or esterification reaction between the heat stabilizer and any monomer used to make the polyester, as well as between the 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 a heat stabilizer, but as a color stabilizer. 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: 10-200ppm 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, based on the total weight of the 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 contains at least one titanium compound for the esterification reaction. In one embodiment, the catalyst system contains at least one residue of a titanium compound 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 the following: titanium carbonate, titanium acetate, titanium benzoate, titanium succinate, titanium isopropoxide, titanium methoxide, titanium oxalate, titanium nitrate, titanium ethoxide, titanium hydroxide, titanium hydride, titanium alkoxide, titanium alkyl hydride, titanium zinc hydride, titanium borohydride, titanium oxide, titanium acetylacetonate, titanium triisopropoxide chloride, titanium bis (acetylacetonate), titanium n-butoxide, titanium t-butoxide.

In one embodiment, the catalyst combination 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 combination 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 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 naphthalate, 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), isopropyl alcohol zinc, 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 naphthalate and/or zinc carbonate and/or residues thereof are absent.

In one embodiment, the polyesters and/or polyester compositions of the invention may contain titanium atoms in an amount of: 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.

In one embodiment, the polyesters and/or polyester compositions of the invention may contain zinc atoms in an amount of: 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 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 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 embodiment, the polyesters and/or polyester compositions of the invention, wherein the ratio of titanium atoms to zinc atoms is 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 0.70-1.2 to 1:4, or 0.60-1:2 to 1:4, in ppm relative to the mass of the final polyester: 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 1:4 to 4:1, or 0.80-1:3 to 3:1, or 0.80-1:2 to 2:1, or 0.80-1.2 to 1:4.

In one embodiment, the ratio of titanium atoms to zinc atoms in the polyester and/or polyester composition of the invention is 1:5 to 5:1, 1:4 to 4:1, or 1:3 to 3:1, or 1:2 to 2:1 in ppm relative to the mass of the final polyester produced.

In one embodiment, the total amount of catalyst metal atoms present in the polyester and/or polyester composition of the present invention may be 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 produced.

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

In one embodiment, suitable catalysts for use in the process of the present invention to prepare the polyesters and/or polyester compositions of 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 any tin atom.

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 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 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 of any tin atom and/or germanium atom.

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 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 tin atom and/or manganese atom.

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 tin atom and/or aluminum atom.

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 lithium and/or aluminum atom.

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 lithium atom and/or aluminum atom.

In one embodiment, the polyesters and/or polyester compositions of the invention may comprise any of the following: no tin atoms, and/or no manganese atoms, and/or no magnesium atoms, and/or no germanium atoms, and/or no antimony atoms, no cobalt atoms, and/or no cadmium atoms, and/or no sodium atoms, and/or no gallium atoms, and any combination of these or all of these may be excluded.

In one embodiment, the polyesters and/or polyester compositions of the invention may comprise any of the following: no tin atoms, no manganese atoms, no magnesium atoms, no germanium atoms, no antimony atoms, no cobalt atoms, and/or no calcium atoms, and any combination of these or all of these may be excluded.

In one embodiment, the polyesters and/or polyester compositions of the invention may comprise any of the following: no tin atoms, no manganese atoms, no lithium atoms, no germanium atoms, and no cobalt atoms, and any combination of these may be excluded or all of these 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 one embodiment, the polyesters and/or polyester compositions of the invention may have a Tg for TMCD-EG polyesters of 85-130 ℃, or 100-125 ℃, or 100-120 ℃, and the Tg may be one of the following ranges; 85 to 100 ℃;86-99 ℃;87 to 98 ℃;88-97 ℃;89-96 ℃;90-95 ℃; 91-95 ℃; the glass transition temperature (Tg) of the polyester was measured at a scan rate of 20℃per minute using a TADSC2920 from a thermal analyzer at 92-94 ℃.

In one embodiment, the polyesters and/or polyester compositions of the invention may comprise polyesters having the following degree of polymerization: 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.

Unless otherwise indicated, it is contemplated that the compositions useful in the present invention may have at least one inherent viscosity range as described herein and at least one monomer range of the compositions described herein. It is also contemplated that the compositions used in the present invention may have at least one Tg range as described herein and at least one monomer range of the compositions described herein, unless otherwise indicated. It is also contemplated that the compositions used in the present invention may have at least one inherent viscosity range described herein, at least one Tg range described herein, and at least one monomer range of the compositions described herein, unless otherwise indicated.

In an embodiment of the present invention, the polyester may comprise: a glycol component comprising 15 to 27 mole% TMCD and 73 to 85 mole% EG, an inherent viscosity of 0.60 to 0.70dL/g and a Tg of 90 to 96 ℃; or a glycol component comprising 20-25 mole% TMCD and 75-80 mole% EG, an inherent viscosity of 0.63-0.67dL/g and a Tg of 92-94 ℃.

The polyester fraction of the polyesters and/or polyester compositions of the invention can be prepared by methods known in the literature, for example by means of a process in homogeneous solution, by means of transesterification in the melt and by means of a two-phase interfacial process. 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. See U.S. Pat. No. 3,772,405 for a process for producing polyesters, the disclosure of such a process being incorporated herein by reference.

Polyesters can generally be prepared by the following methods: the dicarboxylic acid or ester is condensed with the diol in an inert atmosphere at elevated temperatures during the condensation process, up to a temperature of about 225 ° -310 ℃ and at low pressure in the latter part of the condensation, as described in further detail in us patent 2,720,507 incorporated herein by reference, in the presence of a titanium catalyst and zinc (and optionally other catalysts), as described herein.

In another embodiment, the present invention relates to a process for preparing the copolyester of the present invention. In one embodiment, the process involves preparing a copolyester comprising terephthalic acid or an ester thereof, TMCD, and EG. In an embodiment, the method comprises the steps of:

(A) Heating a mixture comprising monomers useful in the polyesters of the invention in the presence of at least one titanium catalyst and at least one zinc catalyst at a temperature of from 150 to 300 ℃ for a time sufficient to produce an initial polyester;

(B) Polycondensing the product of step (a) by heating it at a temperature of 230-320 ℃ for 1-6 hours; and

(C) Any unreacted diol is removed.

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

In one embodiment, step (a) may be performed until 50wt% or more of TMCD has reacted. Step (A) may also be carried out at a pressure of 0 to 100 psig. The term "reaction product" as used in connection with any catalyst used in the present invention refers to any product of a polycondensation or esterification reaction with the catalyst and any monomer used to make the polyester, as well as between the catalyst and any other type of additive.

In certain embodiments, step (B) and step (C) may be performed. These steps can be performed by methods known in the art, for example, by placing the reaction mixture at a pressure of 0.002psig to below atmospheric pressure, or by blowing hot nitrogen through the mixture.

In one embodiment, the present invention relates to a process for preparing 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 50 mole% TMCD residues; and

(ii) 50 to 90 mole% of residues of at least one modifying diol;

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 about 50 mole%, optionally such that TMCD is converted in the reaction by at least 30%, and a final polymer having about 10 to 50 mole% TMCD is obtained;

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

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

wherein the inherent viscosity of the polyester is from 0.35 to 0.80dL/g, measured in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.25g/50ml at 25 ℃; and wherein the polyester has an L color value of 75 or more or greater than 75 as determined by an L x a x b x color system as measured according to astm d6290-98 and astm e308-99 performed on polymer particles milled to pass a 1mm screen. In certain embodiments, the catalyst is free of tin. In one embodiment, the polyesters and/or polyester compositions of the 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 (II). In certain embodiments, the at least one phosphorus compound may be added to step (I) alone or to step (II) alone.

In embodiments of the present invention, at least one phosphorus compound, reaction products thereof, and combinations 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 esterification. 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 esterification and polycondensation, it is added in an amount of 0.01 to 2 wt.%, 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 may be used to make the polyesters and/or polyester compositions of the 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 selected.

In one embodiment, the pressure used in step (II) of any of the methods of the present invention may consist 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 may be from 10 torr to 0.02 torr; in one embodiment, the pressure used in step (II) of any of the methods of the present invention may be from 5 torr to 0.02 torr; in one embodiment, the pressure used in step (II) of any of the methods of the present invention may be from 3 torr to 0.02 torr; in one embodiment, the pressure used in step (II) of any of the methods of the present invention may be from at least one 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 may be from 10 torr to 0.1 torr; in one embodiment, the pressure used in step (II) of any of the methods of the present invention may consist 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 may consist 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 process for preparing the polyesters of the invention, 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 1.5-3 hours.

In one embodiment, the polyesters, polyester compositions, and/or methods used in the present invention can comprise titanium atoms, zinc atoms, and optionally phosphorus atoms.

The invention further relates to polyesters prepared by the above process.

In certain 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 the b-value of the resulting polyester polymer melt phase product. Such bluing agents include blue inorganic and organic toners. In order to adjust the a-color, a red toner may be used. Organic toners, such as blue and red organic toners, may be used, such as those described in U.S. Pat. nos. 5,372,864 and 5,384,377, the entire contents of which are incorporated herein by reference. The toner 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 polyester raw materials, such as EG.

The total amount of toner components added may depend on the amount of yellow inherent in the base polyester and the effectiveness of the toner. In one embodiment, a combined toner component concentration of up to about 15ppm and a minimum concentration of about 0.5ppm is used. In one embodiment, the total amount of bluing additive may be in the range of 0.5 to 10 ppm. In one embodiment, the toner may be added to the esterification zone or polycondensation zone. Preferably, the toner is added to an early stage of the esterification or polycondensation zone, for example, to a prepolymerization reactor.

The invention also 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 100mol%. .

Suitable examples of polymer components include, but are not limited to, nylon; polyesters other than those described herein, such as PET; polyamides, such as ZYTEL from DuPont; a polystyrene; a polystyrene copolymer; styrene acrylonitrile copolymer; acrylonitrile butadiene styrene copolymer; poly (methyl methacrylate); an acrylic acid copolymer; poly (ether-imide), such as ULTEM (poly (ether-imide) s available from General Electric); polyphenylene ethers, such as poly (2, 6-dimethyl-phenyl ether) or poly (phenyl ether)/polystyrene blends, such as NORYL 1000 (a blend of poly (2, 6-dimethyl-phenyl ether) and polystyrene resin) from General Electric; polyphenylene sulfide; polyphenylene sulfide/sulfone; poly (ester-carbonate); polycarbonates such as LEXAN (polycarbonate of general electric company); polysulfone; polysulfone ether; and poly (ether-ketone) s of aromatic dihydroxy compounds; or a combination 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 polyethylene terephthalate (rPET).

In embodiments, the polyester compositions and polymer blend compositions may also contain from 0.01 to 25 weight percent of the total composition of common additives such as 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 these additives are also contemplated as 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 includes glass, such as glass fiber filaments, a combination of glass and talc, glass and mica, and glass and polymer fibers.

In one embodiment, the polyester composition can be used to prepare 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 components, sheets, and/or fibers.

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

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

In one embodiment, the present invention relates to films and/or sheets comprising the polyester compositions and/or polymer blends of the present invention. Methods of forming polyesters and/or blends into films and/or sheets are well known in the art. Examples of films and/or sheets of the present invention include, but are not limited to, 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, paints, coated articles, painted articles, shoe stiffener, laminates, medical packaging, general packaging, and/or multilayer 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 include injection stretch blow molded bottles, solar glass frames, lenses, sports bottles, drinking tools, food containers, medical devices and connectors, medical housings, electronics housings, cable assemblies, sound attenuating articles, cosmetic containers, wearable electronics, toys, promotional articles, electrical parts, automotive interior parts, and consumer household articles.

In one embodiment, in an embodiment of the present invention, certain polyesters and/or polyester compositions of the present invention may have a unique combination of some or all of the following properties: a certain notched Izod impact strength, a certain inherent viscosity, a certain glass transition temperature (Tg), good thermal stability, good transparency and good color.

In one embodiment, the process for preparing the polyesters and/or polyester compositions of the invention comprises a continuous process.

In one embodiment, a process for preparing any of the polyesters and/or polyester compositions of the invention is provided.

In one embodiment, the present invention also relates to a method of making an article made from any of the polyesters and/or polyester compositions described herein.

In one embodiment, there is provided a product made by the method of the present invention.

In one embodiment, certain polyesters useful in the present invention may be visually transparent. The term "visually transparent" is defined herein as the absence of turbidity, blurring, and/or sludge that is perceived when visually inspected.

In one embodiment, the polyesters and/or polyester compositions of the invention and/or the polyester compositions of the invention [ in one embodiment, in the presence and/or absence of a toner ] can have color values L, a, and b, which can be measured using a Hunter Lab Ultrascan spectrocolorimeter manufactured by Hunter Associates Lab company, reston, va. Color determination is the average of values measured on polyester pellets or board or other articles injection molded or extruded from them. They are determined by the color system (translation) of L x a x b x of the CIE (international commission on illumination), where L x represents the luminance coordinates, a x the red/green coordinates, and b x the yellow/blue coordinates.

In any of the polyesters, polyester compositions, and/or methods of the invention, when additional zinc and/or titanium are added or present, the b-color of any given polyester of the invention may remain stable at a particular inherent 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 the CIE (international commission on illumination).

In some embodiments of the present invention, in some embodiments, the polyesters and/or polyester compositions of the invention may have a b value of from-10 to less than 20, or from-10 to less than 18, or from-10 to less than 15, or from-10 to less than 14, or from-10 to less than 10, or from 1 to less than 20, or from 1 to less than 18, or from 5 to less than 20, or from 5 to less than 18, or from 8 to less than 20, or from 8 to less than 18, or from 8 to less than 15, or from-3 to 10, or from-5 to 5, or from-5 to 4, or from-5 to 3, or from 1 to 20, or from 1 to 18, or from 1 to 15, or from 1 to 14, or from 1 to less than 10, or from 1 to 9, or from 1 to 8, from 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 CIE (international commission on illumination) L x a x b x color system.

In certain examples, 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 x b color system of the CIE (international commission on illumination).

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

Notched Izod impact strength is a common method of measuring toughness, as described in astm d 256. In one embodiment, the polyesters and/or polyester compositions of the present invention can have a notched Izod impact strength of at least 1 ft-lbs/inch, or at least 2 ft-lbs/inch, or at least 3 ft-lbs/inch, or at least 7.5ft-lbs/in, or at least 10ft-lbs/in, in a 1/8 inch thick bar according to ASTM D256, having a 10 mil notch at 23 ℃.

Notched Izod impact strength is herein measured at 23℃in a 3.2mm (1/8 inch) thick bar using a 10 mil notch according to ASTMD 256. In one embodiment, certain polyesters and/or polyester compositions of the invention may exhibit a notched Izod impact strength of at least 25J/m (0.47 ft-lb/in) at 23℃with a 10 mil notch in a 3.2mm (1/8 inch) thick bar as determined according to ASTMD 256. In one embodiment, certain polyesters and/or polyester compositions of the present 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) at 23℃with a 10 mil notch in a 3.2mm (1/8 inch) thick rod, as determined according to ASTMD 256. In another embodiment, certain polyesters and/or polyester compositions of the present invention may exhibit a notched Izod impact strength of about 50J/m (0.94 ft-lb/in) to about 75J/m (1.41 ft-lb/in) at 23℃with a 10 mil notch in a 3.2mm (1/8 inch) thick rod, as determined according to ASTMD 256.

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

In one embodiment, certain polyesters and/or polyester compositions of the invention may exhibit a useful thermal stability of no more than 0.20dL/g inherent viscosity loss, or no more than 0.15dL/g inherent viscosity loss, or no more than 0.12dL/g inherent viscosity loss, or no more than 0.10dL/g inherent viscosity loss, when heated at 300℃for 1 to 5 hours, or 1 to 4 hours, or 2 to 3 hours, or 2.5 hours, wherein the inherent viscosity is measured in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5g/100ml at 25 ℃.

In one embodiment, certain polyesters and/or polyester compositions of the invention may have a flexural modulus at 23 ℃ equal to or greater than 2000MPa (290,000 psi), as defined in astm d 790. In another embodiment, certain polyesters and/or polyester compositions of the invention may exhibit a tensile strength of about 2000MPa (290,000 psi) to about 2551MPa (370,000 psi) at 23 ℃ as defined in astm d 638. In another embodiment, certain polyesters and/or polyester compositions of the invention have a flexural modulus at 23℃of from about 2000MPa (290,000 psi) to about 2413MPA (350,000 psi), as defined in ASTMD 790.

In one embodiment, certain polyesters and/or polyester compositions of the invention may have a flexural modulus at 23 ℃ equal to or greater than 2000MPa (290,000 psi), as defined in astm d 790. In another embodiment, certain polyesters of the invention may exhibit a tensile strength of about 2000MPa (290,000 psi) to about 2551MPa (370,000 psi) at 23 ℃ as defined in astm d 638. In another embodiment, certain polyesters of the invention have flexural moduli at 23℃of about 2000MPa (290,000 psi) to about 2413MPA (350,000 psi), as defined in ASTMD 790.

Certain polyesters and/or polyester compositions of the invention can have at least one of the following properties: tg of about 85 ℃ to about 130 ℃ measured by a TA2100 thermal analyzer at a scan rate of 20 ℃/min; flexural modulus at 23 ℃ equal to or greater than 2000MPa (290,000 psi), as defined by ASTM D790; and notched Izod impact strength equal to or greater than 25J/m (0.47 ft-lb/in) as measured at 23℃with a 10 mil notch using a 1/8 inch thick bar according to ASTMD 256.

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, or 0.50 mole% or less.

In one embodiment, any method of preparing polyesters useful in the present invention and described herein or known to one of ordinary skill in the art may be used to prepare any polyester and/or polyester composition of the present invention.

In one embodiment, any polyesters and/or polyester compositions described herein are also considered to be within the scope of the invention, regardless of which method is used to make them, and any products made therefrom.

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

Since certain polyesters of the present invention exhibit a long crystallization half-life (e.g., greater than 5 minutes) at 170 ℃, articles can be made, 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 provided by the present invention. The polyesters of the invention may be amorphous or semi-crystalline. In one embodiment, certain polyesters and/or polyester compositions of the invention may have relatively low crystallinity. Thus, certain polyesters and/or polyester compositions of the invention can have a substantially amorphous morphology, meaning that the polyester comprises substantially disordered polymer regions.

In one embodiment, the polyesters and/or polyester compositions of the invention can be used in non-coating compositions, non-adhesive compositions, thermoplastic polyester compositions, articles, 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 includes 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 of the invention are useful in electrical parts. As used herein, "appliance component" refers to a rigid member that is used in conjunction with an appliance. In one example, the implement portion may be partially or completely separated from the implement. In another embodiment, the appliance component is an appliance component that is typically made of a polymer. In one example, the implement portion is visually transparent.

In one embodiment, the polyesters of the invention can be used in bottles and containers, including those that are injection molded, injection blow molded, injection stretch blow molded, or reheat blow molded. Articles made by these methods include double wall drums, water bottles, sports bottles, bulk water containers, and baby bottles.

The following examples further illustrate how the polyesters of the invention are prepared and evaluated, and are merely illustrative of the invention and are not intended to limit the scope of the invention. Unless otherwise indicated, parts are parts by weight, temperature is degrees celsius or room temperature, and pressure is at or near atmospheric pressure.

Examples

The following examples generally illustrate how to prepare copolyesters of the invention and the effect of using TMCD and modified diol, certain catalysts, and optionally, stabilizers on various copolyester properties such as color and Inherent Viscosity (IV).

Measurement method

The inherent viscosity of the polyester was measured at 25℃in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5g/100ml and reported as 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 600MHz NMR spectrometer using chloroform-trifluoroacetic acid (70-30 v/v) for the polymer or 60/40 (wt/wt) phenol/tetrachloroethane for the oligomeric sample, with deuterated chloroform added for locking. Peak assignment of TMCD resonance was performed by comparison with model mono-and dibenzoates of TMCD. These model compounds are very close to the resonance sites found in polymers and oligomers.

The color values reported herein are CIELAB L, a, and b values measured according to ASTM D6290-98 and ASTM E308-99 using measurements from a Hunter Lab Ultrascan XE spectrophotometer (Hunter Associates Laboratory company, reston, VA) using the following parameters: d65 illuminant, (2) 10 degree observer, (3) reflection mode including specular angle, (4) large area observation, (5) 1 "port size. Unless otherwise indicated, measurements were made on polymer particles ground to pass a 1mm screen.

In the following examples, the amounts of titanium (Ti) and zinc (Zn) 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 expressed in ppm of elemental phosphorus, also measured by ICP using the same instrument. The values reported in the "P measurement" column in the following examples are obtained by measuring phosphorus as described above.

Unless otherwise indicated, TMCD used in the examples below has a cis/trans ratio of about 60/40 and may be 45/55 to 99/1.

IV or IV refers to the inherent viscosity measured as described herein unless otherwise indicated.

Preparation of copolyesters of examples 1-52

The process for preparing the copolyesters of examples 1-52 shown in tables 1-4 is illustrated by the preparation of the copolyester of example 51, wherein the target compositions are 100 mole% dimethyl terephthalate residues, 35 mole% TMCD residues, and 65 mole% CHDM residues. A mixture of 77.7g of dimethyl terephthalate, 37.5g of CHDM, 25.9g of TMCD, 0.130g of titanium acetylacetonate and 0.077g of 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 metal bath that had been heated to 220 ℃, the stirring speed was set to 175RPM, and held for 15 minutes. The contents of the flask were heated to 230 ℃ over 5 minutes while stirring was increased to 225 ℃ over that time. The contents were then slowly raised to 245 ℃ over 45 minutes. The contents were maintained at 245 c 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 further reduced to 3.5 torr over the course of eight 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 in 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 inherent viscosity of 0.62dl/g. NMR analysis indicated that the polymer consisted of 31.47 mole% TMCD residues.

Table 1-copolyester comprising TMCD, DEG and DMT; ti and Zn

Table 2-copolyester comprising TMCD, NPG and DMT; ti and Zn

Table 3-copolyester containing TMCD, EG, DEG (in situ), DMT-100 mole%; ti and Zn

Table 4-copolyester comprising TMCD, CHDM, optionally EG, and 100 mole% DMT; ti and Zn

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* Examples 31 and 32 have air exposure; examples 41-48 are part of a molar ratio study, varying the excess diol throughout the process; example 33 added water; example 34 methanol was added; examples 35-38, varying the final temperature and pressure; examples 39 and 40, modified molar ratios

Taken together, these results demonstrate that titanium and zinc are able to significantly incorporate TMCD into these polyesters, resulting in good intrinsic viscosity. Taken together, these results also demonstrate a good range of TMCD incorporation, which can be controlled by the molar ratio of diol charges. Unexpectedly, when the amount of titanium and/or zinc catalyst is higher, this does not appear to have a negative effect on color.

Preparation of copolyesters of examples 53-58

A series of comparative polymers were prepared essentially as for the other polyesters, but using the tin and phosphorus catalyst packages shown in table 5. Similar intrinsic viscosities and TMCD conversions were observed compared to titanium and zinc.

Table 5: comprises TMCD; CHDM;100mol% DMT of copolyester Sn (ppm) and phosphorus (P) (ppm); [ the Sn source is monobutyltin tris (2-ethylhexanoate) ]

Unexpectedly, the Ti/Zn catalyst system is advantageous over the use of tin catalyst systems in achieving good inherent viscosity and similar or improved TMCD incorporation.

The present disclosure has been described in detail with particular reference to preferred examples 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 at least one modified diol residue;

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

(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.

2. The polyester composition of claim 1, wherein the modified glycol 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, p-xylene glycol, neopentyl glycol, isosorbide, polytetramethylene glycol, or a combination 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 from about 10 to 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 1-3, wherein the polyester comprises 1, 4-cyclohexanedimethanol residues in an amount of about 40 to about 90 mole%, or about 40 to about 80 mole%, or about 40 to about 75 mole%, or about 45 to about 70 mole%, or about 50 to about 90 mole%, or 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%; or alternatively

Wherein the polyester comprises ethylene glycol residues in an amount of about 40 to about 90 mole%, or about 40 to about 80 mole%, or about 40 to about 75 mole%, or about 45 to about 70 mole%, or about 50 to about 90 mole%, or about 50 to about 80 mole%, or about 50 to about 70 mole%, or about 60 to about 90 mole%, or about 60 to about 80 mole%, or about 65 to about 90 mole%, or about 65 to about 80 mole%, or about 70 to about 90 mole%; or alternatively

Wherein the polyester comprises diethylene glycol residues in an amount of from about 50 to about 90 mole%, or from about 50 to about 85 mole%, or from about 50 to about 80 mole%, or from about 50 to about 75 mole%, or from about 50 to about 65 mole%, or from about 55 to about 90 mole%, or from about 55 to about 85 mole%, or from about 55 to about 80 mole%, or from about 55 to about 75 mole%, or from about 55 to about 65 mole%, or from about 60 to about 90 mole%, or from about 60 to about 85 mole%, or from about 60 to about 80 mole%, or from about 60 to about 75 mole%; or alternatively

Wherein the polyester comprises neopentyl glycol residues in an amount of about 40 to about 90 mole%, or about 40 to about 85 mole%, or about 40 to about 80 mole%, or about 40 to about 75 mole%, or about 40 to about 70 mole%, or about 45 to about 90 mole%, or about 45 to about 85 mole%, or about 45 to about 80 mole%, or about 45 to about 75 mole%, or about 45 to about 70, or about 50 to about 90 mole%, or about 50 to about 85 mole%, or about 50 to about 80 mole%, or about 50 to about 75 mole%, or about 50 to about 70 mole%, or about 55 to about 90 mole%, or about 55 to about 85 mole%, or about 55 to about 80 mole%, or about 55 to about 75 mole%, or about 55 to about 70 mole%, or about 60 to about 90 mole%, or about 60 to about 85 mole%, or about 60 to about 80 mole%, or about 60 to about 75 mole%, or about 60 to about 70 mole%, or about 70 to about 90 mole%.

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

6. The polyester composition according to any one of claims 1 to 5, wherein, the inherent viscosity is from 0.25dL/g to 1.2dL/g, or from 0.30dL/g to 1.2dL/g, or from 0.35 to 1.2dL/g, or from 0.40 to 1.2dL/g, or from 0.45 to 1.2dL/g, or from 0.50 to 1.2dL/g, or from 0.55 to 1.2dL/g, or from 0.60 to 1.2dL/g, or from 0.25dL/g to 0.80dL/g, or from 0.30dL/g to 0.80dL/g, or from 0.35 to 0.80dL/g, or from 0.40 to 0.80dL/g, or from 0.45 to 0.80dL/g, or from 0.50 to 0.80dL/g, or from 0.55 to 0.80dL/g, or from 0.60 to 0.80dL/g or 0.25dL/g to 0.75dL/g, or 0.30dL/g to 0.75dL/g, or 0.35 to 0.75dL/g, or 0.40 to 0.75dL/g, or 0.45 to 0.75dL/g, or 0.50 to 0.75dL/g, or 0.55 to 0.75dL/g, or 0.60 to 0.75dL/g, or 0.25dL/g to 0.70dL/g, or 0.30dL/g to 0.70dL/g, or 0.35 to 0.70dL/g, or 0.40 to 0.70dL/g, or 0.45 to 0.70dL/g, or 0.50 to 0.70dL/g, or 0.55 to 0.70dL/g, or 0.60 to 0.70dL/g, or 0.25 to 0.50dL/g, as determined at 25℃in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5g/100 ml.

7. The polyester composition of any of claims 1 to 6 comprising 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 manganese atoms.

8. The polyester composition of any of claims 1 to 7 comprising less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or 0-30ppm, or 0-20ppm, or 0-10ppm, or 0ppm gallium atoms.

9. The polyester composition of any of claims 1-8, wherein zinc atoms are present in an amount of 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 200ppm, or 200 to 300ppm, or 200 to 250ppm relative to the mass of the final polyester produced.

10. The polyester composition according to any of claims 1 to 9, wherein, relative to the mass of the final polyester produced, the ratio of titanium atoms to zinc atoms in ppm is 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 0.70-1.2 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 1:4 to 4:1, or 0.80-1:3 to 3:1, or 0.80-1:2 to 2:1, or 0.80-1.2 to 1:4.

11. The polyester composition of any of claims 1-10, 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 725ppm, or 350 to 700ppm, or 350 to 500ppm, or 350 to 450ppm, relative to the mass of the final polyester produced.

12. The polyester composition according to any one of claim 1 to 11, it has from-10 to less than 20, or from-10 to less than 18, or from-10 to less than 15, or from-10 to less than 14, or from-10 to less than 10, or from 1 to less than 20, or from 1 to less than 18, or from 5 to less than 20, or from 5 to less than 18, or from 8 to less than 20, or from 8 to less than 15, or from-3 to 10, or from-5 to 5, or from-5 to 4, or from-5 to 3, or from 1 to 20, or from 1 to 18, or from 1 to 15, or from 1 to 14, or from 1 to less than 10, or from 1 to 9, or from 1 to 8, from 1 to 7, or from 1 to 6, or from 1 to 5 or b x value of 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, or less than 7, or less than 6, or less than 5, or less than 4, or less than 3, as determined by the CIE (international commission on illumination) L x a x b x color system; and/or

Having 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, or 80 to 90, as determined by the L-ab color system of the CIE (international commission on illumination); and/or

Wherein the b-color value of the polyester remains stable at a particular inherent viscosity or decreases by less than 20%, or less than 15%, or less than 10%, or less than 5% when additional zinc is added, as determined by the L-a-b color system of the CIE (international commission on illumination); and/or

Wherein the polyester has an a-x color 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.

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

14. The polyester composition of any of claims 1-13, wherein at least one zinc source is selected from zinc borate, zinc oxide, zinc naphthalate, 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.

15. The polyester composition of any of claims 1-14, wherein the 2, 4-tetramethyl-1, 3-cyclobutanediol residues is a combination of: 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 more 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-2, 4-tetramethyl-1, 3-cyclobutanediol and less than 25 mole% of trans-2, 4-tetramethyl-1, 3-cyclobutanediol; or more than 80 mole% of cis-2, 4-tetramethyl-1, 3-cyclobutanediol and less than 20 mole% of trans-2, 4-tetramethyl-1, 3-cyclobutanediol; or more than 85 mole% of cis-2, 4-tetramethyl-1, 3-cyclobutanediol and less than 15 mole% of trans-2, 4-tetramethyl-1, 3-cyclobutanediol; 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.

16. The polyester composition of any of claims 1 to 15 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 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, or 0.50 mole% or less.

17. The polyester composition of any of claims 1-16, wherein the polyester composition comprises at least one polymer selected from at least one of: other polyesters, polyetherimides, polyphenylene oxides, poly (benzene oxide)/polystyrene blends, polystyrene resins, polyphenylene sulfide/sulfone, poly (ester carbonate), polycarbonates, polysulfones, polysulfone ethers, and poly (ether ketone); 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 1-17 comprising residues of at least one phosphorus compound.

19. The polyester composition of any of claims 1-18, wherein the degree of TMCD incorporation or conversion 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%.

20. An article made from the polyester composition of any of claims 1-19.