CN117043226A - Polyester compositions comprising tetramethylcyclobutanediol and cyclohexanedimethanol with improved catalyst systems comprising lithium and aluminum atoms - Google Patents

Polyester compositions comprising tetramethylcyclobutanediol and cyclohexanedimethanol with improved catalyst systems comprising lithium and aluminum atoms Download PDF

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Publication number
CN117043226A
CN117043226A CN202180093367.0A CN202180093367A CN117043226A CN 117043226 A CN117043226 A CN 117043226A CN 202180093367 A CN202180093367 A CN 202180093367A CN 117043226 A CN117043226 A CN 117043226A
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mole
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aluminum
polyester
lithium
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CN202180093367.0A
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Chinese (zh)
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B·A·舍费尔
K·E·艾伦
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Eastman Chemical Co
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Eastman Chemical Co
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Priority claimed from PCT/US2021/063661 external-priority patent/WO2022132998A1/en
Publication of CN117043226A publication Critical patent/CN117043226A/en
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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 1, 4-cyclohexanedimethanol residues; wherein the total mole% of the dicarboxylic acid component is 100 mole%, wherein the total mole% of the diol component is 100 mole%; and (2) a residue of the catalyst system comprising lithium atoms, aluminum atoms, and less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of tin atoms.

Description

Polyester compositions comprising tetramethylcyclobutanediol and cyclohexanedimethanol with improved catalyst systems comprising lithium and aluminum atoms
Technical Field
The present invention relates to polyester compositions made from residues of terephthalic acid or an ester thereof, 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) and 1, 4-Cyclohexanedimethanol (CHDM). The polyester compositions can be catalyzed with catalyst systems containing lithium and aluminum and can provide good TMCD incorporation, improved color, and reactivity to achieve the desired intrinsic viscosity over a range of compositions.
Background
Tin (Sn) based catalysts are generally most effective in incorporating TMCD into polyesters (Caldwell et al, CA740050 and Kelsey et al, macromolecules2000,33,581). However, tin-based catalysts typically produce yellow to amber copolyesters in the presence of EG, see, e.g., kelsey, U.S. patent 5,705,575; and Morris et al, U.S. Pat. No. 5,955,565.
Titanium (Ti) -based catalysts have been reported to be ineffective in incorporating 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) into polyesters (Caldwell et al, CA74005, kelsey et al, macromolecules2000,33,5810).
U.S. patent application No.2007/0142511 discloses that a titanium based catalyst can be used to prepare polyesters having a glycol component comprising TMCD and EG and optionally a level of CHDM. It is pointed out that TMCD incorporation can be improved by using tin-based catalysts in addition to titanium-based catalysts. It is further pointed out that the color of these copolyesters can be improved by adding a certain amount of phosphorus-containing compounds. This publication discloses a broad compositional range, wherein the glycol component comprises: (i) about 1 to about 90 mole% TMCD residues; and (ii) about 99 to about 10 mole% EG residues. However, as long as relatively high amounts of EG are present, such as polymers containing TMCD and EG only, the catalyst system requires significant amounts of Sn.
There is a commercial need for polymeric materials having a combination of properties that make them desirable for injection molding, blow molding, extrusion, and thermoforming film and sheet applications, including combinations of two or more, or three or more of the following properties: specific notched Izod impact strength, specific intrinsic viscosity, specific glass transition temperature (Tg), specific flexural modulus, good tensile strength, good clarity and good color.
Summary of The Invention
It has been found that when DMT, TMCD and CHDM are catalyzed with at least one lithium catalyst and at least one aluminum catalyst, significant amounts of TMCD can be incorporated into the polymer. It has also been found that a catalyst system comprising a combination of lithium and aluminum catalysts may provide a combination of one or more, two or more, or three or more of the following: good notched Izod impact strength, good intrinsic viscosity, good glass transition temperature (Tg), good flexural modulus, good tensile strength, good clarity, good color, good dishwashing, good TMCD incorporation and good/improved melt and/or thermal stability.
In certain aspects, a catalyst combination of lithium and aluminum can produce reactive copolyesters with good TMCD incorporation and achieving the desired intrinsic viscosity over a broad compositional range, including but not limited to: (a) a dicarboxylic acid component comprising: (i) 70 to 100 mole% terephthalic acid and/or dimethyl terephthalate residues; and (ii) from about 0 to about 30 mole% of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a glycol component comprising about 10 to about 50 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) residues and about 50 to about 90 mole% 1, 4-cyclohexanedimethanol residues (CHDM), based on the glycol component total of 100 mole% and the diacid component total of 100 mole%.
It is unexpected that the polyesters and/or polyester compositions of the invention will possess these properties when they are prepared using catalyst systems that do not require the use of tin catalysts and/or titanium catalysts.
In one aspect, the polyesters of the invention can comprise TMCD residues in an amount of about 10 to about 45 mole%, or about 10 to about 40 mole%, or about 15 to about 45 mole%, or about 15 to about 40 mole%, or about 20 to about 40 mole%, or about 10 to about 30 mole%, or about 20 to about 30 mole%, or about 25 to about 40 mole%, or about 30 to about 40 mole%.
In one aspect, the polyesters of the invention can comprise CHDM residues in an amount of about 55 to about 90 mole%, or about 55 to about 85 mole%, or about 60 to about 90 mole%, or about 60 to about 85 mole%, or about 60 to about 80 mole%, or about 70 to about 90 mole%, or about 70 to about 80 mole%, or about 60 to about 75 mole%, or about 60 to about 70 mole%.
In one aspect, the polyesters of the invention may comprise 2, 4-tetramethyl-1, 3-cyclobutanediol residues in an amount of from 20 to 45 mole% and CHDM residues in an amount of from 55 to 80 mole%, or 2, 4-tetramethyl-1, 3-cyclobutanediol residues in an amount of from 20 to 40 mole% and CHDM residues in an amount of from 60 to 80 mole%, or 2, 4-tetramethyl-1, 3-cyclobutanediol residues in an amount of 20 to 35 mole% and CHDM residues in an amount of 65 to 80 mole%, or CHDM residues in an amount of 25 to 45 mole% and 55 to 75 mole%, or TMCD residues in an amount of 25 to 40 mole% and CHDM residues in an amount of 60 to 75 mole%, or TMCD residues in an amount of 25 to 35 mole% and CHDM residues in an amount of 65 to 75 mole%; or TMCD residues in an amount of 30 to 35 mole% and CHDM residues in an amount of 65 to 70 mole%.
In one aspect, the polyesters of the invention may optionally include modified diol residues.
In aspects of the invention, the polyester may contain a second modified diol having 3 to 16 carbon atoms. It should be understood that some other diol residues may be formed in situ during processing.
In one aspect, for the diol component, the polyesters of the invention may contain at least one modified diol selected from at least one of the following: 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 aspect, the polyesters of the invention can comprise less than 40 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 less than 2 mole% of modified glycol residues, such as ethylene glycol residues.
In one aspect, the polyesters of the invention may contain ethylene glycol residues, or may be free of ethylene glycol residues.
In one aspect, the polyester composition may be free of hexylene glycol, and/or free of propylene glycol, and/or free of butylene glycol.
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 or terephthalic acid.
In one aspect, the polyesters and/or polyester compositions of the invention can comprise CHDA in an amount of less than 30 mole%, or less than 20 mole%, or less than 10 mole%, or less than 5 mole%, or 0 to 30 mole%, or 0 to 20 mole%, or 0 to 10 mole%, or 0 to 5 mole%, or 0 to 1 mole%, or 0.01 to 10 mole%, or 0.1 to 10 mole%, or 1 or 10 mole%, or 5 to 10 mole%, or 0 mole%, based on the total mole percent of diacid residues in the final polyester equaling 100 mole%.
In one aspect, the polyesters and/or polyester compositions of the invention can comprise trans-CHDA in an amount of less than 30 mole%, or less than 20 mole%, or less than 10 mole%, or less than 5 mole%, or from 0 to 30 mole%, or from 0 to 20 mole%, or from 0 to 10 mole%, or from 0 to 5 mole%, or from 0 to 1 mole%, or from 0.01 to 10 mole%, or from 0.1 to 10 mole%, or from 1 or 10 mole%, or from 5 to 10 mole%, or 0 mole% based on the total mole percent of diacid residues in the final polyester equaling 100 mole%.
In one aspect, the polyester composition of the present invention may comprise:
(1) At least one polyester comprising:
(a) A dicarboxylic acid component comprising:
(i) About 70 to about 100 mole% of the residues of terephthalic acid or an ester thereof;
(ii) About 0 to about 30 mole% of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms;
(b) A glycol component comprising:
(i) About 10 to about 50 mole%, or about 15 to about 40 mole% TMCD residues;
(ii) About 50 to about 90 mole%, or about 60 to about 85 mole% CHDM residues;
wherein the total mole% of the dicarboxylic acid component is 100 mole%,
wherein the total mole% of the glycol component is 100 mole%; and
(2) A residue of the catalyst system comprising lithium atoms and aluminum atoms; and optionally 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 titanium atoms and/or tin atoms;
wherein the intrinsic viscosity as measured in 60/40 (weight/weight) phenol/tetrachloroethane at a concentration of 0.5g/100ml at 25 ℃ is from 0.55 to 0.75dL/g; and having a b-value of 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 10, or 1 to 9, or 1 to 8, or 1 to 7, or 1 to 6, or 1 to 5 as determined by the L-a-b color system of CIE (InternationalCommissiononIllumination); and L values of 75 to 90.
In one aspect, the intrinsic viscosity for all polyesters and/or polyester compositions of the invention, as measured in 60/40 (weight/weight) phenol/tetrachloroethane at a concentration of 0.5g/100ml at 25 ℃, can be 0.35 to 1.2dL/g, or 0.35 to 0.80dL/g, or 0.35 to 0.75dL/g, or 0.50 to 1.2dL/g, or 0.50 to 0.80dL/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, or 0.55 to 0.75dL/g, or 0.55 to 0.70dL/g, or 0.60 to 0.75dL/g, or 0.60 to 0.70dL/g.
In one aspect, the polyesters and/or polyester compositions of the invention can have a Tg of 85 to 130 ℃, or 100 to 125 ℃, or 100 to 120 ℃.
In one aspect, in the polyesters and/or polyester compositions of the invention, the molar ratio of TMCD to 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 can comprise TMCD residues that are a mixture comprising greater than 50 mole% cis-TMCD and less than 50 mole% 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.
In one aspect, the degree of TMCD incorporation or conversion in the final polymer may be greater than 55 mole%; or greater than 50 mole%; or greater than 45 mole%; or 45 mole% or more; greater than 40 mole%; or greater than 35 mole%; or greater than 30 mole%.
In one aspect, the polyesters and/or polyester compositions of the invention can have a number average molecular weight of from 4,800 to 16,000.
In one aspect, the polyesters and/or polyester compositions of the invention can comprise residues of at least one branching agent in an amount of 0.01 to 10 mole%, or 0.01 to 5 mole%, based on the total mole percent of diacid or diol residues.
In one aspect, the polyesters and/or polyester compositions of the invention can have a melt viscosity of less than 30,000, or less than 20,000, or less than 12,000, or less than 10,000, or less than 7,000, or less than 5,000 poise, or less than 3,000 poise 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 7.5 ft-lbs/inch, or 10 ft-lbs/inch at 23℃with a 10-mil notch in a 1/8 inch thick bar according to ASTM D256.
In one aspect, the polyesters and/or polyester compositions of the invention comprise at least one lithium source comprising at least one of: lithium carbonate, lithium acetate, lithium benzoate, lithium succinate, lithium acetylacetonate, lithium methoxide, lithium oxalate, lithium nitrate, lithium ethoxide, lithium hydroxide, lithium hydride, lithium glycol (lithium alkoxide), lithium alkyl, lithium aluminum hydride, lithium borohydride, and lithium oxide.
In one aspect, the polyesters and/or polyester compositions of the invention comprise at least one lithium source comprising at least one of: lithium acetate, lithium acetylacetonate, lithium hydroxide, lithium carbonate, lithium oxalate or lithium nitrate.
In one aspect, the polyesters and/or polyester compositions of the invention comprise at least one lithium source, which is lithium acetylacetonate.
In one aspect of the present invention, the polyesters and/or polyester compositions of the invention may comprise from 5 to 500ppm, or from 5 to 450ppm, or from 5 to 400ppm, or from 5 to 350ppm, or from 5 to 300ppm, or from 5 to 250ppm, or from 5 to 200ppm, or from 5 to 150ppm, or from 5 to 125ppm, or from 5 to 100ppm, or from 5 to 90ppm, or from 5 to 85ppm, or from 5 to 80ppm, or from 5 to 75ppm, or from 5 to 70ppm, or from 5 to 65ppm, or from 5 to 60ppm, or from 10 to 500ppm, or from 10 to 450ppm, or from 10 to 400ppm, or from 10 to 350ppm, based on the mass of the final polyester produced or 10 to 300ppm, or 10 to 250ppm, or 10 to 200ppm, or 10 to 150ppm, or 10 to 125ppm, or 10 to 100ppm, or 10 to 90ppm, or 10 to 80ppm, or 10 to 75ppm, or 10 to 70ppm, or 10 to 65ppm, or 10 to 60ppm, or 25 to 500ppm, or 25 to 450ppm, or 25 to 400ppm, or 25 to 350ppm, or 25 to 300ppm, or 25 to 250ppm, or 25 to 200ppm, or 25 to 150ppm, or 25 to 125ppm, or 25 to 100ppm, or 25 to 90ppm, or 25 to 80ppm or 10 to 300ppm, or 10 to 250ppm, or 10 to 200ppm, or 10 to 150ppm, or 10 to 125ppm, or 10 to 100ppm, or 10 to 90ppm, or 10 to 80ppm, or 10 to 75ppm, or 10 to 70ppm, or 10 to 65ppm, or 10 to 60ppm or 25 to 500ppm, or 25 to 450ppm, or 25 to 400ppm, or 25 to 350ppm, or 25 to 300ppm, or 25 to 250ppm, or 25 to 200ppm, or 25 to 150ppm, or 25 to 125ppm, or 25 to 100ppm, or 25 to 90ppm, or 25 to 80ppm, or lithium atoms in an amount of 50 to 60 ppm.
In one aspect, the amount of lithium atoms present in the polyester and/or polyester composition of the invention may generally be at least 5ppm, or at least 8ppm, or at least 10ppm, or at least 15ppm, or at least 20ppm, or at least 25ppm, or at least 30ppm, or at least 35ppm, or at least 40ppm, or at least 45ppm, or at least 50ppm, and less than 100ppm, or less than 90ppm, or less than 80ppm, or less than 75ppm, or less than 70ppm, or less than 65ppm, or less than 60ppm, based on the total weight of the polymer, relative to the mass of the final polyester produced.
In one aspect, the lithium atom present in the polyesters and/or polyester compositions of the invention may generally range from 10ppm to 100ppm, or from 20ppm to 100ppm, or from 25ppm to 100ppm, or from 30ppm to 100ppm, or from 35ppm to 100ppm, or from 40ppm to 100ppm, or from 45ppm to 100ppm, or from 50ppm to 100ppm, or from 10ppm to 75ppm, or from 15ppm to 75ppm, or from 20ppm to 75ppm, or from 25ppm to 75ppm, or from 30ppm to 75ppm, or from 35ppm to 75ppm, or from 40ppm to 75ppm, or from 45ppm to 75ppm, or from 50ppm to 75ppm, or from 10ppm to 65ppm, or from 20ppm to 65ppm, or from 30ppm to 65ppm, or from 35ppm to 65ppm, or from 40ppm to 65ppm, or from 45ppm to 65ppm, or from 50ppm to 65ppm, relative to the mass of the final polyesters produced.
In one aspect, the polyesters and/or polyester compositions of the invention can comprise at least one catalytically active aluminum source. These aluminum compounds may include aluminum compounds having at least one organic substituent.
Suitable examples of the aluminum compound may include at least one of: aluminum carboxylates such as aluminum acetate (if dissolved), aluminum benzoate, aluminum sulfate, aluminum lactate, aluminum laurate, aluminum stearate, aluminum alkoxide, aluminum ethoxide, aluminum isopropoxide (also known as aluminum isopropoxide), aluminum tri-n-butoxide, aluminum tri-t-butoxide, aluminum di-iso-butoxide, and aluminum chelates in which the alkoxy groups of the aluminum alkoxide are partially or fully substituted with a chelating agent such as alkyl acetoacetates or acetylacetone, such as ethyl acetoacetate aluminum di-isopropoxide, aluminum tri (ethylacetoacetate) aluminumtris (ethylacetoacetate), alkyl acetoacetates, aluminum di-isopropoxide, aluminum monoacetoacetate bis (ethylacetoacetate) aluminummonoacetylacetatebis (ethylacetoacetate), aluminum tri (ethylacetoacetate) aluminumtris (acetylacetate), or aluminum acetylacetonate.
In one aspect, the polyesters and/or polyester compositions of the invention may contain aluminum hydroxide, aluminum acetylacetonate, aluminum acetate, aluminum isopropoxide, or aluminum sulfate.
In one aspect, the polyesters and/or polyester compositions of the invention can comprise at least one aluminum source selected from aluminum acetylacetonate and aluminum isopropoxide.
In one aspect, the polyesters and/or polyester compositions of the invention can comprise aluminum acetylacetonate.
In one aspect of the present invention, the polyesters and/or polyester compositions of the invention may comprise from 5 to 500ppm, or from 5 to 450ppm, or from 5 to 400ppm, or from 5 to 350ppm, or from 5 to 300ppm, or from 5 to 250ppm, or from 5 to 200ppm, or from 5 to 150ppm, or from 5 to 125ppm, or from 5 to 100ppm, or from 5 to 90ppm, or from 5 to 85ppm, or from 5 to 80ppm, or from 5 to 75ppm, or from 5 to 70ppm, or from 5 to 65ppm, or from 5 to 60ppm, or from 10 to 500ppm, or from 10 to 450ppm, or from 10 to 400ppm, or from 10 to 350ppm, based on the mass of the final polyester produced or 10 to 300ppm, or 10 to 250ppm, or 10 to 200ppm, or 10 to 150ppm, or 10 to 125ppm, or 10 to 100ppm, or 10 to 90ppm, or 10 to 80ppm, or 10 to 75ppm, or 10 to 70ppm, or 10 to 65ppm, or 10 to 60ppm, or 25 to 500ppm, or 25 to 450ppm, or 25 to 400ppm, or 25 to 350ppm, or 25 to 300ppm, or 25 to 250ppm, or 25 to 200ppm, or 25 to 150ppm, or 25 to 125ppm, or 25 to 100ppm, or 25 to 90ppm, or 25 to 80ppm or 10 to 300ppm, or 10 to 250ppm, or 10 to 200ppm, or 10 to 150ppm, or 10 to 125ppm, or 10 to 100ppm, or 10 to 90ppm, or 10 to 80ppm, or 10 to 75ppm, or 10 to 70ppm, or 10 to 65ppm, or 10 to 60ppm or 25 to 500ppm, or 25 to 450ppm, or 25 to 400ppm, or 25 to 350ppm, or 25 to 300ppm, or 25 to 250ppm, or 25 to 200ppm, or 25 to 150ppm, or 25 to 125ppm, or 25 to 100ppm, or 25 to 90ppm, or 25 to 80ppm, or an aluminum atom in an amount of 50 to 60 ppm.
In one aspect, the amount of aluminum atoms present in the polyesters and/or polyester compositions of the invention can generally be at least 5ppm, or at least 8ppm, or at least 10ppm, or at least 15ppm, or at least 20ppm, or at least 25ppm, or at least 30ppm, or at least 35ppm, or at least 40ppm, or at least 45ppm, or at least 50ppm, and less than 100ppm, or less than 90ppm, or less than 80ppm, or less than 75ppm, or less than 70ppm, or less than 65ppm, or less than 60ppm, relative to the mass of the final polyester produced.
In one aspect, the amount of aluminum atoms present in the polyester and/or polyester composition of the present invention may generally be from 10ppm to 100ppm, or from 20ppm to 100ppm, or from 25ppm to 100ppm, or from 30ppm to 100ppm, or from 35ppm to 100ppm, or from 40ppm to 100ppm, or from 45ppm to 100ppm, or from 50ppm to 100ppm, or from 10ppm to 75ppm, or from 15ppm to 75ppm, or from 20ppm to 75ppm, or from 25ppm to 75ppm, or from 30ppm to 75ppm, or from 35ppm to 75ppm, or from 40ppm to 75ppm, or from 45ppm to 75ppm, or from 50ppm to 75ppm, or from 10ppm to 65ppm, or from 20ppm to 65ppm, or from 30ppm to 65ppm, or from 35ppm to 65ppm, or from 40ppm to 65ppm, or from 45ppm to 65ppm, or from 50ppm to 65ppm, relative to the mass of the final polyester produced.
In one aspect, the ratio of lithium atoms to aluminum atoms in ppm relative to the mass of the final polyester produced in the polyester and/or polyester composition of the present invention is from 1:5 to 5:1, from 1:4 to 4:1, or from 1:3 to 3:1, or from 1:2 to 2:1, or from 1-1.25:1.
In one aspect of the present invention, the polyesters and/or polyester compositions of the invention may have a concentration of 10 to 1000ppm, or 10 to 800ppm, or 10 to 600ppm, or 10 to 500ppm, or 10 to 450ppm, or 10 to 400ppm, or 10 to 300ppm, or 10 to 250ppm, or 10 to 200ppm, or 10 to 150ppm, or 50 to 1000ppm, or 50 to 800ppm, or 50 to 600ppm, or 50 to 500ppm, or 50 to 450ppm, or 50 to 400ppm, or 50 to 300ppm, or 50 to 250ppm, or 50 to 200ppm, or 50 to 150ppm, or 100 to 1000ppm, or 100 to 800ppm, or 100 to 600ppm, or 100 to 500ppm, or 100 to 400ppm, or 100 to 300ppm, or 100 to 250ppm, relative to the mass of the final polyester produced or 100 to 200ppm, or 100 to 150ppm, or 80 to 150ppm, or 200 to 1000ppm, or 200 to 800ppm, or 200 to 600ppm, or 200 to 500ppm, or 200 to 400ppm, or 300 to 1000ppm, or 300 to 800ppm, or 300 to 600ppm, or 300 to 500ppm, or 300 to 400ppm, or 400 to 1000ppm, or 400 to 800ppm, or 400 to 600ppm, or 500 to 1000ppm, or 500 to 800ppm, or 500 to 700ppm, or less than 500ppm, or less than 400ppm, or less than 300ppm, or less than 250ppm, or less than 225ppm, or less than 200ppm, or less than 150ppm, or less than 130ppm, or less than 120ppm of the total atomic amount of catalyst metal present in the composition.
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 titanium atoms and/or tin atoms.
In certain aspects, the catalyst combinations useful in the present invention may be tin-free and/or titanium-free.
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 zinc 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 titanium atoms, tin atoms, and/or manganese atoms.
In one aspect, the polyesters and/or polyester compositions of the invention can comprise less than 10ppm, or less than 5ppm, or less than 2ppm, or 0ppm of titanium atoms, tin atoms, and/or zinc 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 titanium atoms, tin atoms, manganese atoms, and/or zinc atoms.
In one aspect, the polyesters and/or polyester compositions of the invention may have a b-value of-10 to less than 20, or-10 to less than 10, or 1 to less than 20, or 5 to less than 20, or 8 to less than 20, or-3 to 10, or-5 to 5, or-5 to 4, or-5 to 3, or 1 to 10, or 1 to 9, or 1 to 8, 1 to 7, or 1 to 6, or 1 to 5, or less than 20, or less than 15, or less than 10, 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 L-a-b color system of CIE (InternationalCommissiononIllumination).
In one aspect, the polyesters and/or polyester compositions of the invention may have an L-value of 50 to 99, or 50 to 90, or 60 to 99, or 60 to 90, or 60 to 85, or 60 to 80, or 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 75 to 85, or 70 to 80, or 75 to 95, or 75 to 90, or 75 to 85, or 80 to 90 as determined by the L-x b color system of CIE (InternationalCommissiononIllumination).
In one aspect, b and/or L and/or a values may be obtained in the presence and/or absence of a toner.
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 polyester composition of the present invention may comprise at least one polyester of the present invention blended with at least one polymer selected from at least one of the following: other polyesters (such as polyethylene terephthalate (PET), including recycled PET, poly (cyclohexanediol terephthalate) (e.g., PCT), modified PET or PET modified with 1, 4-cyclohexanedimethanol CHDM (e.g., PETG), poly (etherimide), polyphenylene oxide, poly (phenylene ether)/polystyrene blends, polystyrene resins, polyphenylene sulfide/sulfone, poly (ester-carbonate), polycarbonate, polysulfone ethers, and poly (ether-ketone).
In one aspect, the polyester composition of the present invention may comprise the polyester of the present invention blended with recycled poly (ethylene terephthalate) (rPET).
In one aspect, the polyester compositions of the present invention may comprise at least one polycarbonate, or be free of carbonate groups.
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 invention can comprise at least one of substituted or unsubstituted alkyl phosphates, substituted or unsubstituted aryl phosphates, substituted or unsubstituted mixed alkyl aryl phosphates, bisphosphites, phosphates, phosphine oxides, and mixed aryl alkyl phosphites, reaction products thereof, and/or mixtures thereof.
In one aspect, the polyesters and/or polyester compositions of the invention can comprise at least one of substituted or unsubstituted alkyl phosphates, substituted or unsubstituted aryl phosphates, mixed substituted or unsubstituted alkyl aryl phosphates, reaction products thereof, and mixtures thereof.
In one aspect, the polyesters and/or polyester compositions of the invention may be free of phosphorus compounds.
In one aspect, there is provided a method of making any of the polyesters and/or polyester compositions herein 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) 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 an aliphatic dicarboxylic acid having up to 16 carbon atoms; and
(b) A glycol component comprising:
(i) 10 to 50 mole% TMCD residues; and
(ii) 50 to 90 mole% CHDM residues;
wherein the molar ratio of diol component/dicarboxylic acid component added in step (I) is from 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 range of final pressure of step (I) to 0.02torr absolute;
wherein the mixture in step (I) or (II) is heated in the presence of at least one catalyst selected from the group consisting of at least one aluminum compound and one lithium compound while heating; and
wherein the final product after step (II) comprises lithium atoms and aluminum atoms;
wherein the total mole% of dicarboxylic acid component of the final polyester is 100 mole%;
wherein the total mole% of the glycol component of the final polyester is 100 mole%;
wherein the intrinsic viscosity of the final polyester as measured in 60/40 (weight/weight) phenol/tetrachloroethane at a concentration of 0.25g/50ml at 25 ℃ is from 0.35 to 1.2dL/g; and
wherein the final polyester has a Tg of 85 ℃ to 200 ℃.
In one aspect, the above process is provided except that the lithium catalyst source is added in step I) and the aluminum catalyst source is added in step (II).
In one aspect, the process for making polyesters useful in the present invention can comprise a batch or continuous process.
In one aspect, the process for making the polyesters useful in the present invention comprises a continuous process.
In one aspect, the present invention relates to a method of making 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% 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% CHDM residues;
wherein the molar ratio of diol component/dicarboxylic acid component added in step (I) is from 1.01 to 3.0/1.0, and wherein TMCD is added in an amount of about 10 to 50 mole% to obtain a final polymer having about 10 to 50 mole% TMCD residues;
wherein the mixture in step (I) is heated in the presence of:
(i) At least two catalysts comprising lithium and aluminum; and (ii) 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 range of final pressure of step (I) to 0.02torr absolute pressure to form a final polyester;
wherein the total mole% of dicarboxylic acid component of the final polyester is 100 mole%; and wherein the total mole% of the glycol component of the final polyester is 100 mole%;
Wherein the intrinsic viscosity of the polyester as measured in 60/40 (weight/weight) phenol/tetrachloroethane at a concentration of 0.25g/50ml at 25 ℃ is from 0.50 to 0.80dL/g; and wherein the L color value of the polyester as determined by the L x a x b x color system of CIE (International Commission on Illumination) is 75 or greater.
In one aspect, the polyesters useful in the present invention may comprise at least one phosphate ester, whether present as a heat stabilizer or not.
In one aspect, the polyesters useful in the present invention are free of branching agents, or alternatively at least one branching agent is added prior to or during polymerization of the polyester.
In one aspect, the polyesters useful in the present invention contain at least one branching agent, regardless of the method or sequence of addition.
In one aspect, certain polyesters useful in the present invention may be amorphous or semi-crystalline. In one aspect, certain polyesters useful in the present invention may have relatively low crystallinity. Certain polyesters useful in the present invention may thus have a substantially amorphous state, 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 useful in the present invention may comprise at least one aryl phosphate.
In one aspect, at least one phosphorus compound useful in the present invention may comprise at least one unsubstituted aryl phosphate.
In one aspect, at least one phosphorus compound useful in the present invention may comprise at least one aryl phosphate ester that is not substituted with a benzyl group.
In one aspect, the at least one phosphorus compound useful in the present invention may comprise at least one triaryl phosphate ester.
In one aspect, at least one phosphorus compound useful in the present invention may comprise at least one triaryl phosphate ester that is not substituted with a benzyl group.
In one aspect, the at least one phosphorus compound useful in the present invention may comprise at least one alkyl phosphate.
In one aspect, the at least one phosphorus compound useful in the present invention may comprise triphenyl phosphate and/or MerpolA. In one embodiment, any of the polyester compositions of the present invention may comprise triphenyl phosphate.
In one aspect, any of the methods described herein for making any polyester composition and/or polyester can 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 making any of the polyester compositions and/or polyesters can comprise at least one phosphine oxide.
In one aspect, any of the methods described herein for making any polyester composition and/or polyester can comprise at least one phosphate salt, such as KH 2 PO 4 And Zn 3 (PO 4 ) 2 。
In one aspect of the invention, any method of making polyesters useful in the present invention and described herein or known to one of ordinary skill in the art may be used to make any polyester and/or polyester composition of the present invention.
In one aspect of the invention, any polyesters and/or polyester compositions described herein are also considered to be within the scope of the invention, regardless of the method used to make them.
In one aspect, the pressure used in step (I) of any of the methods of the present invention consists of at least one pressure selected from the group consisting of 0psig to 75 psig. In one embodiment, the pressure used in step (I) of any of the methods of the present invention consists of at least one pressure selected from the group consisting of 0psig to 50 psig.
In one aspect, the pressure used in step (II) of any of the methods of the present invention consists of at least one pressure selected from the group consisting of 20torr absolute to 0.02torr absolute; in one embodiment, the pressure used in step (II) of any of the methods of the present invention consists of at least one pressure selected from the group consisting of 10torr absolute to 0.02torr absolute; in one embodiment, the pressure used in step (II) of any of the methods of the present invention consists of at least one pressure selected from the group consisting of 5torr absolute to 0.02torr absolute; in one embodiment, the pressure used in step (II) of any of the methods of the present invention consists of at least one pressure selected from the group consisting of 3torr absolute to 0.02torr absolute; in one embodiment, the pressure used in step (II) of any of the methods of the present invention consists of at least one pressure selected from the group consisting of 20torr absolute to 0.1torr absolute; in one embodiment, the pressure used in step (II) of any of the methods of the present invention consists of at least one pressure selected from the group consisting of 10torr absolute to 0.1torr absolute; in one embodiment, the pressure used in step (II) of any of the methods of the present invention consists of at least one pressure selected from the group consisting of 5torr absolute to 0.1torr absolute; in one embodiment, the pressure used in step (II) of any of the methods of the present invention consists of at least one pressure selected from the group consisting of 3torr absolute to 0.1torr absolute.
In one aspect, the molar ratio of diol 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 diol 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 diol 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 diol 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 diol 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 diol 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 diol 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 diol component/dicarboxylic acid component added in step (I) of any of the methods of the present invention is from 1.01 to 1.75/1.0; in one aspect, the molar ratio of glycol component/dicarboxylic acid component added in step (I) of any of the methods of the present invention is from 1.01 to 1.5/1.0.
In any of the process embodiments for making the polyesters and/or polyester compositions useful in the present invention, the heating time of step (II) may be from 1 to 5 hours. In any of the process embodiments for making polyesters useful in the present invention, the heating time of step (II) may be from 1 to 4 hours. In any of the process embodiments for making polyesters useful in the present invention, the heating time of step (II) may be from 1 to 3 hours. In any of the process embodiments for making polyesters useful in the present invention, the heating time of step (II) may be from 1.5 to 3 hours. In any of the process embodiments for making polyesters useful in the present invention, the heating time of step (II) may be from 1 to 2 hours.
The weight of aluminum atoms and lithium atoms present in the final polyester can be measured in the final polyester, for example, in any of the weight ratios described above.
In one aspect, certain inventive polyesters and/or polyester compositions useful in the present invention may exhibit useful thermal stability of no greater than 0.20dL/g, or no greater than 0.15dL/g, or no greater than 0.12dL/g, or no greater than 0.10dL/g, 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 intrinsic viscosity is measured in 60/40 (weight/weight) phenol/tetrachloroethane at a concentration of 0.5g/100ml at 25 ℃.
In certain aspects, 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 aspect, the polyester compositions of the present invention may be used in non-coating compositions, non-adhesive compositions, thermoplastic polyester compositions, articles of manufacture (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 kettles 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 (cast extrusion articles), profile extruded articles, melt spun articles, thermoformed articles, extruded 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 polyester compositions useful in the present invention can be used in various types of films and/or sheets, including but not limited to extruded film(s) and/or sheet(s), compression molded film(s) and/or sheet(s), solution cast film(s) and/or sheet(s). 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 film(s) and/or sheet(s) comprising the polyester(s) and/or polyester composition of the present invention.
In one aspect, the present invention relates to an article comprising the thermoformed film and/or sheet of the present invention.
In one aspect, any method of making polyesters useful in the present invention and described herein or known to one of ordinary skill in the art may be used to make 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 the method used to make them, and 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.
In one aspect, the present invention relates to articles of manufacture, such as shaped articles, comprising any of the polyesters and/or polyester compositions of the invention.
Detailed Description
The present invention may be understood more readily by reference to the following detailed description of certain embodiments and examples of the invention. In accordance with the object(s) of the present invention, certain embodiments of the invention are described in the summary of the invention and are further described below. Other embodiments of the invention are also 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 CHDM residues, and further comprising certain catalysts and optionally stabilizers, reaction products thereof, and mixtures thereof, may have one or more, two or more, or a combination of three or more of the following: good notched Izod impact strength, good intrinsic viscosity, good glass transition temperature (Tg), good flexural modulus, good tensile strength, good clarity, good color, good dishwashing, good TMCD incorporation and good/improved melt and/or thermal stability.
In one embodiment, copolyesters containing TMCD and CHDM residues over a wide composition range can be prepared with at least one lithium catalyst and at least one aluminum catalyst.
The present invention relates to polyesters based on terephthalic acid or an ester thereof, TMCD and at least one modified diol catalyzed with certain catalyst types that provide improved properties (as discussed herein). In certain embodiments, the use of at least one lithium catalyst and at least one aluminum catalyst may bring about good TMCD incorporation and achieve the desired Intrinsic Viscosity (IV) reactivity within the compositional ranges described herein.
When lithium is added to the polyester and/or polyester composition and/or the process for making a polyester of the present invention, it is added to the process for making a polyester in the form of a lithium compound. The amount of lithium 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 lithium atoms present in the final polyester, for example in ppm by weight.
When aluminum is added to the polyester and/or polyester composition and/or the process for making a polyester of the present invention, it is added to the process for making a polyester in the form of an aluminum compound. The amount of aluminum 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 aluminum atoms present in the final polyester, for example in ppm by weight.
When phosphorus is added to the polyester and/or polyester composition and/or the process for making a polyester of the present invention, it is added to the process for making a polyester in the form of a phosphorus compound. In one embodiment, such phosphorus compounds may comprise at least one phosphate ester. The amount of phosphorus compound [ e.g., phosphate(s) ] added to the polyester of the invention and/or the polyester composition of the invention and/or the process of the invention can be measured in terms of phosphorus atoms present in the final polyester, e.g., measured in ppm by weight.
The term "polyester" as used herein is intended to include "copolyesters" and is understood to mean a synthetic polymer made 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 dihydric alcohol, such as glycols and diols. 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 that is incorporated into a polymer from the corresponding monomer by polycondensation and/or esterification reactions. The term "repeat unit" as used herein refers to an organic structure having dicarboxylic acid residues and diol residues bonded through a carbonyloxy group. Thus, for example, the dicarboxylic acid residues may be derived from dicarboxylic acid monomers or related acid halides, esters, salts, anhydrides, and/or mixtures thereof. Furthermore, the term "diacid" as used herein includes polyfunctional acids, such as branching agents. Thus, the term "dicarboxylic acid" as used herein is intended to include dicarboxylic acids and any derivatives of dicarboxylic acids, including the related acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, and/or mixtures thereof, that may be used in the process for making polyesters by reaction with diols. The term "terephthalic acid" as used herein is intended to include terephthalic acid itself and residues thereof, as well as any derivatives of terephthalic acid, including the relevant acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, and/or mixtures thereof or residues thereof, which may be used in a process for making polyesters by reaction with diols.
The polyesters used in the present invention may 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. The polyesters of the invention may thus contain substantially equimolar proportions of acid residues (100 mole%) and glycol (and/or polyfunctional hydroxy compound) residues (100 mole%) such that the total number of moles of repeating units is equal to 100 mole%. Thus, the mole percentages provided in the present 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 out of the total 100 mole% acid residues. Thus, there are 10 moles of isophthalic acid residues 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 out of a total of 100 mole% glycol residues. Thus, there are 25 moles of TMCD residues per 100 moles.
In certain embodiments, the present invention includes a polyester composition comprising at least one polyester comprising: (a) a dicarboxylic acid component comprising: (i) 70 to 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 about 10 to about 50 mole% 2, 4-tetramethyl-1, 3-cyclobutanediol (TMCD) residues and about 50 to about 90 mole% CHDM residues, based on 100 mole% of the glycol component and 100 mole% of the diacid component.
In one embodiment, the polyesters and/or polyester compositions of the invention can comprise TMCD residues in an amount of about 10 to about 45 mole%, or about 10 to about 40 mole%, or about 15 to about 45 mole%, or about 15 to about 40 mole%, or about 20 to about 40 mole%, or about 10 to about 30 mole%, or about 20 to about 30 mole%, or about 25 to about 40 mole%, or about 30 to about 40 mole%.
In one embodiment, the polyesters and/or polyester compositions of the invention can comprise CHDM residues in an amount of about 55 to about 90 mole%, or about 55 to about 85 mole%, or about 60 to about 90 mole%, or about 60 to about 85 mole%, or about 60 to about 80 mole%, or about 70 to about 90 mole%, or about 70 to about 80 mole%, or about 60 to about 75 mole%, or about 60 to about 70 mole%, or 20 to 40 mole%.
In one embodiment, the polyesters and/or polyester compositions of the invention may comprise TMCD residues in an amount of 20 to 45 mole% and CHDM residues in an amount of 55 to 80 mole%, or TMCD residues in an amount of 20 to 40 mole% and CHDM residues in an amount of 60 to 80 mole%, or TMCD residues in an amount of 20 to 35 mole% and CHDM residues in an amount of 65 to 80 mole%, or CHDM residues in an amount of 25 to 45 mole% and 55 to 75 mole%, or TMCD residues in an amount of 25 to 40 mole% and CHDM residues in an amount of 60 to 75 mole%, or TMCD residues in an amount of 25 to 35 mole% and CHDM residues in an amount of 65 to 75 mole%; or TMCD residues in an amount of 30 to 35 mole% and CHDM residues in an amount of 65 to 70 mole%.
In one embodiment, the degree of TMCD incorporation or conversion in the final polymer may be greater than 55 mole%; or greater than 50 mole%; or greater than 45 mole%; or 45 mol% or more; greater than 40 mole%; or greater than 35 mole%; or greater than 30 mole%.
The modified diol may constitute the remaining mole percent.
In one embodiment, the polyesters and/or polyester compositions of the invention can comprise less than 40 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% of modified glycol residues, such as ethylene glycol residues.
In one embodiment the polyesters and/or polyester compositions of the present invention may include, but are not limited to, modified diols comprising at least one member selected from the group consisting of 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, the polyesters and/or polyester compositions of the invention may comprise ethylene glycol residues, or may be free of ethylene glycol residues.
In one embodiment, the polyesters and/or polyester compositions of the invention may comprise 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 less than 2 mole%, or 0 mole% neopentyl glycol residues.
In one embodiment, terephthalic acid can be used as a starting material. In another embodiment, dimethyl terephthalate may be used as a raw material. In yet another embodiment, a mixture of terephthalic acid and dimethyl terephthalate may be used as a raw material and/or as an intermediate material.
In certain embodiments, terephthalic acid or an ester thereof, such as dimethyl terephthalate or a mixture of terephthalic acid residues and esters thereof, may constitute a portion or all of the dicarboxylic acid component used to form the polyesters useful in the present invention. In certain embodiments, the terephthalic acid residues can comprise a portion or all of the dicarboxylic acid component used to form the polyesters useful in the present invention. In certain embodiments, higher amounts of terephthalic acid may be used to produce polyesters of higher impact strength. For 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, 70 to 100 mole% may be used; or 80 to 100 mole%; or 90 to 100 mole%; or 99 to 100 mole%; or 100 mole% terephthalic acid and/or dimethyl terephthalate and/or mixtures thereof.
In addition to terephthalic acid, the dicarboxylic acid component of the polyesters of the invention may comprise less than 30 mole%, or less than 20 mole%, or less than 10 mole%, or less than 5 mole%, or 0 to 30 mole%, or 0 to 20 mole%, or 0 to 10 mole%, or 0 to 5 mole%, or 0 to 1 mole%, or 0.01 to 10 mole%, or 0.1 to 10 mole%, or 1 or 10 mole%, or 0.01 to 5 mole%, or 0.1 to 5 mole%, or 1 or 5, or 0.01 to 1 mole%, or 0.1 to 1 mole%, or 5 to 10 mole%, or 0 mole% of one or more modified aromatic dicarboxylic acids. Yet another embodiment contains 0 mole% of the modified aromatic dicarboxylic acid. Thus, if present, it is contemplated that the amount of one or more modified aromatic dicarboxylic acids may begin from any of these aforementioned end point values, 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, 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 '-biphthalic 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 and/or polyester compositions of the invention may be further modified with less than 30 mole%, or less than 20 mole%, or less than 10 mole%, or less than 5 mole%, or 0 to 30 mole%, or 0 to 20 mole%, or 0 to 10 mole%, or 0 to 5 mole%, or 0 to 1 mole%, or 0.01 to 10 mole%, or 0.1 to 10 mole%, or 1 or 10 mole%, or 0.01 to 5 mole%, or 0.1 to 5 mole%, or 1 or 5, or 0.01 to 1 mole%, or 0.1 to 1 mole%, or 5 to 10 mole%, or 0 mole% of one or more aliphatic dicarboxylic acids containing 2-16 carbon atoms, such as cyclohexanedicarboxylic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and/or dodecanedicarboxylic acid. Certain embodiments may also comprise from 0.01 to 10 mole%, such as from 0.1 to 10 mole%, 1 or 10 mole%, 5 to 10 mole% of one or more modified aliphatic dicarboxylic acids. Yet another embodiment contains 0 mole% of the modified aliphatic dicarboxylic acid. The total mole% of the dicarboxylic acid component was 100 mole%. In one embodiment, adipic acid and/or glutaric acid is provided in the modified aliphatic dicarboxylic acid component of the present invention.
Instead of dicarboxylic acids, esters of terephthalic acid and other modified dicarboxylic acids or their corresponding esters and/or salts may be used. Suitable examples of dicarboxylic acid esters include, but are not limited to, dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, and diphenyl esters. In one embodiment, the ester is selected from at least one of the following: methyl, ethyl, propyl, isopropyl and phenyl esters. In one embodiment, the diacid component of the polyester and/or polyester composition of the invention may comprise residues of dimethyl terephthalate. In one embodiment, the diacid component comprises 0 to 30 mole percent, or 0 to 20 mole percent, or 0 to 10 mole percent aliphatic diacid residues, including but not limited to 1, 4-cyclohexanedicarboxylic acid (CHDA), based on the total mole percent diacid residues in the final polyester equaling 100 mole percent.
In one embodiment, the polyesters and/or polyester compositions of the invention can comprise CHDA in an amount of less than 30 mole%, or less than 20 mole%, or less than 10 mole%, or less than 5 mole%, or from 0 to 30 mole%, or from 0 to 20 mole%, or from 0 to 10 mole%, or from 0 to 5 mole%, or from 0 to 1 mole%, or from 0.01 to 10 mole%, or from 0.1 to 10 mole%, or from 1 or 10 mole%, or from 5 to 10 mole%, or 0 mole%, based on 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 can comprise trans-CHDA in an amount of less than 30 mole%, or less than 20 mole%, or less than 10 mole%, or less than 5 mole%, or from 0 to 30 mole%, or from 0 to 20 mole%, or from 0 to 10 mole%, or from 0 to 5 mole%, or from 0 to 1 mole%, or from 0.01 to 10 mole%, or from 0.1 to 10 mole%, or from 1 or 10 mole%, or from 5 to 10 mole%, or 0 mole% based on the total mole percent of diacid residues in the final polyester equaling 100 mole%.
In one embodiment, in the polyesters and/or polyester compositions of the invention, the molar ratio of TMCD to CHDM is from 1:9 to 1:1, or from 1:4 to 1:1, or from 1:3 to 1:1.5, or from 1:3 to 1:1, or from 1:2 to 1:1, or from 1:1.5 to 1:1.
In one embodiment, the polyester composition of the present invention may have a number average molecular weight of 4,800 to 16,000.
In one embodiment, the polyesters and/or polyester compositions of the invention may comprise:
(1) At least one polyester comprising:
(a) A dicarboxylic acid component comprising:
(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 15 to about 40 mole% TMCD residues;
(ii) About 60 to about 85 mole% CHDM residues;
wherein the total mole% of the dicarboxylic acid component is 100 mole%,
wherein the total mole% of the glycol component is 100 mole%; and
(2) A residue of the catalyst system comprising lithium atoms and aluminum atoms; and optionally, 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 titanium atoms and/or tin atoms;
wherein the intrinsic viscosity as measured in 60/40 (weight/weight) phenol/tetrachloroethane at a concentration of 0.5g/100ml at 25 ℃ is from 0.50 to 0.75dL/g; and having a b-value of 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 10, or 1 to 9, or 1 to 8, or 1 to 7, or 1 to 6, or 1 to 5 as determined by the L-a-b color system of CIE (International Commission on Illumination); and L values of 75 to 90.
The molar ratio of cis/trans TMCD may vary for the desired polyester, both in pure form and in combination. In certain embodiments, the mole percent of residues of cis and/or trans-2, 4, -tetramethyl-1, 3-cyclobutanediol is 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 70 mole% cis-TMCD and 50 to 30 mole% trans-TMCD; or 60 to 70 mole% cis-TMCD and 30 to 40 mole% 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 another embodiment, the molar ratio of cis/trans TMCD may vary from 50/50 to 0/100, for example between 40/60 and 20/80.
In some embodiments, polyesters and/or polyester compositions according to the present invention may comprise from 0 to 10 mole%, for example from 0.01 to 5 mole%, from 0.01 to 1 mole%, from 0.05 to 5 mole%, from 0.05 to 1 mole%, or from 0.1 to 0.7 mole%, based on the total mole percent of diol or diacid residues, respectively, of residues of one or more branching monomers (also referred to herein as branching agents) having 3 or more carboxyl substituents, hydroxyl substituents, or combinations thereof. In certain embodiments, the branching monomer or branching agent may be added before and/or during and/or after polymerization of the polyester. In embodiments, the polyester(s) useful in the present invention may thus be linear or branched.
Examples of branching monomers include, but are not limited to, polyfunctional acids or alcohols such as trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylol propane, glycerol, pentaerythritol, citric acid, tartaric acid, 3-hydroxyglutaric acid, and the like. In one embodiment, the branched monomer residues may comprise from 0.1 to 0.7 mole% of one or more residues selected from at least one of the following: trimellitic anhydride, pyromellitic dianhydride, glycerol, sorbitol, 1,2, 6-hexanetriol, pentaerythritol, trimethylolethane and/or pyromellitic acid. The branching monomers may be added to the polyester reaction mixture or blended with the polyester as a concentrate as described, for example, in U.S. patent nos. 5,654,347 and 5,696,176, the disclosures of which are incorporated herein by reference for branching monomers.
The polyesters and/or polyester compositions of the invention may comprise at least one chain extender. Suitable chain extenders include, but are not limited to, polyfunctional (including, but not limited to difunctional) isocyanates, polyfunctional epoxides including, for example, epoxidized novolac resins and phenoxy resins. In certain embodiments, the chain extender may be added at the end of the polymerization process or after the polymerization process. If added after the polymerization process, the chain extender may be incorporated by compounding or by addition during the conversion process, 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, such as from about 0.1 to about 5 weight percent, based on the total weight of the polyester.
In one embodiment, at least one phosphorus compound may be included with the polyesters and/or polyester compositions of the invention.
In one embodiment, the phosphorus compound may be an organic compound, such as a phosphorous acid (phosphorusacid) ester containing a halogenated or non-halogenated organic substituent. In certain embodiments, the phosphorus compound may comprise a wide variety of phosphorus compounds, such as phosphines, phosphites, phosphinites, phosphonites, phosphine oxides, and phosphates.
Examples of the phosphorus compound which can be used in the present invention may include tributyl phosphate, triethyl phosphate, tributyloxyethyl phosphate, t-butylphenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, ethyldimethyl phosphate, isodecyl diphenyl phosphate, trilauryl phosphate, triphenyl phosphate, tricresyl phosphate, tri (xylene) phosphate, t-butylphenyl diphenyl phosphate, resorcinol bis (diphenyl phosphate), tribenzyl phosphate, phenylethyl phosphate, trimethyl thiophosphate, phenylethyl thiophosphate, dimethyl methylphosphonate, diethyl pentylphosphonate, dilauryl methylphosphonate, diphenyl methylphosphonate, dibenzyl methylphosphonate, diphenyl methylphosphonate, dimethyl tolylphosphonate, dimethyl methylphosphonate, dimethyl methylphosphinate phenyl diphenylphosphinate, benzyl diphenylphosphinate, methyl diphenylphosphinate, trimethylphosphine oxide, triphenylphosphine oxide, tribenzyl phosphine oxide, 4-methyldiphenylphosphine oxide, triethyl phosphite, tributyl phosphite, trilauryl phosphite, triphenyl phosphite, tribenzyl phosphite, phenyl diethyl phosphite, phenyl dimethyl phosphite, benzyl dimethyl phosphite, dimethyl methylphosphinate, diethyl pentylphosphinate, diphenyl methylphosphinate, dibenzyl methylphosphinate, dimethyl tolylphosphinate, methyl dimethylphosphinate, methyl diethylphosphinate, phenyl diphenylphosphinate, methyl diphenylphosphinate, benzyl diphenylphosphinate, triphenylphosphine, tribenzyl triphenylphosphine and methyl diphenylphosphine. In one embodiment, triphenylphosphine oxide is excluded as a heat stabilizer in the process (es) for making the polyester of the invention and/or in the polyester composition(s) of the invention.
In one embodiment, the phosphorus compounds useful in the present invention can be any of the above-described phosphorus-based acids in which one or more hydrogen atoms of the acid compound (bonded to an oxygen or phosphorus atom) are replaced with an alkyl, branched alkyl, substituted alkyl, alkyl ether, substituted alkyl ether, alkyl-aryl, alkyl-substituted aryl, substituted aryl, and mixtures thereof. In another embodiment, phosphorus compounds useful in the present invention include, but are not limited to, the above compounds in which at least one hydrogen atom bonded to an oxygen atom of the compound is replaced with a metal ion or an ammonium ion.
The esters may contain alkyl groups, branched alkyl groups, substituted alkyl groups, alkyl ethers, aryl groups, and/or substituted aryl groups. The esters may also have at least one alkyl group and at least one aryl group. The number of ester groups present in a particular phosphorus compound may be from 0 to the maximum allowable based on the number of hydroxyl groups present on the phosphorus compound used. For example, the alkyl phosphate esters may include one or more of mono-, di-, and tri-alkyl phosphate esters; aryl phosphates include one or more of mono-, di-, and tri-aryl phosphates; and alkyl and/or aryl phosphates also include, but are not limited to, mixed alkyl aryl phosphates having at least one alkyl group and at least 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, aryl, or mixed alkylaryl or partial esters of phosphinic acid. The alkyl or aryl group may contain one or more substituents.
In one embodiment, the phosphorus compounds useful in the present invention comprise at least one phosphorus compound selected from at least one of substituted or unsubstituted alkyl phosphates, substituted or unsubstituted aryl phosphates, substituted or unsubstituted mixed alkyl aryl phosphates, bisphosphites, phosphates, phosphine oxides, and mixed aryl alkyl phosphites, reaction products thereof, and mixtures thereof. The 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 alkyl aryl phosphates, reaction products thereof, and mixtures thereof. The 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 another embodiment, the phosphate esters useful in the present invention may include, but are not limited to, alkyl phosphate esters, aryl phosphate esters, mixed alkyl aryl phosphate esters, and/or mixtures thereof.
In certain embodiments, the phosphates useful in the present invention are those wherein the 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. Certain preferred embodiments include trialkyl phosphates, triaryl phosphates, alkyl diaryl phosphates, dialkyl aryl phosphates, and mixtures of these phosphates, wherein alkyl groups are preferably those containing 2 to 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 the aryl is phenyl or substituted phenyl, wherein groups such as alkyl, branched alkyl, aryl, hydroxy, etc., replace a hydrogen at any carbon position on the phenyl ring. Preferred aryl groups include phenyl or substituted phenyl wherein groups such as alkyl, branched alkyl, aryl, hydroxy and the like are substituted for 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 mixtures thereof, including in particular mixtures of tributyl phosphate and tricresyl phosphate, and mixtures of isocetyl diphenyl phosphate and 2-ethylhexyl diphenyl phosphate.
In one embodiment, at least one phosphorus compound useful in the present invention comprises at least one aryl phosphate.
In one embodiment, at least one phosphorus compound useful in the present invention comprises at least one unsubstituted aryl phosphate.
In one embodiment, at least one phosphorus compound useful in the present invention comprises at least one aryl phosphate ester that is not substituted with a benzyl group.
In one embodiment, any phosphorus compound useful in the present invention may comprise at least one alkyl phosphate.
In one embodiment, the phosphate esters useful as heat stabilizers and/or color stabilizers in the present invention include, but are not limited to, at least one of the following: trialkyl phosphates, triaryl phosphates, alkyl diaryl phosphates, and mixed alkyl aryl phosphates.
In one embodiment, the phosphate esters useful as heat stabilizers and/or color stabilizers in the present invention include, but are not limited to, at least one of the following: triaryl phosphates, alkyl diaryl phosphates, and mixed alkyl aryl phosphates.
In one embodiment, the phosphate esters useful as heat stabilizers and/or color stabilizers in the present invention 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, the at least one heat stabilizer includes, but is not limited to, merpol a. In one embodiment, the at least one heat stabilizer useful in the present invention includes, but is not limited to, at least one of triphenyl phosphate and Merpol a. Merpol A is a phosphate ester available from Stepan Chemical Co and/or E.I.duPont de Nemours & Co. The CAS Registry number for Merpol A is believed to be CAS Registry #37208-27-8.
In one embodiment, any phosphorus compound useful in the present invention may comprise at least one triaryl phosphate ester that is not substituted with a benzyl group.
In one embodiment, the polyester compositions and/or methods of the present invention can comprise 2-ethylhexyl diphenyl phosphate.
In one embodiment, any of the methods described herein for making any polyester composition and/or polyester may comprise at least one mixed alkylaryl phosphite, such as bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, also known as dovephos-9228 (Dover Chemicals, CAS # 15486243-8).
In one embodiment, any of the methods described herein for making any of the polyester compositions and/or polyesters can comprise at least one phosphine oxide.
In one embodiment, any of the methods described herein for making any of the polyester compositions and/or polyesters may comprise at least one phosphate salt, such as KH 2 PO 4 And Zn 3 (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 a polyester, as well as the product of a polycondensation or esterification reaction between a catalyst and any other type of additive.
In one embodiment of the present invention, the phosphorus compounds useful in the present invention may act as heat stabilizers. In one embodiment of the present invention, the phosphorus compounds useful in the present invention may not act as heat stabilizers but may act as color stabilizers. In one embodiment of the present invention, the phosphorus compounds useful in the present invention may act as both a heat stabilizer and a color stabilizer.
In one embodiment, the amount of phosphate of the present invention added during the polymerization is selected from the following: 10 to 200ppm based on the total weight of the polyester composition and measured as phosphorus atoms in the final polyester. In embodiments of the present 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 lithium compound. In one embodiment, the lithium compound may be used in an esterification reaction or a polycondensation reaction or both. In one embodiment, the catalyst system comprises at least one lithium compound for the esterification reaction. In one embodiment, the catalyst system contains at least one lithium compound for the polycondensation reaction.
In one embodiment of the present invention, in one embodiment, the polyester composition of the present invention may comprise 5 to 500ppm, or 5 to 450ppm, or 5 to 400ppm, or 5 to 350ppm, or 5 to 300ppm, or 5 to 250ppm, or 5 to 200ppm, or 5 to 150ppm, or 5 to 125ppm, or 5 to 100ppm, or 5 to 90ppm, or 5 to 85ppm, or 5 to 80ppm, or 5 to 75ppm, or 5 to 70ppm, or 5 to 65ppm, or 5 to 60ppm, or 10 to 500ppm, or 10 to 450ppm, or 10 to 400ppm, or 10 to 350ppm, or 10 to 300ppm, based on the mass of the final polyester produced or 10 to 250ppm, or 10 to 200ppm, or 10 to 150ppm, or 10 to 125ppm, or 10 to 100ppm, or 10 to 90ppm, or 10 to 80ppm, or 10 to 75ppm, or 10 to 70ppm, or 10 to 65ppm, or 10 to 60ppm, or 25 to 500ppm, or 25 to 450ppm, or 25 to 400ppm, or 25 to 350ppm, or 25 to 300ppm, or 25 to 250ppm, or 25 to 200ppm, or 25 to 150ppm, or 25 to 125ppm, or 25 to 100ppm, or 25 to 90ppm, or 25 to 80ppm, or 25 to 75ppm or 10 to 250ppm, or 10 to 200ppm, or 10 to 150ppm, or 10 to 125ppm, or 10 to 100ppm, or 10 to 90ppm, or 10 to 80ppm, or 10 to 75ppm, or 10 to 70ppm, or 10 to 65ppm, or 10 to 60ppm, or 25 to 500ppm or 25 to 450ppm, or 25 to 400ppm, or 25 to 350ppm, or 25 to 300ppm, or 25 to 250ppm, or 25 to 200ppm, or 25 to 150ppm, or 25 to 125ppm, or 25 to 100ppm, or 25 to 90ppm, or 25 to 80ppm, or 25 to 75 ppm.
In one embodiment, the amount of lithium atoms present in the polyesters of the invention can generally be at least 5ppm, or at least 8ppm, or at least 10ppm, or at least 15ppm, or at least 20ppm, or at least 25ppm, or at least 30ppm, or at least 35ppm, or at least 40ppm, or at least 45ppm, or at least 50ppm, and less than 100ppm, or less than 90ppm, or less than 80ppm, or less than 75ppm, or less than 70ppm, or less than 65ppm, or less than 60ppm, based on the total weight of the polymer.
In one embodiment, the lithium atom may range from 10ppm to 100ppm, or 20ppm to 100ppm, or 25ppm to 100ppm, or 30ppm to 100ppm, or 35ppm to 100ppm, or 40ppm to 100ppm, or 45ppm to 100ppm, or 50ppm to 100ppm, or 10ppm to 75ppm, or 15ppm to 75ppm, or 20ppm to 75ppm, or 25ppm to 75ppm, or 30ppm to 75ppm, or 35ppm to 75ppm, or 40ppm to 75ppm, or 45ppm to 75ppm, or 50ppm to 75ppm, or 10ppm to 65ppm, or 20ppm to 65ppm, or 30ppm to 65ppm, or 35ppm to 65ppm, or 40ppm to 65ppm, or 45ppm to 65ppm, or 50ppm to 65ppm, based on the total weight of the copolyester.
In one embodiment of the present invention, in one embodiment, the polyester composition of the present invention may comprise 5 to 500ppm, or 5 to 450ppm, or 5 to 400ppm, or 5 to 350ppm, or 5 to 300ppm, or 5 to 250ppm, or 5 to 200ppm, or 5 to 150ppm, or 5 to 125ppm, or 5 to 100ppm, or 5 to 90ppm, or 5 to 85ppm, or 5 to 80ppm, or 5 to 75ppm, or 5 to 70ppm, or 5 to 65ppm, or 5 to 60ppm, or 10 to 500ppm, or 10 to 450ppm, or 10 to 400ppm, or 10 to 350ppm, or 10 to 300ppm, based on the mass of the final polyester produced or 10 to 250ppm, or 10 to 200ppm, or 10 to 150ppm, or 10 to 125ppm, or 10 to 100ppm, or 10 to 90ppm, or 10 to 80ppm, or 10 to 75ppm, or 10 to 70ppm, or 10 to 65ppm, or 10 to 60ppm, or 25 to 500ppm, or 25 to 450ppm, or 25 to 400ppm, or 25 to 350ppm, or 25 to 300ppm, or 25 to 250ppm, or 25 to 200ppm, or 25 to 150ppm, or 25 to 125ppm, or 25 to 100ppm, or 25 to 90ppm, or 25 to 80ppm, or 25 to 75ppm or 10 to 250ppm, or 10 to 200ppm, or 10 to 150ppm, or 10 to 125ppm, or 10 to 100ppm, or 10 to 90ppm, or 10 to 80ppm, or 10 to 75ppm, or 10 to 70ppm, or 10 to 65ppm, or 10 to 60ppm, or 25 to 500ppm or 25 to 450ppm, or 25 to 400ppm, or 25 to 350ppm, or 25 to 300ppm, or 25 to 250ppm, or 25 to 200ppm, or 25 to 150ppm, or 25 to 125ppm, or 25 to 100ppm, or 25 to 90ppm, or 25 to 80ppm, or 25 to 75 ppm.
In one embodiment, the amount of aluminum atoms present in the polyesters of the invention can generally be at least 5ppm, or at least 8ppm, or at least 10ppm, or at least 15ppm, or at least 20ppm, or at least 25ppm, or at least 30ppm, or at least 35ppm, or at least 40ppm, or at least 45ppm, or at least 50ppm, and less than 100ppm, or less than 90ppm, or less than 80ppm, or less than 75ppm, or less than 70ppm, or less than 65ppm, or less than 60ppm, based on the total weight of the polymer.
In one embodiment, the amount of aluminum atoms by weight relative to the mass of the final polyester produced may be 10ppm to 100ppm, or 20ppm to 100ppm, or 25ppm to 100ppm, or 30ppm to 100ppm, or 35ppm to 100ppm, or 40ppm to 100ppm, or 45ppm to 100ppm, or 50ppm to 100ppm, or 10ppm to 75ppm, or 15ppm to 75ppm, or 20ppm to 75ppm, or 25ppm to 75ppm, or 30ppm to 75ppm, or 35ppm to 75ppm, or 40ppm to 75ppm, or 45ppm to 75ppm, or 50ppm to 75ppm, or 10ppm to 65ppm, or 20ppm to 65ppm, or 30ppm to 65ppm, or 35ppm to 65ppm, or 40ppm to 65ppm, or 45ppm to 65ppm, or 50ppm to 65ppm.
In one embodiment, the ratio of lithium atoms to aluminum atoms in ppm relative to the mass of the final polyester produced in the polyester composition of the present invention is 1:5 to 5:1, 1:4 to 4:1, or 1:3 to 3:1, or 1:2 to 2:1, or 1-1.25:1.
In one embodiment of the present invention, in one embodiment, the polyester composition of the present invention may have a concentration of 10 to 1000ppm, or 10 to 800ppm, or 10 to 600ppm, or 10 to 500ppm, or 10 to 450ppm, or 10 to 400ppm, or 10 to 300ppm, or 10 to 250ppm, or 10 to 200ppm, or 10 to 150ppm, or 50 to 1000ppm, or 50 to 800ppm, or 50 to 600ppm, or 50 to 500ppm, or 50 to 450ppm, or 50 to 400ppm, or 50 to 300ppm, or 50 to 250ppm, or 50 to 200ppm, or 50 to 150ppm, or 100 to 1000ppm, or 100 to 800ppm, or 100 to 600ppm, or 100 to 500ppm, or 100 to 400ppm, or 100 to 300ppm, or 100 to 250ppm, based on the mass of the final polyester produced or 100 to 200ppm, or 100 to 150ppm, or 80 to 150ppm, or 200 to 1000ppm, or 200 to 800ppm, or 200 to 600ppm, or 200 to 500ppm, or 200 to 400ppm, or 300 to 1000ppm, or 300 to 800ppm, or 300 to 600ppm, or 300 to 500ppm, or 300 to 400ppm, or 400 to 1000ppm, or 400 to 800ppm, or 400 to 600ppm, or 500 to 1000ppm, or 500 to 800ppm, or 500 to 700ppm, or less than 500ppm, or less than 400ppm, or less than 300ppm, or less than 250ppm, or less than 225ppm, or less than 200ppm, or less than 150 ppm.
In one embodiment, the ratio of lithium atoms to aluminum atoms in ppm relative to the mass of the final polyester produced in the polyester composition of the present invention is from 1:5 to 5:1, from 1:4 to 4:1, or from 1:3 to 3:1, or from 1:2 to 2:1.
The lithium-containing compounds useful in the present invention include any lithium-containing compound including, but not limited to, at least one of the following: lithium carbonate, lithium acetate, lithium benzoate, lithium succinate, lithium acetylacetonate, lithium methoxide, lithium oxalate, lithium nitrate, lithium ethoxide, lithium hydroxide, lithium hydride, lithium glycol (lithium glycoxide), lithium alkyl, lithium aluminum hydride, lithium borohydride, and lithium oxide.
In one embodiment, the polyester composition of the present invention comprises at least one lithium source comprising at least one of: lithium acetate, lithium acetylacetonate, lithium hydroxide, lithium carbonate, lithium oxalate or lithium nitrate.
In one embodiment, the polyester composition of the present invention comprises at least one lithium source which is lithium acetylacetonate.
In one embodiment, the amount of lithium atoms present in the polyesters of the invention may generally be at least 5ppm, or at least 8ppm, or at least 10ppm, or at least 15ppm, or at least 20ppm, or at least 25ppm, or at least 30ppm, or at least 35ppm, or at least 40ppm, or at least 45ppm, or at least 50ppm, and less than 100ppm, or less than 90ppm, or less than 80ppm, or less than 75ppm, or less than 70ppm, or less than 65ppm, or less than 60ppm, or less than 55ppm, relative to the mass of the final polyesters produced.
In one embodiment, the polyester is produced, relative to the mass of the final polyester produced, the range of lithium atom by weight may be 10ppm to 100ppm, or 20ppm to 100ppm, or 25ppm to 100ppm, or 30ppm to 100ppm, or 35ppm to 100ppm, or 40ppm to 100ppm, or 45ppm to 100ppm, or 50ppm to 100ppm, or 10ppm to 75ppm, or 15ppm to 75ppm, or 20ppm to 75ppm, or 25ppm to 75ppm, or 30ppm to 75ppm, or 35ppm to 75ppm, or 40ppm to 75ppm, or 45ppm to 75ppm, or 50ppm to 75ppm, or 10ppm to 65ppm, or 20ppm to 65ppm, or 30ppm to 65ppm, or 35ppm to 65ppm, or 40ppm to 65ppm, or 45ppm to 65ppm, 10ppm to 50ppm, or 20ppm to 50ppm, or 30ppm to 50ppm, or 35ppm to 50ppm, or 40ppm to 50ppm, 10ppm to 40ppm, or 20ppm to 40ppm, or 30ppm to 40ppm, or 10ppm to 35ppm, or 35ppm to 35ppm, or 20ppm to 65ppm, or 30ppm to 30ppm, or 30ppm to 65 ppm.
In one embodiment, the catalyst mixture contains at least one aluminum compound. In one embodiment, the aluminum compound may be used in an esterification reaction or a polycondensation reaction or both. In one embodiment, the catalyst system comprises at least one aluminum compound for the esterification reaction. In one embodiment, the catalyst mixture contains at least one aluminum compound for the polycondensation reaction.
In one embodiment, the polyester composition may comprise at least one catalytically active aluminum source. These aluminum compounds may include aluminum compounds having at least one organic substituent.
Suitable examples of the aluminum compound may include at least one of: aluminum carboxylates such as aluminum acetate (if dissolved), aluminum benzoate, aluminum sulfate, aluminum lactate, aluminum laurate, aluminum stearate, aluminum alkoxide, aluminum ethoxide, aluminum isopropoxide (also known as aluminum isopropoxide), aluminum tri-n-butoxide (aluminum tri-tert-butoxide), aluminum di-iso-butoxide and aluminum chelates in which the alkoxy groups of the aluminum alkoxide are partially or completely substituted with a chelating agent such as alkyl acetoacetates or acetylacetones such as aluminum acetoacetate di-iso-propoxide (ethyl acetoacetate aluminum diisopropylate), aluminum tri (acetoacetate) tris (ethyl acetoacetate), alkyl acetoacetates, aluminum di-iso-propoxide (aluminum diisopropylate), aluminum mono-acetoacetate bis (acetoacetate) aluminum monoacetylacetate bis (ethyl acetoacetate), aluminum tri (acetoacetate) or aluminum acetylacetonate.
In one embodiment, the polyester composition of the present invention may contain aluminum hydroxide, aluminum acetylacetonate, aluminum acetate, aluminum isopropoxide, or aluminum sulfate.
In one embodiment, the polyester composition of the present invention may comprise at least one aluminum source selected from aluminum acetylacetonate and aluminum isopropoxide.
In one embodiment, the polyester composition of the present invention may comprise at least one aluminum source selected from aluminum acetylacetonate.
In one embodiment, the amount of aluminum atoms present in the polyesters of the invention may generally be at least 5ppm, or at least 8ppm, or at least 10ppm, or at least 15ppm, or at least 20ppm, or at least 25ppm, or at least 30ppm, or at least 35ppm, or at least 40ppm, or at least 45ppm, or at least 50ppm, and less than 100ppm, or less than 90ppm, or less than 80ppm, or less than 75ppm, or less than 70ppm, or less than 65ppm, or less than 60ppm, or less than 55ppm, relative to the mass of the final polyesters produced.
In one embodiment, the polyester is produced, relative to the mass of the final polyester produced, the aluminum atom may range from 10ppm to 100ppm, or from 20ppm to 100ppm, or from 25ppm to 100ppm, or from 30ppm to 100ppm, or from 35ppm to 100ppm, or from 40ppm to 100ppm, or from 45ppm to 100ppm, or from 50ppm to 100ppm, or from 10ppm to 75ppm, or from 15ppm to 75ppm, or from 20ppm to 75ppm, or from 25ppm to 75ppm, or from 30ppm to 75ppm, or from 35ppm to 75ppm, or from 40ppm to 75ppm, or from 45ppm to 75ppm, or from 50ppm to 75ppm, or from 10ppm to 65ppm, or from 20ppm to 65ppm, or from 30ppm to 65ppm, or from 35ppm to 65ppm, or from 45ppm to 65ppm, from 10ppm to 50ppm, or from 20ppm to 50ppm, or from 30ppm to 50ppm, or from 35ppm to 50ppm, or from 40ppm, from 10ppm to 40ppm, or from 20ppm to 40ppm, or from 30ppm to 40ppm, or from 10ppm to 35ppm, or from 20ppm to 65ppm, or from 30ppm to 30ppm, or from 30ppm.
In one embodiment, suitable catalysts for use in the process of the present invention for making polyesters useful in the present invention include at least one lithium compound and one aluminum compound. In certain embodiments, other catalysts are possible for use in the present invention in combination with the at least one lithium compound and the at least one aluminum compound. Other catalysts may include, but are not limited to, those based on gallium, zinc, 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, 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 titanium atoms and/or tin atoms.
In one embodiment, the polyester composition of the present invention may comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of manganese atoms.
In one embodiment, the polyester composition of the present invention may comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of zinc atoms.
In one embodiment, the polyester composition of the present invention may comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of any of titanium atoms, tin atoms, and/or manganese atoms.
In one embodiment, the polyester composition of the present invention may comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of any of titanium atoms, tin atoms, and/or zinc atoms.
In one embodiment, the polyester composition of the present invention may comprise less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of any of titanium atoms, tin atoms, manganese atoms, and/or zinc atoms.
In embodiments of the invention, the Tg of the polyester may be selected from one of the following ranges: 85 to 130 ℃, or 100 to 125 ℃, or 100 to 120 ℃.
In one embodiment, the polyester composition of the present invention may comprise a polyester 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 embodiment, the intrinsic viscosity for all of the polyester compositions of the present invention, as measured in 60/40 (weight/weight) phenol/tetrachloroethane at a concentration of 0.5g/100ml at 25 ℃, can 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 0.50 to 1.2dL/g, or from 0.50 to 0.80dL/g, or from 0.50 to 0.75dL/g, or from 0.50 to 0.70dL/g, or from 0.50 to 0.65dL/g, or from 0.50 to 0.60dL/g, or from 0.55 to 0.75dL/g, or from 0.55 to 0.70dL/g, or from 0.60 to 0.75dL/g, or from 0.60 to 0.70dL/g.
The compositions useful in the present invention are expected to have at least one intrinsic viscosity range as described herein and at least one monomer range of the compositions described herein, unless otherwise indicated. The compositions useful in the present invention are also contemplated to have at least one T as described herein, unless otherwise indicated g Ranges and at least one monomer range of the compositions described herein. The compositions useful in the present invention are also contemplated to have at least one intrinsic viscosity range as described herein, at least one T as described herein, unless otherwise indicated g Ranges and at least one monomer range of the compositions described herein.
The polyester fraction useful in the polyester compositions of the invention can be produced by methods known in the literature, for example by means of a process in homogeneous solution, by means of transesterification in the melt and by means of a two-phase interface 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 ℃ and a pressure of 0.1 to 760mmHg for a time sufficient to form a polyester. For a process for producing polyesters, see U.S. Pat. No.3,772,405, the disclosure of which is incorporated herein by reference for such a process.
As described in more detail in U.S. patent No.2,720,507, incorporated herein by reference, polyesters can generally be prepared by condensing a dicarboxylic acid or ester with a glycol in an inert atmosphere in the presence of lithium catalyst(s) and aluminum(s) (and optionally other catalysts) as described herein at elevated temperatures, which gradually increase to temperatures of up to about 225-310 ℃ during condensation, and at low pressure at a later stage of the condensation.
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, TMCD, and ethylene glycol. In an embodiment, this 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 lithium catalyst and at least one aluminum catalyst at a temperature of 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 to 320 ℃ for 1 to 6 hours; and
(C) Any unreacted diol is removed.
The reaction time for the esterification step (a) depends on the temperature, pressure and the diol/dicarboxylic acid feed mole ratio selected.
In one embodiment, step (a) may be performed until more than 50% by weight of the TMCD has reacted. Step (a) may be performed at a pressure of 0psig to 100psig or not. The term "reaction product" as used in connection with any catalyst useful in the present invention refers to any product of a polycondensation or esterification reaction between the catalyst and any monomer used to make a polyester, as well as products of a polycondensation or esterification reaction between the catalyst and any other type of additive.
In certain embodiments, step (B) and step (C) may be performed simultaneously. These steps can be performed by methods known in the art, for example, by exposing the reaction mixture to a pressure of 0.002psig to below atmospheric pressure, or by bubbling hot nitrogen through the mixture.
In one embodiment, the present invention relates to a method of making 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% dimethyl terephthalate 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% CHDM residues;
wherein the molar ratio of diol component/dicarboxylic acid component added in step (I) is from 1.01 to 3.0/1.0, and wherein TMCD is added in an amount of about 10 to 50 mole% to obtain a final polymer having about 10 to 50 mole% TMCD residues;
wherein the mixture in step (I) is heated in the presence of:
(i) At least two catalysts comprising Li and Al; and (ii) 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 range of final pressure of step (I) to 0.02torr absolute pressure to form a final polyester;
wherein the total mole% of dicarboxylic acid component of the final polyester is 100 mole%; and wherein the total mole% of the glycol component of the final polyester is 100 mole%;
wherein the intrinsic viscosity of the polyester as measured in 60/40 (weight/weight) phenol/tetrachloroethane at a concentration of 0.25g/50ml at 25 ℃ is from 0.50 to 0.80dL/g; and wherein the L color value of the polyester as determined by the L x a x b x color system of CIE (International Commission on Illumination) is 75 or greater, or greater than 75.
In one embodiment, the polyesters useful in the present invention may comprise at least one phosphate compound, 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, at least one phosphorus compound may be added to step (I) only or step (II) only.
In embodiments of the present invention, at least one phosphorus compound, reaction products thereof, and mixtures thereof may be added during esterification, polycondensation, or both, and/or it may be added after polymerization. In one embodiment, the phosphorus compounds useful in any of the methods of the present invention may be added during the esterification process. In one embodiment, if the phosphorus compound is added after esterification and polycondensation, it is added in an amount of 0 to 2 weight percent 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 weight percent based on the total weight of the final polyester. In one embodiment, the phosphorus compound may comprise at least one phosphate ester. In one embodiment, the phosphorus compound may comprise at least one phosphorus compound added during the esterification step. In one embodiment, the phosphorus compound may comprise at least one phosphate ester added, for example, during the esterification step.
The reaction time of esterification step (I) for any of the processes of the present invention depends on the temperature, pressure and the diol/dicarboxylic acid feed molar ratio selected.
In one embodiment, the pressure used in step (II) of any of the methods of the present invention consists of at least one pressure selected from the group consisting of 20torr absolute to 0.02torr absolute; in one embodiment, the pressure used in step (II) of any of the methods of the present invention consists of at least one pressure selected from the group consisting of 10torr absolute to 0.02torr absolute; in one embodiment, the pressure used in step (II) of any of the methods of the present invention consists of at least one pressure selected from the group consisting of 5torr absolute to 0.02torr absolute; in one embodiment, the pressure used in step (II) of any of the methods of the present invention consists of at least one pressure selected from the group consisting of 3torr absolute to 0.02torr absolute; in one embodiment, the pressure used in step (II) of any of the methods of the present invention consists of at least one pressure selected from the group consisting of 20torr absolute to 0.1torr absolute; in one embodiment, the pressure used in step (II) of any of the methods of the present invention consists of at least one pressure selected from the group consisting of 10torr absolute to 0.1torr absolute; in one embodiment, the pressure used in step (II) of any of the methods of the present invention consists of at least one pressure selected from the group consisting of 5torr absolute to 0.1torr absolute; in one embodiment, the pressure used in step (II) of any of the methods of the present invention consists of at least one pressure selected from the group consisting of 3torr absolute to 0.1torr absolute.
In one embodiment, the molar ratio of diol component/dicarboxylic acid component added in step (I) of the process of the present invention is from 1.0 to 2.0/1.0; in one embodiment, the molar ratio of diol component/dicarboxylic acid component added in step (I) of the process of the present invention is from 1.01 to 2.0/1.0; in one embodiment, the molar ratio of diol component/dicarboxylic acid component added in step (I) of the process of the present invention is from 1.01 to 1.75/1.0; in one embodiment, the molar ratio of diol component/dicarboxylic acid component added in step (I) of the process of the present invention is from 1.01 to 1.7/1.0; in one embodiment, the molar ratio of diol component/dicarboxylic acid component added in step (I) of the process of the present invention is from 1.01 to 1.5/1.0; in one embodiment, the molar ratio of diol component/dicarboxylic acid component added in step (I) of the process of the present invention is from 1.01 to 1.2/1.0.
In embodiments of the present invention for the process for making polyesters, the heating time of step (II) may be from 1 to 5 hours or from 1 to 4 hours or from 1 to 3 hours or from 1.5 to 3 hours or from 1 to 2 hours. In one embodiment, the heating time of step (II) may be 1.5 to 3 hours.
In one embodiment, the polyesters, polyester compositions and/or methods of the invention useful in the present invention can comprise lithium atoms, aluminum atoms, and optionally, phosphorus atoms.
The invention further relates to a polyester composition made by the above process.
In embodiments of the present invention, certain agents that color the polymer may be added to the melt. In one embodiment, a blue-emitting toner is added to the melt to reduce b-x of the resulting polyester polymer melt phase product. Such bluing agents include blue inorganic and organic toner(s). In addition, red toner(s) may also be used to adjust a color. Toner(s) may be used, such as blue and red toner(s), as described in U.S. Pat. nos. 5,372,864 and 5,384,377, which are incorporated herein by reference in their entirety. The toner(s) 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 ethylene glycol.
The total amount of added toner components may depend on the amount of yellow color inherent in the base polyester and the effectiveness of the toner. In one embodiment, a total toner component concentration of up to about 15ppm is used, with a minimum concentration of about 0.5 ppm. In one embodiment, the total amount of bluing additives may be from 0.5 to 10ppm. In one embodiment, the toner may be added to the esterification zone or polycondensation zone. The toner is preferably added to the esterification zone or to an early stage of the polycondensation zone, such as a prepolymerization reactor.
The invention also relates to a polymer blend. 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.
Suitable examples of polymer components include, but are not limited to, nylon; polyesters other than those described herein, such as PET; polyamides, e.g. from DuPontA polystyrene; a polystyrene copolymer; styrene acrylonitrile copolymer; acrylonitrile butadiene styrene copolymer; poly (methyl methacrylate); an acrylic copolymer; poly (ether-imides), e.g. +.>(poly (ether-imide) from general electric); polyphenylene ethers, such as poly (2, 6-dimethyl-phenyl ether) or poly (phenyl ether)/polystyrene blends, such as NORYL +>(blend of poly (2, 6-dimethyl-phenyl ether) and polystyrene resin from General Electric); polyphenylene sulfide; polyphenylene sulfide/sulfone; poly (ester-carbonate); polycarbonates, e.g.(polycarbonate from General Electric); polysulfone; polysulfone ether; and poly (ether-ketone) s of aromatic dihydroxy compounds; or a mixture of any of the foregoing polymers. The blend may be prepared by conventional processing techniques known in the art, such as melt blending or solution blending.
In one embodiment, the final polyester composition of the present invention may be blended with recycled poly (ethylene terephthalate) (rPET).
In embodiments, the polyester compositions and polymer blend compositions may also contain from 0.01 to 25 weight percent of the total composition of conventional additives such as colorants, toner(s), dyes, mold release agents, flame retardants, plasticizers, nucleating agents, stabilizers, including but not limited to ultraviolet stabilizers, heat stabilizers other than the phosphorus compounds described herein and/or reaction products thereof, fillers and impact modifiers. Examples of commercially available impact modifiers include, but are not limited to, ethylene/propylene terpolymers, functionalized polyolefins such as those containing methyl acrylate and/or glycidyl methacrylate, styrene-based block copolymer impact modifiers, and various acrylic core/shell impact modifiers. Residues of such additives are also 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 fiberglass, a mixture of glass and talc, a mixture of glass and mica, and a mixture of glass and polymeric fibers.
In one embodiment, the polyester composition can be used in shaped articles, including but not limited to extruded and/or molded articles, including but not limited to injection molded articles, extruded articles, cast extruded articles (cast extrusion 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 film(s) and/or sheet(s) comprising the polyester(s) and/or polyester composition of the present invention.
In one embodiment, the present invention relates to an article of manufacture comprising a thermoformed film and/or sheet 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 possible 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 resistant glass, skylights, coating(s), coated articles, painted articles, shoe stiffener(s), laminates, medical packaging, universal 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, sunglass frames, lenses, sports kettles, drinking ware, food containers, medical devices and connectors, medical housings, electronic housings, cable assemblies, sound absorbing articles, cosmetic containers, wearable electronics, toys, promotional articles, electrical parts, automotive interior parts and consumer household articles.
In one embodiment, the process for making polyesters useful in the present invention may comprise a batch or continuous process.
In one embodiment, the process for making polyesters useful in the present invention comprises a continuous process.
In one embodiment, any method of making polyesters useful in the present invention and described herein or known to one of ordinary skill in the art may be used to make 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 the method used to make them, and any products made therefrom.
In one embodiment, the present invention relates to an article of manufacture, such as a shaped article, comprising any of the polyesters and/or polyester compositions of the invention.
Because of the long semi-crystallization time at 170 ℃ (e.g., greater than 5 minutes) exhibited by certain polyesters useful in the present invention, it is possible to produce articles 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 an article of manufacture provided by the present invention. The polyesters of the invention may be amorphous or semi-crystalline. In one embodiment, certain polyesters useful in the present invention may have relatively low crystallinity. Certain polyesters useful in the present invention may thus have a substantially amorphous state, meaning that the polyester comprises substantially disordered polymer regions.
In one embodiment, certain polyesters and/or polyester compositions of the invention may be visually clear. The term "visually clear" is defined herein as the apparent absence of haze (cloudiness), blurriness (haziness), or uncleanness (muldiness) upon visual inspection.
In one embodiment, the polyesters of the invention and/or the polyester compositions of the invention [ in one embodiment, with and/or without the presence of toner(s) ] can have color values L, a, and b that can be determined using Hunter Lab Ultrascan Spectra Colorimeter manufactured by Hunter Associates Lab inc., reston, va. Color measurements are the average values measured on polyester pellets or on plaques or other objects injection molded or extruded from them. They were determined by the color system of L x a x b x CIE (International Commission on Illumination) (translation), where L x represents the luminance coordinates, a x represents the red/green coordinates, and b x represents the yellow/blue coordinates.
In certain embodiments, the b-value of the polyesters and/or polyester compositions of the invention, as determined by the L-a-b color system of CIE (International Commission on Illumination), can be from-10 to less than 20, or from-10 to less than 10, or from 1 to less than 20, or from 5 to less than 20, or from 8 to less than 20, or from-3 to 10, or from-5 to 5, or from-5 to 4, or from-5 to 3, or from 1 to 10, or from 1 to 9, or from 1 to 8, 1 to 7, or from 1 to 6, or from 1 to 5, or less than 20, or less than 15, or less than 10, or less than 8, or less than 7, or less than 6, or less than 5, or less than 4, or less than 3.
In certain embodiments, the L values of the polyesters and/or polyester compositions of the invention as determined by the L x a x b x color system of CIE (International Commission on Illumination) 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 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 75 to 85, or 70 to 80, or 75 to 95, or 75 to 90, or 75 to 85, or 80 to 90.
In one embodiment, these values may be obtained in the presence and/or absence of toner(s). Notched Izod impact strength as described in ASTM D256 is a common method of measuring toughness. In one embodiment, the polyesters and/or polyester compositions of the invention can have a notched Izod impact strength of at least 1 ft-lbs/inch, or at least 2 ft-lbs/inch, or at least 3 ft-lbs/inch, or 7.5 ft-lbs/inch, or 10 ft-lbs/inch at 23℃with a 10-mil notch in a 1/8 inch thick bar according to ASTM D256.
Notched Izod impact strength was measured at 23℃using a 10-mil notch in a 3.2mm (1/8 inch) thick bar according to ASTM D256. In one embodiment, certain polyesters and/or polyester compositions of the invention can exhibit a notched Izod impact strength of at least 25J/m (0.47 ft-lb/in) measured at 23℃with a 10-mil notch in a 3.2mm (1/8 inch) thick bar according to ASTM D256. In one embodiment, certain polyesters and/or polyester compositions of the invention can exhibit notched Izod impact strength of about 25J/m (0.47 ft-lb/in) to about 75J/m (1.41 ft-lb/in) measured with a 10-mil notch at 23℃in a 3.2mm (1/8 inch) thick rod according to ASTM D256. In another embodiment, certain polyesters and/or polyester compositions of the invention can exhibit notched Izod impact strength of about 50J/m (0.94 ft-lb/in) to about 75J/m (1.41 ft-lb/in) measured with a 10-mil notch at 23℃in a 3.2mm (1/8 inch) thick bar according to ASTM D256.
In one embodiment, certain polyesters and/or polyester compositions of the invention may exhibit at least one of the following densities: a density of greater than 1.2g/ml at 23 ℃.
In one embodiment, certain inventive polyesters and/or polyester compositions useful in the present invention may exhibit useful thermal stability of no greater than 0.20dL/g, or no greater than 0.15dL/g, or no greater than 0.12dL/g, or no greater than 0.10dL/g of intrinsic viscosity, when heated at 300℃for 1 to 5 hours, or 1 to 4 hours, or 1 to 3 hours, or 2 to 3 hours, or 2.5 hours, wherein the intrinsic viscosity is measured in 60/40 (weight/weight) phenol/tetrachloroethane at a concentration of 0.5g/100ml at 25 ℃.
In one embodiment, certain polyesters and/or polyester compositions of the invention may exhibit a flexural modulus at 23 ℃ equal to or greater than 2000MPa (290,000 psi) as specified by ASTM D790. In another embodiment, certain polyesters useful in the present invention may exhibit a tensile strength at 23 ℃ of about 2000MPa (290,000 psi) to about 2551MPa (370,000 psi) as specified in ASTM D638. In another embodiment, certain polyesters useful in the present invention may exhibit flexural modulus at 23 ℃ of about 2000MPa (290,000 psi) to about 2413MPa (350,000 psi) as specified in ASTM D790.
In one embodiment, certain polyesters and/or polyester compositions of the invention may exhibit a flexural modulus at 23 ℃ equal to or greater than 2000MPa (290,000 psi) as specified by astm d 790. In another embodiment, certain polyesters of the invention may exhibit a tensile strength at 23 ℃ of about 2000MPa (290,000 psi) to about 2551MPa (370,000 psi) as specified in ASTM D638. In another embodiment, certain polyesters of the invention may exhibit a flexural modulus at 23 ℃ of about 2000MPa (290,000 psi) to about 2413MPa (350,000 psi) as specified in astm d 790.
Certain polyesters and/or polyester compositions of the invention can have at least one of the following properties: a Tg of about 85 to about 130 ℃ as measured by TA 2100 Thermal Analyst Instrument at a scan rate of 20 ℃/min; flexural modulus at 23 ℃ equal to or greater than 2000MPa (290,000 psi) as specified by astm d 790; and notched Izod impact strength equal to or greater than 25J/m (0.47 ft-lb/in) at 23℃using a 1/8 inch thick bar according to ASTM D256.
In certain embodiments, the final polyesters and/or polyester compositions of the invention can comprise methyl groups in an amount of 5.0 mole% or less, or 4.5 mole% or less, or 4 mole% or less, or 3 mole% or less, or 2.5 mole% or less, or 2.0 mole% or less, or 1.5 mole% or less, or 1.0 mole% or less, or 0.50 mole% or less.
In one embodiment, the polyester compositions of the present invention may be used in non-coating compositions, non-adhesive compositions, thermoplastic polyester compositions, articles of manufacture (articles of manufacture), shaped articles, thermoplastic shaped articles, molded articles, extruded articles, injection molded articles, blow molded articles, films and/or sheets (e.g., calendered, cast or extruded), thermoformed films or sheets, containers or bottles (e.g., baby bottles or sports kettles or water bottles).
In one embodiment, the present invention comprises a thermoplastic article, typically in sheet form, having embedded therein a decorative material comprising any of the compositions described herein.
In one embodiment, the polyesters according to the invention can be used in electrical parts. As used herein, "electrical component" refers to a rigid member used in conjunction with an electrical appliance. In one embodiment, the electrical component may be partially or completely separated from the electrical appliance. In another embodiment, the electrical component is a component typically made of a polymer. In one embodiment, the electrical component is visually clear.
In one embodiment, the polyesters according to the invention can be used for bottles and containers, including those injection molded, injection blow molded, injection stretch blow molded, blow molded or reheat blow molded. Articles made by these methods include double-walled cups, water bottles, sports kettles, bulk water containers and baby bottles.
The following examples further illustrate how the polyesters of the invention may be manufactured and evaluated, and are intended to be merely illustrative of the invention and are not intended to limit the scope thereof. Unless otherwise indicated, parts are parts by weight, temperature is in degrees celsius or room temperature, and pressure is at or near atmospheric pressure.
Examples
The following examples generally illustrate how the copolyesters of the invention are prepared and the effect of using certain catalysts on various copolyester properties, such as color and Intrinsic Viscosity (IV).
Measurement method
The intrinsic viscosity of the polyesters was determined in 60/40 (weight/weight) phenol/tetrachloroethane at 25℃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 MHz NMR spectrometer using chloroform-trifluoroacetic acid (70-30 v/v) for the polymer or 60/40 (wt/wt) phenol/tetrachloroethane with deuterated chloroform added for locking for the oligomer samples. Peak assignment to 2, 4-tetramethyl-1, 3-cyclobutanediol resonances was performed by comparison with the mono-and dibenzoates of model 2, 4-tetramethyl-1, 3-cyclobutanediol. These model compounds are very close to the resonance sites found in the polymers and oligomers.
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 inc., reston, va.) having the following parameters: (1) D65 light source, (2) 10 degree observer, (3) reflection mode including specular angle, (4) large area viewing angle, (5) 1 "port size. Unless otherwise specified, measurements were made on polymer particles ground to pass through a 1mm screen.
The amounts of aluminum (Al) and lithium (Li) in the following examples are reported in parts per million (ppm) of metal and measured by x-ray fluorescence (xrf) using a PANanalytical Axios Advanced wavelength dispersive x-ray fluorescence spectrometer. The phosphorus amount was similarly reported as ppm of elemental phosphorus and was also measured by xrf using the same instrument. The values reported in the "measured P" column in the examples below were obtained by measuring phosphorus as described above.
Unless otherwise specified, the cis/trans ratio of 2, 4-tetramethyl-1, 3-cyclobutanediol used in the examples below is about 50/50 and may be 45/55 to 55/45.
Preparation of the copolyesters of examples 1-17-examples 1-17
The preparation of the copolyesters of examples 1-17 as shown in Table 1 is illustrated by the preparation of the copolyester of example 5 having the target composition of 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, 0.077g of lithium acetylacetonate and 0.060g of aluminum acetylacetonate was placed in a 500 ml flask equipped with a nitrogen inlet, a metal stirrer and a short distillation column. The flask was placed in a Wood's metal bath which had been heated to 220 ℃. The stirring speed was set to 175RPM and held for 15 minutes. The flask contents were heated to 230 ℃ over 5 minutes while stirring was increased to 225RPM during this time. The contents were then warmed to 245 ℃ over 45 minutes. The contents were maintained at 245 ℃ while the pressure was reduced to 250torr over 3 minutes. The temperature was again raised to 265 ℃ over 15 minutes. The pressure was then reduced further to 3.5torr over 8 minutes. Finally, the temperature was raised to 277 ℃ over a 20 minute period while the stirring rate was slowly reduced to 50RPM and the pressure was reduced to 1torr. The reaction was maintained at such final temperature, pressure and stirring rate for 35 minutes. A high melt viscosity, visually clear polymer was obtained with an intrinsic viscosity of 0.64dl/g. NMR analysis showed the polymer to consist of 32.98% tmcd residues.
Table 1 contains TMCD; CHDM;100 mole% DMT; copolyester of LiAcAc (ppm) and aluminum isopropoxide (ppm)
Earlier experiments showed that lithium and aluminum co-operate to significantly incorporate TMCD into polyesters to give high intrinsic viscosities (examples 1, 2). Significant color improvement was observed with reduced total catalyst loading while TMCD incorporation and viscosity build remained very good (examples 3-6). Together, these results also demonstrate a good range of TMCD incorporation, which can be controlled by the molar ratio of the ethylene glycol charge.
A series of comparative polymers were prepared using tin and phosphorus catalyst packages as shown in table 2. Similar intrinsic viscosities and TMCD conversions were observed compared to lithium and aluminum, but it should be noted that phosphorus was believed to be required to reduce the color values to near those observed with lithium and aluminum.
Table 2 contains TMCD; CHDM;100 mole% DMT; copolyesters of Sn (ppm) and phosphorus (P) (ppm); [ the Sn source is butyltin tris (2-ethylhexanoate) ]
It is unexpected that Li/Al catalyst systems are advantageous compared to the use of tin catalyst systems in achieving similar good intrinsic viscosities and/or similar good colors (no phosphorus is required) as shown in table 2.
The present disclosure has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the disclosure.

Claims (21)

1. 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 1, 4-cyclohexanedimethanol residues;
wherein the total mole% of the dicarboxylic acid component is 100 mole%,
wherein the total mole% of the glycol component is 100 mole%; and
(2) A residue of the catalyst system comprising lithium atoms, aluminum atoms, and less than 30ppm, or less than 20ppm, or less than 10ppm, or less than 5ppm, or less than 2ppm, or from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of tin atoms.
2. The polyester composition of claim 1, wherein the polyester comprises a modified glycol comprising at least one of 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.
3. The polyester composition of claim 1 or 2 wherein the polyester comprises 2, 4-tetramethyl-1, 3-cyclobutanediol residues in an amount of from about 10 to about 45 mole%, or from about 15 to about 45 mole%, or from about 10 to about 40 mole%, or from about 20 to about 40 mole%, or from about 10 to about 30 mole%, or from about 20 to about 30 mole%, or from about 25 to about 40 mole%, or from about 30 to about 40 mole%.
4. The polyester composition of any of claims 1 to 3 wherein the polyester comprises 1, 4-cyclohexanedimethanol residues in an amount of about 55 to about 90 mole%, or about 55 to about 85 mole%, or about 60 to about 90 mole%, or about 60 to about 80 mole%, or about 70 to about 90 mole%, or about 70 to about 80 mole%, or about 60 to about 75 mole%, or about 60 to about 70 mole%, or 20 to 40 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 of any of claims 1-5, wherein the inherent viscosity of the polyester is 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 0.50 to 1.2dL/g, or from 0.50 to 0.80dL/g, or from 0.50 to 0.75dL/g, or from 0.50 to 0.70dL/g, or from 0.50 to 0.65dL/g, or from 0.50 to 0.60dL/g, or from 0.55 to 0.75dL/g, or from 0.55 to 0.70dL/g, or from 0.60 to 0.75dL/g, or from 0.60 to 0.70dL/g, as measured in 60/40 (weight/weight) phenol/tetrachloroethane at 25 ℃.
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 from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of titanium 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 from 0 to 30ppm, or from 0 to 20ppm, or from 0 to 10ppm, or 0ppm of manganese atoms.
9. The polyester composition of any of claims 1 to 8 comprising 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 zinc atoms.
10. The polyester composition of any of claims 1 to 9 comprising 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 germanium atoms.
11. The polyester composition of any of claims 1 to 10, wherein lithium atoms are present in an amount of 10 to 100ppm, or 20 to 100ppm, or 25 to 100ppm, or 30 to 100ppm, or 35 to 100ppm, or 40 to 100ppm, or 45 to 100ppm, or 50 to 100ppm, or 10 to 75ppm, or 15 to 75ppm, or 20 to 75ppm, or 25 to 75ppm, or 30 to 75ppm, or 35 to 75ppm, or 40 to 75ppm, or 45 to 75ppm, or 50 to 75ppm, or 10 to 65ppm, or 20 to 65ppm, or 30 to 65ppm, or 35 to 65ppm, or 40 to 65ppm, or 45 to 65ppm, based on the mass of the final polyester produced.
12. The polyester composition of any of claims 1 to 11, wherein aluminum atoms are present in an amount of 10 to 100ppm, or 20 to 100ppm, or 25 to 100ppm, or 30 to 100ppm, or 35 to 100ppm, or 40 to 100ppm, or 45 to 100ppm, or 50 to 100ppm, or 10 to 75ppm, or 15 to 75ppm, or 20 to 75ppm, or 25 to 75ppm, or 30 to 75ppm, or 35 to 75ppm, or 40 to 75ppm, or 45 to 75ppm, or 50 to 75ppm, or 10 to 65ppm, or 20 to 65ppm, or 30 to 65ppm, or 35 to 65ppm, or 40 to 65ppm, or 45 to 65ppm, based on the mass of the final polyester produced.
13. The polyester composition of any of claims 1 to 12, wherein the ratio of lithium atoms to aluminum atoms in ppm relative to the mass of the final polyester produced is 1:5 to 5:1, or 1:4 to 4:1, or 1:3 to 3:1, or 1:2 to 2:1.
14. The polyester composition according to any one of claim 1 to 13, wherein the total catalyst metal atoms present in the composition are in the range of 10 to 500ppm, or 10 to 450ppm, or 10 to 400ppm, or 10 to 300ppm, or 10 to 250ppm, or 10 to 200ppm, or 10 to 150ppm, or 50 to 1000ppm, or 50 to 800ppm, or 50 to 600ppm, or 50 to 500ppm, or 50 to 450ppm, or 50 to 400ppm, or 50 to 300ppm, or 50 to 250ppm, or 50 to 200ppm, or 50 to 150ppm, or 100 to 1000ppm, or 100 to 800ppm, or 100 to 600ppm, or 100 to 500ppm, or 100 to 400ppm, or 100 to 300ppm, or 100 to 250ppm, based on the mass of the final polyester produced or 100 to 200ppm, or 100 to 150ppm, or 80 to 150ppm, or 200 to 1000ppm, or 200 to 800ppm, or 200 to 600ppm, or 200 to 500ppm, or 200 to 400ppm, or 300 to 1000ppm, or 300 to 800ppm, or 300 to 600ppm, or 300 to 500ppm, or 300 to 400ppm, or 400 to 1000ppm, or 400 to 800ppm, or 400 to 600ppm, or 500 to 1000ppm, or 500 to 800ppm, or 500 to 700ppm, or less than 500ppm, or less than 400ppm, or less than 300ppm, or less than 250ppm, or less than 225ppm, or less than 200ppm, or less than 150ppm, or less than 130ppm, or less than 120ppm.
15. The polyester composition of any of claims 1 to 14, wherein at least one lithium source is selected from lithium carbonate, lithium acetate, lithium benzoate, lithium succinate, lithium acetylacetonate, lithium methoxide, lithium oxalate, lithium nitrate, lithium ethoxide, lithium hydroxide, lithium hydride, lithium ethylene glycol (lithium glycoxide) or alkyl lithium, lithium aluminum hydride, lithium borohydride, lithium oxide; or wherein at least one lithium source is lithium acetylacetonate.
16. The polyester composition of any of claims 1 to 15, wherein at least one aluminum source is selected from aluminum acetate, aluminum benzoate, aluminum sulfate, aluminum lactate, aluminum laurate, aluminum stearate, aluminum alkoxide, aluminum ethoxide, aluminum isopropoxide, aluminum tri-n-butoxide (aluminum tri-butyl), aluminum tri-tert-butoxide (aluminum tri-tert-butoxide), aluminum di-iso-butoxide, and aluminum chelate, aluminum acetoacetate di-iso-propoxide (ethyl acetoacetate aluminum diisopropylate), aluminum tri (acetoacetate) s (aluminum tris (ethyl acetoacetate)), alkyl acetoacetates, aluminum di-iso-propoxide (aluminum diisopropylate), aluminum monoacetoacetates bis (acetoacetate) s (aluminummonoacetylacetate bis (ethyl acetoacetate)), aluminum tri (acetoacetate) s (acetyl acetate), or aluminum acetylacetonates; or wherein at least one aluminum source is selected from aluminum hydroxide, aluminum acetylacetonate, aluminum acetate, aluminum isopropoxide, or aluminum sulfate; or wherein the at least one aluminum source is selected from aluminum acetylacetonate and aluminum isopropoxide.
17. The polyester composition according to any one of claim 1 to 16, wherein the 2, 4-tetramethyl-1, 3-cyclobutanediol residues is a composition comprising greater than 50 mole% of cis-2, 4-tetramethyl-1, 3-cyclobutanediol and less than 50 mole% of trans-2, 4-tetramethyl-1, 3-cyclobutanediol or 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 more 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 70 mole% of cis-2, 4-tetramethyl-1, 3-cyclobutanediol and less than 30 mole% of trans-2, 4-tetramethyl-1, 3-cyclobutanediol or more than 75 mole% of cis-2, 4-tetramethyl-1, 3-cyclobutanediol and less than 25 mole% of trans-2, 4-tetramethyl-1, 3-cyclobutanediol.
18. The polyester composition of any of claims 1 to 17 comprising a blend with at least one polymer selected from at least one of the following: polyesters, poly (etherimides), polyphenylene oxides, poly (phenylene oxide)/polystyrene blends, polystyrene resins, polyphenylene sulfides, polyphenylene sulfide/sulfones, poly (ester-carbonates), polycarbonates, polysulfones other than those of claim 1; polysulfone ethers, and poly (ether-ketones); or wherein the polyester composition comprises a blend of the polyester with recycled poly (ethylene terephthalate) (rPET).
19. The polyester composition of any of claims 1 to 18 comprising residues of at least one phosphorus compound.
20. A method of making the polyester or polyester composition of any of claims 1 to 19 wherein the degree of incorporation or conversion of TMCD in the final polymer 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%.
21. An article made from the polyester composition of any of claims 1-20.
CN202180093367.0A 2020-12-18 2021-12-16 Polyester compositions comprising tetramethylcyclobutanediol and cyclohexanedimethanol with improved catalyst systems comprising lithium and aluminum atoms Pending CN117043226A (en)

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US202063199304P 2020-12-18 2020-12-18
US63/199305 2020-12-18
US63/199304 2020-12-18
US63/199310 2020-12-18
US63/199309 2020-12-18
US63/199303 2020-12-18
US63/199306 2020-12-18
US63/199308 2020-12-18
PCT/US2021/063661 WO2022132998A1 (en) 2020-12-18 2021-12-16 Polyester compositions comprising tetramethyl cyclobutanediol and cyclohexanedimethanol having an improved catalyst system comprising lithium and aluminum atoms

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