Novel polyester compositions containing ethylene glycol residues and improved process for preparing polyesters from oligomeric ethylene terephthalate

Abstract

The present invention relates to a polyester composition comprising: (1) at least one polyester comprising: (a) a dicarboxylic acid component comprising: (i) from about 70 mol% to about 100 mol% residues of terephthalic acid or an ester thereof; (ii) from about 0 mol% to about 30 mol% of an aromatic or aliphatic dicarboxylic acid residue having up to 20 carbon atoms, or a combination thereof; (b) a diol component comprising: (i) from about 50 mol% to about 100 mol% ethylene glycol residues; (ii) from about 0 mol% to about 50 mol% of a modified diol residue comprising a linear residue or alicyclic residue comprising from 2 to 20 carbon atoms; wherein the total mole% of the dicarboxylic acid component is 100 mole%, and wherein the total mole% of the diol component is 100 mole%; and (2) a residue of a single metal catalyst system consisting essentially of germanium atoms in an amount of less than 75 ppm relative to the mass of the final polyester prepared; and wherein the final polyester has an intrinsic viscosity of from 0.45 dL / g to 1.2 dL / g, as determined at 25 DEG C at a concentration of 0.5 g / 100 ml in 60 / 40 (weight / weight) phenol / tetrachloroethane.

Description

Technical Field

[0001] The present invention relates to polyester compositions prepared by polycondensation of oligoethylene terephthalate (BHET).

[0002] The polyester composition can be catalyzed by a catalyst system containing germanium, resulting in good molecular weight, good color, good environmental benefits, circular economy benefits and other benefits. The final polyester contains almost no catalyst residues. Background Art

[0003] Germanium catalysts have been used to prepare polyesters. U.S. Patents 2,578,660, 3,074,913 and 3,377,320 disclose polyesters prepared using transesterification catalysts and germanium compounds as polycondensation catalysts.

[0004] US Patent No. 5,378,796 discloses the use of a germanium catalyst as a polycondensation catalyst in certain polyesters containing 1,4-cyclohexanedimethanol and ethylene glycol.

[0005] US Patent 7,153,811 teaches against using germanium alone as a catalyst due to its high cost. This patent teaches certain multi-component germanium-based catalyst systems.

[0006] EP1153193 teaches the use of bis(2-hydroxyethyl)terephthalate to prepare PET. It also teaches that "germanium catalysts are problematically expensive and tend to distill out of the reaction system during polymerization, resulting in variations in the catalyst concentration in the reaction system, which makes polymerization difficult to control." EP1153193 also mentions that "another problem unique to germanium catalysis is the volatility of the germanium compound. Consequently, significant germanium loss occurs under the high temperatures and high vacuum conditions of prior art final polycondensation processes. Since germanium is much more expensive than antimony, this loss is economically very disadvantageous. This expense, coupled with the need for solid-state polymerization, limits the use of germanium catalysts."

[0007] Other methods have been used to prepare PET-type polymers without catalysts, such as catalyst deactivation and filtration. However, due to the viscous nature of the polymer melt, filtering the polymer melt is highly impractical. Another approach reported in the literature uses heterogeneous catalysis. Achieving polymer flow over such catalysts is difficult and impractical. In many cases, heterogeneous catalysts can decompose under these conditions and form chemical entities that ultimately end up in the final polymer and essentially act as homogeneous catalysts.

[0008] In US2008 / 0051530 A1, the following is described: "Polyesters prepared using a germanium catalyst in the final polycondensation stage at temperatures below 285°C exhibit low Ge catalyst losses and excellent low acetaldehyde generation characteristics. After reaching an It.V. of 0.72 dL / g at a temperature of 275°C or less, a post-final polycondensation process for removing the catalyst can be applied by subjecting the polymer melt to a temperature above 275°C (e.g., 280°C-305°C), typically for a relatively short period of time, to reduce the germanium catalyst content in the polyester to 40% or less of the initial input amount. Removal of the germanium catalyst by a post-final polycondensation process (after the final polycondensation reactor) in this manner can be achieved by rerouting volatiles from the reactor so that the germanium can be recovered and preferably recycled." In US2008 / 0051530 A1, it is also stated that "it is desirable to lose as little germanium catalyst as possible."

[0009] There is a commercial need for polyesters containing ethylene glycol that have low to no catalyst levels and that have good color, good molecular weight, good intrinsic viscosity, good thermal stability, and other combinations of properties that make them useful for injection molding, blow molding, extrusion, and film and sheet applications. It would be useful if a process for making these polyesters did not require heterogeneous catalysis, filtration, a final polycondensation postreactor or vessel, catalyst deactivation, solidification, addition of phosphorus stabilizers, or crystallization promoters.

[0010] There also exists a commercial need for a simple process for preparing polyesters using a germanium catalyst in a final polycondensation reactor that provides high germanium catalyst loss (low catalyst levels remaining in the polymer) and high germanium catalyst recovery while still retaining a high intrinsic viscosity polymer without requiring a post-final polycondensation step to remove the catalyst from the higher intrinsic viscosity polymer obtained in the final polycondensation reactor. Summary of the Invention

[0011] The present invention relates to novel polyesters and / or polyester compositions containing ethylene glycol residues, which contain minimal catalyst residues and can have one or more, two or more, or a combination of three or more of the following properties: good color, good molecular weight, good intrinsic viscosity, good thermal stability, and a combination of other properties that make them ideal for injection molding. The polyesters of the present invention are desirable because high catalyst residues often lead to degradation or other problems during chemical and mechanical recycling of polyesters.

[0012] Unexpectedly, there are simple methods to prepare PET and other EG-containing copolyesters to high molecular weight (as shown by IV) that have the above-mentioned properties and have little to no residual catalyst in the final polyester. Other advantages also exist, including but not limited to environmental benefits, circular economy benefits, and performance benefits. There is an environmental desire to reduce the amount of additives and catalyst metals in the product. Given that germanium-catalyzed PET has excellent color, preparing PET with excellent color requires using less toner dye in the final product to achieve the desired almost completely neutral color. In addition to environmental issues, in a world where materials can be chemically or mechanically recycled, it is desirable to have nearly clean PET. In chemical recycling technology, removing catalysts and other additive chemicals from plastics is quite complex, so such a product free of catalyst residues and additives would be advantageous. It is also expected that having lower catalyst residues in the final polyester will improve the thermal stability of PET and EG-based copolyesters.

[0013] While the process may result in little or no catalyst levels in the final product, it may also include steps for catalyst removal and catalyst recovery, allowing the catalyst to be reused in another process. The process may minimize catalyst loss. It is also believed that germanium catalyst removed from the reaction process in the final polycondensation vessel or final polycondensation reactor may be recovered, processed, and reused, thereby minimizing catalyst loss. The one or more processes of the present invention for preparing these polyesters may achieve desirable and useful intrinsic viscosities and reasonable production times.

[0014] In one aspect, the polyester can be recovered without having to remove significant catalyst content.

[0015] In one aspect, the process of the present invention does not require at least one or more of the following: heterogeneous catalysis, filtration, post-polycondenser operations, catalyst deactivation of the final product, solid-stateization, addition of phosphorus stabilizers, or crystallization promoters.

[0016] In one aspect, the process of the present invention does not require at least one or more of the following: high processing temperatures (e.g., 290°C or higher), a final polycondensation reactor, a final post-polycondensation reaction, a final post-polycondensation step to achieve the high intrinsic viscosity of the polyesters of the present invention.

[0017] Generally, the present invention also relates to a method for preparing a polymer using a germanium catalyst (Ge) in the final polycondensation stage at a temperature of 240° C. to 300° C., and the method exhibits high loss of Ge catalyst (low catalyst levels remaining in the polymer) while still retaining a high intrinsic viscosity polymer without the need for a post-final polycondensation step. Advantages of this method may include, but are not limited to, eliminating the additional process step of removing the germanium catalyst while having minimal catalyst levels remaining in the polymer, and the ability to recover large amounts of germanium catalyst so that the germanium catalyst can be recycled. Due to the high price of germanium catalyst, this can further lead to lower costs.

[0018] In aspect 1, the present invention is directed to a polyester composition comprising:

[0019] (1) at least one polyester comprising:

[0020] (a) a dicarboxylic acid component comprising:

[0021] (i) from about 70 mole % to about 100 mole % of residues of terephthalic acid or an ester thereof;

[0022] (ii) from about 0 mole % to about 30 mole % of aromatic or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, or combinations thereof;

[0023] (b) a diol component comprising:

[0024] (i) from about 50 mole % to about 100 mole % ethylene glycol residues;

[0025] (ii) from about 0 mole % to about 50 mole % of modifying glycol residues comprising linear or alicyclic residues containing from 2 to 20 carbon atoms;

[0026] Wherein the total mole % of the dicarboxylic acid component is 100 mole %,

[0027] wherein the total mole % of the diol component is 100 mole %; and

[0028] (2) residues of a metal catalyst system consisting essentially of, or consisting of, germanium atoms, wherein the amount of germanium atoms present in the final polyester is less than 75 ppm, or less than 70 ppm, or less than 65 ppm, or less than 60 ppm, or less than 55 ppm, or less than 50 ppm, or less than 45 ppm, or less than 40 ppm, or less than 35 ppm, or less than 30 ppm, or less than 25 ppm, or less than 20 ppm, or less than 15 ppm, or 10 ppm or less, or 5 ppm or less, relative to the mass of the final polyester produced; and

[0029] wherein the final polyester has an intrinsic viscosity of 0.35 dL / g to 1.2 dL / g, or 0.45 dL / g to 1.2 dL / g, or 0.50 dL / g to 1.2 dL / g, or 0.55 dL / g to 1.2 dL / g, or 0.60 dL / g to 1.2 dL / g, or 0.65 dL / g to 1.2 dL / g, or 0.65 dL / g to 0.90 dL / g, as measured at 25°C in 60 / 40 (weight / weight) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml.

[0030] In aspect 2, the present invention is directed to a polyester composition comprising:

[0031] (1) at least one polyester comprising:

[0032] (a) a dicarboxylic acid component comprising:

[0033] (i) from about 70 mole % to about 100 mole % of residues of terephthalic acid or an ester thereof;

[0034] (ii) from about 0 mole % to about 30 mole % of aromatic or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, or combinations thereof;

[0035] (b) a diol component comprising:

[0036] (i) from about 50 mole % to about 100 mole % ethylene glycol residues;

[0037] (ii) from about 0 mole % to about 50 mole % of modifying glycol residues comprising linear or alicyclic residues containing from 2 to 20 carbon atoms;

[0038] Wherein the total mole % of the dicarboxylic acid component is 100 mole %,

[0039] wherein the total mole % of the diol component is 100 mole %; and

[0040] (2) residues of a metal catalyst system consisting essentially of or consisting of germanium atoms, wherein the amount of germanium atoms present in the final polyester is less than 30 ppm, or less than 25 ppm, or less than 20 ppm, or less than 15 ppm, or 10 ppm or less, or 5 ppm or less, or less than 5 ppm, relative to the mass of the final polyester produced; and

[0041] wherein the final polyester has an intrinsic viscosity of 0.35 dL / g to 1.2 dL / g, or 0.45 dL / g to 1.2 dL / g, or 0.50 dL / g to 1.2 dL / g, or 0.55 dL / g to 1.2 dL / g, or 0.60 dL / g to 1.2 dL / g, or 0.65 dL / g to 1.2 dL / g, or 0.65 dL / g to 0.90 dL / g, as measured at 25°C in 60 / 40 (weight / weight) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml.

[0042] In aspect 3, the present invention is directed to a polyester composition comprising:

[0043] (1) at least one polyester comprising:

[0044] (a) a dicarboxylic acid component comprising:

[0045] (i) from about 70 mole % to about 100 mole % of residues of terephthalic acid or an ester thereof;

[0046] (ii) from about 0 mole % to about 30 mole % of aromatic or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, or combinations thereof;

[0047] (b) a diol component comprising:

[0048] (i) from about 50 mole % to about 100 mole % ethylene glycol residues;

[0049] (ii) from about 0 mole % to about 50 mole % of modifying glycol residues comprising linear or alicyclic residues containing from 2 to 20 carbon atoms;

[0050] Wherein the total mole % of the dicarboxylic acid component is 100 mole %,

[0051] wherein the total mole % of the diol component is 100 mole %; and

[0052] (2) residues of a metal catalyst system consisting essentially of, or consisting of, germanium atoms, in an amount of 5 ppm or less, or less than 5 ppm, relative to the mass of the final polyester produced; and

[0053] wherein the final polyester has an intrinsic viscosity of 0.35 dL / g to 1.2 dL / g, or 0.45 dL / g to 1.2 dL / g, or 0.50 dL / g to 1.2 dL / g, or 0.55 dL / g to 1.2 dL / g, or 0.60 dL / g to 1.2 dL / g, or 0.65 dL / g to 1.2 dL / g, or 0.65 dL / g to 0.90 dL / g, as measured at 25°C in 60 / 40 (weight / weight) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml.

[0054] In aspect 4, the present invention relates to a polyester composition according to any one of aspects 1 to 3, wherein the modifying diol comprises at least one of the following: diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methyl-1,3-propanediol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, p-xylene glycol, neopentyl glycol, isosorbide, polytetramethylene glycol, or a combination thereof.

[0055] In aspect 5, the present invention relates to a polyester composition according to any one of aspects 1-4, wherein the modifying diol comprises the residue of 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

[0056] In aspect 6, the present invention relates to the polyester composition according to any one of aspects 1-5, wherein the modifying diol comprises the residue of 1,4-cyclohexanedimethanol.

[0057] In aspect 7, the present invention relates to a polyester composition according to any one of aspects 1 to 6, wherein the amount of the modifying glycol is from about 10 mol% to about 45 mol%, or from about 15 mol% to about 45 mol%, or from about 10 mol% to about 40 mol%, or from about 20 mol% to about 40 mol%, or from about 10 mol% to about 30 mol%, or from about 20 mol% to about 35 mol%, or from about 20 mol% to about 30 mol%, or from about 25 mol% to about 40 mol%, or from about 30 mol% to about 40 mol%.

[0058] In aspect 8, the present invention relates to a polyester composition according to any of aspects 1-7, wherein the polyester comprises residues of ethylene glycol in an amount of about 55 mol% to about 90 mol%, or about 55 mol% to about 85 mol%, or about 60 mol% to about 90 mol%, or about 60 mol% to about 80 mol%, or about 65 mol% to about 80 mol%, or about 70 mol% to about 90 mol%, or about 70 mol% to about 80 mol%, or about 60 mol% to about 75 mol%, or about 60 mol% to about 70 mol%.

[0059] In aspect 9, the present invention is directed to a polyester composition according to any one of aspects 1-8, wherein the polyester comprises the residue of a diacid component comprising an aromatic or aliphatic dicarboxylic acid ester residue, or a combination thereof.

[0060] In aspect 10, the present invention is directed to a polyester composition according to any one of aspects 1-9, wherein the polyester comprises from about 80 mol% to about 100 mol%, or from about 90 mol% to about 100 mol%, or from about 95 mol% to about 100 mol%, or from about 99 mol% to about 100 mol% of residues of terephthalic acid or an ester thereof.

[0061] In aspect 11, the present invention relates to a polyester composition according to any one of aspects 1 to 10, wherein the intrinsic viscosity of the polyester is 0.45 dL / g to 1.2 dL / g, or 0.45 dL / g to 1.0 dL / g, or 0.45 dL / g to 0.90 dL / g, or 0.45 dL / g to 0.85 dL / g, or 0.45 dL / g to 0.80 dL / g, or 0.45 dL / g to 0.75 dL / g, or 0.45 dL / g to 0.70 dL / g, or 0.50 dL / g to 1.2 dL / g, or 0.50 dL / g to 1. dL / g, or 0.50 dL / g to 0.90 dL / g, or 0.50 dL / g to 0.85 dL / g, or 0.50 dL / g to 0.80 dL / g, or 0.50 dL / g to 0.75 dL / g, or 0.50 dL / g to 0.70 dL / g, or 0.55 dL / g to 1.2 dL / g, or 0.55 dL / g to 1.0 dL / g, or 0.55 dL / g to 0.90 dL / g, or 0.55 dL / g to 0.85 dL / g, or 0.55 dL / g to 0.80 dL / g, or 0.55 dL / g to 0. dL / g, or 0.55 dL / g to 0.70 dL / g, or 0.60 dL / g to 1.2 dL / g, or 0.60 dL / g to 1.0 dL / g, or 0.60 dL / g to 0.90 dL / g, or 0.60 dL / g to 0.85 dL / g, or 0.60 dL / g to 0.80 dL / g, or 0.60 dL / g to 0.75 dL / g, or 0.60 dL / g to 0.70 dL / g, or 0.65 dL / g to 1.2 dL / g, or 0.65 dL / g to 1.0 dL / g, or 0.65 dL / g to 0. dL / g, or 0.65 dL / g to 0.85 dL / g, or 0.65 dL / g to 0.80 dL / g, or 0.65 dL / g to 0.75 dL / g, or 0.68 dL / g to 1.2 dL / g, or 0.60 dL / g to 1.0 dL / g, or 0.68 dL / g to 0.90 dL / g, or 0.68 dL / g to 0.85 dL / g, or 0.68 dL / g to 0.80 dL / g, which is measured at 25°C in 60 / 40 (weight / weight) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml.

[0062] In aspect 12, the present invention is directed to a polyester composition according to any one of aspects 1-11, wherein the intrinsic viscosity of the polyester is 0.45 dL / g to 0.85 dL / g, or 0.45 dL / g to 0.80 dL / g, or 0.55 dL / g to 0.85 dL / g, or 0.65 dL / g to 0.85 dL / g, or 0.65 dL / g to 0.80 dL / g, or 0.65 dL / g to 0.85 dL / g. 0.75 dL / g, or 0.60 dL / g to 0.85 dL / g, or 0.60 dL / g to 0.80 dL / g, or 0.60 dL / g to 0.75 dL / g, or 0.65 dL / g to 0.85 dL / g, or 0.68 dL / g to 0.85 dL / g, as measured at 25°C in 60 / 40 (weight / weight) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml.

[0063] In aspect 13, the present invention relates to a polyester composition according to any one of aspects 1-12, wherein less than 70 ppm, or less than 65 ppm, or less than 60 ppm, or less than 55 ppm, or less than 50 ppm, or less than 45 ppm, or less than 40 ppm, or less than 35 ppm, or less than 30 ppm, or less than 25 ppm, or less than 20 ppm, or less than 15 ppm, or 25 ppm or less, or 20 ppm or less, or 15 ppm or less, or 10 ppm or less, or 5 ppm or less, or less than 5 ppm of germanium atoms are present in the final polyester composition.

[0064] In aspect 14, the present invention relates to a polyester composition according to any one of aspects 1-13, wherein the inherent viscosity of the polyester is 0.50 dL / g to 1.2 dL / g, or 0.50 dL / g to 1.0 dL / g, or 0.50 dL / g to 0.90 dL / g, or 0.50 dL / g to 0.85 dL / g, or 0.50 dL / g to 0.80 dL / g, or 0.50 dL / g to 0.80 dL / g, and the amount of germanium atoms present in the final polyester composition is 18 ppm or less, or 15 ppm or less, or 10 ppm or less, or 5 ppm or less, or less than 5 ppm.

[0065] In aspect 15, the present invention relates to a polyester composition according to any one of aspects 1-14, wherein the inherent viscosity of the polyester is 0.50 dL / g to 1.2 dL / g, or 0.50 dL / g to 1.0 dL / g, or 0.60 dL / g to 1.2 dL / g, or 0.60 dL / g to 1.0 dL / g, or 0.60 dL / g to 0.90 dL / g, or 0.60 dL / g to 0.85 dL / g, or 0.65 dL / g to 1.2 dL / g, or 0.65 dL / g to 1.0 dL / g, or 0.65 dL / g to 0.90 dL / g, or 0.65 dL / g to 0.85 dL / g.

[0066] In aspect 16, the present invention relates to a polyester composition according to any one of aspects 1-15, wherein the amount of germanium atoms present in the final polyester composition is 20 ppm or less, or 18 ppm or less, or 15 ppm or less, or 10 ppm or less, or 5 ppm or less.

[0067] In aspect 17, the present invention relates to a polyester composition according to any one of aspects 1-16, wherein the final amount of germanium atoms in the final polyester composition is 5 ppm or less, or less than 5 ppm, or less than 4 ppm, or less than 3 ppm, or less than 2 ppm, or less than 1 ppm, or 0 ppm.

[0068] In aspect 18, the present invention relates to a polyester composition according to any one of aspects 1-17, having a b* value of -10 to less than 20, -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 15, or 1 to 14, or 1 to 13, or 1 to 12, or 1 to 11, or 1 to 10, or 1 to 9, or 1 to 8, or 1 to 7, or 1 to 6, or 1 to 5, or 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 (International Commission on Illumination).

[0069] In aspect 19, the present invention relates to a polyester composition according to any one of aspects 1-18, having a b* value of 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.

[0070] In aspect 20, the present invention relates to a polyester composition according to any one of aspects 1-19, having an L* value of 50 to 99, or 50 to 90, or 60 to 99, or 60 to 90, or 60 to 85, or 60 to 80, or 65 to 99, or 65 to 90, or 65 to 85, or 65 to 80, or 65 to 75, or 70 to 90, or 70 to 99, or 70 to 90, or 70 to 85, or 70 to 80, or 75 to 95, or 75 to 90, or 75 to 85, or 80 to 90, as determined by the L*a*b* color system of CIE (International Commission on Illumination).

[0071] In aspect 21, the present invention relates to a polyester composition according to any one of aspects 1-20, wherein the polyester comprises the residue of at least one branching agent or comprises no branching agent or comprises 1 mol % or less of a branching agent.

[0072] In aspect 22, the present invention relates to a polyester composition according to any one of aspects 1 to 21, wherein the at least one germanium compound is selected from a germanium alcoholate, a germanium carboxylate, an organic germanium compound, or an ester of germanic acid.

[0073] In aspect 23, the present invention relates to the polyester composition according to any one of aspects 1 to 22, wherein the at least one germanium compound is selected from the group consisting of germanium alcoholates and germanium carboxylates.

[0074] In aspect 24, the present invention relates to a polyester composition according to any one of aspects 1 to 23, wherein the germanium compound is selected from the group consisting of germanium ethoxide, germanium isopropoxide, and germanium acetate or germanium dioxide.

[0075] In aspect 25, the present invention relates to a polyester composition according to any of aspects 1-24, comprising a blend with at least one polymer selected from at least one of the following: polyesters other than those in aspects 1-24, poly(etherimides), polyphenylene ethers, poly(phenylene ether) / polystyrene blends, polystyrene resins, polyphenylene sulfide, polyphenylene sulfide / polyphenylene sulfone, poly(ester-carbonates), polycarbonates, polysulfones; polysulfone ethers; and poly(ether-ketones).

[0076] In aspect 26, the present invention is directed to a method of preparing any of the polyesters according to aspects 1-24.

[0077] In aspect 27, the present invention is directed to a process for preparing any of the polyesters of aspects 1-24, wherein the catalyst loss or catalyst removal is greater than 70%, or greater than 75%, or greater than 80%, or greater than 85%, or greater than 86%, or greater than 87%, or greater than 88%, or greater than 89%, or greater than 90%, or greater than 95%, or greater than 96%, or greater than 97%, or greater than 98%, or greater than 99%.

[0078] In aspect 28, the present invention relates to any one of the methods according to aspects 26-27, wherein the loss of catalyst or removal of catalyst occurs by applying a vacuum or by nitrogen purging. In one aspect, the loss of catalyst or removal of catalyst occurs in the final polycondenser or final polycondensation reactor and / or does not occur in the post-final polycondensation stage.

[0079] In aspect 29, the present invention relates to any one of the methods according to aspects 26-28, wherein the amount of germanium catalyst introduced into the polycondensation zone can be an amount of at least 20 ppm, or at least 50 ppm, or at least 100 ppm, or 20 ppm to 500 ppm, or 20 ppm to 450 ppm, or 20 ppm to 400 ppm, or 20 ppm to 350 ppm, or 20 ppm to 300 ppm, or 20 ppm to 250 ppm, or 50 ppm to 500 ppm, or 50 ppm to 450 ppm, or 50 ppm to 400 ppm, or 50 ppm to 350 ppm, or 50 ppm to 300 ppm, or 50 ppm to 250 ppm, or 100 ppm to 500 ppm, or 100 ppm to 450 ppm, or 20 ppm to 400 ppm, or 100 ppm to 350 ppm, or 20 ppm to 350 ppm, or 20 ppm to 300 ppm, or 20 ppm to 250 ppm ppm, or from 100 ppm to 300 ppm, or from 100 ppm to 250 ppm, or from 150 ppm to 500 ppm, or from 150 ppm to 450 ppm, or from 150 ppm to 400 ppm, or from 150 ppm to 350 ppm, or from 150 ppm to 300 ppm, or from 150 ppm to 250 ppm, or from 175 ppm to 500 ppm, or from 175 ppm to 450 ppm, or from 175 ppm to 400 ppm, or from 175 ppm to 350 ppm, or from 175 ppm to 300 ppm, or from 175 ppm to 250 ppm, or from 200 ppm to 500 ppm, or from 200 ppm to 450 ppm, or from 200 ppm to 400 ppm, or from 200 ppm to 350 ppm, or from 200 ppm to 300 ppm, or from 200 ppm to 250 ppm.

[0080] In aspect 30, the present invention relates to any one of the methods according to aspects 26-29, wherein the reactor, or the plurality of reactors, or the final polycondensation reactor can be selected from a thin film reactor or a vertical final polycondensation reactor. These reactors may include, but are not limited to, falling film evaporators, falling film reactors, zimmer (horizontal) final polycondensation reactors and tray final polycondensation reactors, other horizontal final polycondensation reactors, such as horizontal cylindrical reactors (see U.S. Patent 3,728,083A, which is incorporated herein by reference, which describes a reactor in which a wagon wheel pulls up and makes a thin polymer film from which volatile compounds such as EG and in this case Ge can be removed). In addition, see, for example, U.S. Patent 4,196,168A, which is incorporated herein by reference.

[0081] In aspect 31, the present invention relates to any one of the methods according to aspects 26-30, wherein at least one compound containing dihydroxy terephthalate is fed to a final polycondensation reactor, the final polycondensation reactor being operated in the range of 180°C to 300°C, with a vacuum level between 0.1 Torr and 5 Torr, and a total process time of 15 minutes to 8 hours, wherein germanium is the catalyst, and wherein the final product has an intrinsic viscosity of at least 0.45 dL / g and contains less than 75 ppm of germanium atoms.

[0082] In aspect 32, the present invention relates to any one of the methods according to aspects 26-31, wherein at least one compound containing dihydroxy terephthalate is fed to a final polycondensation reactor, the final polycondensation reactor being operated in the range of 240°C to 300°C, with a vacuum level between 0.1 Torr and 5 Torr, and a total process time of 15 minutes to 8 hours, wherein germanium is the catalyst, and wherein the final product has an intrinsic viscosity of at least 0.45 dL / g, or 0.45 dL / g to 1.2 dL / g, or 0.50 dL / g to 1.2 dL / g, or 0.55 dL / g to 1.2 dL / g, or 0.60 dL / g to 1.2 dL / g, or 0.65 dL / g to 1.2 dL / g, or 0.65 dL / g to 0.90 dL / g, and contains less than 75 ppm of germanium atoms.

[0083] In aspect 33, the present invention is directed to a process for preparing any of the polyesters of the present invention, wherein at least one dihydroxy terephthalate-containing compound is fed to a final polycondensation reactor, the final polycondensation reactor being operated in the range of 240°C to 300°C, with a vacuum level between 0.1 Torr and 1 Torr, and a total process time of 15 minutes to 8 hours, wherein germanium is the catalyst, and wherein the final product has an intrinsic viscosity of at least 0.65 dL / g and contains less than 75 ppm, or less than 50 ppm, or less than 25 ppm, or less than 15 ppm, or less than 10 ppm of germanium atoms.

[0084] In aspect 34, the present invention relates to a method for preparing a polyester composition according to any one of aspects 26-33, wherein the dihydroxy terephthalate-containing compound comprises:

[0085]

[0086] In aspect 35, the present invention relates to any one of the methods according to aspects 26-34, wherein the dihydroxy terephthalate-containing compound, component (A), and optionally a diol are reacted in the presence of a polycondensation catalyst consisting essentially of or consisting of germanium atoms.

[0087] In aspect 36, the present invention relates to any one of the methods according to aspects 26-35, wherein the dihydroxyterephthalate-containing compound is bis-2-hydroxyethyl terephthalate (BHET).

[0088] In aspect 37, the present invention provides a process wherein the dihydroxyterephthalate-containing compound (e.g., BHET or an oligomer thereof) can be added to a finishing polycondensation reactor having features that provide a high surface area to volume ratio.

[0089] In aspect 38, the present invention relates to any one of the methods according to aspects 26-37, wherein the modifying glycol is 1,4-cyclohexanedimethanol.

[0090] In aspect 39, the present invention relates to any one of the methods according to aspects 26-38, wherein the modifying diol is 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

[0091] In aspect 40, the invention relates to any one of the methods according to aspects 26-39, wherein the method is carried out at a temperature of: 180°C to 300°C, or 200°C to 300°C; or 200°C to 285°C; or 200°C to 280°C; or 200°C to 275°C; or 225°C to 300°C; or 225°C to 285°C; or 225°C to 280°C; or 245°C to 280°C; or 245°C to 275°C; or 245°C to 270°C; or 280°C or below 280°C, or 275°C or below 275°C, or 240°C to 300°C, or 240°C to 290°C, or 240°C to below 290°C, or 240°C to 285°C, or 260°C to 290°C, or 260°C to below 290°C, or 260°C to 285°C, or 270°C to 290°C, or 270°C to below 290°C, or 270°C to 285°C, or 270°C to 280°C, with a total process time of 0.10 hour to 12 hours, or 0.10 hour to 8 hours, or 0.10 hour to 5 hours, or 0.10 hour to 4 hours, or 0.10 hour to 3 hours, or 0.10 hour to 2 hours, or 0.25 hour to 8 hours, or 0.25 hour to 5 hours, or 0.25 hour to 4 hours, or 0.25 hour to 3 hours, or 0.25 hour to 2 hours.

[0092] In aspect 41, the present invention relates to any one of the methods according to aspects 26-40, which is carried out at a temperature of 240°C to 290°C, or 240°C to below 290°C, or 240°C to 285°C, or 260°C to 290°C, or 260°C to below 290°C, or 260°C to 285°C, or 270°C to 290°C, or 270°C to below 290°C, or 270°C to 285°C, or 270°C to 280°C, for a total process time of 0.25 hours to 8 hours.

[0093] In aspect 42, the present invention relates to any of the methods according to aspects 26-41, which may be performed at a pressure of 0.10 Torr to 5 Torr.

[0094] In aspect 43, the present invention relates to any of the methods according to aspects 26-42, which may be performed at a pressure of 0.10 Torr to 3 Torr.

[0095] In aspect 44, the invention relates to any one of the methods according to aspects 26-43, which is performed at a pressure of 0.10 Torr to 1 Torr.

[0096] In aspect 45, the present invention relates to a product that can be prepared by any of the methods according to aspects 26-44.

[0097] In aspect 46, the present invention is directed to an article that can be prepared with any of the polyester compositions according to any of aspects 1-25 or by any of the methods according to aspects 26-44.

[0098] In aspect 47, the present invention is directed to a shaped article prepared with any of the polyester compositions according to any of aspects 1-25 or by any of the methods according to aspects 26-44.

[0099] In aspect 48, the polyesters and / or polyester compositions of the present invention can be used in thermoplastic polyester compositions, articles, shaped articles, thermoplastic shaped articles, molded articles, extruded articles, injection molded articles, blow molded articles, films and / or sheets (e.g., calendared, cast, or extruded), containers, and / or bottles (e.g., beverage bottles, water bottles).

[0100] In aspect 49, the polyesters and / or polyester compositions of the present invention can be used in films, sheets, preforms, beverage preforms, and blown bottles made therefrom.

[0101] In aspect 50, the polyester compositions of the present invention can be used to form articles, including but not limited to extruded and / or molded articles, including but not limited to injection molded articles, extruded articles, cast extruded articles, profile extruded articles, melt-spun articles, thermoformed articles, extrusion molded articles, injection blow molded articles, injection stretch blow molded articles, extrusion blow molded articles, and extrusion stretch blow molded articles. These articles can include but are not limited to films, bottles, containers, drinkware, medical components, sheets, and / or fibers.

[0102] In aspect 51, the polyester composition of the present invention can be used for various types of films and / or sheets, including but not limited to extruded one or more films and / or one or more sheets, compression molded one or more films and / or one or more sheets, solution cast one or more films and / or one or more sheets. Methods for preparing the film and / or sheet include but are not limited to extrusion, compression molding and solution casting.

[0103] In aspect 52, the present invention is directed to an article, for example, a shaped article, comprising any of the polyesters or polyester compositions of the present invention.

[0104] In aspect 53, any of the methods for preparing polyesters useful in the present invention and described herein or known to one of ordinary skill in the art can be used to prepare any of the polyesters and / or polyester compositions of the present invention.

[0105] In aspect 54, any of the polyesters and / or polyester compositions described herein, and any products made therefrom, are also considered to be within the scope of the present invention, regardless of the method used to make the polyester and / or polyester composition.

[0106] In aspect 55, any of the methods for preparing polyesters useful in the present invention and described herein or known to one of ordinary skill in the art can be used to prepare any of the polyesters and / or polyester compositions of the present invention.

[0107] For any of the aspects of the present invention, the metal catalyst system referred to herein may be a single metal catalyst system. BRIEF DESCRIPTION OF THE DRAWINGS

[0108] Figure 1-Figure 1 The synthesis of PET using BHET oligomers is shown.

[0109] Figure 2-Figure 2 Germanium (Ge) levels in the polymer and polymer intrinsic viscosity (IV) based on reaction scale (BHET charge size) at a final vacuum level of 0.3 Torr are shown.

[0110] Figure 3-Figure 3 The germanium levels in the polymer based on the reaction scale (BHET charge) at different final vacuum levels are shown. DETAILED DESCRIPTION

[0111] By reference to the following detailed description of certain embodiments of the present invention and working examples, the present invention can be more easily understood. According to the purpose of the present invention, certain embodiments of the present invention are described in the summary of the invention of the present invention, and are further described hereinafter. In addition, other embodiments of the present invention are also described herein.

[0112] The present invention relates to the preparation of polyethylene terephthalate or modified polyethylene terephthalate, and more particularly to a method for preparing polyethylene terephthalate or modified polyethylene terephthalate by polycondensation of oligoethylene terephthalate (BHET).

[0113] As used herein, the term "polyester" is intended to include "copolyesters" and should be understood to mean a synthetic polymer prepared by the reaction of one or more difunctional carboxylic acids and / or polyfunctional carboxylic acids with one or more difunctional hydroxyl compounds and / or polyfunctional hydroxyl compounds (e.g., branching agents). Typically, the difunctional carboxylic acid can be a dicarboxylic acid, and the difunctional hydroxyl compound can be a dihydric alcohol, such as, for example, a diol and a glycol. As used herein, the term "diol" includes, but is not limited to, diols, diols and / or polyfunctional hydroxyl compounds, such as branching agents. Alternatively, the difunctional carboxylic acid can be a hydroxycarboxylic acid, such as, for example, p-hydroxybenzoic acid, and the difunctional hydroxyl compound can be an aromatic core with two hydroxyl substituents, such as, for example, hydroquinone. As used herein, the term "residue" means any organic structure introduced into a polymer by polycondensation and / or esterification of the corresponding monomers. As used herein, the term "repeat unit" means an organic structure having a dicarboxylic acid residue and a diol residue bonded by a carbonyloxy group. Thus, for example, a dicarboxylic acid residue can be derived from a dicarboxylic acid monomer or its associated acyl halides, esters, salts, anhydrides, and / or mixtures thereof. In addition, as used herein, the term "diacid" includes polyfunctional acids, such as branching agents. Thus, as used herein, the term "dicarboxylic acid" is intended to include dicarboxylic acids and any derivatives of dicarboxylic acids, including their associated acyl halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, and / or mixtures thereof, which can be used in a reaction process with a diol to prepare a polyester. As used herein, the term "terephthalic acid" is intended to include terephthalic acid itself and its residues and any derivatives of terephthalic acid, including their associated acyl halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, and / or mixtures thereof, or residues thereof, which can be used in a reaction process with a diol to prepare a polyester.

[0114] The polyesters used in the present invention can typically be prepared from a dicarboxylic acid and a diol that react in substantially equal proportions and are incorporated into the polyester polymer as their respective residues. Thus, the polyesters of the present invention can contain substantially equal molar proportions of acid residues (100 mole %) and diol (and / or polyfunctional hydroxy compound) residues (100 mole %) such that the total moles of repeating units equal 100 mole %. Thus, the mole percentages provided in the present disclosure can be based on the total moles of acid residues, the total moles of diol residues, or the total moles of repeating units. For example, a polyester containing 10 mole % of isophthalic acid based on the total acid residues means that the polyester contains 10 mole % of isophthalic acid residues out of a total of 100 mole % of acid residues. Thus, there are 10 moles of isophthalic acid residues for every 100 moles of acid residues. In another example, a polyester containing 80 mole % of EG based on the total diol residues means that the polyester contains 80 mole % of EG residues out of a total of 100 mole % of diol residues.

[0115] In one embodiment, the present invention provides a process for preparing a polymer at a temperature of 240° C. to 300° C., optionally using a germanium catalyst in the final polycondensation stage, and wherein the process exhibits high loss of the Ge catalyst (low catalyst levels remaining in the polymer) while still retaining a high intrinsic viscosity polymer without the need for a post-final polycondensation step. Advantages of this process may include, but are not limited to, eliminating the additional process step of removing the germanium catalyst while having minimal catalyst levels remaining in the polymer, and the ability to recover large amounts of germanium catalyst so that the germanium catalyst can be recycled. This further results in lower costs due to the high price of germanium catalyst.

[0116] In one embodiment, a polyester composition is provided comprising:

[0117] (1) at least one polyester comprising:

[0118] (a) a dicarboxylic acid component comprising:

[0119] (i) from about 70 mole % to about 100 mole % of residues of terephthalic acid or an ester thereof;

[0120] (ii) from about 0 mole % to about 30 mole % of aromatic or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, or combinations thereof;

[0121] (b) a diol component comprising:

[0122] (i) from about 50 mole % to about 100 mole % ethylene glycol residues;

[0123] (ii) from about 0 mole % to about 50 mole % of modifying glycol residues comprising linear or alicyclic residues containing from 2 to 20 carbon atoms;

[0124] Wherein the total mole % of the dicarboxylic acid component is 100 mole %,

[0125] wherein the total mole % of the diol component is 100 mole %; and

[0126] (2) residues of a metal catalyst system consisting essentially of, or consisting of, germanium atoms, wherein the amount of germanium atoms present in the final polyester is less than 75 ppm, or less than 70 ppm, or less than 65 ppm, or less than 60 ppm, or less than 55 ppm, or less than 50 ppm, or less than 45 ppm, or less than 40 ppm, or less than 35 ppm, or less than 30 ppm, or less than 25 ppm, or less than 20 ppm, or less than 15 ppm, or 10 ppm or less, or 5 ppm or less, or less than 5 ppm, relative to the mass of the final polyester produced; and

[0127] wherein the final polyester has an intrinsic viscosity of 0.35 dL / g to 1.2 dL / g, or 0.45 dL / g to 1.2 dL / g, or 0.50 dL / g to 1.2 dL / g, or 0.55 dL / g to 1.2 dL / g, or 0.60 dL / g to 1.2 dL / g, or 0.65 dL / g to 1.2 dL / g, or 0.65 dL / g to 0.90 dL / g, as measured at 25°C in 60 / 40 (weight / weight) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml.

[0128] In one embodiment, a polyester composition is provided comprising:

[0129] (1) at least one polyester comprising:

[0130] (a) a dicarboxylic acid component comprising:

[0131] (i) from about 70 mole % to about 100 mole % of residues of terephthalic acid or an ester thereof;

[0132] (ii) from about 0 mole % to about 30 mole % of aromatic or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, or combinations thereof;

[0133] (b) a diol component comprising:

[0134] (i) from about 50 mole % to about 100 mole % ethylene glycol residues;

[0135] (ii) from about 0 mole % to about 50 mole % of modifying glycol residues comprising linear or alicyclic residues containing from 2 to 20 carbon atoms;

[0136] Wherein the total mole % of the dicarboxylic acid component is 100 mole %,

[0137] wherein the total mole % of the diol component is 100 mole %; and

[0138] (2) residues of a metal catalyst system consisting essentially of or consisting of germanium atoms, wherein the amount of germanium atoms is less than 30 ppm, or less than 25 ppm, or less than 20 ppm, or less than 15 ppm, or 10 ppm or less, or 5 ppm or less, or less than 5 ppm, relative to the mass of the final polyester produced; and

[0139] wherein the final polyester has an intrinsic viscosity of 0.35 dL / g to 1.2 dL / g, or 0.45 dL / g to 1.2 dL / g, or 0.50 dL / g to 1.2 dL / g, or 0.55 dL / g to 1.2 dL / g, or 0.60 dL / g to 1.2 dL / g, or 0.65 dL / g to 1.2 dL / g, or 0.65 dL / g to 0.90 dL / g, as measured at 25°C in 60 / 40 (weight / weight) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml.

[0140] In one embodiment, a polyester composition is provided comprising:

[0141] (1) at least one polyester comprising:

[0142] (a) a dicarboxylic acid component comprising:

[0143] (i) from about 70 mole % to about 100 mole % of residues of terephthalic acid or an ester thereof;

[0144] (ii) from about 0 mole % to about 30 mole % of aromatic or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, or combinations thereof;

[0145] (b) a diol component comprising:

[0146] (i) from about 50 mole % to about 100 mole % ethylene glycol residues;

[0147] (ii) from about 0 mole % to about 50 mole % of modifying glycol residues comprising linear or alicyclic residues containing from 2 to 20 carbon atoms;

[0148] Wherein the total mole % of the dicarboxylic acid component is 100 mole %,

[0149] wherein the total mole % of the diol component is 100 mole %; and

[0150] (2) residues of a metal catalyst system consisting essentially of, or consisting of, germanium atoms, in an amount of 5 ppm or less, or less than 5 ppm, relative to the mass of the final polyester produced; and

[0151] wherein the final polyester has an intrinsic viscosity of 0.35 dL / g to 1.2 dL / g, or 0.45 dL / g to 1.2 dL / g, or 0.50 dL / g to 1.2 dL / g, or 0.55 dL / g to 1.2 dL / g, or 0.60 dL / g to 1.2 dL / g, or 0.65 dL / g to 1.2 dL / g, or 0.65 dL / g to 0.90 dL / g, as measured at 25°C in 60 / 40 (weight / weight) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml.

[0152] In one embodiment, for the diol component, the modifying diol may include at least one of diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methyl-1,3-propanediol, 1,4-cyclohexanedimethanol (CHDM), 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, p-xylene glycol, neopentyl glycol, isosorbide, polytetramethylene glycol, or a mixture thereof.

[0153] In one embodiment, the polyesters and / or polyester compositions of the present invention may comprise residues of TMCD or CHDM in an amount of from about 10 mol% to about 50 mol%, or from about 10 mol% to about 45 mol%, or from about 10 mol% to about 40 mol%, or from about 10 mol% to about 35 mol%, or from about 15 mol% to about 45 mol%, or from about 15 mol% to about 40 mol%, or from about 15 mol% to about 35 mol%, or from about 20 mol% to about 45 mol%, or from about 20 mol% to about 40 mol%, or from about 20 mol% to about 35 mol%, or from about 25 mol% to about 45 mol%, or from about 25 mol% to about 40 mol%. Other modifying glycols may make up the remaining mole percentages.

[0154] In one embodiment, the polyesters and / or polyester compositions of the present invention may comprise EG residues in an amount of from about 50 mol% to about 90 mol%, or from 55 mol% to about 90 mol%, or from about 60 mol% to about 90 mol%, or from about 65 mol% to about 90 mol%, or from about 55 mol% to about 85 mol%, or from about 60 mol% to about 85 mol%, or from about 65 mol% to about 85 mol%, or from about 55 mol% to about 80 mol%, or from about 60 mol% to about 80 mol%, or from about 65 mol% to about 80 mol%, or from about 60 mol% to about 75 mol%.

[0155] In one embodiment, the at least one polyester prepared by one or more processes of the present invention may comprise TMCD residues in an amount of 20 to 45 mol% and EG residues in an amount of 55 to 80 mol%, or TMCD residues in an amount of 20 to 40 mol% and EG residues in an amount of 60 to 80 mol%, or TMCD residues in an amount of 20 to 35 mol% and EG residues in an amount of 65 to 80 mol%, or TMCD residues in an amount of 25 to 45 mol% and EG residues in an amount of 55 to 75 mol%, or TMCD residues in an amount of 25 to 40 mol% and EG residues in an amount of 60 to 75 mol%, or TMCD residues in an amount of 25 to 35 mol% and EG residues in an amount of 65 to 75 mol%, or TMCD residues in an amount of 30 to 35 mol% and EG residues in an amount of 65 to 70 mol%, based on the total mole percentages of diol residues in the final polyester equal to 100 mol%.

[0156] In one embodiment, the at least one polyester prepared by the one or more processes of the present invention may comprise CHDM residues in an amount of 20 to 45 mol% and EG residues in an amount of 55 to 80 mol%, or CHDM residues in an amount of 20 to 40 mol% and EG residues in an amount of 60 to 80 mol%, or CHDM residues in an amount of 20 to 35 mol% and EG residues in an amount of 65 to 80 mol%, or CHDM residues in an amount of 25 to 45 mol% and EG residues in an amount of 55 to 75 mol%, or CHDM residues in an amount of 25 to 40 mol% and EG residues in an amount of 60 to 75 mol%, or CHDM residues in an amount of 25 to 35 mol% and EG residues in an amount of 65 to 75 mol%, or CHDM residues in an amount of 30 to 35 mol% and EG residues in an amount of 65 to 70 mol%, based on the total mole percentages of diol residues in the final polyester equal to 100 mol%.

[0157] In one embodiment, the polyesters and / or polyester compositions of the present invention may contain no CHDM residues, no more than 10 mole percent, or no more than 5 mole percent CHDM residues, based on the total mole percent of diol residues in the final polyester equal to 100 mole percent.

[0158] In one embodiment, the polyesters and / or polyester compositions of the present invention may comprise ethylene glycol residues in an amount from about 60 mol % to about 100 mol %, or from about 60 mol % to about 90 mol %, or from about 65 mol % to about 90 mol %, or from about 70 mol % to about 90 mol %, based on the total mole percentage of glycol residues in the final polyester equal to 100 mol %.

[0159] In one embodiment, the polyesters and / or polyester compositions of the present invention may comprise residues of ethylene glycol and no residues of CHDM, or no more than 10 mole percent, or no more than 5 mole percent, of CHDM residues, wherein the remaining modifying glycol optionally comprises at least one of diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, p-xylene glycol, neopentyl glycol, isosorbide, polytetramethylene glycol, or mixtures thereof.

[0160] In one embodiment, the polyesters and / or polyester compositions of the present invention may comprise residues of at least one of: 1,3-propylene glycol, 1,4-butanediol, and NPG.

[0161] In other embodiments, the glycol component for the polyester and / or polyester composition may include any of the following ranges, based on the total mole percentage of glycol residues in the final polyester equal to 100 mole percent: about 10 mole percent to about 27 mole percent TMCD and about 90 mole percent to about 73 mole percent ethylene glycol; about 15 mole percent to about 26 mole percent TMCD and about 85 mole percent to about 74 mole percent ethylene glycol; about 18 mole percent to about 26 mole percent TMCD and about 82 mole percent to about 77 mole percent ethylene glycol; about 20 mole percent to about 25 mole percent TMCD and about 80 mole percent to about 75 mole percent ethylene glycol; about 21 mole percent to about 24 mole percent TMCD and about 79 mole percent to about 76 mole percent ethylene glycol; or about 22 mole percent to about 24 mole percent TMCD and about 78 mole percent to about 76 mole percent ethylene glycol. In this embodiment, diethylene glycol may be present, either added or formed in situ. If formed in situ, diethylene glycol may be present in amounts of up to 5 mole %, up to 4 mole %, up to 3 mole %, and up to 2 mole %.

[0162] In other embodiments, the diol component for the polyester and / or polyester composition may include any of the following ranges, based on the total mole percentages of diol residues in the final polyester equal to 100 mole percent: 15 mole percent to 27 mole percent TMCD and 73 mole percent to 85 mole percent ethylene glycol; 18 mole percent to 27 mole percent TMCD and 73 mole percent to 82 mole percent ethylene glycol; 19 mole percent to 26 mole percent TMCD and 74 mole percent to 81 mole percent ethylene glycol; 20 mole percent to 25 mole percent TMCD and 75 mole percent to 80 mole percent ethylene glycol.

[0163] In one embodiment, the polyester may comprise: a diol component comprising 15 to 27 mol% TMCD and 73 to 85 mol% ethylene glycol, an intrinsic viscosity of 0.60 to 0.70 dL / g, and a Tg of 90°C to 96°C; or a diol component comprising 20 to 25 mol% TMCD and 75 to 80 mol% ethylene glycol, an intrinsic viscosity of 0.63 to 0.67 dL / g, and a Tg of 92°C to 94°C.

[0164] The molar ratios of cis / trans TMCD and cis / trans CHDM can be varied from their respective pure forms and combinations thereof for the desired polyester.

[0165] In one embodiment, terephthalic acid can be used as the starting material. In another embodiment, dimethyl terephthalate can be used as the starting material. In yet another embodiment, a mixture of terephthalic acid and dimethyl terephthalate can be used as the starting material and / or intermediate material.

[0166] In certain embodiments, terephthalic acid or its esters (such as, for example, dimethyl terephthalate) or a mixture of terephthalic acid residues and their esters may constitute part or all of the dicarboxylic acid component used to form the polyesters and / or polyester compositions of the present invention. In certain embodiments, terephthalic acid residues may constitute part or all of the dicarboxylic acid component used to form the polyesters and / or polyester compositions of the present invention. In certain embodiments, higher amounts of terephthalic acid may be used in order to produce polyesters with higher impact strength. For the purposes of this disclosure, the terms "terephthalic acid" and "dimethyl terephthalate" are used interchangeably herein. In one embodiment, dimethyl terephthalate is part or all of the dicarboxylic acid component used to prepare the polyesters useful in the present invention. In certain embodiments, terephthalic acid and / or dimethyl terephthalate and / or mixtures thereof may be used in a range of 70 mol% to 100 mol%; or 80 mol% to 100 mol%; or 90 mol% to 100 mol%; or 99 mol% to 100 mol%; or 100 mol% of terephthalic acid and / or dimethyl terephthalate and / or mixtures thereof may be used. In addition to terephthalic acid or an ester thereof (e.g., dimethyl terephthalate), the dicarboxylic acid component of the polyester of the present invention may comprise less than 30 mol%, or less than 20 mol%, or less than 10 mol%, or less than 5 mol%, or from 0 mol% to 30 mol%, or from 0 mol% to 20 mol%, or from 0 mol% to 10 mol%, or from 0 mol% to 5 mol%, or from 0 mol% to 1 mol%, or from 0.01 mol% to 10 mol%, or from 0.1 mol% to 10 mol%, or from 1 mol% to 10 mol%, or from 0.01 mol% to 5 mol%, or from 0.1 mol% to 5 mol%, or from 1 mol% to 5 mol%, or from 0.01 mol% to 1 mol%, or from 0.1 mol% to 1 mol%, or from 5 mol% to 10 mol%, or from 0 mol%. Another embodiment contains 0 mol% of a modifying aromatic dicarboxylic acid. Thus, if present, it is contemplated that the amount of one or more modified aromatic dicarboxylic acids may be within the range of any of these aforementioned endpoint values, for example, ranges include 0.01 mol % to 10 mol %, 0.01 mol % to 5 mol % and 0.01 mol % to 1 mol %. In one embodiment, modified aromatic dicarboxylic acids useful in the present invention include, but are not limited to, those having up to 20 carbon atoms and 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, 4,4′-biphenyl dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid and trans-4,4′-stilbene dicarboxylic acid and esters thereof. In one embodiment, the modified aromatic dicarboxylic acid is isophthalic acid.

[0167] In addition to terephthalic acid or an ester thereof (e.g., dimethyl terephthalate), the dicarboxylic acid component of the polyester of the present invention may comprise less than 30 mol%, or less than 20 mol%, or less than 10 mol%, or less than 5 mol%, or from 0 mol% to 30 mol%, or from 0 mol% to 20 mol%, or from 0 mol% to 10 mol%, or from 0 mol% to 5 mol%, or from 0 mol% to 1 mol%, or from 0.01 mol% to 10 mol%, or from 0.1 mol% to 10 mol%, or from 1 mol% to 10 mol%, or from 0.01 mol% to 5 mol%, or from 0.1 mol% to 5 mol%, or from 1 mol% to 5 mol%, or from 0.01 mol% to 1 mol%, or from 0.1 mol% to 1 mol%, or from 5 mol% to 10 mol%, or from 0 mol%. Another embodiment contains 0 mol% of a modifying aromatic dicarboxylic acid. Thus, if present, it is contemplated that the amount of one or more modified aromatic dicarboxylic acids may be within the range of any of these aforementioned endpoint values, for example, ranges include 0.01 mol % to 10 mol %, 0.01 mol % to 5 mol % and 0.01 mol % to 1 mol %. In one embodiment, modified aromatic dicarboxylic acids useful in the present invention include, but are not limited to, those having up to 20 carbon atoms and 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, 4,4′-biphenyl dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid and trans-4,4′-stilbene dicarboxylic acid and esters thereof. In one embodiment, the modified aromatic dicarboxylic acid is isophthalic acid.

[0168] The carboxylic acid component of the polyester and / or polyester composition of the present invention may be further modified with less than 30 mol%, or less than 20 mol%, or less than 10 mol%, or less than 5 mol%, or from 0 mol% to 30 mol%, or from 0 mol% to 20 mol%, or from 0 mol% to 10 mol%, or from 0 mol% to 5 mol%, or from 0 mol% to 1 mol%, or from 0.01 mol% to 10 mol%, or from 0.1 mol% to 10 mol%, or from 1 mol% to 10 mol%. In one embodiment, the present invention provides the aliphatic dicarboxylic acid of one or more carbon atoms containing 2-16 carbon atoms, or 0.01 mol % to 5 mol % or 0.1 mol % to 5 mol % or 1 mol % to 5 mol % or 0.01 mol % to 1 mol % or 0.1 mol % to 1 mol % or 5 mol % to 10 mol % or 0 mol % of one or more aliphatic dicarboxylic acids (such as, for example, cyclohexanedicarboxylic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and dodecanedioic acid) modification. Some embodiments can also include 0.01 mol % to 10 mol %, such as 0.1 mol % to 10 mol %, 1 mol % to 10 mol %, 5 mol % to 10 mol % of one or more modified aliphatic dicarboxylic acids. Another embodiment contains the modified aliphatic dicarboxylic acid of 0 mol %. The total mole % of dicarboxylic acid component is 100 mol %. In one embodiment, adipic acid and / or glutaric acid are provided in the modified aliphatic dicarboxylic acid component of the present invention.

[0169] Can use ester of terephthalic acid and other modified dicarboxylic acids or their corresponding ester and / or salt to replace dicarboxylic acid.Suitable example of dicarboxylic acid ester includes but not limited to dimethyl ester, diethyl ester, dipropyl ester, diisopropyl ester, dibutyl ester and diphenyl ester.In one embodiment, ester is selected from at least one of following: methyl ester, ethyl ester, propyl ester, isopropyl ester and phenyl ester.

[0170] In one embodiment, a polyester composition is provided wherein the polyester comprises from about 80 mol% to about 100 mol%, or from about 90 mol% to about 100 mol%, or from about 95 mol% to about 100 mol%, or from about 99 mol% to about 100 mol% of residues of terephthalic acid or one or more esters thereof;

[0171] In one embodiment, the polyesters and / or polyester compositions of the present invention may comprise CHDA in an amount of less than 30 mol%, or less than 20 mol%, or less than 10 mol%, or less than 5 mol%, or from 0 mol% to 30 mol%, or from 0 mol% to 20 mol%, or from 0 mol% to 10 mol%, or from 0 mol% to 5 mol%, or from 0 mol% to 1 mol%, or from 0.01 mol% to 10 mol%, or from 0.1 mol% to 10 mol%, or from 1 mol% to 10 mol%, or from 0.01 mol% to 5 mol%, or from 0.1 mol% to 5 mol%, or from 1 mol% to 5 mol%, or from 0.01 mol% to 1 mol%, or from 0.1 mol% to 1 mol%, or from 5 mol% to 10 mol%, or from 0 mol%, based on the total mole percentage of diacid residues in the final polyester equal to 100 mol%.

[0172] In one embodiment, the polyesters and / or polyester compositions of the present invention may comprise less than 30 mol%, or less than 20 mol%, or less than 10 mol%, or less than 5 mol%, or from 0 mol% to 30 mol%, or from 0 mol% to 20 mol%, or from 0 mol% to 10 mol%, or from 0 mol% to 5 mol%, or from 0 mol% to 1 mol%, or from 0.01 mol% to 10 mol%, or from 0.1 mol% to 10 mol%, or from 1 mol% to 10 mol%, or from 0.01 mol% to 5 mol%, or from 0.1 mol% to 5 mol%, or from 1 mol% to 5 mol%, or from 0.01 mol% to 1 mol%, or from 0.1 mol% to 1 mol%, or from 5 mol% to 10 mol%, or from 0 mol%, based on the total mole percentage of diacid residues in the final polyester equal to 100 mol%.

[0173] The amount of metal or germanium reported (eg, ppm) is based on the amount of atoms present in the solution, polymer, or article, not the amount of the compound or salt, unless specifically stated as such.

[0174] In one embodiment, the polyester compositions of the present invention comprise at least one germanium compound.

[0175] In one embodiment, the polyester composition of the present invention comprises at least one germanium compound selected from the group consisting of germanium alcoholates, germanium carboxylates, germanium glycolates, organic germanium compounds, or esters of germanic acid.

[0176] In one embodiment, the polyester composition of the present invention comprises at least one germanium compound selected from the group consisting of germanium alcoholates and germanium carboxylates.

[0177] In one embodiment, the polyester composition of the present invention comprises germanium ethoxide, germanium isopropoxide, and germanium acetate or germanium dioxide.

[0178] The germanium compound must be present in the final polycondenser and is desirably present in the prepolymerization zone and the final polycondensation zone. The germanium catalyst can be added, for example, after the intrinsic viscosity of the polymer reaches 0.2 dL / g. However, it can also be added before or near the start of the polycondensation zone, and this mode of addition is preferred, particularly because the polycondensation rate will be much faster in the presence of a germanium catalyst and because the pre-final polycondensation stage operates at a lower temperature and higher pressure (lower vacuum). For example, the germanium catalyst can be added between the end of the esterification zone and the start of the polycondensation zone. Single or multiple additions can be used.

[0179] The term "residue of a metal catalyst system consisting essentially of" means that the other catalyst cannot be present in an amount exceeding 5 ppm, wherein the weight of germanium catalyst is calculated as the weight of germanium atoms relative to the total weight of ingredients introduced into the polycondensation zone.

[0180] The germanium catalyst may include, for example, germanium dioxide in crystalline and amorphous states or a solution obtained by dissolving germanium dioxide in a glycol or other solution, or alternatively, may include an organic germanium compound or various esters of germanic acid.

[0181] The oligoethylene terephthalates to be polycondensed according to the invention are produced in a conventional manner by esterification of terephthalic acid with an excess of ethylene glycol or by transesterification of a terephthalate ester, preferably dimethyl terephthalate, with an excess of ethylene glycol and as described in US Pat. No. 3,651,018.

[0182] The polycondensation process is carried out in a final polycondensation reactor. The final polycondensation reactor is a reactor (e.g., a final reactor) used to increase the molecular weight of the polymer in the melt before solidification during the polycondensation process. In one embodiment, the final polycondensation reactor is a final reactor used to increase the molecular weight of the polymer in the melt before solidification during the polycondensation process.

[0183] The polyester polymer melt is polycondensed in the finishing polycondensation reactor / zone in the presence of at least 20 ppm, or at least 30 ppm, or at least 50 ppm of a germanium catalyst (added before, in, or in the finishing polycondensation reactor), calculated as the weight of germanium atoms relative to the total weight of the ingredients introduced into the polycondensation zone. The amount of germanium catalyst introduced into the polycondensation zone may be in an amount from 20 ppm to 500 ppm, or from 20 ppm to 450 ppm, or from 20 ppm to 400 ppm, or from 20 ppm to 350 ppm, or from 20 ppm to 300 ppm, or from 20 ppm to 250 ppm, or from 50 ppm to 500 ppm, or from 50 ppm to 450 ppm, or from 50 ppm to 400 ppm, or from 50 ppm to 350 ppm, or from 50 ppm to 300 ppm, or from 50 ppm to 250 ppm, or from 100 ppm to 500 ppm, or from 100 ppm to 450 ppm, or from 20 ppm to 400 ppm, or from 100 ppm to 350 ppm, or from 100 ppm to 300 ppm, or from 100 ppm to 250 ppm. ppm, or from 150 ppm to 500 ppm, or from 150 ppm to 450 ppm, or from 150 ppm to 400 ppm, or from 150 ppm to 350 ppm, or from 150 ppm to 300 ppm, or from 150 ppm to 250 ppm, or from 175 ppm to 500 ppm, or from 175 ppm to 450 ppm, or from 175 ppm to 400 ppm, or from 175 ppm to 350 ppm, or from 175 ppm to 300 ppm, or from 175 ppm to 250 ppm, or from 200 ppm to 500 ppm, or from 200 ppm to 450 ppm, or from 200 ppm to 400 ppm, or from 200 ppm to 350 ppm, or from 200 ppm to 300 ppm, or from 200 ppm to 250 ppm.

[0184] The polyester polymer melt is polycondensed in the finishing polycondensation reactor / zone in the presence of a germanium catalyst (added before the finishing polycondensation reactor, at the finishing polycondensation reactor, or in the finishing polycondensation reactor but after 90% conversion is obtained during esterification, or after the esterification zone and before the finishing or final polycondensation reactor), the germanium catalyst being calculated as the weight of germanium atoms.

[0185] In one embodiment, any of the polyesters and / or polyester compositions of the present invention may have an intrinsic viscosity within one of the following ranges: 0.45 dL / g to 1.2 dL / g, or 0.45 dL / g to 1.0 dL / g, or 0.45 dL / g to 0.90 dL / g, or 0.45 dL / g to 0.85 dL / g, or 0.45 dL / g to 0.80 dL / g, or 0.45 dL / g to 0.75 dL / g, or 0.45 dL / g to 0.70 dL / g, or 0.50 dL / g to 1.2 dL / g, or 0.50 dL / g to 1 0 dL / g, or 0.50 dL / g to 0.90 dL / g, or 0.50 dL / g to 0.85 dL / g, or 0.50 dL / g to 0.80 dL / g, or 0.50 dL / g to 0.75 dL / g, or 0.50 dL / g to 0.70 dL / g, or 0.55 dL / g to 1.2 dL / g, or 0.55 dL / g to 1.0 dL / g, or 0.55 dL / g to 0.90 dL / g, or 0.55 dL / g to 0.85 dL / g, or 0.55 dL / g to 0.80 dL / g, or 0.55 dL / g to 0.75 dL / g, or 0.50 dL / g to 0.70 dL / g, or 0.55 dL / g to 1.2 dL / g, or 0.55 dL / g to 1.0 dL / g, or 0.55 dL / g to 0.90 dL / g, or 0.55 dL / g to 0.85 dL / g, or 0.55 dL / g to 0.80 dL / g, or 0.55 dL / g to dL / g, or 0.55 dL / g to 0.70 dL / g, or 0.60 dL / g to 1.2 dL / g, or 0.60 dL / g to 1.0 dL / g, or 0.60 dL / g to 0.90 dL / g, or 0.60 dL / g to 0.85 dL / g, or 0.60 dL / g to 0.80 dL / g, or 0.60 dL / g to 0.75 dL / g, or 0.60 dL / g to 0.70 dL / g, or 0.65 dL / g to 1.2 dL / g, or 0.65 dL / g to 1.0 dL / g, or 0.65 dL / g to dL / g, or 0.65 dL / g to 0.85 dL / g, or 0.65 dL / g to 0.80 dL / g, or 0.65 dL / g to 0.75 dL / g, or 0.68 dL / g to 1.2 dL / g, or 0.60 dL / g to 1.0 dL / g, or 0.68 dL / g to 0.90 dL / g, or 0.68 dL / g to 0.85 dL / g, or 0.68 dL / g to 0.80 dL / g, which is measured at 25°C in 60 / 40 (weight / weight) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml.

[0186] In one embodiment, a polyester composition is provided wherein the intrinsic viscosity of the polyester can be from 0.45 dL / g to 1.2 dL / g, or from 0.45 dL / g to 1.0 dL / g, or from 0.45 dL / g to 0.85 dL / g, or from 0.45 dL / g to 0.80 dL / g, or from 0.55 dL / g to 1.2 dL / g, or from 0.55 dL / g to 1.0 dL / g, or from 0.55 dL / g to 0.85 dL / g, or from 0.65 dL / g to 1.2 dL / g, or from 0.65 dL / g to 1.0 dL / g, or from 0.65 dL / g to 0. dL / g, or 0.65 dL / g to 0.80 dL / g, or 0.65 dL / g to 0.75 dL / g, or 0.60 dL / g to 1.2 dL / g, or 0.60 dL / g to 1.0 dL / g, or 0.60 dL / g to 0.85 dL / g, or 0.60 dL / g to 0.80 dL / g, or 0.60 dL / g to 0.75 dL / g, or 0.68 dL / g to 0.85 dL / g, which is measured at 25°C in 60 / 40 (weight / weight) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml.

[0187] In one embodiment, a polyester composition is provided wherein less than 70 ppm, or less than 65 ppm, or less than 60 ppm, or less than 55 ppm, or less than 50 ppm, or less than 45 ppm, or less than 40 ppm, or less than 35 ppm, or less than 30 ppm, or less than 25 ppm, or less than 20 ppm, or less than 15 ppm, or 10 ppm or less, or 25 ppm or less, or 20 ppm or less of germanium atoms are present in the final polyester composition.

[0188] In one embodiment, a polyester composition is provided wherein the intrinsic viscosity of the polyester is from 0.50 dL / g to 1.2 dL / g, or from 0.50 dL / g to 1.0 dL / g, or from 0.50 dL / g to 0.90 dL / g, or from 0.50 dL / g to 0.85 dL / g, or from 0.50 dL / g to 0.80 dL / g, or from 0.50 dL / g to 0.80 dL / g, and the amount of germanium atoms present in the final polyester composition is 18 ppm or less, or 15 ppm or less, or 10 ppm or less, or 5 ppm or less.

[0189] In one embodiment, a polyester composition is provided wherein the intrinsic viscosity of the polyester is from 0.60 dL / g to 1.2 dL / g, or from 0.60 dL / g to 1.0 dL / g, or from 0.60 dL / g to 0.90 dL / g, or from 0.60 dL / g to 0.85 dL / g, or from 0.65 dL / g to 1.2 dL / g, or from 0.65 dL / g to 1.0 dL / g, or from 0.65 dL / g to 0.90 dL / g, or from 0.65 dL / g to 0.85 dL / g.

[0190] In one embodiment, a polyester composition is provided wherein the amount of germanium atoms present in the final polyester composition is 20 ppm or less, or 18 ppm or less, or 15 ppm or less, or 10 ppm or less, or 5 ppm or less.

[0191] In one embodiment, a polyester composition is provided wherein the amount of germanium atoms present in the final polyester composition is 5 ppm or less, or less than 5 ppm, or less than 4 ppm, or less than 3 ppm, or less than 2 ppm, or less than 1 ppm, or 0 ppm.

[0192] Intrinsic viscosity is measured herein at 25° C. in 60 / 40 (weight / weight) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml.

[0193] The intrinsic viscosity can be measured on amorphous or crystalline pellets obtained after the cutter of the polymer melt feed leaving the final polycondensation reactor (without subjecting the pellets to any further process to increase their molecular weight), or by sampling the effluent from the final polycondensation reactor.

[0194] In one embodiment, a method of making any of the polyesters of the present invention is provided.

[0195] In one embodiment, the process of the present invention enhances the ability to remove catalyst during the polycondensation reaction, resulting in a final product that is substantially catalyst-free. Catalyst recovered from the final polycondensation vessel can be recycled and reused for other purposes. In one embodiment, the loss of catalyst or removal of catalyst occurs in the final polycondensation vessel or final polycondensation reactor and / or does not occur in the post-final polycondensation stage.

[0196] For purposes of this invention, the greater the "catalyst loss," the better the process is considered. "Catalyst loss" is defined herein as the total amount of catalyst no longer present in the reactor, and is further defined below, for example, by catalyst being removed or lost from the reaction, thereby resulting in a lower catalyst level in the final polyester composition. The percentage of germanium loss is calculated by subtracting the amount of germanium remaining measured in the final polymer from the amount of germanium added just before and / or into the final polycondenser, dividing the difference by the amount of germanium added just before the final polycondenser, and multiplying the quotient by 100.

[0197] In one embodiment, a process for preparing any of the polyesters of the present invention is provided wherein the catalyst loss or catalyst removal is greater than 70%, or greater than 75%, or greater than 80%, or greater than 85%, or greater than 86%, or greater than 87%, or greater than 88%, or greater than 89%, or greater than 90%, or greater than 95%, or greater than 96%, or greater than 97%, or greater than 98%, or greater than 99%.

[0198] In one embodiment, a method for preparing any of the polyesters of the present invention is provided, wherein the loss of the catalyst or the removal of the catalyst can occur by applying a vacuum, by nitrogen purging or a combination thereof, or by any other method known to those of ordinary skill in the art. Removal of the germanium catalyst in the final polycondensation reactor (optionally, not in a final polycondensation postreactor, reaction, or step) can be achieved by removing the catalyst from the final polycondensation reactor at multiple time intervals in the final polycondensation reactor in the method, once or throughout the method, so that the germanium can be recovered and preferably recycled. Removing the catalyst in the final polycondensation reactor without the need for subsequent removal and without the need for additional removal steps is one of the benefits of the present invention.

[0199] In one embodiment, there is provided a method for preparing any one of the polyesters of the present invention, wherein the method occurs in at least one final polycondensation reactor selected from a thin film reactor or a vertical final polycondensation reactor. These reactors may include, but are not limited to, falling film evaporators, falling film reactors, Zimmer (horizontal) final polycondensation reactors and tray final polycondensation reactors, other horizontal final polycondensation reactors, such as horizontal cylindrical reactors (see U.S. Patent No. 3,728,083A, which is incorporated herein by reference, which describes a reactor in which a wheel-type film puller is pulled up and a thin polymer film is made, from which volatile compounds such as ethylene glycol and in this case germanium can be removed). In addition, for example, see U.S. Patent No. 4,196,168A, which is incorporated herein by reference. The reactors listed above are only examples, and any reactor (e.g., film) with a reactor design having a high surface area to volume ratio can be used in the present invention.

[0200] In one embodiment, the present invention provides a process wherein a dihydroxyterephthalate-containing compound (e.g., BHET or an oligomer thereof) can be added to a finishing polycondensation reactor having features that provide a high surface area to volume ratio.

[0201] In one embodiment, a process for preparing any of the polyesters of the present invention is provided wherein at least one dihydroxy terephthalate-containing compound is fed to a finishing polycondensation reactor, the finishing polycondensation reactor being operated in the range of 180°C to 300°C or 180°C to 285°C, with a vacuum level between 0.1 Torr and 5 Torr, and a total process time of 15 minutes to 8 hours, wherein germanium is the catalyst, and wherein the final product has an intrinsic viscosity of at least 0.45 dL / g, or 0.45 dL / g to 1.2 dL / g, or 0.50 dL / g to 1.2 dL / g, or 0.55 dL / g to 1.2 dL / g, or 0.60 dL / g to 1.2 dL / g, or 0.65 dL / g to 1.2 dL / g, or 0.65 dL / g to 0.90 dL / g, and contains less than 75 ppm of germanium atoms.

[0202] In one embodiment, a process for preparing any of the polyesters of the present invention is provided wherein at least one dihydroxy terephthalate-containing compound is fed to a finishing polycondensation reactor, the finishing polycondensation reactor being operated in the range of 240°C to 300°C or 240°C to 285°C, with a vacuum level between 0.1 Torr and 5 Torr, and a total process time of 15 minutes to 8 hours, wherein germanium is the catalyst, and wherein the final product has an intrinsic viscosity of at least 0.65 dL / g and contains less than 75 ppm of germanium atoms.

[0203] In one embodiment, a process for preparing any of the polyesters of the present invention is provided wherein at least one dihydroxy terephthalate-containing compound is fed to a finishing polycondensation reactor, the finishing polycondensation reactor being operated in the range of 240°C to 300°C or 240°C to 285°C, with a vacuum level between 0.1 Torr and 1 Torr, and a total process time of 15 minutes to 8 hours, wherein germanium is the catalyst, and wherein the final product has an intrinsic viscosity of at least 0.65 dL / g and contains less than 75 ppm, or less than 50 ppm, or less than 25 ppm, or less than 15 ppm, or less than 10 ppm of germanium atoms.

[0204] In one embodiment, there is provided a process for preparing any of the polyesters of the present invention, wherein the dihydroxy terephthalate-containing compound comprises:

[0205]

[0206] In one embodiment, a process for preparing any of the polyesters of the present invention is provided wherein a dihydroxy terephthalate-containing compound and optionally at least one modifying glycol are reacted in the presence of a single polycondensation catalyst consisting essentially of or consisting of germanium atoms.

[0207] In one embodiment, a process for preparing any of the polyesters of the present invention is provided wherein the dihydroxyterephthalate-containing compound is bis-2-hydroxyethyl terephthalate (BHET).

[0208] In one embodiment, a method of preparing any of the polyesters of the present invention is provided wherein the modifying diol is 1,4-cyclohexanedimethanol.

[0209] In one embodiment, a method of preparing any of the polyesters of the present invention is provided wherein the modifying diol is 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

[0210] In one embodiment, the process of the present invention may be carried out at a temperature of from 180°C to 300°C, or from 200°C to 300°C; or from 200°C to 285°C; or from 200°C to 280°C; or from 200°C to 275°C; or from 200°C to 270°C; or from 225°C to 300°C; or from 225°C to 285°C; or from 225°C to 280°C; or from 245°C to 280°C; or from 245°C to 275°C; or from 280°C or below 280°C, or from 275°C or below 275°C, or from 240°C to 300°C, or from 240°C to 290°C, or from 240°C to below 290°C, or from 240°C to 285°C, or from 260°C to 290°C, or from 260°C to below 290°C, or from 260°C to 285°C, or from 270°C to 285°C. ℃ to 290°C, or 270°C to below 290°C, or 270°C to 285°C, or 270°C to 280°C, or above 270°C to 290°C, or above 270°C to below 290°C, or above 270°C to 285°C, or above 270°C to 280°C, with a total process time of 0.10 hour to 12 hours, or 0.10 hour to 8 hours, or 0.10 hour to 5 hours, or 0.10 hour to 4 hours, or 0.10 hour to 3 hours, or 0.10 hour to 2 hours, or 0.25 hour to 8 hours, or 0.25 hour to 7 hours, or 0.25 hour to 6 hours, or 0.25 hour to 5 hours, or 0.25 hour to 4 hours, or 0.25 hour to 3 hours, or 0.25 hour to 2 hours.

[0211] In one embodiment, the process of the present invention may be carried out at a temperature of 240°C to 290°C, or 240°C to below 290°C, or 240°C to 285°C, or 260°C to 290°C, or 240°C to 285°C, or 260°C to 290°C, or 260°C to below 290°C, or 260°C to 285°C, or 270°C to 290°C, or 270°C to below 290°C, or 270°C to 285°C, or 270°C to 280°C, with a total process time of 0.25 hours to 8 hours.

[0212] In one embodiment, the method of the present invention can be performed at a pressure of 0.10 Torr to 5 Torr, or 0.10 Torr to 4 Torr, or 0.10 Torr to 3 Torr, or 0.10 Torr to 2 Torr, or 0.10 Torr to 1 Torr.

[0213] In some embodiments, the polyesters according to the present invention may contain 0 to 10 mol%, e.g., 0.01 to 5 mol%, 0.01 to 1 mol%, 0.05 to 5 mol%, 0.05 to 1 mol%, or 0.1 to 0.7 mol% (based on the total mol% of diol or diacid residues) of one or more residues of a branching monomer (also referred to herein as a branching agent) having 3 or more carboxyl substituents, hydroxyl substituents, or a combination thereof. In certain embodiments, the branching monomer or branching agent may be added before and / or during and / or after polymerization of the polyester. In various embodiments, therefore, the one or more polyesters useful in the present invention may be linear or branched.

[0214] Examples of branching monomers include, but are not limited to, polyfunctional acids or polyfunctional alcohols such as trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, glycerol, pentaerythritol, citric acid, tartaric acid, 3-hydroxyglutaric acid, and the like. In one embodiment, the branching monomer residues may comprise from 0.1 mol % to 0.7 mol % of one or more residues selected from at least one of trimellitic anhydride, pyromellitic dianhydride, glycerol, sorbitol, 1,2,6-hexanetriol, pentaerythritol, trimethylolethane, and / or trimesic acid. The branching monomers may be added to the polyester reaction composition or blended with the polyester in the form of a concentrate, for example, as described in U.S. Pat. Nos. 5,654,347 and 5,696,176, the disclosures of which regarding branching monomers are incorporated herein by reference.

[0215] The polyesters of the present invention may contain at least one chain extender. Suitable chain extenders include, but are not limited to, multifunctional (including but not limited to difunctional) isocyanates, multifunctional epoxides (including, for example, epoxidized novolacs), and phenoxy resins. In certain embodiments, the chain extender may be added at the end of the polymerization process or after the polymerization process. If added after the polymerization process, the chain extender may be introduced by compounding or by addition during a conversion process (e.g., injection molding or extrusion). The amount of chain extender used may vary depending on the specific monomer composition used and the desired physical properties, but is typically from about 0.1% to about 10% by weight, such as from about 0.1% to about 5% by weight, based on the total weight of the polyester.

[0216] In one embodiment, certain polyesters useful in the present invention may be visually clear.The term "visually clear" is defined herein as being visibly free from cloudiness, haziness, and / or turbidity upon visual inspection.

[0217] In one embodiment, the polyester and / or polyester composition of the present invention (in one embodiment, in the presence and / or absence of one or more colorants) can have color values ​​L*, a*, and b* that can be measured using a Hunter Lab Ultrascan spectrocolorimeter manufactured by Hunter Associates Lab Inc., Reston, Va. The color measurements are the average of the values ​​measured on pellets of the polyester or plaques or other articles injection molded or extruded therefrom. They are determined (converted) using the L*a*b* color system of the CIE (International Commission on Illumination), where L* represents the photometric coordinate, a* represents the red / green coordinate, and b* represents the yellow / blue coordinate.

[0218] In certain embodiments of the present invention, the Tg of the polyester may be selected from one of the following ranges: 72° C. to 100° C., or 85° C. to 100° C., or 90° C. to 100° C. For TMCD-EG polyester, Tg may be one of the following ranges: 85° C. to 100° C.; 86° C. to 99° C.; 87° C. to 98° C.; 88° C. to 97° C.; 89° C. to 96° C.; 90° C. to 95° C.; 91° C. to 95° C.; 92° C. to 94° C. The glass transition temperature (Tg) of the polyester was measured using a TA DSC 2920 from Thermal Analyst Instrument at a scan rate of 20° C. / min.

[0219] Unless otherwise specified, it is contemplated that compositions useful in the present invention may have at least one of the inherent viscosity ranges described herein and at least one of the monomer ranges for compositions described herein. It is also contemplated that compositions useful in the present invention may have at least one of the Tg ranges described herein and at least one of the monomer ranges for compositions described herein, unless otherwise specified. It is also contemplated that compositions useful in the present invention may have at least one of the inherent viscosity ranges described herein, at least one of the Tg ranges described herein, and at least one of the monomer ranges for compositions described herein.

[0220] The melt phase process utilizes an esterification or transesterification zone and a polycondensation zone. The diol and acid are first esterified, most typically with an excess of diol, to produce low molecular weight esters and oligomers in the esterification zone, which typically have an average DP based on number average molecular weight ranging from 2 to 20, or 2 to 10, or 2 to 5. This reaction is generally uncatalyzed in direct esterification processes. After the esterification is complete, in one embodiment achieving at least 80% conversion, or in one embodiment achieving at least 90% conversion, the monomer mixture is removed from the esterification zone and fed to the polycondensation zone. The polycondensation is typically characterized by the initial application of a vacuum and / or the removal of primarily an alkylene glycol to build molecular weight, such as ethylene glycol. In some processes, the polycondensation can be conceptually divided into a number of sub-stages, such as "prepolymerization" and "final polycondensation," but the terminology used in the industry is inconsistent. In most processes, the polycondensation occurs in multiple reactors or in a reactor containing multiple reaction zones. As the polymer undergoes polycondensation and passes to subsequent reactors and / or reaction zones, the temperature and amount of applied vacuum are typically increased to drive the polycondensation to completion, as described herein, unless otherwise indicated.

[0221] The present invention further relates to a polymer blend. The blend comprises:

[0222] (a) 5 to 95 weight percent of at least one of the above polyesters; and

[0223] (b) 5 to 95 weight percent of at least one of the polymer components.

[0224] Suitable examples of polymer components include, but are not limited to, nylon; polyesters other than those originally described herein; polyamides such as Available from DuPont; polystyrene; polystyrene copolymers; styrene acrylonitrile copolymers; acrylonitrile butadiene styrene copolymers; poly(methyl methacrylate); acrylic copolymers; poly(ether-imides), such as (poly(ether-imide) from General Electric); polyphenylene ether, such as poly(2,6-dimethylphenylene ether), or poly(phenylene ether) / polystyrene blends, such as NORYL (a blend of poly(2,6-dimethylphenylene oxide) and polystyrene resin available from General Electric); polyphenylene sulfide; polyphenylene sulfide / polyphenylene sulfone; poly(ester-carbonate); polycarbonates such as (polycarbonate, available from General Electric); polysulfone; polysulfone ether; and poly(ether-ketone) of an aromatic dihydroxy compound; or a combination of any of the foregoing polymers. Blends can be prepared by conventional processing techniques known in the art, such as melt blending or solution blending.

[0225] In one embodiment, the final polyester composition of the present invention may be blended with or contain recycled poly(ethylene terephthalate) (rPET).

[0226] In certain embodiments, the polyester compositions and polymer blend compositions may also contain from 0.01% to 25% by weight of the total composition of common additives such as colorants, one or more tinting agents, dyes, release agents, flame retardants, plasticizers, nucleating agents, stabilizers (including but not limited to UV stabilizers, thermal stabilizers other than the phosphorus compounds described herein and / or their reaction products), 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.

[0227] Reinforcement can be added in the composition of the present invention.Reinforcement can include but is not limited to carbon filament, silicate, mica, clay, talc, titanium dioxide, wollastonite, glass flake, glass beads and fiber and polymer fiber and combination thereof.In one embodiment, reinforcing material comprises glass, such as the combination of fiberglass yarn, glass and talc, the combination of glass and mica, and the combination of glass and polymer fiber.

[0228] In one embodiment, the process for preparing the polyesters of the present invention comprises a continuous process or a semi-continuous process.

[0229] In certain embodiments, the polyesters and / or polyester compositions of the present invention may have a b* value of from -10 to less than 20, -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 15, or 1 to 14, or 1 to 13, or 1 to 12, or 1 to 11, or 1 to 10, or 1 to 9, or 1 to 8, or 1 to 7, or 1 to 6, or 1 to 5, or 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 one embodiment, the polyesters and / or polyester compositions of the present invention may have a b* value of 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 the CIE (International Commission on Illumination).

[0230] In certain embodiments, the polyesters and / or polyester compositions of the present 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 70 to 80, or 75 to 95, or 75 to 90, or 75 to 85, or 80 to 90, as determined by the L*a*b* color system of the CIE (International Commission on Illumination).

[0231] In one embodiment, there is provided a product that can be prepared using any of the polyester compositions of the present invention or by any of the methods of the present invention.

[0232] In one embodiment, an article of manufacture that can be prepared using any of the polyester compositions of the present invention or by any of the methods of the present invention is provided.

[0233] In one embodiment, there is provided a shaped article made with any of the polyester compositions of the present invention or by any of the methods of the present invention.

[0234] In one embodiment, the polyesters and / or polyester compositions of the present invention can be used in thermoplastic polyester compositions, articles, shaped articles, thermoplastic shaped articles, molded articles, extruded articles, injection molded articles, blow molded articles, films and / or sheets (e.g., calendared, cast, or extruded), containers and / or bottles (e.g., beverage bottles, water bottles).

[0235] In one embodiment, the polyesters and / or polyester compositions of the present invention can be used in films, sheets, bottle preforms, beverage preforms, and blow-molded bottles made therefrom.

[0236] In one embodiment, the polyester compositions of the present invention can be used to form articles, including but not limited to extruded and / or molded articles, including but not limited to injection molded articles, extruded articles, cast extruded articles, profile extruded articles, melt-spun articles, thermoformed articles, extrusion molded articles, injection blow molded articles, injection stretch blow molded articles, extrusion blow molded articles, and extrusion stretch blow molded articles. These articles can include but are not limited to films, bottles, containers, drinkware, medical components, sheets, and / or fibers.

[0237] In one embodiment, the polyester compositions of the present invention can be used in various types of films and / or sheets, including but not limited to extruded one or more films and / or one or more sheets, compression molded one or more films and / or one or more sheets, solution cast one or more films and / or one or more sheets. Methods for preparing films and / or sheets include but are not limited to extrusion, compression molding, and solution casting.

[0238] In one embodiment, the present invention is directed to an article, for example, a shaped article, comprising any of the polyesters or polyester compositions of the present invention.

[0239] In one embodiment, any of the methods for making polyesters useful in the present invention and described herein or known to those of ordinary skill in the art can be used to prepare any of the polyesters and / or polyester compositions of the present invention.

[0240] In one embodiment, any of the polyesters and / or polyester compositions described herein, and any products made therefrom, are also considered to be within the scope of the present invention, regardless of the method used to make the polyester and / or polyester composition.

[0241] In one embodiment, any of the methods for making polyesters useful in the present invention and described herein or known to those of ordinary skill in the art can be used to prepare any of the polyesters and / or polyester compositions of the present invention.

[0242] The following examples further illustrate how to prepare and evaluate the polyesters of the present invention and are intended to be purely exemplary embodiments of the present invention and are not intended to limit the scope thereof. Unless otherwise indicated, parts are parts by weight, temperatures are in degrees Celsius or are room temperature, and pressures are at or near atmospheric pressure.

[0243] Example

[0244] The following examples summarize how the copolyesters of the present invention are prepared and the effects of certain catalysts and stabilizers on various copolyester properties, such as color and intrinsic viscosity (IV).

[0245] Measurement method

[0246] Unless otherwise indicated, IV or IV refers to intrinsic viscosity measured as described herein.

[0247] The intrinsic viscosity (IV) of the polyesters was determined in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml at 25° C. and is reported in dL / g. The amount of germanium (Ge) metal in the experimental samples was reported in parts per million (ppm) of metal and was measured by x-ray fluorescence (XRF) using a PAN analytical Axios Advanced wavelength dispersive x-ray fluorescence spectrometer.

[0248] Examples 1-17

[0249] Experiment (Example 1-17) is carried out to check the effect of increasing surface area and volume ratio by reducing the amount of BHET that drops into given reactor.In these experiments, the charging amount of BHET ranges from 0.1 mole (high surface area and volume ratio) to 0.5 mole (low surface area and volume ratio).The catalyst used is the germanium isopropoxide (about 2.29 weight / volume % Ge) in n-butanol, and wherein based on final polyester quality, target concentration is 200ppm germanium (Ge).Table 1 shows the BHET of various mole scale operations and the charging amount of Ge and the expected amount of the polyethylene terephthalate (PET) formed, and the final Ge concentration of expection when assuming that there is no loss.

[0250] Table 1: Material input and output for PET production from BHET at different scales.

[0251]

[0252] Place BHET in a 500 mL round-bottom flask. Add the catalyst using a pipette. Equip the round-bottom flask with a stainless steel stirrer and distillation head, then clamp it to the polymerization apparatus. Attach the distillation sidearm and Erlenmeyer flask with the distillation head. Attach the vacuum system to the Erlenmeyer flask. Procedure by Camile The TG data acquisition and process control system followed the reaction profile listed in Table 2. Prior to the start of the process, the Belmont metal bath was preheated to 250°C. During the reaction, a 0.2 scfh N2 flow was maintained over the flask contents until vacuum was applied. Once the synthesis process was complete, the polymer was pulled, removed from the stir bar, and placed in a black bag. The material was then ground to 6 mm and tested using the various methods described below.

[0253] Table 2: Camile reaction spectrum for the synthesis of PET from BHET.

[0254]

[0255]

[0256] Figure 2 The effect of varying the amount of BHET added to the reaction flask on the amount of Ge remaining in the final polymer and the intrinsic viscosity (IV) of PET, based on a final vacuum level of 0.3 Torr (X, in stages 4 and 5), is shown. As the BHET charge decreases in a reactor of a given size, the surface area to volume ratio increases. This theoretically allows for easier removal of Ge and ethylene glycol (EG). In the limit of a "perfect" film, in the limit of no charge, essentially all of the Ge can be removed despite an initial charge of 200 ppm of Ge. Thus, even at BHET charges of 0.1 mol and 0.15 mol, nearly 99% of the Ge is removed. One risk of removing the catalyst is a potential loss of catalytic activity, resulting in a lower IV. However, surprisingly, for the same reaction spectrum, there is no effect on catalytic activity in terms of achieving IV. This clearly demonstrates that catalyst-free polyethylene terephthalate (PET) with high intrinsic viscosity or very low residual catalyst levels (<5 ppm Ge) can be produced in a final polycondensation reactor design with a high surface area to volume ratio (thin film). Low BHET feed levels to a given reactor can also produce high surface area to volume ratios. These polymers have good color.

[0257] Additional experiments were conducted at final vacuum levels of 1.0 Torr and 3.0 Torr instead of 0.3 Torr (Stages 4 and 5 in the reaction spectrum in Table 2). Figure 3 As shown, Ge is readily removed at high surface area to volume ratios (i.e., reduced BHET loadings) even at 1.0 Torr and 3.0 Torr. It should be noted that, unsurprisingly, the same reaction time of 120 minutes and vacuum levels of 1 Torr and 3 Torr did result in lower IV at all BHET loading levels, likely due to less EG removal.

[0258] Table 3

[0259]

[0260]

[0261] The percent germanium weight loss for Examples 1-17 is calculated in Table 4. For example, in Example 1, the calculation is as follows: (200-30) / (200) x 100 equals 85 wt% germanium loss. In Example 1, germanium was fed to the reaction at 200 ppm, 30 ppm of germanium was found in the final polymer, and 170 ppm of Ge was removed by vacuum.

[0262] Table 4

[0263]

[0264] Unexpectedly, the use of germanium as a catalyst in the process of the present invention results in these polyesters having good intrinsic viscosity, with virtually no catalyst residue remaining in the final polyester.

[0265] The disclosure has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the disclosure.

Claims

1. A polyester composition comprising: (1) at least one polyester comprising: (a) a dicarboxylic acid component comprising: (i) from about 70 mole % to about 100 mole % of residues of terephthalic acid or an ester thereof; (ii) from about 0 mole % to about 30 mole % of aromatic or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, or combinations thereof; (b) a diol component comprising: (i) from about 50 mole % to about 100 mole % ethylene glycol residues; (ii) from about 0 mole % to about 50 mole % of modifying glycol residues comprising linear or alicyclic residues containing from 2 to 20 carbon atoms; 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) residues of a metal catalyst system consisting essentially of germanium atoms, said germanium atoms being present in an amount of 75 ppm or less relative to the mass of the final polyester produced; and The final polyester has an intrinsic viscosity of 0.45 dL / g to 1.2 dL / g, as measured at 25° C. in 60 / 40 (w / w) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml.

2. The polyester composition according to claim 1, wherein the modifying diol comprises at least one of the following: diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methyl-1,3-propanediol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, p-xylene glycol, neopentyl glycol, isosorbide, polytetramethylene glycol, or a combination thereof.

3. The polyester composition of claim 1, wherein the modifying diol comprises the residue of 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

4. The polyester composition of claim 1, wherein the modifying diol comprises the residue of 1,4-cyclohexanedimethanol.

5. The polyester composition of claim 1 , wherein the modifying glycol is present in an amount of from about 10 mol% to about 45 mol%, or from about 15 mol% to about 45 mol%, or from about 10 mol% to about 40 mol%, or from about 20 mol% to about 40 mol%, or from about 10 mol% to about 30 mol%, or from about 20 mol% to about 35 mol%, or from about 20 mol% to about 30 mol%, or from about 25 mol% to about 40 mol%, or from about 30 mol% to about 40 mol%.

6. The polyester composition of claim 1 , wherein the polyester comprises residues of ethylene glycol in an amount of from about 55 mol% to about 90 mol%, or from about 55 mol% to about 85 mol%, or from about 60 mol% to about 90 mol%, or from about 60 mol% to about 80 mol%, or from about 65 mol% to about 80 mol%, or from about 70 mol% to about 90 mol%, or from about 70 mol% to about 80 mol%, or from about 60 mol% to about 75 mol%, or from about 60 mol% to about 70 mol%.

7. The polyester composition of claim 1, wherein the polyester comprises the residue of a diacid component comprising an aromatic or aliphatic dicarboxylic acid ester residue, or a combination thereof.

8. The polyester composition of claim 1 , wherein the polyester comprises from about 80 mol % to about 100 mol %, or from about 90 mol % to about 100 mol %, or from about 95 mol % to about 100 mol %, or from about 99 mol % to about 100 mol % residues of terephthalic acid or an ester thereof.

9. The polyester composition of claim 1 , wherein the intrinsic viscosity is 0.45 dL / g to 1.2 dL / g, or 0.45 dL / g to 1.0 dL / g, or 0.45 dL / g to 0.90 dL / g, or 0.45 dL / g to 0.85 dL / g, or 0.45 dL / g to 0.80 dL / g, or 0.45 dL / g to 0.75 dL / g, or 0.45 dL / g to 0.70 dL / g, or 0.50 dL / g to 1.2 dL / g, or 0.50 dL / g to 1.0 dL / g, or 0.50 ... / g to 0.90 dL / g, or 0.50 dL / g to 0.85 dL / g, or 0.50 dL / g to 0.80 dL / g, or 0.50 dL / g to 0.75 dL / g, or 0.50 dL / g to 0.70 dL / g, or 0.55 dL / g to 1.2 dL / g, or 0.55 dL / g to 1.0 dL / g, or 0.55 dL / g to 0.90 dL / g, or 0.55 dL / g to 0.85 dL / g, or 0.55 dL / g to 0.80 dL / g, or 0.55 dL / g to 0.75 dL / g, or 0.55 dL / g to 0.70 dL / g, or 0.60 dL / g to 1.2 dL / g, or 0.60 dL / g to 1.0 dL / g, or 0.60 dL / g to 0.90 dL / g, or 0.60 dL / g to 0.85 dL / g, or 0.60 dL / g to 0.80 dL / g, or 0.60 dL / g to 0.75 dL / g, or 0.60 dL / g to 0.70 dL / g, or 0.65 dL / g to 1.2 dL / g, or 0.65 dL / g to 1.0 dL / g, or 0.65 dL / g to 0.90 dL / g L / g, or 0.65 dL / g to 0.85 dL / g, or 0.65 dL / g to 0.80 dL / g, or 0.65 dL / g to 0.75 dL / g, or 0.68 dL / g to 1.2 dL / g, or 0.60 dL / g to 1.0 dL / g, or 0.68 dL / g to 0.90 dL / g, or 0.68 dL / g to 0.85 dL / g, or 0.68 dL / g to 0.80 dL / g, which is measured at 25°C in 60 / 40 (weight / weight) phenol / tetrachloroethane at a concentration of 0.5g / 100ml.

10. The polyester composition of claim 1 , wherein the intrinsic viscosity of the polyester is 0.45 dL / g to 0.90 dL / g, or 0.45 dL / g to 0.85 dL / g, or 0.45 dL / g to 0.80 dL / g, or 0.45 dL / g to 0.75 dL / g, or 0.45 dL / g to 0.70 dL / g, or 0.50 dL / g to 0.90 dL / g, or 0.50 dL / g to 0.85 dL / g, or 0.50 dL / g to 0.80 dL / g, or 0.55 dL / g to 0.90 dL / g, or 0.55 dL / g to 0.85 dL / g, or 0.55 dL / g to 0.80 dL / g, or 0.60 dL / g to 0.90 dL / g. g, or 0.60 dL / g to 0.85 dL / g, or 0.60 dL / g to 0.80 dL / g, or 0.60 dL / g to 0.75 dL / g, or 0.60 dL / g to 0.70 dL / g, or 0.65 dL / g to 0.90 dL / g, or 0.65 dL / g to 0.85 dL / g, or 0.65 dL / g to 0.8 0 dL / g, or 0.65 dL / g to 0.75 dL / g, or 0.68 dL / g to 0.90 dL / g, or 0.68 dL / g to 0.85 dL / g, or 0.68 dL / g to 0.80 dL / g, as measured at 25°C in 60 / 40 (weight / weight) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml.

11. The polyester composition of claim 1 , wherein the intrinsic viscosity of the polyester is 0.45 dL / g to 0.90 dL / g, or 0.45 dL / g to 0.85 dL / g, or 0.45 dL / g to 0.80 dL / g, or 0.50 dL / g to 0.90 dL / g, or 0.50 dL / g to 0.85 dL / g, or 0.50 dL / g to 0.80 dL / g, or 0.55 dL / g to 0.90 dL / g, or 0.55 dL / g to 0.85 dL / g, or 0.55 dL / g to 0.80 dL / g, or 0.60 dL / g, or 0.60 dL / g to 0.85 dL / g, or 0.60 dL / g to 0.80 dL / g, or 0.65 dL / g to 0.90 dL / g, or 0.65 dL / g to 0.85 dL / g, or 0.65 dL / g to 0.80 dL / g, and the amount of germanium atoms present in the final polyester composition is 70 ppm or less, or 65 ppm or less, or 55 ppm or less, or 45 ppm or less, or 40 ppm or less, or 30 ppm or less, or 25 ppm or less, or 20 ppm or less.

12. The polyester composition of claim 1, wherein the intrinsic viscosity of the polyester is 0.50 dL / g to 0.90 dL / g, or 0.50 dL / g to 0.85 dL / g, or 0.50 dL / g to 0.80 dL / g, or 0.55 dL / g to 0.90 dL / g, or 0.55 dL / g to 0.85 dL / g, or 0.55 dL / g to 0.80 dL / g, or 0.60 dL / g to 0.9 dL / g, or 0.60 dL / g to 0.85 dL / g, or 0.60 dL / g to 0.80 dL / g, or 0.65 dL / g to 0.90 dL / g, or 0.65 dL / g to 0.85 dL / g, or 0.65 dL / g to 0.80 dL / g, and the amount of germanium atoms present in the final polyester composition is 18 ppm or less, or 15 ppm or less, or 10 ppm or less, or 5 ppm or less.

13. The polyester composition of claim 1 or claim 10, wherein less than 70 ppm, or less than 65 ppm, or less than 60 ppm, or less than 55 ppm, or less than 50 ppm, or less than 45 ppm, or less than 40 ppm, or less than 35 ppm, or less than 30 ppm, or less than 25 ppm, or less than 20 ppm, or less than 18 ppm, or less than 15 ppm, or 10 ppm or less, or 5 ppm or less, or less than 5 ppm of germanium atoms are present in the final polyester composition.

14. The polyester composition of claim 1, wherein the amount of germanium atoms present in the final polyester composition is 18 ppm or less, or 15 ppm or less, or 10 ppm or less, or 5 ppm or less, or less than 5 ppm.

15. The polyester composition of claim 1 having a b* value of -10 to less than 20, -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 15, or 1 to 14, or 1 to 13, or 1 to 12, or 1 to 11, or 1 to 10, or 1 to 9, or 1 to 8, or 1 to 7, or 1 to 6, or 1 to 5, or 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 (International Commission on Illumination).

16. The polyester composition of claim 1 having an L* value of 50 to 99, or 50 to 90, or 60 to 99, or 60 to 90, or 60 to 85, or 60 to 80, or 65 to 99, or 65 to 90, or 65 to 85, or 65 to 80, or 65 to 75, or 70 to 90, or 70 to 99, or 70 to 90, or 70 to 85, or 70 to 80, or 75 to 95, or 75 to 90, or 75 to 85, or 80 to 90 as determined by the L*a*b* color system of CIE (International Commission on Illumination).

17. The polyester composition of claim 1, wherein the polyester comprises the residue of at least one branching agent or comprises no branching agent or comprises 1 mole percent or less of a branching agent.

18. The polyester composition of claim 1, wherein the at least one germanium compound is selected from the group consisting of germanium alcoholates, germanium carboxylates, organic germanium compounds, and esters of germanic acid.

19. The polyester composition of claim 1, wherein the at least one germanium compound is selected from the group consisting of germanium alcoholates and germanium carboxylates.

20. The polyester composition of claim 1, wherein the germanium compound is selected from the group consisting of germanium ethoxide, germanium isopropoxide, and germanium acetate or germanium dioxide.

21. The polyester composition of claim 1 , wherein the polyester composition comprises a blend with at least one polymer selected from the group consisting of polyesters other than those in claim 1 , poly(etherimides), polyphenylene ethers, poly(phenylene ether) / polystyrene blends, polystyrene resins, polyphenylene sulfide, polyphenylene sulfide / polyphenylene sulfone, poly(ester-carbonates), polycarbonates, polysulfones; polysulfone ethers; and poly(ether-ketones).

22. A process for preparing the polyester according to claim 1.

23. The process of claim 22, wherein the total loss of catalyst or removal of catalyst is greater than 70%, or greater than 75%, or greater than 80%, or greater than 85%, or greater than 86%, or greater than 87%, or greater than 88%, or greater than 89%, or greater than 90%, or greater than 95%, or greater than 96%, or greater than 97%, or greater than 98%, or greater than 99%.

24. The process of claim 23, wherein the loss of catalyst or removal of catalyst occurs in a final polycondensation vessel or final polycondensation reactor.

25. The process of claim 22, 23, or 24, wherein the amount of germanium catalyst introduced into the polycondensation zone can be an amount of at least 20 ppm, or at least 50 ppm, or at least 100 ppm, or from 20 ppm to 500 ppm, or from 20 ppm to 450 ppm, or from 20 ppm to 400 ppm, or from 20 ppm to 350 ppm, or from 20 ppm to 300 ppm, or from 20 ppm to 250 ppm, or from 50 ppm to 500 ppm, or from 50 ppm to 450 ppm, or from 50 ppm to 400 ppm, or from 50 ppm to 350 ppm, or from 50 ppm to 300 ppm, or from 50 ppm to 250 ppm, or from 100 ppm to 500 ppm, or from 100 ppm to 450 ppm, or from 20 ppm to 400 ppm, or from 100 ppm to 350 ppm, or 100 ppm to 300 ppm, or 100 ppm to 250 ppm, or 150 ppm to 500 ppm, or 150 ppm to 450 ppm, or 150 ppm to 400 ppm, or 150 ppm to 350 ppm, or 150 ppm to 300 ppm, or 150 ppm to 250 ppm, or 175 ppm to 500 ppm, or 175 ppm to 450 ppm, or 175 ppm to 400 ppm, or 175 ppm to 350 ppm, or 175 ppm to 300 ppm, or 175 ppm to 250 ppm, or 200 ppm to 500 ppm, or 200 ppm to 450 ppm, or 200 ppm to 400 ppm, or 200 ppm to 350 ppm, or 200 ppm to 300 ppm, or 200 ppm to 250 ppm.

26. The method of claim 22, comprising the dihydroxyterephthalate-containing compound being bis-2-hydroxyethyl terephthalate (BHET).

27. The process of claim 22, wherein at least one dihydroxy terephthalate containing compound is fed to a finishing polycondensation reactor, the finishing polycondensation reactor being operated in the range of 240°C to 300°C, with a vacuum level between 0.1 Torr and 5 Torr, and a total process time of 15 minutes to 8 hours, wherein germanium is the catalyst, and wherein the final product has an intrinsic viscosity of at least 0.45 dL / g and contains less than 75 ppm of germanium atoms.

28. The process of claim 22, wherein at least one dihydroxy terephthalate-containing compound is fed to a finishing polycondensation reactor, the finishing polycondensation reactor being operated in the range of 240°C to 300°C, with a vacuum level between 0.1 Torr and 1 Torr, and a total process time of 15 minutes to 8 hours, wherein germanium is the catalyst, and wherein the final product has an intrinsic viscosity of at least 0.65 dL / g and contains less than 75 ppm, or less than 50 ppm, or less than 25 ppm, or less than 15 ppm, or less than 10 ppm of germanium atoms.

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