Catalyst system for crystallizable reactor-grade resins with recyclable content

Abstract

The present disclosure relates to a catalyst system for producing crystallizable polyester compositions comprising residues of terephthalic acid, neopentyl glycol (NPG), 1,4-cyclohexanedimethanol (CHDM), ethylene glycol (EG), and diethylene glycol (DEG) in a specific composition range with particular advantages and improved properties, including recyclability. The present disclosure further relates to a catalyst system for producing crystallizable polyester compositions comprising residues of recycled terephthalic acid, recycled neopentyl glycol (NPG), recycled 1,4-cyclohexanedimethanol (CHDM), recycled ethylene glycol (EG), and / or recycled diethylene glycol (DEG) in a specific composition range with particular advantages and improved properties, including recyclability.

Description

Field of Invention

[0001]

[0001] The present disclosure relates to a catalyst system for producing a crystallizable polyester composition comprising residues of terephthalic acid, neopentyl glycol (NPG), 1,4-cyclohexanedimethanol (CHDM), ethylene glycol (EG), and diethylene glycol (DEG) within a specific composition range having certain advantages and improved properties, including recyclability. The present disclosure further relates to a catalyst system for producing a crystallizable polyester composition comprising residues of recycled terephthalic acid, recycled neopentyl glycol (NPG), recycled 1,4-cyclohexanedimethanol (CHDM), recycled ethylene glycol (EG), and / or recycled diethylene glycol (DEG) within a specific composition range having certain advantages and improved properties, including recyclability. [Background technology]

[0002]

[0002] Polyester compositions containing certain glycols with moderate reactivity, such as neopentyl glycol (NPG; 2,2-dimethyl-1,3-propanediol), are well known and used in a variety of applications. However, these glycols are often less reactive than other glycols such as ethylene glycol (EG) and 1,4-cyclohexanedimethanol (CHDM) in esterification reactions, and in the production of compositions incorporating these glycols, extreme reaction conditions, excessively high loading amounts of glycols, special catalysts, stepwise addition of reactants, or a combination of several of these influencing factors may be required to achieve the desired molecular weight of the product with reasonable production efficiency. Furthermore, measures commonly used to improve production efficiency and glycol incorporation in compositions produced from these glycols often result in high levels of glycol degradation, poor product color, the formation of undesirable polymer end group clusters, and poor incorporation of this glycol into polyesters produced in combination with other glycols.

[0003]

[0003] Historically, titanium alone has been a preferred catalyst for the production of copolymer polyester compositions produced from combinations of terephthalic acid (TPA), ethylene glycol (EG), 1,4-cyclohexanedimethanol (CHDM), and diethylene glycol (DEG). These catalyst systems typically contain 20-25 ppm of titanium and 25 ppm of phosphorus acting as a modifier. However, because these compositions contain NPGs, these titanium alone systems have not been suitable for the crystallizable polyester compositions of the present disclosure.

[0004]

[0004] In this disclosure, it has been found that crystallizable polyester compositions containing residues of terephthalic acid, neopentyl glycol (NPG), 1,4-cyclohexanedimethanol (CHDM), ethylene glycol (EG), and diethylene glycol (DEG) are recyclable in the PET recycling process. The inclusion of NPG in these crystallizable polyester compositions necessitates a novel catalyst system. Specifically, when prepared using a titanium-only catalyst system, the color tone of the polyesters in this disclosure is very high. * The sample exhibited a value (i.e., a very yellow color). Increasing the phosphorus load reduced the polymerization rate, but did not reduce the intense yellow color. Reducing the titanium concentration only slightly improved the color, but still reduced the polymerization rate, as could be seen by monitoring the intrinsic viscosity achieved over time.

[0005]

[0005] It has been found that when the titanium-antimony catalyst system is used in combination with a phosphorus compound, polyester compositions with far superior color tones can be produced at the same or improved polymerization rate compared to compositions produced using a titanium-only system.

[0006]

[0006] In the context of PET recycling, which exhibits excellent performance characteristics, there is a commercial demand for crystallizable polyester compositions that can be recycled. There is also a commercial demand for catalyst systems for producing crystallizable polyester compositions having excellent polymerization rates and excellent color tones. [Overview of the project]

[0007]

[0007] It has been found that by using specific combinations of glycol monomers, it is possible to produce crystallizable polyester compositions that do not affect the recycling of accompanying PET during the recycling process. Articles produced using these crystallizable polyester resins are processed together with PET articles and ultimately become components of recyclable PET flakes generated from the recycling process. It has also been found that the selection of specific combinations of glycol monomers and their amounts are important for producing polyesters that have excellent performance properties and are crystallizable. The optimal polyester resin compositions of this disclosure are amorphous but crystallizable. For this reason, these compositions have a high melting point of strain-induced crystals, exhibiting excellent properties in applications such as films and sheets, including shrinkable films and thermoformable sheets, thereby providing suitability for the recycling process. Articles produced using the polyester compositions of this disclosure do not need to be removed during the recycling process and do not affect the recycling process.

[0008]

[0008] Furthermore, it has been found that a catalyst system containing a low concentration of titanium compound combined with an antimony compound and incorporating a phosphorus compound can produce a crystallizable copolymer polyester composition containing neopentyl glycol that has superior color and comparable reaction rate compared to conventional titanium-only systems incorporating phosphorus as a stabilizer / catalyst dampener. The low titanium-antimony combination is effective over a wide temperature range, and even at the highest phosphorus concentration disclosed, it is possible to use reaction temperatures exceeding 300°C without sacrificing the color of the product.

[0009]

[0009] In one embodiment, a heat-shrinkable film manufactured from the crystallizable polyester composition of the Disclosure must meet various suitability criteria for use. The film must be tough, shrink in a controlled manner, and provide sufficient shrinkage force to hold the film on the bottle surface without crushing the contents. Furthermore, if these labels are to be fitted to polyester containers or bottles, these polyester shrinkable film labels must not interfere with the recycling process of the polyester containers or bottles. The shrinkable films of the Disclosure are advantageous because the labels can be recycled together with the bottles or containers. Thus, the entire container or bottle, including the labels, can be recycled and transformed into a new product without creating additional work requirements or new environmental problems. Heat-shrinkable films have been manufactured from various raw materials to meet a certain range of material requirements. The Disclosure describes unique and unexpected effects mitigated by specific monomer combinations for shrinkable film resin compositions.

[0010]

[0010] Polyester shrink film compositions have been commercially used as shrink film labels for food, beverages, personal care products, household goods, etc. In many cases, these shrink films are used in combination with transparent polyethylene terephthalate (PET) bottles or containers. The entire container, including the bottle and label, is then sent to the recycling process. In a typical recycling center, PET and shrink film material are processed together at the end of this process because they have similar composition and density. The PET flakes need to be dried to remove any moisture remaining with the PET during the recycling process. Typically, the PET is dried at temperatures above 200°C. At these temperatures, the common polyester shrink film resin softens and becomes sticky, often forming clumps with the PET flakes. These clumps need to be removed before the next processing. These clumps reduce the yield of PET flakes from the process and require additional processing steps. In one aspect of this disclosure, the agglomeration evaluation was conducted using the APR agglomeration test: PET-S-08 “PET Flake Clumping Evaluation” revised on November 16, 2018, and the judgment regarding suitability for the recycling process was made in accordance with document number PET-CG-02 “Critical Guidance Protocol for Clear PET Articles with Labels and Closures” dated April 11, 2019.

[0011]

[0011] In this disclosure, it has been found that by certain combinations of glycol monomers in a polyester composition, a composition with excellent performance properties can be produced, and that such combinations allow for crystallization without affecting the recycling of PET. Furthermore, it has been found that by certain combinations of glycol monomers in a film or sheet resin composition, a film or sheet with excellent performance properties can be produced, and that such combinations allow for crystallization without affecting the recycling of PET flakes. These crystallizable film or sheet resins are processed together with recycled PET and ultimately become components of recyclable PET flakes generated from the recycling process. Furthermore, it has been found that the selection and amount of specific combinations of glycol monomers are important for producing films or sheets with excellent performance properties and that are crystallizable. In other words, although the polyester compositions of this disclosure are amorphous, they are "crystallizable" in the sense that they have a high melting point for strain-induced crystals. Therefore, these polyester compositions exhibit excellent properties in film or sheet applications, including shrinkable films, formed, thermoformed, or molded parts and / or articles, but they also have high strain-induced crystal melting points, so that when recycled PET flakes are subjected to high-temperature drying conditions, the crystallizable polyesters of the Disclosure can be recycled together with PET, as they do not form lumps that interfere with normal mechanical operations such as flake formation, drying, and feeding into an extruder for further processing into (recyclable) polyester pellets. Similarly, extruded sheets produced from the resin compositions of the Disclosure do not need to be removed during the recycling process and therefore do not adversely affect the recycling process. (For example, https: / / www.thebalancesmb.com / recycling-polyethylene-terephthalate-pet-2877869 (See reference).

[0012]

[0012] One embodiment of the present disclosure is a crystallizable reactor-grade polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mol% of terephthalic acid residues and (ii) about 0 to about 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises about 75 mol% or more of ethylene glycol residues and (i) about 0.1 to less than 24 mol% of neopentyl glycol residues, (ii) 0 to less than 24 mol% of 1,4-cyclohexanedimethanol residues and (iii) about 1 to less than 10 mol% of the total diethylene glycol residues in the final polyester composition, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%.

[0013]

[0013] One embodiment of the present disclosure is a crystallizable reactor-grade polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mol% of terephthalic acid residues and (ii) 0 to about 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises about 80 mol% or more of ethylene glycol residues and (i) about 5 to less than 17 mol% of neopentyl glycol residues, (ii) about 2 to less than 10 mol% of 1,4-cyclohexanedimethanol residues and (iii) about 1 to less than 5 mol% of total diethylene glycol residues in the final polyester composition, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%.

[0014]

[0014] One embodiment of the present disclosure is a crystallizable reactor-grade polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mol% of terephthalic acid residues and (ii) about 0 to about 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises about 76 mol% or more of ethylene glycol residues and an amorphous content of about 24 mol% or less selected from (i) neopentyl glycol residues, (ii) cyclohexanedimethanol residues and (iii) diethylene glycol residues in the final polyester composition, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%.

[0015]

[0015] One embodiment of the present disclosure is a crystallizable reactor-grade polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mol% terephthalic acid residues and (ii) about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, the (b) diol component comprises (i) about 1 to about 30 mol% neopentyl glycol residues, (ii) about 1 to less than 30 mol% 1,4-cyclohexanedimethanol residues, and (iii) about 1.5 to 6 mol% diethylene glycol residues, wherein the remainder of the glycol component comprises (iv) ethylene glycol residues and (v) 0 to 20 mol% at least one modified glycol residue, the total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the diol component is 100 mol%.

[0016]

[0016] One embodiment of the present disclosure is a crystallizable reactor-grade polyester composition of any one of the embodiments described above, which further comprises a catalyst system residue comprising 2 to 15 ppm of titanium, 50 to 150 ppm of antimony, and 0 to 60 ppm of phosphorus, where the concentration of the catalyst system residue is based on the weight of the polyester.

[0017]

[0017] One embodiment of the present disclosure is a crystallizable reactor-grade polyester composition of any one of the embodiments described above, which further comprises a catalyst system residue comprising 3 to 10 ppm of titanium, 50 to 125 ppm of antimony, and 0 to 50 ppm of phosphorus, where the concentration of the catalyst system residue is based on the weight of the polyester.

[0018]

[0018] One embodiment of the present disclosure is a crystallizable reactor-grade polyester composition of any one of the embodiments described above, which further comprises a catalyst system residue comprising 4 to 12 ppm of titanium, 100 to 120 ppm of antimony, and 2 to 50 ppm of phosphorus, where the amount of the catalyst system residue is based on the weight of the polyester.

[0019]

[0019] One embodiment of the present disclosure is a crystallizable reactor-grade polyester composition of any of the embodiments described above, the composition having a strain-induced crystal melting point of 190°C or higher or 200°C or higher.

[0020]

[0020] One embodiment of the present disclosure is a crystallizable reactor-grade polyester composition of any of the embodiments described above, the composition having a strain-induced crystal melting point of 200°C or higher.

[0021] One embodiment of the present disclosure is a crystallizable polyester composition or crystallizable polyester blend comprising at least one polyester comprising (a) a dicarboxylic acid component, (b) a diol component, and (c) a catalyst system residue, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mol% of terephthalic acid residues and (ii) about 0 to about 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises about 75 mol% or more of ethylene glycol residues and (i) about 0.1 to less than 24 mol% of neopentyl glycol residues, (ii) about 0.1 to less than 24 mol% of 1,4-cyclohexanedimethanol residues, and (iii) about 1 to less than 10 mol% of the total diethylene glycol residues in the final polyester composition, comprising about 25 mol% or less of other The (c) catalyst system residue contains glycol, where the total molar percentage of the dicarboxylic acid component is 100 mol%, and the total molar percentage of the diol component is 100 mol%, and the (c) catalyst system residue contains 2-15 ppm of titanium, 50-150 ppm of antimony, and 0-60 ppm of phosphorus, where the amount of the catalyst system residue is based on the weight of the polyester, or the (c) catalyst system residue essentially consists of 2-15 ppm of titanium, 50-150 ppm of antimony, and 0-60 ppm of phosphorus, where the amount of the catalyst system residue is based on the weight of the polyester, or the (c) catalyst system residue consists of 2-15 ppm of titanium, 50-150 ppm of antimony, and 0-60 ppm of phosphorus, where the amount of the catalyst system residue is based on the weight of the polyester, and the melting point of the strain-induced crystal of this polyester is 190°C or higher or 200°C or higher.

[0021]

[0022] One embodiment of the present disclosure is a process for preparing a crystallizable reactor-grade polyester composition, the process of which (a) reacting a diacid component containing a terephthalic acid residue with a diol component containing a neopentyl glycol residue, a 1,4-cyclohexanedimethanol residue, a diethylene glycol residue, and an ethylene glycol residue, in the presence of 2 to 15 ppm of a titanium compound and 50 to 150 ppm of an antimony compound at an esterification reaction temperature of 240 to 270°C and a pressure of 5 to 50 psi to produce an esterified product The process includes: (b) a step of producing a polycondensation product by prepolymerizing the esterification product in the presence of 0 to 60 ppm of phosphorus stabilizer at a prepolymerization temperature of 255 to 275°C and a pressure of 200 to 500 mmHg; and (c) a step of finishing the polycondensation product to produce a polyester, wherein the polyester has an intrinsic viscosity of at least 0.50 dL / g or 0.50 to 0.90 dL / g, and the polymerization temperature during the finishing treatment is increased to 280 to 320°C and the pressure is 0.3 to 7 mmHg.

[0022]

[0023] One embodiment of the present disclosure is a process for preparing a crystallizable reactor-grade polyester composition, the process comprising (a) reacting a diacid component containing terephthalic acid residues with a diol component containing neopentyl glycol residues, 1,4-cyclohexanedimethanol residues, diethylene glycol residues, and ethylene glycol residues at an esterification reaction temperature of 240-270°C and a pressure of 5-50 psi to produce an esterified product; and (b) adding 2-15 ppm titan to the esterified product. (c) A step of producing a polycondensation product by prepolymerization at a pre-condensation temperature of 255 to 275°C in the presence of a phosphate compound, 50 to 150 ppm of an antimony compound, and 0 to 90 ppm of a phosphorus stabilizer; and (c) a step of producing a polyester by finishing treatment of this polycondensation product, wherein the polyester has an intrinsic viscosity of at least 0.50 dL / g or 0.50 to 0.90 dL / g, and the polymerization temperature during the finishing treatment is increased to 280 to 320°C and the pressure is 0.3 to 7 mmHg.

[0023]

[0024] One embodiment of the present disclosure is a process of any of the foregoing embodiments, where the polyester has an excellent color tone or a b value of 20 or less. * It has a value.

[0025] One embodiment of the present disclosure is a catalyst system for producing a crystallizable reactor-grade polyester composition, the system comprising 2 to 15 ppm of a titanium compound, 50 to 150 ppm of an antimony compound, and 0 to 90 ppm of a phosphorus compound, and the polyester composition comprising terephthalic acid, 1,4-cyclohexanedimethanol, neopentyl glycol, ethylene glycol, and diethylene glycol.

[0024]

[0026] One embodiment of the present disclosure is a crystallizable film comprising a polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component, (b) a diol component, and (c) a catalyst system residue, wherein the (a) dicarboxylic acid component comprises (i) from about 70 to about 100 mol% of terephthalic acid residues and (ii) from about 0 to about 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, the (b) diol component comprises at least about 75 mol% of ethylene glycol residues and (i) less than about 0.1 to about 24 mol% of neopentyl glycol residues, (ii) less than about 0.1 to about 24 mol% of 1,4-cyclohexanedimethanol residues, and (iii) less than about 1 to about 10 mol% of one or more of the total diethylene glycol residues in the final polyester composition, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%, and the (c) catalyst system residue comprises 2 to 15 ppm of titanium, 50 to 150 ppm of antimony, and 0 to ६0 ppm of phosphorus, wherein the concentration of the catalyst system residue is based on the weight of the polyester.

[0025]

[0027] One embodiment of the present disclosure is a crystallizable film comprising a polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component, (b) a diol component, and (c) a catalyst system residue, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mol% of terephthalic acid residues and (ii) about 0 to about 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises about 75 mol% or more of ethylene glycol residues and (i) 0 to less than about 24 mol% of neopentyl glycol residues (ii) a 1,4-cyclohexanedimethanol residue of about 0 to less than 24 mol%, and (iii) a total diethylene glycol residue of about 1 to less than 10 mol%, comprising about 25 mol% or less of other glycols, where the total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the diol component is 100 mol%, and this (c) catalyst system residue comprises 2 to 15 ppm titanium, 50 to 150 ppm antimony, and 0 to 60 ppm phosphorus, where the concentration of the catalyst system residue is based on the weight of the polyester.

[0028] One embodiment of the present disclosure is a crystallizable film comprising a polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component, (b) a diol component, and (c) a catalyst system residue, wherein the (a) dicarboxylic acid component comprises (i) from about 70 to about 100 mol % terephthalic acid residues and (ii) from about 0 to about 30 mol % aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, the (b) diol component comprises at least about 75 mol % ethylene glycol residues and (i) less than about 0.1 to about 24 mol % neopentyl glycol residues, (ii) less than about 0.1 to about 24 mol % 1,4 - cyclohexanedimethanol residues, and (iii) up to about 25 mol % of other glycols comprising one or more of the total diethylene glycol residues in the final polyester composition less than about 1 to about 10 mol %, wherein the total mol % of the dicarboxylic acid component is 100 mol % and the total mol % of the diol component is 100 mol %, and the (c) catalyst system residue comprises 2 to 15 ppm titanium, 50 to 150 ppm antimony, and 0 to 60 ppm phosphorus, wherein the concentration of the catalyst system residue is based on the weight of the polyester.

[0029] One embodiment of the present disclosure is a crystallizable film comprising a polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component, (b) a diol component, and (c) a catalyst system residue, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mol% of terephthalic acid residues and (ii) about 0 to about 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises about 80 mol% or more of ethylene glycol residues and (i) about 5 to about 17 mol% of neopentyl glycol (ii) a chol residue, (ii) a 1,4-cyclohexanedimethanol residue of about 2 to less than 10 mol%, and (iii) a total diethylene glycol residue in the final polyester composition of about 1 to less than 5 mol%, with a total mol% of dicarboxylic acid components being 100 mol%, and a total mol% of diol components being 100 mol%, and (c) a catalyst system residue comprising 2 to 15 ppm titanium, 50 to 150 ppm antimony, and 0 to 60 ppm phosphorus, where the concentration of the catalyst system residue is based on the weight of the polyester.

[0026]

[0030] One embodiment of the present disclosure is a crystallizable film comprising a polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component, (b) a diol component, and (c) a catalyst system residue, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mol% of terephthalic acid residues and (ii) about 0 to about 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises about 76 mol% or more of ethylene glycol residues and (i (ii) Neopentyl glycol residues, (ii) Cyclohexanedimethanol residues, and (iii) Diethylene glycol residues in the final polyester composition, comprising an amorphous content of approximately 24 mol% or less, where the total mol% of the dicarboxylic acid components is 100 mol%, and the total mol% of the diol components is 100 mol%, and this (c) catalyst system residues comprises 2 to 15 ppm of titanium, 50 to 150 ppm of antimony, and 0 to 60 ppm of phosphorus, where the concentration of the catalyst system residues is based on the weight of the polyester.

[0027]

[0031] One embodiment of the present disclosure is a crystallizable film comprising a polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component, (b) a diol component, and (c) a catalyst system residue, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mol% of terephthalic acid residues and (ii) about 0 to about 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises (i) about 1 to about 30 mol% of neopentyl glycol residues, and (ii) about 1 to about 30 mol% (iii) comprising less than 1,4-cyclohexanedimethanol residues, and (iii) about 1.5 to 6 mol% of diethylene glycol residues, the remainder of the glycol component comprising (iv) ethylene glycol residues and (v) 0 to 10 mol% of at least one modified glycol residue, where the total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the diol component is 100 mol%, and this (c) catalyst system residue comprises 2 to 15 ppm of titanium, 50 to 150 ppm of antimony, and 0 to 60 ppm of phosphorus, where the concentration of the catalyst system residue is based on the weight of the polyester.

[0028]

[0032] One embodiment of the present disclosure is a crystallizable film of any of the embodiments described above, wherein the film is stretched in at least one direction, and the stretched film has a strain-induced crystal melting point of 190°C or higher.

[0029]

[0033] One embodiment of the present disclosure is a crystallizable film of any of the embodiments described above, wherein the film is stretched in at least one direction, and the stretched film has a strain-induced crystal melting point of 200°C or higher.

[0030]

[0034] One embodiment of the present disclosure is a crystallizable film of any of the embodiments described above, wherein the film is stretched in at least one direction, and the stretched film has a strain-induced crystal melting point of 190-200°C.

[0031]

[0035] One embodiment of the present disclosure is an extruded or rolled film comprising a crystallizable film of any of the embodiments described above.

[0036] One embodiment of the present disclosure is a thermoformable sheet comprising a polyester composition comprising (a) a dicarboxylic acid component, (b) a diol component, and (c) a catalyst system residue, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mol% of terephthalic acid residues and (ii) about 0 to about 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises about 75 mol% or more of ethylene glycol residues and (i) about 0.1 to less than 24 mol% of neopentyl glycol residues. (ii) containing about 0.1 to less than 24 mol% of 1,4-cyclohexanedimethanol residues, and (iii) containing about 25 mol% or less of other glycols, including one or more of the total diethylene glycol residues in the final polyester composition, where the total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the diol component is 100 mol%, and this (c) catalyst system residue contains 2 to 15 ppm of titanium, 50 to 150 ppm of antimony, and 0 to 60 ppm of phosphorus, where the concentration of the catalyst system residue is based on the weight of the polyester.

[0032]

[0037] One embodiment of the present disclosure is a thermoformable sheet having a thickness of about 0.25 mm to about 6.4 mm, comprising a polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component, (b) a diol component, and (c) a catalyst system residue, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mol% of terephthalic acid residues and (ii) about 0 to about 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises about 80 mol% or more of ethylene glycol residues and (i) about 5 to about 17 mol% of neopene (i) a chloroglycol residue, (ii) a 1,4-cyclohexanedimethanol residue of about 2 to less than 10 mol%, and (iii) one or more of the total diethylene glycol residues in the final polyester composition of about 1 to less than 5 mol%, wherein the total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the diol component is 100 mol%, and this (c) catalyst system residue contains 2 to 15 ppm titanium, 50 to 150 ppm antimony, and 0 to 60 ppm phosphorus, wherein the concentration of the catalyst system residue is based on the weight of the polyester.

[0033]

[0038] One embodiment of the present disclosure is a thermoformable sheet having a thickness of about 0.25 mm to about 6.4 mm, comprising a polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component, (b) a diol component, and (c) a catalyst system residue, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mol% of terephthalic acid residues and (ii) about 0 to about 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises about 76 mol% or more of ethylene glycol residues, The (c) catalyst system residues consist of 2 to 15 ppm titanium, 50 to 150 ppm antimony, and 0 to 60 ppm phosphorus, where the concentration of the catalyst system residues is based on the weight of the polyester.

[0034]

[0039] One embodiment of the present disclosure is a thermoformable sheet having a thickness of about 0.25 mm to about 6.4 mm, comprising a polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component, (b) a diol component, and (c) a catalyst system residue, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mol% of terephthalic acid residues and (ii) about 0 to about 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises (i) about 1 to about 30 mol% of neopentyl glycol residues, and (ii) about 1 to about 30 mol% (iii) comprising less than 1,4-cyclohexanedimethanol residues, and (iii) about 1.5 to about 6 mol% of diethylene glycol residues, the remainder of the glycol component comprising (iv) ethylene glycol residues and (v) optionally 0 to 10 mol% or 0 to 5 mol% of at least one modified glycol residue, where the total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the diol component is 100 mol%, and this (c) catalyst system residue comprises 2 to 15 ppm of titanium, 50 to 150 ppm of antimony, and 0 to 60 ppm of phosphorus, where the concentration of the catalyst system residues is based on the weight of the polyester.

[0035]

[0040] One embodiment of the present disclosure is a formed, thermoformed, or molded article comprising, or prepared from, any sheet of the above-described embodiments, wherein the sheet has a strain-induced crystal melting point of 190°C or higher.

[0036]

[0041] One embodiment of the present disclosure is a formed, thermoformed, or molded article comprising, or prepared from, any sheet of the above-described embodiments, wherein the sheet has a strain-induced crystal melting point of 200°C or higher.

[0037]

[0042] One embodiment of the present disclosure is a formed, thermoformed, or molded article comprising, or prepared from, any sheet of the above-described embodiments, wherein the sheet has a strain-induced crystal melting point of 190°C to 215°C.

[0038]

[0043] One embodiment of the present disclosure is a formed, thermoformed, or molded article comprising, or prepared from, any of the sheets of the embodiments described above.

[0044] One embodiment of the present disclosure is an article selected from among medical device packaging, medical-related packaging, healthcare product packaging, commercial food supply products, trays, containers, food dishes, tumblers, storage boxes, bottles, cooking utensils, blenders and mixing bowls, household goods, water bottles, vegetable trays, washing machine parts, refrigerator parts, vacuum cleaner parts, ophthalmic lenses, and framing materials or toys, which includes or is prepared from any of the sheets of the embodiments described above.

[0039]

[0045] One embodiment of the present disclosure is a method for producing an article or part formed or thermoformed from a sheet of any of the embodiments described above, the method comprising: A) heating a sheet comprising the polyester composition of the present disclosure; B) applying pneumatic pressure, vacuum, and / or physical pressure to the heat-softened sheet; C) conforming the sheet to a mold shape by vacuum or pressurization; D) cooling the sheet to a temperature below its Tg; and E) removing the formed or thermoformed part or article from the mold.

[0040]

[0046] One embodiment of the present disclosure is a polyester recycling process flow comprising recycled polyethylene terephthalate flakes mixed together with at least about 0.1% by weight of the crystallizable recyclable shrink film of the present disclosure.

[0041]

[0047] One embodiment of the present disclosure is a polyester recycling process flow comprising recycled polyethylene terephthalate flakes mixed together with at least about 0.1% by weight of the crystallizable reactor-grade polyester composition of the present disclosure.

[0042]

[0048] One embodiment of the present disclosure is a polyester recycling process that includes recycled polyethylene terephthalate flakes mixed with at least about 0.1% by weight of a crystallizable, recyclable thermoformable sheet of the present disclosure.

[0043]

[0049] One embodiment of the present disclosure is a polyester recycling process flow comprising recycled polyethylene terephthalate flakes mixed with at least about 0.1% by weight of the crystallizable recyclable shrink film of the present disclosure, the flow passing the Association for Plastic Recyclers (APR) test item PET-CG-02.

[0044]

[0050] Thus, the crystallizable compositions of the present disclosure are provided as components favorable to PET recycling flows, insofar as the compositions can accompany PET in the recycling flow without requiring additional separation steps. Accordingly, one embodiment of the present disclosure provides a polyester recycling process flow comprising recycled polyethylene terephthalate flakes mixed together with at least about 0.1% by weight of the crystallizable composition of the present disclosure. In another embodiment, the flow complies with Document No. PET-CG-02 dated April 11, 2019, “Key Instructions for Transparent PET Articles with Labels and Sealings”.

[0045]

[0051] One embodiment of the present disclosure is a crystallizable polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component, (b) a diol component, and (c) a catalyst system residue, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mol% of terephthalic acid residues and (ii) about 0 to about 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises about 75 mol% or more of ethylene glycol residues and (i) about 0.1 to less than 24 mol% of neopentyl glycol residues, (ii) about 0.1 to less than 24 mol% of 1,4-cyclohexanedimethanol residues, and (iii) about 1 to less than 10 mol% of total diethylene glycol residues in the final polyester composition, wherein The total molar percentage of the dicarboxylic acid component is 100 mol%, the total molar percentage of the diol component is 100 mol%, and this (c) catalyst system residue contains 2-15 ppm of titanium, 50-150 ppm of antimony, and 0-60 ppm of phosphorus, where the amount of catalyst system residue is based on the weight of polyester, or this (c) catalyst system residue essentially consists of 2-15 ppm of titanium, 50-150 ppm of antimony, and 0-60 ppm of phosphorus, where the amount of catalyst system residue is based on the weight of polyester, or this (c) catalyst system residue consists of 2-15 ppm of titanium, 50-150 ppm of antimony, and 0-60 ppm of phosphorus, where the amount of catalyst system residue is based on the weight of polyester, and the melting point of the strain-induced crystal of this polyester is 190°C or higher or 200°C or higher.

[0046]

[0052] One aspect of this disclosure is a process for preparing copolymer polyesters from recycled copolymer polyesters. Another aspect of this disclosure is a process for preparing copolymer polyesters from recycled polyesters and / or recycled copolymer polyesters.

[0047]

[0053] In one aspect, the present disclosure relates to (A) a recyclable polyester and / or recyclable copolymer polyester having an acid component of at least 70 mol% terephthalic acid and a diol component of at least 70 mol% ethylene glycol, or (B) a recyclable copolymer polyester having an acid component of at least 70 mol% terephthalic acid and a diol component of at least 70 mol% ethylene glycol, 1,4-cyclohexanedimethanol, and diethylene glycol in a molar ratio of 96:3:1 to 20:68:12, or (C) a recyclable copolymer polyester having an acid component of at least 70 mol% terephthalic acid and a diol component of at least 70 mol% ethylene glycol (EG The present invention provides a process for preparing a linear, high molecular weight copolymer polyester from either (D) a recycled copolymer polyester comprising a mixture of two or more glycols including diethylene glycol (DEG), 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), butanediol, and isosorbide, or (D) a recycled copolymer polyester comprising a mixture of ethylene glycol and 1,4-cyclohexanedimethanol, wherein the acid component is at least 70 mol% terephthalic acid and the diol component is at least 70 mol%, with a molar ratio of 3.5:96.5 to 100:0.

[0048]

[0054] This process provides a rapid polymerization rate, and the polymer thus produced can be used to manufacture plastics, fibers, films, shrinkable films, sheets, molded articles, and other molded products with excellent physical properties. In one aspect, the disclosed process describes a method for converting waste products from factories and consumers into high-quality copolymer polyester resins that can be used to produce new plastics with a high recyclability content. In another aspect, the disclosed process describes a method for converting waste products from factories and consumers into resins that can be used to produce high-quality shrinkable films.

[0049]

[0055] One aspect of this disclosure is a process for producing copolymer polyester from recycled copolymer polyester, which is a process that A process of introducing recycled PET, recycled PETG, recycled PCT, recycled PCTG, recycled PCTA, recycled PCTM, and / or recycled PETM, terephthalic acid (TPA), and ethylene glycol (EG) into a paste tank and stirring and heating at a maximum temperature of 150°C to produce a slurry; A step of delivering the slurry from the paste tank to the first reaction area; The process involves introducing at least one additional glycol, including 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), into a first reaction area, and optionally adding additional recycled PET, recycled PETG, recycled PCTM, and / or recycled PETM, and terephthalic acid (TPA) and ethylene glycol (EG) in an EG:TPA molar ratio of 1:1 to 4:1, and optionally adding a catalyst; A step of reacting TPA with EG and at least one additional glycol (such as CHDM) in a first reaction area at a melting temperature of at least 200°C and a pressure of up to 40 psi to produce a first esterification product comprising an oligomer and unreacted TPA, EG, and the additional glycol (such as CHDM); A step of delivering the first esterification product to the second reaction area; A step of producing a second esterification product containing a copolymerized polyester oligomer by esterifying unreacted TPA, EG, and additional glycols (such as CHDM) in the first esterification product in a second reaction area at a melting temperature of at least 200°C and a pressure of up to 20 psi; A step of delivering the second esterification product to the third reaction area; A step of polycondensing the second esterification product in a third reaction area to produce a prepolymerization product containing a copolymerized polyester, if necessary, in the presence of a polycondensation catalyst; and The process includes delivering the prepolymerization product to one or more finishing areas.

[0050]

[0056] One aspect of this disclosure is a process for producing a polyester composition from recycled polyester using the catalyst system of this disclosure, which is: (a) A step of introducing terephthalic acid (TPA) and ethylene glycol (EG) and recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG into a paste tank, and stirring and heating at a maximum temperature of 150°C to produce a slurry; (b) A step of delivering the slurry from the paste tank to the first reaction area; (c) A step of introducing at least one additional glycol, including 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG), into the first reaction area, and adding additional terephthalic acid (TPA) and ethylene glycol (EG) as needed, in the presence of an esterification catalyst containing stabilizers, including titanium compounds and antimony compounds and / or phosphorus compounds, such that the total glycol:TPA molar ratio is 1:1 to 4:1, if necessary; (d) A step of reacting TPA and EG and recycled polyester in a first reaction area with at least one additional glycol at a melting temperature of at least 200°C to produce a first esterification product comprising oligomers and unreacted TPA, EG, and the additional glycol; (e) A step of delivering the first esterification product to the second reaction area; (f) In a second reaction area, the first esterification product and optionally additional glycols are further reacted at a melting temperature of at least 200°C in the presence of an esterification catalyst which optionally includes a stabilizer containing a titanium compound, an antimony compound, and / or a phosphorus compound, to produce a second esterification product containing a polyester oligomer; (g) A step of delivering the second esterification product to the third reaction area; and (h) The process includes polycondensing the second esterification product in a third reaction area in the presence of a polycondensation catalyst containing a stabilizer, optionally including a titanium compound and an antimony compound, and / or a phosphorus compound, to produce a polymerization product containing a polyester.

[0051] One aspect of this disclosure is a process for producing a polyester composition from recycled polyester, which is: (a) A step of introducing terephthalic acid (TPA) and ethylene glycol (EG) and recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG into a paste tank, and stirring and heating at a maximum temperature of 150°C to produce a slurry; (b) A step of delivering the slurry from the paste tank to the first reaction area; (c) In the first reaction area, introduce at least one additional glycol, including 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG), and optionally add additional terephthalic acid (TPA) and ethylene glycol (EG) in the presence of an esterification catalyst containing stabilizers, optionally including titanium compounds and antimony compounds and / or phosphorus compounds, such that the total glycol:TPA molar ratio is 1:1 to 4:1; (d) A step of reacting TPA and EG and recycled polyester with at least one additional glycol in a first reaction area at a melting temperature of at least 200°C to produce an oligomer and an esterification product containing unreacted TPA, EG, and the additional glycol; (e) If necessary, the step of delivering the product from the first reaction area to the second reaction area; (f) In a second reaction area, if necessary, the product from the first area is further reacted with additional glycols, if necessary, in the presence of an esterification catalyst containing a stabilizer, which may include a titanium compound, an antimony compound, and / or a phosphorus compound, at a melting temperature of at least 200°C to produce a second esterification product containing a polyester oligomer; (g) A step of delivering the esterification product from one or more reaction areas to a third reaction area; and (h) The process includes a step of further reacting the product delivered from the first reaction area (or optionally the second reaction area) to the third reaction area in the presence of a polycondensation catalyst containing a stabilizer, optionally a titanium compound and an antimony compound, and / or a phosphorus compound, to produce a polymerization product containing a polyester.

[0052]

[0057] One aspect of the present disclosure is a process of any one of the aforementioned aspects, which further comprises the step of adding a catalyst or additive via the addition of recycled polyester, the catalyst or additive being a component of the recycled polyester such as Sb, Ti, Co, Mn, Li, Al, P.

[0053]

[0058] One aspect of this disclosure is a method for introducing or forming a recyclable content in polyester produced by the process of the aforementioned aspect, and this method is (a) A step of obtaining an allocation or limit for a recyclable monomer for at least one recyclable monomer, including TPA, EG, DMT, CHDM, NPG, or DEG; (b) A process of producing polyester by converting recycled monomers within the synthesis process; (c) a step of designating at least a portion of the polyester as corresponding to at least a portion of the recycled monomer quota or limit; and (d) The process includes, if necessary, marketing or selling polyester containing or obtained using a recycled monomer content corresponding to that specification. [Brief explanation of the drawing]

[0054] [Figure 1]

[0059] Figure 1 shows the PET aggregation rate (%) against relative crystallinity. Triangular dots indicate PET aggregation rates greater than 1%. Circular dots indicate PET aggregation rates less than 1%, and therefore these meet the requirements of document number PET-CG-02, "Key Guidelines for Transparent PET Articles with Labels and Sealings," dated April 11, 2019. [Figure 2]

[0060] Figure 2 shows flowcharts of the various processes described herein. [Figure 3]

[0061] Figure 3 shows the concentration of Sb catalyst in the final material as a function of the packing concentration of the starting material for rPET (recycled PET). Detailed description of the invention

[0055]

[0062] A deeper understanding of this disclosure can be gained by referring to the following detailed descriptions of specific embodiments and examples of this disclosure. In accordance with the purpose of this disclosure, specific embodiments of this disclosure are described in the "Summary of the Invention" and are further described herein as follows. Other embodiments of this disclosure are also described herein.

[0056]

[0063] This disclosure reveals that a crystallizable polyester resin with excellent performance properties can be produced by specific combinations of glycol monomers in a polyester composition, and that because the resin is crystallizable, it does not affect the recycling of PET flakes during the recycling process. Articles such as shrinkable films and thermoformable sheets manufactured using the crystallizable resin of this disclosure can be processed together with PET bottles and ultimately become components of recyclable PET flakes generated from the recycling process. Furthermore, it was found that the selection and amount of specific combinations of glycol monomers are important for producing articles such as shrinkable films or sheets that have excellent performance properties and are crystallizable.

[0057]

[0064] As used herein, the term "polyester" is intended to include "copolymerized polyester" and is understood to mean a synthetic polymer prepared by the reaction of one or more difunctional carboxylic acids and / or polyfunctional carboxylic acids with one or more difunctional hydroxyl compounds and / or polyfunctional hydroxyl compounds, such as branching agents. Typically, the difunctional carboxylic acid may be a dicarboxylic acid, and the difunctional hydroxyl compound may be a dihydric alcohol, such as a glycol and a diol. As used herein, the term "glycol" includes, but is not limited to, diols, glycols, and / or polyfunctional hydroxyl compounds, such as branching agents. Alternatively, the difunctional carboxylic acid may be a hydroxycarboxylic acid, such as p-hydroxybenzoic acid, and the difunctional hydroxyl compound may have an aromatic nucleus holding two hydroxyl substituents, such as a hydroquinone. As used herein, the term "residue" means any organic structure incorporated into the polymer by polycondensation and / or esterification reactions from the corresponding monomer. As used herein, the term "repeating unit" means an organic structure having dicarboxylic acid residues and diol residues linked via an ester group. Therefore, for example, dicarboxylic acid residues may be derived from dicarboxylic acid monomers, or their associated acid halides, esters, salts, anhydrides, and / or mixtures thereof. Furthermore, the term “diacid” as used herein includes polyfunctional acids, such as branching agents. Therefore, the term “dicarboxylic acid” as used herein is intended to include dicarboxylic acids useful in reaction steps with diols for the production of polyesters, and any derivatives of dicarboxylic acids, such as their associated acid halides, esters, semi-esters, salts, semi-salts, anhydrides, mixed anhydrides, and / or mixtures thereof. The term “terephthalic acid” as used herein is intended to include terephthalic acid itself and its residues useful in reaction steps with diols for the production of polyesters, as well as any derivatives of terephthalic acid, such as its associated acid halides, esters, semi-esters, salts, semi-salts, anhydrides, mixed anhydrides, and / or mixtures thereof or residues thereof.

[0058]

[0065] The polyesters used in this disclosure can typically be prepared from dicarboxylic acids and diols that react in substantially equal proportions and are incorporated into the polyester polymer as their corresponding residues. Thus, the polyesters of this disclosure may contain acid residues (100 mol%) and diol (and / or polyfunctional hydroxyl compound) residues (100 mol%) in substantially equimolar ratios such that the total number of moles of repeating units equals 100 mol%. Accordingly, the mol% shown in this disclosure may be based on the total number of moles of acid residues, the total number of moles of diol residues, or the total number of moles of repeating units. For example, a polyester containing 10 mol% isophthalic acid based on total acid residues means that the polyester contains 10 mol% isophthalic acid residues out of 100 mol% of total acid residues. Thus, there are 10 moles of isophthalic acid residues for every 100 moles of acid residues. In another example, a polyester containing 25 mol% 1,4-cyclohexanedimethanol based on total diol residues means that this polyester contains 25 mol% 1,4-cyclohexanedimethanol residues out of 100 mol% total diol residues. Therefore, there are 25 moles of 1,4-cyclohexanedimethanol residues for every 100 moles of diol residues.

[0059]

[0066] In certain embodiments, terephthalic acid or its esters, such as dimethyl terephthalate or a mixture of terephthalic acid residues and their esters, may constitute some or all of the dicarboxylic acid components used to produce polyesters useful in this disclosure. In certain embodiments, terephthalic acid residues may constitute some or all of the dicarboxylic acid components used to produce polyesters useful in this disclosure. For the purposes of this disclosure, the terms “terephthalic acid” and “dimethyl terephthalate” are used interchangeably herein. In one embodiment, dimethyl terephthalate constitutes some or all of the dicarboxylic acid components used to produce polyesters useful in this disclosure. Depending on the embodiment, 70 to 100 mol%, or 80 to 100 mol%, or 90 to 100 mol%, or 99 to 100 mol%, or 100 mol%, of terephthalic acid and / or dimethyl terephthalate and / or mixtures thereof may be used.

[0060]

[0067] In addition to terephthalic acid, the polyester dicarboxylic acid components useful in this disclosure may include one or more modified aromatic dicarboxylic acids in amounts up to 30 mol%, up to 20 mol%, up to 10 mol%, up to 5 mol%, or up to 1 mol%. Yet another embodiment includes 0 mol% of modified aromatic dicarboxylic acids. Thus, if present, the amount of one or more modified aromatic dicarboxylic acids may be in a range from any of these aforementioned endpoint values, for example, 0.01 to 10 mol%, 0.01 to 5 mol%, and 0.01 to 1 mol%. In one embodiment, the modified aromatic dicarboxylic acids that may be used in this disclosure include, but are not limited to, dicarboxylic acids having up to 20 carbon atoms and which may be linear, para-directing, or symmetrical. Examples of modified aromatic dicarboxylic acids that may be used in this disclosure include, but are not limited to, isophthalic acid, 4,4'-biphenyldicarboxylic acid, 1,4-, 1,5-, 2,6-, 2,7-naphthalenedicarboxylic acid, and trans-4,4'-stilbendicarboxylic acid, as well as their esters. In one embodiment, the modified aromatic dicarboxylic acid is isophthalic acid.

[0061]

[0068] The carboxylic acid component of the polyester useful in this disclosure may be further modified with up to 10 mol%, for example, up to 5 mol%, or up to 1 mol%, of one or more aliphatic dicarboxylic acids containing 2 to 16 carbon atoms, such as cyclohexanedicarboxylic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and / or dodecanediic acid dicarboxylic acid. Certain embodiments may also include 0.01 to 10 mol%, for example, 0.1 to 10 mol%, 1 to 10 mol%, or 5 to 10 mol%, of one or more modified aliphatic dicarboxylic acids. Yet another embodiment includes 0 mol% of modified aliphatic dicarboxylic acids. The total mol% of the 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 polyester and are useful in this disclosure.

[0062]

[0069] Terephthalic acid and other modified dicarboxylic acid esters, or their corresponding esters and / or salts, may be used in place of the dicarboxylic acid. Preferred examples of dicarboxylic acid esters include, but are not limited to, dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, and diphenyl esters. In one embodiment, the ester is selected from at least one of methyl, ethyl, propyl, isopropyl, and phenyl esters.

[0063]

[0070] In one embodiment, the diol component of the crystallizable polyester composition useful in this disclosure may include 1,4-cyclohexanedimethanol. In another embodiment, the diol component of the crystallizable polyester composition useful in this disclosure may include 1,4-cyclohexanedimethanol and 1,3-cyclohexanedimethanol. The molar ratio of cis-structured / trans-structured 1,4-cyclohexanedimethanol may be varied in the range of 50 / 50 to 0 / 100, for example, in the range of 40 / 60 to 20 / 80.

[0064]

[0071] In certain embodiments, the diol component of the crystallizable polyester composition useful in this disclosure is, but is not limited, 1 to 30 mol%, or 1 to 25 mol%, 1 to 20 mol%, or 1 to 15 mol%, or 1 to 10 mol%, or 2 to 30 mol%, or 2 to 25 mol%, or 2 to 20 mol%, or 2 to 15 mol%, or 2 to 10 mol%, or 3 to 30 mol%, or 3 to 25 mol%, or 3 to 20 mol%, or 3 to 15 mol%, or 3 to 10 mol%, or 4 to 30 mol%, or 4 to 25 mol%, or 4 to 20 mol%, or 4 to 15 mol%, or 4 to 10 mol%, or 5 to 30 mol%, or 5 to 25 mol%, or 5 to 20 mol%, or 5 to 15 mol%, or 5 to 10 mol%. or 6-30 mol%, or 6-25 mol%, or 6-20 mol%, or 6-15 mol%, or 6-10 mol%, or 7-30 mol%, or 7-25 mol%, or 7-20 mol%, or 7-15 mol%, or 7-10 mol%, or 8-30 mol%, or 8-25 mol%, or 8-20 mol%, or 8-15 mol%, or 8-10 mol%, or 9-30 mol%, or 9-25 mol%, or 9-20 mol%, or 9-15 mol%, or 9-10 mol%, or 10-30 mol%, or 10-25 mol%, or 10-20 mol%, or 10-15 mol%, or 11-30 mol%, or 11-25 mol%, 11-20 mol%, or 11-15 mol%, or 12-30 mol%, 12-25 mol%, or 12-20 mol%, 12-15 mol%, or 13-30 mol%, or 13-25 mol%, 13-20 mol%, or 13-15 mol%, 14-30 mol%, or 14-25 mol%, or 14-20 mol%, or 14-15 mol%, or 15-30 mol%.The composition may include 15-25 mol%, or 15-20 mol%, or 16-20 mol%, or 18-20 mol%, or 10-18 mol%, or 16-18 mol%, or 12-16 mol%, or 16-20 mol%, or 14-18 mol%, or 11-30 mol%, or 13-30 mol%, or 14-30 mol%, or 10-29 mol%, or 11-29 mol%, or 12-29 mol%, or 13-29 mol%, or 14-29 mol%, or 15-29 mol%, or 10-28 mol%, or 11-28 mol%, or 12-28 mol%, or 13-28 mol%, or 14-28 mol%, or 15-28 mol%. In one embodiment, the total amount of 1,4-cyclohexanedimethanol residues and neopentyl glycol residues in the final polyester composition may be 1-16 mol%, 2-14 mol%, 4-15 mol%, or 2-21 mol%, or less than 2-20 mol%, or 4-20 mol%, or 5-18 mol%, or 10-21 mol%, or 12-21 mol%, where the total mole percent of the diol component is 100 mol%.

[0065]

[0072] In one embodiment, the diol component of the crystallizable polyester composition useful in this disclosure may contain 0 to 30 mol% neopentyl glycol based on the total mol% of the diol component, which is 100 mol%. In one embodiment, the diol component of the crystallizable polyester composition useful in this disclosure may contain 0.1 to 30 mol% neopentyl glycol based on the total mol% of the diol component, which is 100 mol%. In one embodiment, the diol component of the crystallizable polyester composition useful in this disclosure may contain 1 to 30 mol% neopentyl glycol based on the total mol% of the diol component, which is 100 mol%. In one embodiment, the diol component of the crystallizable polyester composition useful in this disclosure may contain 1 to 25 mol% neopentyl glycol based on the total mol% of the diol component, which is 100 mol%. In one embodiment, the diol component of the crystallizable polyester composition useful in this disclosure may contain 1 to 17 mol% neopentyl glycol based on the total mol% of the diol component, which is 100 mol%. In one embodiment, the diol component of the crystallizable polyester composition useful in this disclosure may contain 5 to 20 mol% neopentyl glycol based on the total mol% of the diol component, which is 100 mol%. In one embodiment, the diol component of the crystallizable polyester composition useful in this disclosure may contain 10 to 20 mol% neopentyl glycol based on the total mol% of the diol component, which is 100 mol%. In one embodiment, the diol component of the crystallizable polyester composition useful in this disclosure may contain 10 to 15 mol% neopentyl glycol based on the total mol% of the diol component, which is 100 mol%. In one embodiment, the diol component of the crystallizable polyester composition useful in this disclosure may contain 15 to 25 mol% neopentyl glycol, based on the total mol% of the diol component, which is 100 mol%.

[0066]

[0073] In one embodiment, the diol component of the crystallizable polyester composition useful in this disclosure is 0-30 mol%, or 0.01-30 mol%, or 1-30 mol%, or 2-30 mol%, or 0-20 mol%, or 0.1-20 mol%, or 1-20 mol%, or 2-20 mol%, or 0-15 mol%, or 0.01-15 mol%, or 1-15 mol%, or 2-15 mol%, or 0.01-14 mol%, or 0.01-13 mol%, or 0.01-12 mol%, or 0.01-11 mol%, or 0.01-10 mol%, based on the total molar percentage of the diol component being 100 mol%. It may also contain 1,4-cyclohexanedimethanol residues in amounts of %, or 0.01-9 mol%, or 0.01-8 mol%, or 0.01-7 mol%, or 0.01-6 mol%, or 0.01-5 mol%, or 3-15 mol%, or 3-14 mol%, or 3-13 mol%, or 3-12 mol%, or 3-11 mol%, or 3-10 mol%, or 3-9 mol%, or 3-8 mol%, or 3-7 mol%, or 2-10 mol%, or 2-9 mol%, or 2-8 mol%, or 2-7 mol%, or 2-5 mol%, or 1-7 mol%, or 1-5 mol%, or 1-3 mol%.

[0067]

[0074] In one embodiment, the diol component of the polyester composition useful in this disclosure may contain 0.01 to 15 mol% of 1,4-cyclohexanedimethanol based on the total molar percentage of the diol component, which is 100 mol%. In one embodiment, the diol component of the polyester composition useful in this disclosure may contain 0 to less than 15 mol% of 1,4-cyclohexanedimethanol based on the total molar percentage of the diol component, which is 100 mol%. In one embodiment, the diol component of the polyester composition useful in this disclosure may contain 0.01 to 10 mol% of 1,4-cyclohexanedimethanol based on the total molar percentage of the diol component, which is 100 mol%. In one embodiment, the diol component of the polyester composition useful in this disclosure may contain 0 to less than 10 mol% of 1,4-cyclohexanedimethanol based on the total molar percentage of the diol component, which is 100 mol%. In one embodiment, the diol component of the polyester composition useful in this disclosure may contain 0.01 to 5 mol% of 1,4-cyclohexanedimethanol, based on the total mol% of the diol component which is 100 mol%. In one embodiment, the diol component of the polyester composition useful in this disclosure may contain 0 to less than 5 mol% of 1,4-cyclohexanedimethanol, based on the total mol% of the diol component which is 100 mol%.

[0068]

[0075] Naturally, some other diol residues may be generated in situ during processing. In one embodiment, the diol component of the polyester composition described herein may include, intentionally add, or consist of diethylene glycol residues generated in situ during processing, or in any amount of both. For example, in one embodiment, a polyester composition useful in this disclosure may contain 1 to 15 mol%, or 2 to 12 mol%, or 2 to 11 mol%, or 2 to 10 mol%, or 2 to 9 mol%, or 3 to 12 mol%, or 3 to 11 mol%, or 3 to 10 mol%, or 3 to 9 mol%, or 4 to 12 mol%, or 4 to 11 mol%, or 4 to 10 mol%, or 4 to 9 mol%, or 5 to 12 mol%, or 5 to 11 mol%, or 5 to 10 mol%, or 5 to 9 mol%, based on the total mol% of the diol component, which is 100 mol%.

[0069]

[0076] In one embodiment, the total amount of diethylene glycol residues present in the polyester composition useful in this disclosure may be 4 mol% or less, or 3.5 mol% or less, or 3.0 mol% or less, or 2.5 mol% or less, or 2.0 mol% or less, or 1.5 mol% or less, or 1.0 mol% or less, or 1 to 4 mol%, or 1 to 3 mol%, or 1 to 2 mol%, or 2 to 8 mol%, or 2 to 7 mol%, or 2 to 6 mol%, or 2 to 5 mol%, or 3 to 8 mol%, or 3 to 7 mol%, or 3 to 6 mol%, or 3 to 5 mol%, based on the total mol% of the diol component which is 100 mol%, regardless of whether they are formed in situ during processing, intentionally added or both. Alternatively, in some embodiments, intentionally added diethylene glycol residues may not be present based on the total mol% of the diol component which is 100 mol%.

[0070]

[0077] In all embodiments, the remainder of the diol component may contain any amount of ethylene glycol residues based on the total molar percentage of the diol component, which is 100 mol%. In one embodiment, the polyester portion of the polyester composition useful in this disclosure may be 50 mol% or more, or 55 mol% or more, or 60 mol% or more, or 65 mol% or more, or 70 mol% or more, or 75 mol% or more, or 80 mol% or more, or 85 mol% or more, or 90 mol% or more, or 95 mol% or more, or 50-85 mol%, or 50-80 mol%, or 55-80 mol%, or 60-80 mol%, or 50-75 mol%, or 55-75 mol%, or 60-75 mol%, or 65-75 mol%, or 70-80 mol%, or 75-85 mol%, based on the total molar percentage of the diol component, which is 100 mol%.

[0071]

[0078] In one embodiment, the diol component of the polyester composition useful in this disclosure may contain one or more modified diols in up to 20 mol%, or up to 19 mol%, or up to 18 mol%, or up to 17 mol%, or up to 16 mol%, or up to 15 mol%, or up to 14 mol%, or up to 13 mol%, or up to 12 mol%, or up to 11 mol%, or up to 10 mol%, or up to 9 mol%, or up to 8 mol%, or up to 7 mol%, or up to 6 mol%, or up to 5 mol%, or up to 4 mol%, or up to 3 mol%, or up to 2 mol%, or up to 1 mol% (a modified diol is defined as a diol that is not ethylene glycol, diethylene glycol, neopentyl glycol, or 1,4-cyclohexanedimethanol). In a particular embodiment, the polyester composition useful in this disclosure may contain one or more modified diols in an amount of 10 mol% or less. In a particular embodiment, the polyester useful in this disclosure may contain one or more modified diols in an amount of 5 mol% or less. In certain embodiments, the polyester useful in this disclosure may contain one or more modified diols in an amount of 3 mol% or less. In other embodiments, the polyester useful in this disclosure may contain one or more modified diols in an amount of 0 mol%. However, several other diol residues may be formed in situ, and the resulting amount of residues formed in situ is also considered an embodiment of this disclosure.

[0072]

[0079] Depending on the embodiment, the modified diols used in polyesters as defined herein contain 2 to 16 carbon atoms when used. Examples of modified diols include, but are not limited to, 1,2-propanediol, 1,3-propanediol, isosorbide, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, p-xylene glycol, polytetramethylene glycol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), and mixtures thereof. In one embodiment, isosorbide is a modified diol. In another embodiment, the modified diol includes, but is not limited to, at least one of 1,3-propanediol and 1,4-butanediol. In one embodiment, 1,3-propanediol and / or 1,4-butanediol may be excluded. When using 1,4- or 1,3-butanediol, in one embodiment, 4 mol% or more or 5 mol% or more may be provided. In one embodiment, at least one modified diol is 1,4-butanediol, present in an amount of 5 to 25 mol%. In certain embodiments, the polyester composition does not contain any added modified diols.

[0073]

[0080] In one embodiment, a crystallizable polyester composition is provided, in which, based on a total molar percentage of 100 mol% of the diol components, 1,4-cyclohexanedimethanol residues are present in an amount of 0.01 to about 10 mol%, diethylene glycol residues are present in an amount of 2 to 9 mol%, neopentyl glycol residues are present in an amount of 5 to 30 mol%, and ethylene glycol residues are present in an amount of 60 mol% or more.

[0074]

[0081] In one embodiment, the polyester composition useful in this disclosure may contain at least one chain extender. Suitable chain extenders include, but are not limited to, polyfunctional isocyanates (including, but not limited to, bifunctional), polyfunctional epoxides including, for example, epoxidized novolacs, and phenoxy resins. In certain embodiments, the chain extender may be added at the end of the polymerization step or after the polymerization step. If added after the polymerization step, the chain extender may be incorporated by compounding or addition during a conversion step such as injection molding or extrusion molding.

[0075]

[0082] In certain embodiments, the amount of chain extender used may be varied depending on the specific monomer composition used and the desired physical properties, but generally it is about 0.1% to about 10% by weight, for example, about 0.1% to about 5% by weight, based on the total weight of the polyester.

[0076]

[0083] Unless otherwise specified, polyester compositions useful in this disclosure may have at least one of the intrinsic viscosity ranges described herein and at least one of the monomer ranges of polyester compositions described herein. Furthermore, unless otherwise specified, polyester compositions useful in this disclosure may have at least one of the Tg ranges described herein and at least one of the monomer ranges of polyester compositions described herein. Furthermore, unless otherwise specified, polyester compositions useful in this disclosure may have at least one of the intrinsic viscosity ranges described herein, at least one of the Tg ranges described herein and at least one of the monomer ranges of polyester compositions described herein.

[0077]

[0084] In embodiments of the present disclosure, the polyester compositions useful in the present disclosure may exhibit at least one of the following intrinsic viscosities, measured in 60 / 40 (weight / weight) phenol / tetrachloroethane at 25°C and a concentration of 0.5 g / dL: 0.50-1.2 dL / g, 0.50-1.0 dL / g, 0.50-0.90 dL / g, 0.50-0.80 dL / g, 0.55-0.80 dL / g, 0.60-0.80 dL / g, 0.65-0.80 dL / g, 0.70-0.80 dL / g, 0.50-0.75 dL / g, 0.55-0.75 dL / g, or 0.60-0.75 dL / g.

[0078]

[0085] In one embodiment, the glass transition temperature and the melting point of the strain-induced crystal (Tg and Tm, respectively) of the polyester were measured using a Thermal Analyst Instrument TA DSC 2920 at a scanning rate of 20°C / min. Tm was measured during the first heating step of the stretched sample, and Tg was measured during the second heating step. In yet another embodiment, the sample was crystallized in a forced-air oven at 165°C for 30 minutes or at 170°C for 2 hours, and then analyzed by DSC. In all samples, the crystal melting point was typically not present during the second heating step of the DSC scan at a heating rate of 20°C / min.

[0079]

[0086] In certain embodiments, the orientation films, shrink films, and thermoformed sheets of the Disclosure include a crystallizable polyester / polyester composition in which the polyester Tg is 60-80°C, 70-80°C, 65-80°C, 74-77°C, 72-77°C, or 65-75°C. In certain embodiments, the intrinsic viscosity of the polyester is 0.68-0.75 dL / g when measured in 60 / 40 (weight / weight) phenol / tetrachloroethane at 25°C and a concentration of 0.5 g / dL, and the polyester has a Tg of 72-77°C when measured using a Thermal Analyst Instrument TA DSC 2920 at a scanning speed of 20°C / min.

[0080]

[0087] In certain embodiments, these Tg ranges can be met regardless of the presence or absence of at least one plasticizer added during polymerization, extrusion, or compounding.

[0088] In one embodiment, certain crystallizable polyester compositions useful in this disclosure may be visually transparent. The term “visually transparent” is defined herein as the absence of apparent cloudiness, haze, and / or turbidity upon visual inspection.

[0081]

[0089] In one embodiment, the polyester portion of the crystallizable polyester composition useful in this disclosure may be produced by processes known from the literature, such as processes in a homogeneous solution, transesterification processes in a molten material, and two-phase interface processes. For a method of producing polyester, see U.S. Patent No. 3,772,405, the disclosure of this method is incorporated herein by reference.

[0082]

[0090] In certain embodiments, the crystallizable polyester composition may be prepared by a step of condensing a dicarboxylic acid or dicarboxylic acid ester with a diol in the presence of a catalyst, gradually increasing the temperature during a condensation process in an inert atmosphere, and then carrying out the condensation at low pressure in the latter part of the condensation process, these steps are described in more detail in U.S. Patent No. 2,720,507, which is incorporated herein by reference.

[0083]

[0091] In one aspect, the present disclosure is a catalyst system for the preparation of polyester compositions. In one aspect, the present disclosure is a catalyst system for the preparation of polyester compositions comprising neopentyl glycol (NPG or 2,2-dimethyl-1,3-propanediol). In one embodiment, the catalyst system of the present disclosure is suitable for polyesters comprising neopentyl glycol (NPG) and / or 1,4-cyclohexanedimethanol (CHDM). In one embodiment, the catalyst system of the present disclosure is also suitable for use with polyester compositions comprising terephthalic acid, ethylene glycol, diethylene glycol, NPG, and CHDM. In one embodiment, the catalyst system is also suitable for use with polyester compositions that do not contain NPG but comprise terephthalic acid, ethylene glycol, and 1,4-cyclohexanedimethanol. In one embodiment, process improvement is observed when the titanium concentration is kept very low and the reaction temperature is raised to a temperature beyond the temperature range typically used for the production of these types of polyester compositions.

[0084]

[0092] In one aspect, the catalyst system of this disclosure is a combination of low concentrations of titanium and antimony, and this system is active over a wide range of polymerization temperatures, particularly at high polymerization temperatures. In one embodiment, phosphorus is used as a catalyst moderater as needed. In certain embodiments, when phosphorus is used, the concentration of the phosphorus compound is determined based on the concentrations of titanium and antimony used in the catalyst system. In one embodiment, the amount of phosphorus compound used is determined based on the final polymerization temperature.

[0085]

[0093] In one embodiment, the catalyst system of the present disclosure contains a titanium compound at a titanium concentration level of 2 to 15 ppm relative to the weight of the polyester produced. In one embodiment, the catalyst system of the present disclosure contains a titanium compound at a titanium concentration level of 4 to 12 ppm relative to the weight of the polyester produced. In one embodiment, the catalyst system of the present disclosure contains a titanium compound at a titanium concentration level of 3 to 10 ppm relative to the weight of the polyester produced. In one embodiment, the catalyst system of the present disclosure contains a titanium compound at a titanium concentration level of 1 to 20 ppm relative to the weight of the polyester produced. In one embodiment, the catalyst system contains a titanium compound at a titanium concentration level of 20 ppm or less relative to the weight of the polyester produced. In one embodiment, the catalyst system contains a titanium compound at a titanium concentration level of 15 ppm or less relative to the weight of the polyester produced. In one embodiment, the catalyst system contains a titanium compound at a titanium concentration level of 14 ppm or less relative to the weight of the polyester produced. In one embodiment, the catalyst system contains a titanium compound at a titanium concentration level of 13 ppm or less relative to the weight of the polyester produced. In one embodiment, the catalyst system contains a titanium compound at a titanium concentration level of 12 ppm or less relative to the weight of the polyester produced. In another embodiment, the catalyst system contains a titanium compound at a titanium concentration level of 10 ppm or less relative to the weight of the polyester produced. In yet another embodiment, the catalyst system contains a titanium compound at a titanium concentration level of 7 ppm or less relative to the weight of the polyester produced. In yet another embodiment, the catalyst system contains a titanium compound at a titanium concentration level of 5 ppm or less relative to the weight of the polyester produced. In yet another embodiment, the titanium compound is a tetraalkyl titanate such as tetraisopropyl titanate. In yet another embodiment, the titanium compound is selected from titanium tetraalkoxides such as titanium tetraisopropoxide, titanium tetraethoxide, or titanium tetrabutoxide, or tetraalkyl titanates such as tetraisopropyl titanate, and mixtures thereof.

[0086]

[0094] In one embodiment, the catalyst system contains an antimony compound at an antimony concentration level of 50 to 150 ppm relative to the weight of the polyester to be produced. In one embodiment, the catalyst system contains an antimony compound at an antimony concentration level of 70 to 140 ppm relative to the weight of the polyester to be produced. In one embodiment, the catalyst system contains an antimony compound at an antimony concentration level of 90 to 130 ppm relative to the weight of the polyester to be produced. In one embodiment, the catalyst system contains an antimony compound at an antimony concentration level of 100 to 120 ppm relative to the weight of the polyester to be produced. In one embodiment, the antimony compound is antimony trioxide. In one embodiment, the antimony compound is antimony trioxide, antimony acetate, or antimony oxalate. In one embodiment, the antimony compound of the catalyst system is dissolved in one of the glycols used in the polyester composition.

[0087]

[0095] In one embodiment, the phosphorus concentration level is 0 to 90 ppm based on the weight of the polyester produced. In one embodiment, the phosphorus concentration level is 0 to 50 ppm based on the weight of the polyester produced. In one embodiment, the phosphorus concentration level is 2 to 75 ppm based on the weight of the polyester produced. In one embodiment, the phosphorus concentration level is 2 to 50 ppm based on the weight of the polyester produced. In one embodiment, the phosphorus concentration level is 10 to 60 ppm based on the weight of the polyester produced. In one embodiment, the antimony compound concentration level depends on the temperature in the final reaction stage or the finishing area. In one embodiment, the antimony compound concentration level depends on the concentration of titanium used. In one embodiment, the antimony compound concentration level depends on the temperature in the final reaction stage and the concentration of titanium used.

[0088]

[0096] In one aspect of this disclosure, the polymerization temperature is much higher than that of a typical copolymer polyester production reaction. In one embodiment, the polymerization temperature is 275°C to 310°C. In one embodiment, the polymerization temperature is 285°C to 300°C. In one embodiment, the polymerization temperature is 290°C to 300°C.

[0089]

[0097] In one embodiment, to produce a high-IV (intrinsic viscosity) polyester exhibiting excellent color tone, the polymerization temperature is 290°C, the titanium concentration is 8 ppm or less, along with an antimony loading of 125 ppm and a phosphorus loading of 0-8 ppm. In another embodiment, to produce a high-IV polyester exhibiting excellent color tone, the polymerization temperature is 300°C, the titanium concentration is 13 ppm or less, along with an antimony concentration of 100 ppm and a phosphorus concentration of 59-60 ppm.

[0090]

[0098] In one embodiment, both the catalyst component and the phosphorus source are added following the esterification of terephthalic acid. In one embodiment, the conversion rate of terephthalic acid groups to their ester forms by one or more glycols used is 90%. In one embodiment, higher conversion rates of up to 100% of the available carboxylic acid ends can be achieved by the catalytic system of the present disclosure. In one embodiment, the catalyst components may be added together or separately. In another embodiment, phosphorus is added as a separate feed following the addition of the catalyst.

[0091]

[0099] In one embodiment, apart from the option of utilizing a higher finishing (polymerization) temperature, there is no need to modify the reaction procedure typically used in high-titanium-phosphorus systems.

[0100] This catalyst system allows users to prepare NPG-containing polyesters with superior production rates and product color compared to titanium-only systems. Its adaptability allows for the use of high reaction temperatures without adversely affecting color, enabling the use of temperature as a variable to change the production rate. This option is typically unavailable in conventional titanium catalyst systems because they are sensitive to temperature increases.

[0092]

[0101] In one aspect, the polyester compositions of this disclosure may be produced using any polycondensation reaction conditions known in the art. These may be produced by continuous, semi-continuous, and batch operating modes, and various types of reactors may be used. Examples of suitable reactor types, but not limited to, include stirred tanks, continuous stirred tanks, slurry type, tubular type, wiped film type, drop film type, and extrusion type reactors.

[0093]

[0102] As used herein, the term “continuous” means a process in which reactants are introduced and products are removed simultaneously in an uninterrupted manner. This process is conveniently operated as a continuous process for economic reasons and is operated to produce light-colored polymers because prolonged exposure to high temperatures in the reactor can cause deterioration of the polyester’s appearance.

[0094]

[0103] The polyesters of this disclosure can be prepared by any procedure known to those skilled in the art. The reaction between the diol component and the dicarboxylic acid component may be carried out using conventional polyester polymerization conditions. For example, when a polyester is prepared from an esterified form of the dicarboxylic acid component by a transesterification reaction, the reaction step may include at least two steps.

[0095]

[0104] In one embodiment of the present disclosure, polyester is produced in two main steps. The first step involves reacting the starting materials to produce monomers and / or oligomers. If the starting materials entering the first step contain acid-terminated groups such as TPA or isophthalic acid, this first step is called esterification. The second step involves further reacting the monomers and / or oligomers to produce the final polyester product. This second step is generally called polycondensation. The polycondensation step may be a single step or may be divided into a pre-polycondensation (or pre-polymerization) step and a final (or finishing) polycondensation step.

[0096]

[0105] In the first stage, the esterification process, dio such as ethylene glycol is used. The nitrate component and the dicarboxylic acid component, such as terephthalic acid, are mixed at approximately 5-60 pounds / square inch ("psig" or "psi"). (34.5~414kPaG) The reaction is carried out at a temperature of approximately 150°C to approximately 270°C for approximately 0.5 to approximately 8 hours at a pressure in the range of . In one embodiment, the temperature of the esterification or transesterification reaction is approximately 180°C to approximately 230°C over a period of approximately 1 to approximately 4 hours, and the pressure is in the range of approximately 103 kPa (15 psig) to approximately 276 kPa (40 psig) relative to atmospheric pressure. In one embodiment, the temperature of the esterification or transesterification reaction is approximately 240°C to approximately 270°C over a period of approximately 1 to approximately 4 hours, and the pressure is approximately 5 psig to approximately 50 psig (34.5~345kPaG) This is within the range. Subsequently, the reaction product is heated at a higher temperature and under reduced pressure to eliminate the diol and produce a polyester, but this diol readily volatilizes and is removed from the system under these conditions.

[0097]

[0106] The second stage, prepolymerization or polycondensation, is carried out under a higher vacuum and generally for about 0.1 to about 6 hours, or about 0.2 to about 2 hours, at temperatures in the range of about 250°C to about 275°C, or about 255°C to about 270°C, or about 260°C to about 270°C, until a polymer with the desired degree of polymerization, as measured by its intrinsic viscosity, is obtained. The polycondensation step may be carried out under reduced pressure in the range of about 200 mmHg to 500 mmHg. In one embodiment, the temperature of the prepolymerization or polycondensation reaction is in the range of about 240°C to about 270°C for about 1 to about 4 hours, and the pressure is in the range of about 200 mmHg to about 500 mmHg. Stirring or other appropriate means or conditions are used in both stages to ensure sufficient heat transfer and surface regeneration of the reaction mixture.

[0098]

[0107] In certain embodiments, the reaction rates of both stages, esterification and polycondensation, may be increased by the presence of a catalyst. In one embodiment, the catalyst is added to the esterification reaction. In one embodiment, the catalyst is added to the polycondensation reaction. In one embodiment, the titanium compound and the antimony compound are added together, and the phosphorus compound is added as a separate feed following the addition of the catalyst. In one embodiment, the titanium compound, the antimony compound, and the phosphorus compound are added following the esterification of terephthalic acid.

[0099]

[0108] In one embodiment, a finishing step, or final polycondensation step, is included. In this step, the reaction is continued until a desired IV is reached. In one aspect of this disclosure, this final finishing step is carried out at a higher temperature (compared to a titanium-only catalyst system). In one embodiment, a useful finishing temperature is in the range of 280–310°C or 285–300°C. The high finishing temperature enables the production of high-IV polyesters with excellent color tone.

[0100]

[0109] One embodiment of the present disclosure is a process for finishing a polycondensate for producing polyester, wherein the polyester has an intrinsic viscosity of at least 0.50 g / dL or 0.50 to 0.90 g / dL, the polymerization temperature during finishing is raised to 280 to 320°C, and the pressure is 0.3 to 7 mmHg.

[0101]

[0110] For example, one embodiment of the present disclosure is a process for preparing a crystallizable reactor-grade polyester composition, the process of reacting a diacid component containing terephthalic acid residues with a diol component containing neopentyl glycol residues, 1,4-cyclohexanedimethanol residues, diethylene glycol residues, and ethylene glycol residues at an esterification reaction temperature of 240-270°C and a pressure of 5-50 psi in the presence of 2-15 ppm of a titanium compound and 50-150 ppm of an antimony compound to esterify The process includes: a step of producing an esterification product; a step of prepolymerizing this esterification product in the presence of 0 to 90 ppm of a phosphorus compound at a prepolymerization temperature of 255 to 275°C and a pressure of 200 to 500 mmHg to produce a polycondensation product; and a step of finishing the polycondensation product to produce a polyester, wherein the intrinsic viscosity of the polyester is at least 0.50 g / dL or 0.50 to 0.90 g / dL, and the polymerization temperature during the finishing treatment is increased to 280 to 320°C and the pressure is 0.3 to 7 mmHg.

[0102]

[0111] Another embodiment is a process for preparing a crystallizable reactor-grade polyester composition, comprising the steps of: reacting a diacid component containing terephthalic acid residues with a diol component containing neopentyl glycol residues, 1,4-cyclohexanedimethanol residues, diethylene glycol residues, and ethylene glycol residues at an esterification reaction temperature of 240-270°C and a pressure of 5-50 psi to produce an esterification product; prepolymerizing this esterification product at a polycondensation temperature of 255-275°C in the presence of 2-15 ppm of a titanium compound, 50-150 ppm of an antimony compound, and 0-90 ppm of a phosphorus compound to produce a pre-polycondensation product; and finishing the polycondensation product to produce a polyester, wherein the intrinsic viscosity of the polyester is at least 0.50 g / dL or 0.50-0.90 g / dL, the polymerization temperature during the finishing treatment is increased to 280-320°C, and the pressure is 0.3-7 mmHg.

[0103]

[0112] To ensure the completion of the reaction between the diol and dicarboxylic acid components via transesterification, it is sometimes desirable to use an excess amount of approximately 1.05 to 2.5 moles of the diol component for every 1 mole of the dicarboxylic acid component. However, those skilled in the art know that the ratio of diol to dicarboxylic acid components is generally determined by the design of the reactor in which the reaction takes place.

[0104]

[0113] Depending on the embodiment, suitable glycols may include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, p-xylene glycol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, polytetramethylene glycol, isosorbide, or mixtures thereof.

[0105]

[0114] In one embodiment, copolymer polyesters suitable for use in this disclosure are prepared from monomers such as dimethyl terephthalate (DMT), terephthalic acid (TPA), isophthalic acid (IPA), 1,4-cyclohexanedicarboxylic acid (CHDA), ethylene glycol (EG), diethylene glycol (DEG), neopentyl glycol (NPG), 1,4-cyclohexanedimethanol (CHDM), and 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD).

[0106]

[0115] A process for preparing polyester products is provided in accordance with this disclosure.

[0116] In one embodiment, the reaction zones may be separate vessels, typically continuous stirred tank reactors (CSTRs), and these vessels may be integrated units having multiple esterification zones with appropriate partitions and control units. Similarly, the reaction zones may be separate vessels, typically wipe-film or thin-film CSTRs, and these vessels may be combined into one or more integrated units having multiple polycondensation zones with appropriate partitions and control units. Various other types of esterification and polycondensation reactors and reactor configurations are known in the art and may be adapted for use in accordance with this disclosure.

[0107]

[0117] In one embodiment, a paste consisting of EG and TPA in a 2:1 molar ratio is supplied to the paste tank. In one embodiment, additional glycols such as CHDM, TMCD, NPG, and DEG are also supplied to the paste tank. In one embodiment, additional EG is supplied to the first reaction area or reactor 1, and other glycols such as CHDM, TMCD, NPG, and DEG are supplied to the first reaction area at the same location. In one embodiment, these monomers may be added separately and / or directly to the first reaction area.

[0108]

[0118] In one embodiment, the reaction mixture in the first reaction area is heated through a recycle loop including a heat exchanger. Esterification occurs in the first reaction area, forming a first esterification product containing the monomer, oligomer, or both of the copolymerized polyester, and unreacted TPA, EG, and other glycols such as CHDM, TMCD, NPG, or DEG. The reaction product from the first reaction area is then delivered to the second reaction area. Further esterification occurs in the second reaction area, forming a second esterification product containing additional polyester monomer, oligomer, or both. In certain embodiments, the average chain length of the monomer and / or oligomer after the esterification step may be less than 25, 1 to 20, or 5 to 15.

[0109]

[0119] In one embodiment, the second reaction region is optional. In some embodiments, the product is delivered from the first reaction region to the third reaction region.

[0120] In one embodiment, the reaction product from the second reaction area is then delivered to the third reaction area to produce a prepolymerization product containing an oligomer of the copolymerized polyester. In some embodiments, the third reaction area converts the monomer, which has completed the esterification step, into an oligomer having an average chain length in the range of 2-40, 5-35, or 10-30.

[0110]

[0121] The prepolymerization product is then delivered to one or more final reaction or finishing areas. Further polycondensation occurs in the finishing areas to produce copolymerized polyester having the desired mean chain length or IV. The copolymerized polyester is then withdrawn from the finishing areas and subjected to subsequent processing, such as being formed into pellets via an extruder connected to an underwater pelletizing machine.

[0111]

[0122] In one embodiment, the product from the first reaction area (or possibly the second reaction area) is further reacted in a third reaction area, optionally in the presence of a polycondensation catalyst containing a titanium compound and / or an antimony compound and / or a stabilizer containing a phosphorus compound, to produce a polymerization product containing a polyester.

[0112]

[0123] In one embodiment, the average residence time of the reactants in the reaction step is 2 hours or less, 1.75 hours or less, 1.5 hours or less, 1.25 hours or less, 1 hour or less, or 0.75 hours or less. In various embodiments, the average residence time of the reactants in the reaction step is 30 to 40 minutes.

[0113]

[0124] In one embodiment, the average residence time of the reactants in the esterification step is 2 hours or less, 1.75 hours or less, 1.5 hours or less, 1.25 hours or less, 1 hour or less, or 0.75 hours or less. In various embodiments, the average residence time of the reactants in the esterification step (d) is 30 to 40 minutes.

[0114]

[0125] In various embodiments, the overall molar ratio of EG:TPA introduced into the process is in the range of 2.3:1 to 3.0:1.

[0126] In various embodiments, the overall molar ratio of EG:TPA introduced into the process is in the range of 2.3:1 to 2.71:1.

[0115]

[0127] The catalyst may be added during either the esterification step or the polycondensation step. In one embodiment, the catalyst is added to the first reaction area along with the feed material.

[0128] In some embodiments, phosphorus compounds are often added together with a catalyst to improve thermal stability. Phosphorus compounds useful as thermal stabilizers include phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphonic acid, and various esters and salts thereof. Esters may be alkyl, branched alkyl, substituted alkyl, difunctional alkyl, alkyl ether, aryl, and substituted aryl. In some embodiments, triphenyl phosphate is a suitable thermal stabilizer. In one embodiment, phosphorus is added in the range of 0 to 90 ppm based on the weight of the copolymerized polyester.

[0116]

[0129] In various embodiments, one or more other additives may be added to the starting material, copolymerized polyester, and / or copolymerized polyester monomer / oligomer at one or more positions in the process. In various embodiments, suitable additives may include, for example, trifunctional or tetrafunctional comonomers such as trimellitic anhydride, trimethylolpropane, pyromellitic dianhydride, pentaerythritol, or other polyacids or polyols; crosslinking or other branching agents; colorants; toners; pigments; carbon black; glass fibers; fillers; impact modifiers; antioxidants; UV-absorbing compounds; deoxygenating compounds, and the like.

[0117]

[0130] The processes described herein are particularly well-suited for use on an industrial scale. For example, these processes may be implemented in a commercial production line capable of flowing polymers at a rate of 500 to 30,000 pounds per hour.

[0118]

[0131] In another respect, this disclosure relates to copolymer polyesters produced from the processes of this disclosure.

[0132] Depending on the embodiment, certain agents for coloring the polymer, including toners or dyes, may be added to the molten material during the process of producing polyesters useful in this disclosure. In one embodiment, the resulting polyester polymer molten phase product is b * To reduce the value, blue toner is added to the molten material. Such blue-coloring agents include blue inorganic and organic toners and / or dyes. Furthermore, red toner and / or dyes are used. * The color values ​​may be adjusted. Organic toners, such as the blue and red organic toners described in U.S. Patents 5,372,864 and 5,384,377, which are incorporated herein by reference in their entirety. The organic toner may be supplied as a premixed composition. The premixed composition may be a neat blend of red and blue compounds, or the composition may be pre-dissolved or slurryed in one of the polyester raw materials, such as ethylene glycol.

[0119]

[0133] The total amount of toner components added may depend on the inherent yellow content in the substrate polyester and the potency of the toner. In one embodiment, the combined organic toner components may be used at a maximum concentration of about 15 ppm and a minimum concentration of about 0.5 ppm. In one embodiment, the total amount of the blue-coloring additive may be in the range of 0.5 to 10 ppm. In one embodiment, the toner may be added to the esterification area or the polycondensation area. Preferably, the toner is added in the initial stages of the polycondensation area, such as the esterification area or a prepolymerization reactor.

[0120]

[0134] In embodiments, the polyester composition may contain common additives in an amount of 0.01 to 25% by weight of the total composition, such as mold release agents, anti-slip agents, anti-tack agents, flame retardants, plasticizers, glass bubbles, nucleating agents, stabilizers including, but not limited to, UV stabilizers and heat stabilizers, and / or their reaction products, fillers, and impact modifiers. Examples of commercially available impact modifiers include, but not limited to, ethylene / propylene ternary polymers, functionalized polyolefins such as methyl acrylate and / or glycidyl methacrylate, impact modifiers that are styrene-based block copolymers, and various acrylic core / shell type impact modifiers. Residues of such additives are also considered part of the polyester composition.

[0121]

[0135] In one embodiment, the crystallizable compositions of the present disclosure are used in the manufacture of films and sheets, including heat-shrinkable films and thermoformable sheets. The heat-shrinkable plastic films are used as coverings for holding objects together and as outer coverings for bottles, cans, and other types of containers. For example, such films are used to cover the lid, neck, shoulder, body, or the entire bottle for labeling, protection, packaging, or to enhance product value, or for other reasons. Furthermore, such films may be used as coverings for packaging a group of objects such as boxes, bottles, boards, rods, and notebooks, and such films may also be tightly adhered as packaging. The shrinkability and internal shrinkage stress of the films are utilized in the above-described uses.

[0122]

[0136] Historically, polyvinyl chloride (PVC) film has been the dominant force in the shrink film market. However, polyester film has become an important alternative because it does not involve the environmental problems associated with PVC film. Since polyester shrink film ideally possesses properties very similar to PVC film, it can function as a "drop-in" alternative film and can be processed in existing heat shrink tunneling equipment. Desired properties of PVC film compared to the alternative include (1) a relatively low shrinkage initiation temperature, (2) a total shrinkage rate that increases gradually and in a controlled manner with increasing temperature, (3) a low shrinkage force to prevent crushing of containers below, (4) a high total shrinkage rate (e.g., 50% or more), and (5) inherent film toughness to prevent unwanted tearing and splitting of the film before and after shrinkage.

[0123]

[0137] For heat-shrinkable films to be effective in this application, they must meet various compliance requirements for use. The film must be strong, shrink in a controlled manner, and provide sufficient shrinkage force to hold itself on the bottle surface without crushing the contents. Furthermore, when these labels are applied to polyester containers, they must not interfere with the PET bottle recycling process. In fact, it is advantageous if the labels are also recyclable, allowing the entire bottle to be recycled and converted into a new product without creating additional operational requirements or new environmental problems. Heat-shrinkable films are manufactured from a variety of raw materials to meet the demand for a certain range of materials. This disclosure describes the unique and unexpected effects addressed by combinations of specific monomers that improve the recyclability of labels made of polyester shrinkable film.

[0124]

[0138] Polyester shrink film compositions are commercially used as shrink film labels for food, beverages, personal care products, and household goods. Often, these shrink films are used in combination with clear polyethylene terephthalate (PET) bottles or containers. The entire product (bottle and label) is then put into a recycling process. In typical recycling sites, PET and shrink film materials are often mixed at the end of the process due to their similar composition and density. Drying the PET flakes is necessary to remove any residual water that adheres to the PET during the recycling process. Typically, during the recycling process, PET is dried at temperatures above 200°C, at which temperatures the typical polyester shrink film resin often softens and becomes sticky, forming agglomerates with the PET flakes. These agglomerates must be removed before further processing. These agglomerates reduce the yield of PET flakes from this process and necessitate additional handling steps.

[0125]

[0139] In embodiments of the present disclosure, certain oriented films and / or shrinkable films comprising polyesters and / or polyester compositions useful in the present disclosure may have all of the following unique combinations of properties: excellent stretchability, controlled shrinkage properties, specific toughness, specific intrinsic viscosity, specific glass transition temperature (Tg), specific strain-induced crystal melting point, specific flexural modulus, specific density, specific tensile modulus, specific surface tension, excellent melt viscosity, excellent clarity, and excellent color tone.

[0126]

[0140] In one embodiment, the film and shrink film according to this disclosure may contain 0.01 to 10% by weight of a polyester plasticizer, for example, the plasticizer described in U.S. Patent No. 10,329,393, which is incorporated herein by reference. In one embodiment, the shrink film may contain 0.1 to 5% by weight of a polyester plasticizer.

[0127]

[0141] In one aspect, this disclosure relates to shrinkable films, extruded sheets, thermoformed articles, and molded articles comprising the crystallizable polyester compositions of this disclosure. Methods for forming polyester compositions into films and / or sheets are well known in the art. Useful examples of sheets of this disclosure include, but are not limited to, extruded sheets, compression-molded films, rolled films and / or sheets, and solution-cast films and / or sheets. In one aspect, methods for producing films and / or sheets useful for producing shrinkable films of this disclosure include, but are not limited to, extrusion, compression molding, rolling, and solution casting.

[0128]

[0142] In one embodiment, the polyester compositions useful in this disclosure are manufactured into films using any method known in the art for manufacturing films from polyester, such as solution casting, extrusion, compression molding, or rolling. See, for example, U.S. Patents 6,846,440; 6,551,699; 6,551,688; and 6,068,910, which are incorporated herein by reference.

[0129]

[0143] In one embodiment, the as-formed film is subsequently oriented in one or more directions (e.g., as a uniaxial and / or biaxially oriented film). This orientation of the film can be carried out by any method known in the art using standard orientation conditions. In one embodiment, the oriented film of the Disclosure may be manufactured from a film having a thickness of about 100 to 400 μm, for example, an extruded, cast, or rolled film, and this oriented film may be oriented in a ratio of 5:1 to 3:1 at a temperature of Tg to Tg + 55°C, or 70°C to 125°C, for example, in a ratio of 5:1 or 3:1 at a temperature of 70°C to 100°C, and this film may also be oriented to a thickness of 20 to 80 μm. In one embodiment, the initial pre-shrinking orientation of the film may be carried out in a tenter frame according to these orientation conditions. The shrink film of the Disclosure may be manufactured from the oriented film of the Disclosure.

[0130]

[0144] In one embodiment, the shrinkable film of the present disclosure may have a shrinkage initiation temperature of about 55 to about 80°C, or about 55 to about 75°C, or about 55 to about 70°C. The shrinkage initiation temperature is the temperature at which shrinkage begins.

[0131]

[0145] In certain embodiments, the polyester compositions useful in this disclosure may have a density of 1.6 g / cc or less, or 1.5 g / cc or less, or 1.4 g / cc or less, or 1.1 g / cc to 1.5 g / cc, or 1.2 g / cc to 1.4 g / cc, or 1.2 g / cc to 1.35 g / cc.

[0132]

[0146] In one embodiment, the density of a film or molded article is reduced by introducing many small voids or holes into the film. This process is called "voiding," and is sometimes referred to as "cavitating" or "microvoiding." These voids are obtained by incorporating about 1 to about 50% by weight of small organic particles or inorganic particles (including glass microspheres) or "inclusions" (referred to in the art as "voiding agents" or "cavitating agents") into a base polymer and orienting the polymer by stretching it in at least one direction. During stretching, small cavities or voids are formed around the voiding agents. Once voids are introduced into the polymer film, the resulting porous film is not only less dense than a void-free film, but also opaque, resulting in a paper-like surface. This surface also has the advantage of improving printability, meaning the surface can accept a substantially larger volume of ink than a void-free film. Typical examples of perforated films include U.S. Patent Nos. 3,426,754; 3,944,699; 4,138,459; 4,582,752; 4,632,869; 4,770,931; 5,176,954; 5,435,955; 5,843,578; 6,004,664; 6,287,68 It is described in Patent No. 0; 6,500,533; 6,720,085; US Patent Application Publication No. 2001 / 0036545; 2003 / 0068453; 2003 / 0165671; 2003 / 0170427; Japanese Patent Application Publication No. 61-037827; 63-193822; 2004-181863; European Patent No. 0581970B1; European Patent Application Publication No. 0214859A2.

[0133]

[0147] In certain embodiments, the as-extruded film is oriented during stretching. The oriented or shrinkable films of this disclosure can be made from films of any thickness depending on the desired end application. In one embodiment, a desirable condition is that the oriented and / or shrinkable films can be printed with ink for applications such as labels, photographic films that can adhere to substrates such as paper, and / or for other applications where the films are useful for bottles or containers and can be shrunk to surround their outside. It may be desirable to co-extrude the polyester useful in this disclosure with another polymer such as PET to make the film usable as the oriented and / or shrinkable film of this disclosure. One advantage of carrying out the latter co-extrusion is that, depending on the embodiment, a tie layer may not be required.

[0134]

[0148] In certain embodiments, the shrinkable film of the Disclosure shrinks slowly with little to no wrinkles. In certain embodiments, the shrinkable film of the Disclosure has a shrinkage rate of 40% or less in the transverse direction for every 5°C increase in temperature.

[0135]

[0149] In certain embodiments of the present disclosure, the shrinkable film of the present disclosure shrinks by 10% or less, 5% or less, 3% or less, or 2% or less in the mechanical direction when immersed in water at 65°C for 10 seconds, or does not shrink at all. In certain embodiments of the present disclosure, the shrinkable film of the present disclosure shrinks by -10% to 10%, -5% to 5%, or -5% to 3%, or -5% to 2%, or -4% to 4%, or -3% to 4%, or -2% to 4%, or -2% to 2.5%, or -2% to 2%, or does not shrink at all when immersed in water at 65°C for 10 seconds. Here, a negative shrinkage rate in the mechanical direction indicates expansion in the mechanical direction. A positive shrinkage rate in the mechanical direction indicates contraction in the mechanical direction.

[0136]

[0150] In certain embodiments of the present disclosure, the shrinkable film of the present disclosure has a shrinkage rate of 50% or more, or 60% or more, or 70% or more in the principal shrinkage direction when immersed in water at 95°C for 10 seconds.

[0137]

[0151] In certain embodiments of the present disclosure, the shrink film of the present disclosure has a shrinkage rate of 50 to 90% in the principal shrinkage direction and a shrinkage rate of 10% or less or -10% to 10% in the mechanical direction when immersed in water at 95°C for 10 seconds.

[0138]

[0152] In one embodiment, the polyester useful in the present disclosure is made into a film using any method known in the art for producing a film from polyester, e.g., solution casting, extrusion, compression molding, or rolling. The as-extruded (or as-formed) film is then oriented in one or more directions (e.g., a uniaxial and / or biaxially oriented film). This orientation of the film may be carried out by any method known in the art using standard orientation conditions. For example, the uniaxially oriented film of the present disclosure may be made from a film with a thickness of about 100 to 400 μm, e.g., an extruded, cast, or rolled film, which may be stretched at a temperature of film Tg to Tg + 55°C in a ratio of 6.5:1 to 3:1 and stretched to a thickness of 20 to 80 μm. In one embodiment, the initial orientation of the as-extruded film may be carried out in a widthening machine according to these orientation conditions.

[0139]

[0153] In certain embodiments of the present disclosure, the shrinkable film of the present disclosure may have a shrinkage initiation temperature of about 55 to about 80°C, or about 55 to about 75°C, or about 55 to about 70°C. The shrinkage initiation temperature is the temperature at which shrinkage initiation occurs or the shrinkable film begins to shrink.

[0140]

[0154] In certain embodiments of the present disclosure, the shrinkable film of the present disclosure may have a shrinkage initiation temperature of 55°C to 70°C.

[0155] In certain embodiments of the present disclosure, the shrinkage film of the present disclosure may have a breaking strain of more than 200% at a stretching rate of 500 mm / min in a direction perpendicular to the principal shrinkage direction, according to ASTM Method D882.

[0141]

[0156] In certain embodiments of the present disclosure, the shrinkage film of the present disclosure may have a breaking strain of more than 300% at a stretching rate of 500 mm / min in a direction perpendicular to the principal shrinkage direction, according to ASTM Method D882.

[0142]

[0157] In certain embodiments of the present disclosure, the shrinkage film of the present disclosure may have a tensile stress at break (breaking stress) of 20 to 400 MPa, or 40 to 260 MPa, or 42 to 260 MPa, as measured according to ASTM method D882.

[0143]

[0158] In certain embodiments of the present disclosure, the shrink films of the present disclosure may have a shrinkage force of 4 to 18 MPa or 4 to 15 MPa, as measured by ISO Method 14616, depending on the stretching conditions and the desired end use. For example, a particular label made for plastic bottles may have a shrinkage force of 4 to 8 MPa, and a particular label made for glass bottles may have a shrinkage force of 10 to 14 MPa, as measured by ISO Method 14616 using a LabThink FST-02 heat shrinkage tester and recorded in units of MPa.

[0144]

[0159] In one embodiment of the present disclosure, the polyester composition may be produced by reacting monomers by known methods for producing polyesters, typically referred to as reactor-grade compositions.

[0145]

[0160] A molded article made of a shrink film, or a molded article that is not made of a shrink film but contains such film, may also be manufactured from any of the polyester compositions disclosed herein and are included within the scope of this disclosure.

[0146]

[0161] In one embodiment, when a pre-oriented film has a thickness of approximately 100 to 400 μm and is subsequently oriented in a widening machine to a thickness of approximately 20 to approximately 80 μm at a temperature of Tg to Tg + 55°C and a ratio of 6.5:1 to 3:1, the shrink film of the present disclosure has the following characteristics: (1) When immersed in water at 95°C for 10 seconds, it shrinks by more than 60% (or more than 70%) in the main shrinkage direction, i.e., the transverse direction, and shrinks by 10% or less (or -5% to 4%) in the mechanical direction. The shrinkable film may have one or more of the following properties: (1) shrinkage, (2) shrinkage onset temperature of approximately 55°C to approximately 70°C, (3) fracture strain of more than 200%, or 200 to 600%, or 200 to 500%, or 226 to 449%, or 250 to 455%, in the transverse direction, mechanical direction, or both, at a stretching rate of 500 mm / min, according to ASTM method D882, (4) shrinkage of 40% or less for every 5°C temperature increase, and / or (5) melting point of strain-induced crystals above 200°C. Any combination of these properties, or all of these properties, may be present in the shrinkable film of the Disclosure. The shrinkable film of the Disclosure may have two or more combinations of the above shrinkable film properties. The shrinkable film of the Disclosure may have three or more combinations of the above shrinkable film properties. The shrinkable film of the Disclosure may have four or more combinations of the above shrinkable film properties. In certain embodiments, properties (1) to (2) are present. In certain embodiments, characteristics (1) to (5) exist. In certain embodiments, characteristics such as (1) to (3) exist.

[0147]

[0162] The shrinkage rates described herein are based on an initial as-produced film with a thickness of approximately 20 to 80 μm, which is oriented in a widening machine at a ratio of 6.5:1 to 3:1 at temperatures of Tg to Tg+55°C, for example, at a ratio of 5:1 at temperatures of 70°C to 85°C. In one embodiment, the shrinkage characteristics of the oriented film used to produce the shrinkage film of this disclosure did not change even when the film was heat-treated at a temperature higher than the temperature at which it was oriented.

[0148]

[0163] The shape of the film useful for producing the oriented or shrinkable films of this disclosure is not limited in any way. For example, the shape may be a flat film or a film formed into a tubular shape. A film formed into a tubular shape can have its ends joined or held together during shrinkage using a suture solvent or suture adhesive. To produce shrinkable films useful in this disclosure, polyester is first formed into a flat film, then “uniaxially stretched,” meaning that the polyester film is oriented in one direction, and then the ends of the stretched film are joined using a suture solvent or suture adhesive to form a tube or sleeve. The film may also be “biaxially oriented,” meaning that the polyester film is oriented in two different directions, for example, the film is stretched in both the machine direction and a direction opposite to the machine direction. Typically the two directions are substantially perpendicular, but not always. For example, in one embodiment, the two directions are the longitudinal or machine direction ("MD") of the film (the direction in which the film is produced in the film manufacturing machine) and the transverse direction ("TD") of the film (the direction perpendicular to the MD of the film). The biaxially oriented film may be oriented continuously, simultaneously, or by some combination of simultaneous and continuous stretching.

[0149]

[0164] The film may be oriented by any conventional method, such as roll stretching, long-gap stretching, width-extending stretching, and tubular stretching. Continuous biaxial stretching, simultaneous biaxial stretching, uniaxial stretching, or a combination thereof may be performed using any of these methods. The biaxial stretching described above may perform stretching in the machine direction and transverse direction simultaneously. Alternatively, stretching can be performed first in one direction and then in the other to efficiently achieve biaxial stretching. In one embodiment, the film is stretched after preheating it to a temperature 5°C to 80°C above its glass transition temperature (Tg). In another embodiment, the film may be preheated to a temperature 5°C to 30°C above its Tg. In another embodiment, the stretching speed is 0.5 to 20 inches (1.27 to 50.8 cm) per second. The film may then be oriented to 2 to 6 times its original dimensions, for example, in the machine direction, transverse direction, or both directions. The film may be oriented as a single film layer, or it may be co-extruded with another polyester such as PET (polyethylene terephthalate) as a multilayer film and then oriented.

[0150]

[0165] In one embodiment, the Disclosure includes a manufactured or molded article comprising a shrink film from any of the embodiments of the shrink film of the Disclosure. In another embodiment, the Disclosure includes a manufactured or molded article comprising an orientation film from any of the embodiments of the orientation film of the Disclosure.

[0151]

[0166] In certain embodiments, the disclosure includes, but is not limited to, shrink films suitable for containers, plastic bottles, glass bottles, packaging, batteries, high-temperature filling containers, and / or industrial products or other applications. In one embodiment, the disclosure includes, but is not limited to, orientation films suitable for containers, packaging, plastic bottles, glass bottles, photographic substrates such as paper, batteries, high-temperature filling containers, and / or industrial products or other applications.

[0152]

[0167] In certain embodiments of the present disclosure, the shrink film of the present disclosure may be formed into a label or sleeve. The label or sleeve may then be affixed to a manufactured article such as a container wall or a battery, or onto a sheet or film.

[0153]

[0168] The orientation films or shrink films of this disclosure can be applied to molded articles such as tubes or bottles and are commonly used in a variety of packaging applications. For example, films and sheets made from polymers such as polyolefins, polystyrene, polyvinyl chloride, polyester, and polylactic acid (PLA) are frequently used in the manufacture of shrink labels for plastic beverage or food containers. For example, the shrink films of this disclosure can be used in many packaging applications, in which the shrink films applied to molded articles exhibit properties such as excellent printability, excellent shrinkage strength, excellent texture, high shrinkage rate, controlled shrinkage rate, high rigidity, and recyclability.

[0154]

[0169] Improved shrinkage properties and recyclability should provide novel commercial options for shrink films to be applied to containers, plastic bottles, glass bottles, packaging, batteries, high-temperature filled containers, and / or industrial products or other applications, but are not limited to these.

[0155]

[0170] In one aspect of this disclosure, the disclosed polyester compositions are useful as thermoformable sheets and / or thermoformable sheets. This disclosure also covers manufactured articles incorporating the thermoformable sheets of this disclosure. In one embodiment, the polyester compositions of this disclosure are useful as sheets that are readily formed into molded or formed articles or parts. In one embodiment, the films and / or sheets of this disclosure can be processed into molded articles or parts by thermoforming. The polyester compositions of this disclosure may be used in a variety of molding and extrusion applications.

[0156]

[0171] Furthermore, in one embodiment, the polyester composition useful for the thermoformable sheet of the present disclosure may also contain, in an amount of 0.1 to 25% by weight of the total composition, general additives such as colorants, anti-tacks, lubricants, release agents, flame retardants, plasticizers, nucleating agents, stabilizers such as ultraviolet stabilizers and heat stabilizers, fillers, and impact modifiers, but not limited to these.

[0157]

[0172] In one embodiment, the reinforcing material may be included in a thermoformed sheet containing the polyester composition of the present disclosure. Suitable reinforcing materials may include, for example, carbon fibers, silicates, mica, clay, talc, titanium dioxide, wollastonite, glass flakes, glass beads and fibers, polymer fibers, and combinations thereof.

[0158]

[0173] In one embodiment, the thermoformable sheet of the present disclosure is a multilayer sheet. In one embodiment, at least one layer of the multilayer sheet is a foam layer, or a foamed polymer or polyester layer.

[0159]

[0174] One aspect of this disclosure is a method for manufacturing parts and articles formed or molded using thermoforming. The parts and articles formed or molded according to this disclosure can be manufactured using any thermoforming technique or process known to those skilled in the art.

[0160]

[0175] In one embodiment, the thermoforming process can be carried out in several ways, as taught, for example, in “Technology of Thermoforming” (Throne, James; Hanser Publishers; 1996; pp. 16–29), which is incorporated herein by reference. In some embodiments, the process is a thermoforming process of a male mold, in which gas or pneumatic pressure is applied to a softened sheet, the sheet is then stretched and drawn out like a bubble, and a male mold is placed inside the bubble from the inside. Vacuum is then applied to further draw out the part and conform it to the surface of the male mold. In this thermoforming process, biaxial stretching / orientation is mainly performed in a single step when gas or pneumatic pressure is applied to the softened sheet. The forming process is then completed by cooling the sheet to below Tg and using vacuum and a male mold to fix the orientation within the sheet to achieve a good balance of physical and cosmetic properties. In other embodiments, the process involves stretching and drawing the sheet to near final part dimensions, in addition to a heat-softened sheet using vacuum or a physical plug, then drawing the sheet out by positive air pressure from the inside or further external vacuum to fit it into an outer female mold, and cooling the sheet to below Tg to fix its orientation, thereby forming the sheet into an article.

[0161]

[0176] In some embodiments, bubbles may be formed using a plugging aid, followed by covering and molding the rising male mold with a sheet, and then drawing the corners and shelf guides into the mold under vacuum. In some embodiments, after removal from the mold, the formed part or article can be cut, perforated, and the corners trimmed as needed.

[0162]

[0177] In other embodiments, thermoforming is a process in which a sheet of the polyester composition of the Disclosure is heated to a temperature sufficient to deform, and then the heated sheet is conformed to the contour of a mold by means such as vacuum assistance, pneumatic assistance, and matched mold assistance. In yet another embodiment, the heated sheet is placed in a mold and forced to conform to the contour of the mold by, for example, applying pneumatic pressure, using a vacuum plug aid, or using a matched mold. In some embodiments, thermoforming is used to produce thin-walled articles. In some embodiments, thermoforming is used to produce thick-walled articles.

[0163]

[0178] In one embodiment, the thermoforming process shapes a sheet into a desired shape by pressing a male mold onto a heated sheet. In certain embodiments, the thermoforming includes having a male mold of an article supported between a vacuumed surface or table. In these embodiments, heat is directed onto the sheet from an external heat source, such as a hot air blower, a heat lamp, or other radiant heat source. In these embodiments, the sheet is heated to its softening point. In these embodiments, a vacuum is then created around the table, below the table, and around the mold to pull the heat-softened sheet towards the table, positioning the softened sheet in contact with the mold surface. In these embodiments, the vacuum causes the softened sheet to be pulled into tight contact with the contour of the mold surface and to conform to it. This causes the sheet to take the shape of the mold. In these embodiments, after the sheet has cooled, it hardens, and the resulting article or part can be removed from the mold.

[0164]

[0179] In one embodiment, the thermoforming process includes the steps of: forming a sheet from the polyester composition of the Disclosure; heating the sheet until it softens and placing the sheet on a mold; drawing the preheated sheet towards the heated surface of the mold; cooling the sheet; then removing the formed article or part from the mold cavity, or, if necessary, continuing to contact the sheet with the heated mold for a time sufficient to partially crystallize the sheet to heat-cur the formed sheet.

[0165]

[0180] In one embodiment, the thermoforming process includes the steps of: forming a sheet from the polyester composition of the Disclosure; heating the sheet to a temperature above the Tg of polyester; stretching the sheet to substantially final part dimensions by applying gas pressure, vacuum, and / or physical pressure to the heat-softened sheet; conforming the sheet to the shape of a mold by vacuum or pressure; cooling the sheet to a temperature below the Tg of polyester; and then removing the thermoformed article or part from the mold.

[0166]

[0181] The sheets used in the thermoforming process may be manufactured by any conventional method known to those skilled in the art. In one embodiment, the sheets are formed by extrusion. In one embodiment, the sheets are formed by rolling. In one embodiment, during the thermoforming process, the sheets are heated to a temperature above the Tg of polyester. In one embodiment, this temperature is about 10°C to about 60°C higher than the Tg of polyester. In one embodiment, it is necessary to heat the sheets before placing them on the thermoforming mold to achieve a shorter forming time. In one embodiment, the sheets need to be heated to a temperature above their Tg, but below the temperature at which the sheets will flex excessively while being placed on the mold cavity. In one embodiment, it is preferable to cool the formed sheets to a temperature below the Tg of polyester before removing them from the mold. In one embodiment, the thermoforming method may include a vacuum aid, an air aid, a mechanical plug aid, or a matched mold. In some embodiments, the mold is heated to a temperature above the Tg of the sheet. The selection of the optimal mold temperature depends on the mold of the thermoforming apparatus, the structure and thickness of the article to be formed, and other factors.

[0167]

[0182] In some embodiments, a heated sheet is stretched by generating and then evacuating a vacuum.

[0183] In one embodiment, heat curing is a process that thermally induces partial crystallization of the polyester sheet without the presence of apparent orientation. In one embodiment, heat curing is achieved by maintaining contact between the sheet and the heated mold surface for a time sufficient to achieve a level of crystallinity that imparts appropriate physical properties to the finished part. In certain embodiments, the level of crystallinity (relative crystallinity) should be greater than 8 cal / g.

[0168]

[0184] In one embodiment, the heat-cured part may be removed from the mold cavity by known means for removal. For example, in one embodiment, a blowback is used, which involves introducing compressed air to break the vacuum built between the mold and the molded sheet. In some embodiments, any excess portion of the formed article or part is then cut off and the waste is crushed and recycled.

[0169]

[0185] In some embodiments, the addition of a nucleating agent provides faster crystallization during thermoforming, and therefore faster molding. In one embodiment, a nucleating agent such as a particulate inorganic or organic material may be used. For example, in one embodiment, suitable nucleating agents include talc, titanium dioxide, calcium carbonate, and immiscible or crosslinked polymers. In one embodiment, the nucleating agent may be used in an amount that varies from about 0.01% to about 20% based on the weight of the article. In one embodiment, other conventional additives such as pigments, dyes, plasticizers, crack inhibitors, and stabilizers may be used as needed for thermoforming. In some embodiments, crack inhibitors improve impact strength, and nucleating agents provide faster crystallization. In some embodiments, crystallization is necessary to achieve high-temperature stability.

[0170]

[0186] In one embodiment, a foamed polyester sheet is produced by foaming the polyester composition of the Disclosure with a chemical and / or physical foaming agent, extruding the foamed polyester into a sheet, and thermoforming the foamed polyester sheet. Additives to improve the properties of the foamed polyester sheet may be added to the polyester before foaming. Examples of such additives include lubricants, anti-tacks, plasticizers, fluorescent whitening agents, and ultraviolet inhibitors. In one embodiment, the foamed polyester sheet may be an extruded or laminated product coated on one or both sides using conventional techniques to improve its properties. In one embodiment, the coating material may be a printed surface that provides labeling for the product, rather than the foamed sheet itself.

[0171]

[0187] In certain embodiments, the compositions of the Disclosure are useful as formed or molded plastic parts or as solid plastic articles. In some embodiments, the compositions of the Disclosure are useful as thermoformed parts or articles. In some embodiments, the compositions of the Disclosure are suitable for use in any application where a clear, rigid plastic is required. In some embodiments, for example, the compositions of the Disclosure are suitable for use as parts for disposable knives, forks, spoons, plates, cups, straws, as well as eyeglass frames, toothbrush handles, toys, automotive parts, tool handles, camera parts, electronic device parts, razor parts, ink pen barrels, disposable syringes, bottles, and the like. In one embodiment, the compositions of the Disclosure are useful as plastics, films, fibers, and sheets.

[0172]

[0188] In one embodiment, the composition is useful as a plastic for manufacturing bottles, bottle caps, eyeglass frames, knives, disposable knives, knife handles, shelves, shelf dividers, electronic equipment housings, electronic equipment cases, computer monitors, printers, keyboards, tubes, automotive parts, automotive interior parts, automotive equipment, signs, thermoformed letters, wall panels, toys, thermally conductive plastics, ophthalmic lenses, tools, tool handles, and household goods. In another embodiment, the compositions of the present disclosure include films, sheets, fibers, formed articles, molded articles, formed parts, molded parts, medical devices, dental trays, dental instruments, containers, food containers, transport containers, packaging, bottles, bottle caps, eyeglass frames, knives, disposable knives, knife handles, shelves, shelf dividers, furniture parts, electronic equipment housings, electronic equipment cases, computer monitors, printers, keyboards, tubes, toothbrush handles, automotive parts, automotive interior parts, automotive equipment, signs, outdoor signs, skylights, multi-layer films, multilayer films, thermal insulation parts, thermal insulation articles, thermal insulation containers, thermoformed letters, wall panels, toys, toy parts, trays, food trays, teeth Suitable for use as medical trays, thermally conductive plastics, ophthalmic lenses and frames, tools, tool handles, and household goods, healthcare supplies, commercially available food supply products, boxes, graphic art films, plastic films for plastic glass laminates, purchase point displays, skylights, smoke vents, laminate cards, fenestrations, glazing, partitions, ceiling tiles, lighting, machine protective panels, graphic art, lenses, extruded laminate sheets or films, decorative laminates, office furniture, face shields, medical packaging, sign holders for display shelves, and price holders for shelves.

[0173]

[0189] The thermoformable sheets or thermoformable sheets of this disclosure are useful for forming films, formed articles, formed parts, molded articles, molded parts, and sheets. Methods for producing films, formed articles, formed parts, molded articles, molded parts, and sheets from the thermoformable compositions or thermoformable compositions may follow any method known in the art. Examples of formed articles include, but are not limited to, medical device packaging, medical packaging, healthcare supplies, trays, containers, food dishes, tumblers, storage boxes, bottles, food processors, blenders and mixing bowls and other commercially available food supply products, household goods, water bottles, vegetable trays, washing machine parts, refrigerator parts, vacuum cleaner parts, ophthalmic lenses and frames, and toys.

[0174]

[0190] This disclosure further relates to a manufactured article comprising a sheet containing the polyester composition described herein. Depending on the embodiment, the sheet of this disclosure may be of any thickness required for the intended application.

[0175]

[0191] This disclosure further relates to sheets as described herein. Methods for forming polyester compositions into sheets include any method known in the art. Examples of sheets of this disclosure include, but are not limited to, extruded sheets, rolled sheets, compression-molded sheets, and solution-cast sheets. Methods for producing sheets of this disclosure include, but are not limited to, extrusion, rolling, compression molding, wet block processing, dry block processing, and solution casting.

[0176]

[0192] This disclosure further relates to formed or molded articles described herein. Methods for forming polyester compositions into formed or molded articles include any method known in the art. Examples of formed or molded articles of this disclosure include, but are not limited to, thermoformed or thermoformable articles, injection molded articles, extruded articles, injection blow molded articles, injection stretch blow molded articles, and extruded blow molded articles. Methods for manufacturing formed articles include, but are not limited to, thermoforming, injection molding, extrusion, injection blow molding, injection stretch blow molding, and extruded blow molding. The processes of this disclosure may include any thermoforming processes known in the art. The processes of this disclosure may include, but are not limited to, any blow molding processes known in the art, including extruded blow molding, extruded stretch blow molding, injection blow molding, and injection stretch blow molding.

[0177]

[0193] This disclosure includes any injection blow molding manufacturing process known in the art. A typical injection blow molding (IBM) manufacturing process includes, but is not limited to, 1) melting a composition in a reciprocating screw extruder; 2) injecting the molten composition into an injection mold to form a partially cooled tube with one end closed (i.e., a preform); 3) moving the preform into a blow mold having a desired final shape around the preform to close the blow mold around the preform; 4) blowing air into the preform to stretch and expand it to fill the mold; 5) cooling the molded article; and 6) removing the article from the mold.

[0178]

[0194] This disclosure includes any injection stretch blow molding manufacturing process known in the art. A typical injection stretch blow molding (ISBM) manufacturing process, but not limited to, includes: 1) melting a composition in a reciprocating screw extruder; 2) injecting the molten composition into an injection mold to form a partially cooled tube (i.e., a preform) with one end closed; 3) moving the preform into a blow mold having a desired final shape around the preform to close the blow mold around the preform; 4) stretching the preform using an internal stretch rod and blowing air into the preform to stretch and expand the preform to fill the mold; 5) cooling the molded article; and 6) removing the article from the mold.

[0179]

[0195] This disclosure includes any extrusion blow molding manufacturing process known in the art. A typical extrusion blow molding manufacturing process, but not limited to, includes: 1) melting a composition in an extruder; 2) extruding the molten composition through a die to form a tube of molten polymer (i.e., a parison); 3) securing a mold having the desired final shape around the parison; 4) blowing air into the molten preform to stretch and expand the extruder to fill the mold; 5) cooling the molded article; 6) removing the article from the mold; and 7) removing excess plastic (commonly known as burrs) from the article.

[0180]

[0196] In another aspect of the Disclosure, it has been found that the catalyst system of the Disclosure can be used to produce the copolymerized polyester resin of the Disclosure from recycled copolymerized polyester and / or recycled copolymerized polyester.

[0181]

[0197] One embodiment is a process for producing a polyester composition from recycled polyester, and this process is (a) A step of introducing terephthalic acid (TPA) and ethylene glycol (EG) and recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG into a paste tank, and stirring and heating at a maximum temperature of 150°C to produce a slurry; (b) A step of delivering the slurry from the paste tank to the first reaction area; (c) Introducing at least one additional glycol, including 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG), into the first reaction area, and adding additional terephthalic acid (TPA) and ethylene glycol (EG) as needed, such that the total glycol:TPA molar ratio is 1:1 to 4:1, in the presence of an esterification catalyst and / or a stabilizer including a phosphorus compound, as needed, including a titanium compound and an antimony compound; (d) A step of reacting TPA and EG and recycled polyester in a first reaction area with at least one additional glycol at a melting temperature of at least 200°C to produce a first esterification product comprising oligomers and unreacted TPA, EG, and the additional glycol; (e) A step of delivering the first esterification product to the second reaction area; (f) In a second reaction area, the first esterification product and optionally additional glycols are further reacted at a melting temperature of at least 200°C in the presence of an esterification catalyst optionally containing a titanium compound and an antimony compound and / or a stabilizer containing a phosphorus compound to produce a second esterification product containing a polyester oligomer; (g) A step of delivering the second esterification product to the third reaction area; and (h) The process includes polycondensing the second esterification product in a third reaction area in the presence of a polycondensation catalyst containing a titanium compound and an antimony compound, and / or a stabilizer containing a phosphorus compound, to produce a polymerization product containing a polyester.

[0182]

[0198] In one embodiment, recycled polyester and / or copolymerized polyester may be recovered as manufacturing waste, industrial waste, or post-consumer recycling (PCR) waste. Typically, PCR or recycling waste is articles made from used and discarded polyester or copolymerized polyester. Currently, PET is recycled by mechanical means and incorporated into new PET bottles and other PET articles as a mixture with unused material.

[0183]

[0199] Copolymer polyesters having a recyclable content and copolymer polyesters produced from a recyclable content contain dicarboxylic acid monomer residues, diol monomer or glycol monomer residues, and repeating units. Therefore, as used herein, the term "monomer residue" means each residue of a dicarboxylic acid, diol or glycol, or hydroxycarboxylic acid. As used herein, "repeating unit" means an organic structure having two monomer residues linked via a carbonyloxy group. The copolymer polyesters of this disclosure contain acid residues (100 mol%) and glycol residues (100 mol%) that react in substantially equal proportions such that the total number of moles of repeating units equals 100 mol%. Therefore, the mol% shown in this disclosure may be based on the total number of moles of acid residues, the total number of moles of glycol residues, or the total number of moles of repeating units. For example, a copolymer polyester containing 30 mol% monomers, which may be dicarboxylic acids, glycols, or hydroxycarboxylic acids, based on the total number of repeating units means that the copolymer polyester contains 30 mol% monomers out of 100 mol% of total repeating units. Therefore, there are 30 moles of monomer residues for every 100 moles of repeating units. Similarly, a copolymer polyester containing 30 moles of dicarboxylic acid monomers based on total acid residues means that the polyester contains 30 moles of dicarboxylic acid monomers out of 100 moles of total acid residues. In this latter case, there are 30 moles of dicarboxylic acid monomer residues for every 100 moles of acid residues.

[0184]

[0200] As used herein, the term "polyester" encompasses both "homopolymer" and "homopolyester" and "copolymer polyester," and means a synthetic polymer prepared by polycondensation of at least one diacid component containing one or more difunctional carboxylic acids and at least one glycol component containing one or more difunctional hydroxyl compounds. As used herein, the term "copolymer polyester" is intended to mean a polyester formed from the polycondensation of at least three different monomers, for example, a dicarboxylic acid and two or more glycols, or in another example, a diol and two or more different dicarboxylic acids. Typically, the difunctional carboxylic acid is a dicarboxylic acid, and the difunctional hydroxyl compound is a dihydric alcohol such as a glycol and a diol. Alternatively, the difunctional carboxylic acid may be a hydroxycarboxylic acid such as p-hydroxybenzoic acid, and the difunctional hydroxyl compound may be an aromatic nucleus having two hydroxy substituents, such as hydroquinone. As used herein, the term "residue" means any organic structure incorporated into the polymer by a polycondensation reaction containing the corresponding monomer. The dicarboxylic acid residue may be derived from a dicarboxylic acid monomer, or a related acid halide, ester, salt, anhydride, or mixture thereof. For example, in one embodiment, the diacid component in the copolymer polyester of the present disclosure is supplied as terephthalic acid or isophthalic acid.

[0185]

[0201] Recycled polyesters and / or copolymerized polyesters may be repolymerized to copolymerized polyesters using any polycondensation reaction conditions known in the art. These may be produced by continuous, semi-continuous, and batch operating modes, and various types of reactors may be used. Examples of suitable reactor types, but not limited to, include stirred tanks, continuous stirred tanks, slurry type, tubular type, wipe film type, drop film type, or extrusion type reactors. As used herein, the term “continuous” means a process in which reactants are introduced and products are removed simultaneously in an uninterrupted manner. This process is operated profitably as a continuous process for economic reasons and is operated to produce polymers with excellent color tone, as prolonged exposure to high temperatures in the reactor can cause deterioration of the appearance of the copolymerized polyester.

[0186]

[0202] The copolymer polyesters of this disclosure are prepared by procedures known to those skilled in the art. The reaction between the diol component and the dicarboxylic acid component may be carried out using conventional copolymer polyester polymerization conditions. For example, when preparing a copolymer polyester from an esterified form of the dicarboxylic acid component by transesterification, the reaction process may include two steps. In the first step, the diol component and the dicarboxylic acid component, such as terephthalic acid, are reacted at a high temperature of about 150°C to about 250°C for about 0.5 to about 8 hours at a pressure ranging from about 0.0 kPa to about 414 kPa (60 pounds / square inch, "psig") relative to atmospheric pressure. The temperature for the transesterification reaction is in the range of about 180°C to about 230°C for about 1 hour to about 4 hours, and the pressure is in the range of about 103 kPa (15 psig) to about 276 kPa (40 psig) relative to atmospheric pressure. Subsequently, the reaction product is heated at a higher temperature and under reduced pressure to remove the diol and produce a copolymer polyester. Under these conditions, the diol readily volatilizes and is removed from the system.

[0187]

[0203] This second step, the polycondensation step, is carried out under a higher vacuum and at a temperature generally in the range of about 230°C to about 350°C, or about 250°C to about 310°C, or about 260°C to about 290°C, for about 0.1 to about 6 hours, or about 0.2 to about 2 hours, until a polymer with the desired degree of polymerization, determined by its intrinsic viscosity, is obtained. The polycondensation step may also be carried out under reduced pressure in the range of about 53 kPa (400 torr) to about 0.013 kPa (0.1 torr). Stirring conditions or appropriate conditions are used in both steps to ensure sufficient heat transfer and surface regeneration of the reaction mixture, and to ensure the removal of water, excess glycol, or alcohol, thereby promoting the reaction and polymerization. The reaction rates in both steps are increased by appropriate catalysts such as alkoxytitanium compounds, alkali metal hydroxides, and alkoxides, organic carboxylates, alkyltin compounds, and metal oxides. In particular, when using mixed monomer raw materials of acid and ester, a three-step manufacturing procedure similar to the manufacturing procedure described in U.S. Patent No. 5,290,631 may be used.

[0188]

[0204] To ensure the completion of the reaction between the diol and dicarboxylic acid components via transesterification, it is sometimes desirable to use approximately 1.05 to 2.5 moles of diol component for every 1 mole of dicarboxylic acid component, and to remove excess glycol in a subsequent step. However, those skilled in the art know that the ratio of diol component to dicarboxylic acid component is generally determined by the design of the reactor in which the reaction takes place.

[0189]

[0205] For example, in the preparation of copolymer polyesters by direct esterification from the acid form of a dicarboxylic acid component, the copolymer polyester is produced by reacting a dicarboxylic acid or a mixture of dicarboxylic acids with a glycol component or a mixture of glycol components. This reaction is carried out at a pressure of approximately 7 kPa (1 psig) to approximately 1379 kPa (200 psig), or less than 689 kPa (100 psig), to produce a low molecular weight, linear or branched copolymer polyester product with an average degree of polymerization of approximately 1.4 to approximately 10. The temperature used during the direct esterification reaction is approximately 180°C to approximately 280°C, or approximately 220°C to approximately 270°C. This low molecular weight polymer may be further polymerized by polycondensation.

[0190]

[0206] Depending on the embodiment, suitable glycols include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, p-xylene glycol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, polytetramethylene glycol, isosorbide, or mixtures thereof.

[0191]

[0207] Depending on the embodiment, copolymer polyesters containing the following diacides are suitable for use in repolymerization processes or polymerization processes for producing novel copolymer polyesters with a recyclable content: terephthalic acid, isophthalic acid, trimellitic anhydride (or trimellitic acid), naphthalenedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.

[0192]

[0208] Depending on the embodiment, copolymer polyesters containing the following glycols are suitable for use in repolymerization processes or polymerization processes for producing novel copolymer polyesters with a recyclable content: ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, p-xylene glycol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, polytetramethylene glycol, isosorbide, or mixtures thereof.

[0193]

[0209] In one embodiment, recyclable waste materials containing terephthalate polyester and / or copolymer polyester may be used in the repolymerization process. In one embodiment, terephthalate polyester or copolymer polyester prepared by any conventional method may be used in the repolymerization process. In one embodiment, suitable terephthalate polyester and / or copolymer polyesters include polyethylene terephthalate (PET), glycol-modified polyethylene terephthalate (PETG), glycol-modified polycyclohexylenedimethylene terephthalate (PCTG), acid-modified polycyclohexylenedimethylene terephthalate (PCTA), polybutylene terephthalate (PBT), polypropylene terephthalate (PPT), polytrimethylene terephthalate (PTT), polycyclohexanedimethanol terephthalate (PCT), polyethylene naphthalate (PEN), TMCD-modified polyethylene terephthalate (PETM), TMCD-modified polycyclohexylenedimethylene terephthalate (PCTM), and mixtures thereof. In one embodiment, the terephthalate polyester is polyethylene terephthalate (PET). In one embodiment, the copolymer polyester is PETG. In one embodiment, the copolymer polyester is PCT. In one embodiment, the copolymer polyester is PCTG. In one embodiment, the copolymer polyester is PCTA. In one embodiment, the copolymer polyester is PCTM. In one embodiment, the copolymer polyester is PETM.

[0194]

[0210] In one embodiment, a mixture of terephthalate polyester and copolymer polyester is repolymerized together. In one embodiment, PET and PETG are repolymerized together. In one embodiment, PET and PETM are repolymerized together. In one embodiment, PET and PCT are repolymerized together. In one embodiment, PET and PCTA are repolymerized together. In one embodiment, PET and PCTG are repolymerized together. In one embodiment, PET and PCTM are repolymerized together. In one embodiment, PET, PETG, and PETM are repolymerized together. In one embodiment, PET, PETG, and PCTM are repolymerized together. In one embodiment, PET, PETG, PCTM, and PETM are repolymerized together.

[0195]

[0211] In one embodiment, copolymer polyesters suitable for use in this disclosure are prepared from monomers such as dimethyl terephthalate (DMT), terephthalic acid (TPA), isophthalic acid (IPA), 1,4-cyclohexanedicarboxylic acid (CHDA), ethylene glycol (EG), diethylene glycol (DEG), neopentyl glycol (NPG), 1,4-cyclohexanedimethanol (CHDM), and 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD).

[0196]

[0212] One embodiment of the present disclosure relates to a process for preparing copolymer polyesters having a high concentration of recycled content, obtained by repolymerizing waste or used polyester containing terephthalic acid-containing polyester (e.g., PET) and / or copolymer polyester (e.g., PETG) with water, alcohol, or glycol, and using recycled monomers to prepare copolymer polyesters containing a high mol% of recycled monomer residues.

[0197]

[0213] One aspect of this disclosure relates to a high molecular weight copolymer polyester comprising a glycol component and a diacid component, wherein the glycol component comprises ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,4-cyclohexanedicarboxylate dimethyl, trans-1,4-cyclohexanedicarboxylate dimethyl, 1,6-hexanediol, p-xylene glycol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, polytetramethylene glycol, adipic acid, isosorbide, and mixtures thereof, and the diacid component comprises dimethyl terephthalate, terephthalic acid, isophthalic acid (IPA), trimellitic anhydride (or trimellitic acid), salts of 5-sulfoisophthalic acid (SIPA), naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and mixtures thereof. Under conditions where reversible transesterification can occur, the introduction of depolymerization aids or solvents such as water, alcohol, or excess glycol leads to depolymerization by hydrolysis, alcohol decomposition, or glycol decomposition (glycolysis), reducing the chain length (molecular weight) of the polymer. With sufficient solvent, the reaction proceeds to the point where the mixture consists mainly of monomers, glycols, and diesters of acidic components. On one hand, the glycols in the mixture include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,4-cyclohexanedicarboxylate dimethyl, trans-1,4-cyclohexanedicarboxylate dimethyl, 1,6-hexanediol, p-xylene glycol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, polytetramethylene glycol, adipic acid, isosorbide, and mixtures thereof.In one embodiment, the glycol mixture includes ethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, and mixtures thereof. These recycled monomers can then be used to prepare copolymer polyesters containing high molar percentages of recycled monomer residues.

[0198]

[0214] This invention relates to a process for utilizing recycled polyethylene terephthalate (PET) and recycled glycol-modified polyethylene terephthalate copolymer polyester (PETG), particularly post-consumer waste, in the production of linear high molecular weight copolymer polyesters. There is a growing demand for the use of large amounts of recycled materials in plastic articles. This demand for recycled content has created a need to develop novel methods and processes for incorporating existing plastic waste flows and converting them into new plastic products. Particular interest lies in the recycling of PETG waste. In recent years, attempts have been made to legislate the separation of recycled glycol-modified PET (PETG) waste from recycled polyethylene terephthalate (PET) waste with resin identification code (RIC) 1, due to problems in the treatment of these combined wastes. Furthermore, a large amount of PETG currently exists that has not been recycled, and this has the potential to be recovered and converted into new plastic products. In particular, shrink films made from PETG contain inks and other contaminants that need to be removed in the recycling process to produce high-quality transparent recycled PET (rPET). Furthermore, medical packaging materials are manufactured from a high proportion of PETG, and this material is not currently part of the recycling process. The present invention provides a process for producing copolymer polyesters useful for the manufacture of extruded and injection-molded articles such as shrinkable films, fibers, durable consumer goods, and other molded and injection-molded articles, which utilizes recycled PETG and recycled PETG combined with PET as reaction intermediates.

[0199]

[0215] Today, there is a very well-defined and large-scale mechanical recycling process in which polyethylene terephthalate (PET) articles are recovered and converted into semi-crystalline recycled PET (rPET), which is then incorporated into new plastic articles. Glycol modification of PET with other glycols such as 1,4-cyclohexanediol, diethylene glycol, butanediol, or neopentyl glycol is a very common method to increase transparency, improve toughness, and reduce the crystallinity of PET. These glycol-modified materials are generally called glycol-modified PET, or PETG. Although the chemical composition of these materials is very similar to PET, modification with glycols other than ethylene glycol produces materials that are difficult to recycle in the PET recycling process. Novel methods need to be created to recover and recycle these PETG materials.

[0200]

[0216] The process described herein uses recycled PETG as a raw material to produce various new copolymer polyester resins. In this process, recycled PETG (rPETG) is introduced as a paste together with ethylene glycol and terephthalic acid and supplied to a transesterification reactor early in the manufacturing process to produce a new copolymer polyester. During this process, the added glycol decomposes the rPETG into its original acid and glycol residues as starting materials, and new glycol and acid are added, followed by esterification and polymerization of the mixture to produce a new copolymer polyester. This process has the advantage that the resulting acid and glycol do not need to be further purified and recycled PETG can be used as a raw material. Furthermore, this process is valuable because it provides a method for using rPETG, which currently does not go through the mechanical recycling process and therefore has no choice but to be buried in waste disposal sites.

[0201]

[0217] Furthermore, rPETG (or rPCTG, or rPCTM, or rPETM, or rPCTA, or rPCTG, or rPCT) contains divalent or higher expensive monomers not present in rPET, such as CHDM, TMCD, DEG, and NPG. PETG products produced from this process have the same performance as unused PETG and can be used in exactly the same applications without sacrificing any performance by adding recycled materials. Conventionally, rPETG is mixed with unused materials to create physical blends. These blends often lose performance in terms of mechanical properties, or in terms of color and appearance, and are often unsuitable for the same applications as the unused material.

[0202]

[0218] In the synthesis of new PET for the manufacture of water and carbonated beverage bottles, it is commercially desirable to use previously used PET, particularly post-consumer PET. Several chemical processing techniques are known to facilitate the regeneration and recycling of previously used polyester materials. Such techniques can be used to depolymerize the recycled polyester material, thereby reducing the polyester material to monomer and / or oligomer components. The monomer and / or oligomer components can then be repolymerized to produce recycled polyester material.

[0203]

[0219] One known depolymerization technique involves subjecting recycled PET to methanol decomposition. Following methanol decomposition procedures, rPET is reacted with methanol to produce dimethyl terephthalate (DMT) and ethylene glycol (EG). DMT and EG can be easily purified and subsequently used in the production of PET containing recycled polyester material. However, most conventional commercial PET manufacturing facilities worldwide are designed to use either terephthalate (TPA), and while some smaller facilities use DMT, most are not designed to use both TPA and DMT as monomer raw materials. Therefore, additional processing is generally required to convert DMT to TPA, which is necessary as a raw material for many such facilities, and in either case, further purification of the glycol and DMT / TPA is required.

[0204]

[0220] Another known depolymerization technique is hydrolysis, which involves reacting recycled PET with water to depolymerize rPET into TPA and EG. However, it is generally known that removing certain contaminants present in recycled PET from TPA is extremely difficult and expensive. Furthermore, facilities designed to use DMT as a raw material require the conversion of TPA to DMT, necessitating further purification of glycol and DMT / TPA.

[0205]

[0221] Glycol decomposition may also be used for the depolymerization of recycled PET. Glycol decomposition occurs when rPET reacts with EG, thereby producing bis-(2-hydroxyethyl) terephthalate (BHET) and / or its oligomers. Glycol decomposition has significant advantages over either methanol decomposition or hydrolysis, mainly because BHET can be used as a raw material in the manufacturing process of either DMT-based or TPA-based PET without major changes to the manufacturing facility or further purification. Another important advantage offered by glycol decomposition technology is that there is no need to remove glycol from the depolymerization solvent.

[0206]

[0222] Conventional known glycol decomposition processes include the independent and complete glycol decomposition of rPET after consumption, followed by the subsequent addition of some of the glycol decomposition products to a polycondensation process. This glycol decomposition process is described in U.S. Patent No. 5,223,544. This process requires high pressure and a large excess of ethylene glycol. These requirements reduce reactor efficiency by lowering the reactor's potential production capacity.

[0207]

[0223] Typically, these glycol degradation processes have been found to require high temperatures and a large excess of EG to solubilize polyester molecules, thereby allowing them to decompose into their constituent parts, such as BHET and its oligomers. This high temperature and excess EG result in a large amount of diethylene glycol as a byproduct. Since this generated diethylene glycol cannot be easily removed from BHET, when BHET is subsequently used to produce recycled PET, the resulting PET product will have an excessive diethylene glycol content, making it an unacceptable polymer for many commercial applications.

[0208]

[0224] Other known processes, including glycol decomposition, require retaining the ends of BHET oligomers with a degree of polymerization greater than 10 in the reactor at the end of the reaction run to solubilize the consumed rPET, which is insoluble in most solvents. These procedures are described in U.S. Patent No. 4,609,680. Therefore, in the production of new packaging grades of PET, there is clearly still a need in the art for a glycol decomposition process that can efficiently handle consumed rPET used in the past.

[0209]

[0225] This disclosure provides solutions to the problems discussed above. In particular, the process of this disclosure provides an efficient and economical procedure for producing packaging-grade polyester products using recycled polyester and / or recycled copolymer polyester, including recycled PET, recycled PETG, recycled PETM, and recycled PCTM, or mixtures thereof.

[0210]

[0226] In one embodiment, the viscosity of the material in the paste area and the viscosity of the material produced in the paste area are significantly reduced by rPETG (and rPCTM or its mixture with rPET) compared to rPET alone. In one embodiment, TPA dissolves faster in rPET than in EG alone. In one embodiment, TPA can dissolve even faster in rPETG, rPETM, or rPCTM.

[0211]

[0227] In one embodiment, TPA is completely replaced with recycled polyester or copolymerized polyester.

[0228] In one embodiment, the composition of the final polyester product is controlled by a combination of recycled feed and components added to the first reaction zone.

[0212]

[0229] In one embodiment of the present disclosure, the copolymerized polyester is produced in two main steps. In the first step, the starting materials are reacted to produce monomers and / or oligomers. If the starting materials entering the first step contain acid-terminated groups such as TPA or isophthalic acid, the first step is called esterification. The esterification step may be a single step or may be divided into multiple steps. In the second step, the monomers and / or oligomers are further reacted to produce the final copolymerized polyester product. The second step is generally called the polycondensation step. The polycondensation step may be a single step or may be divided into a pre-polycondensation (or pre-polymerization) step and a final (or finishing) polycondensation step.

[0213]

[0230] Figure 1 is a flowchart of a process for producing a copolymerized polyester such as polyester or PETG according to various embodiments of the present disclosure. In this flowchart (Figure 1), the reaction areas are shown as separate vessels, typically continuous stirred tank reactors (CSTRs), but these vessels may be integrated units having multiple esterification areas with appropriate partitions and control units. Similarly, the reaction areas are shown as separate vessels, typically wipe-film or thin-film CSTRs, but these vessels may be combined into one or more integrated units having multiple polycondensation areas with appropriate partitions and control units. Various other types of esterification and polycondensation reactors and reactor configurations are known in the art and may be adapted for use according to the present disclosure.

[0214]

[0231] Referring to Figure 1, in one embodiment, a paste comprising EG and TPA in a 2:1 molar ratio with the recycled copolymer polyester and / or polyester is supplied to a location labeled as the paste tank. Additional EG may be supplied to the first reaction area or reactor 1, and other glycols such as CHDM, TMCD, NPG, and DEG may also be supplied to the first reaction area at the same location based on the target final composition of the copolymer polyester, and additional recycled materials may also be added as needed. In one embodiment, these raw materials may be added separately and / or directly into the first reaction area. Depending on the embodiment, the recycled copolymer polyester and / or polyester may be supplied to at least one of the locations of the paste tank, area #1, area #2, or finishing area.

[0215]

[0232] The reaction mixture in the first reaction area is heated through a recycle loop including a heat exchanger. Esterification occurs in the first reaction area, producing a first esterification product containing monomers, oligomers, or both of the copolymerized polyester, and unreacted TPA, EG, and other glycols such as CHDM, TMCD, NPG, or DEG. The reaction product from the first reaction area is then delivered to the second reaction area. Further esterification occurs in the second reaction area, forming a second esterification product containing additional monomers, oligomers, or both of the copolymerized polyester.

[0216]

[0233] Depending on the embodiment, the average chain length of the monomer and / or oligomer after the esterification step may be less than 25, 1 to 20, or 5 to 15.

[0234] Next, the reaction product from the second reaction area is delivered to the third reaction area. In some embodiments, polycondensation occurs in the third reaction area in the presence of a polycondensation catalyst as needed, generating a prepolymerization product containing a copolymerized polyester oligomer. In some embodiments, polycondensation occurs in the third reaction area without the need for a polycondensation catalyst, generating a prepolymerization product containing a copolymerized polyester oligomer. In some embodiments, the recycled copolymerized polyester and the catalyst residues remaining in the polyester are sufficient to act as a polycondensation catalyst. In some embodiments, the monomer from the esterification step is converted in the third reaction area to an oligomer having an average chain length in the range of 2-40, 5-35, or 10-30.

[0217]

[0235] Next, the prepolymerization product is delivered to one or more reaction or finishing areas. Further polycondensation occurs in the finishing area, if necessary, in the presence of a polycondensation catalyst, to produce a copolymerized polyester having the desired mean chain length or IV. The copolymerized polyester is then recovered from the finishing area and subjected to subsequent processing, such as being produced into pellets via an extruder connected to an underwater pelletizing machine.

[0218]

[0236] In one embodiment, the temperature inside the paste tank is 120-180°C.

[0237] In one embodiment, the temperature in the glycol decomposition and transesterification zone is 200-300°C.

[0219]

[0238] In one embodiment, the reaction step is carried out at a melting temperature of at least 253°C, at least 255°C, or at least 257°C. In another embodiment, the reaction step is further or otherwise carried out at a melting temperature of 320°C or lower, 300°C or lower, 290°C or lower, 285°C or lower, 280°C or lower, 275°C or lower, 270°C or lower, or 265°C or lower. In various embodiments, the reaction step is carried out at a melting temperature of 250 to 320°C, or 260 to 300°C.

[0220]

[0239] In one embodiment, the reaction step is performed at 25-40 psi. (173~276 kPaG) , or 30-40 psig (207~276 kPaG) It will be carried out under pressure.

[0240] In one embodiment, the esterification step is performed at at least 253°C and at least 255°C. The process is carried out at a melting temperature of ℃ or at least 257℃. In one embodiment, the esterification step is further or otherwise carried out at a melting temperature of 290℃ or lower, 285℃ or lower, 280℃ or lower, 275℃ or lower, 270℃ or lower, or 265℃ or lower. In various embodiments, the esterification step is carried out at a melting temperature of 250-270℃ or 257-265℃.

[0221]

[0241] In one embodiment, the esterification step (d) is 8-20 psig (55.2~138kPaG) It will be carried out under pressure.

[0242] In one embodiment, the esterification reaction temperature is 240-270°C, and the pressure is 5-50 psig. (34.5~345kPaG) The polycondensation reaction temperature is 240-270°C, and the pressure is 5-50 psig. (34.5~345kPaG) That is the case.

[0222]

[0243] In one embodiment, the polycondensation temperature is 255 to 275°C.

[0244] In one embodiment, the polycondensation temperature is 280 to 320°C.

[0245] In one embodiment, the average residence time of the reactants in the reaction step is 2 hours or less, 1.75 hours or less, 1.5 hours or less, 1.25 hours or less, 1 hour or less, or 0.75 hours or less. In various embodiments, the average residence time of the reactants in the reaction step is 30 to 40 minutes.

[0223]

[0246] In one embodiment, the average residence time of the reactants in the esterification step is 2 hours or less, 1.75 hours or less, 1.5 hours or less, 1.25 hours or less, 1 hour or less, or 0.75 hours or less. In various embodiments, the average residence time of the reactants in the esterification step (d) is 30 to 40 minutes.

[0224]

[0247] In various embodiments, the overall molar ratio of EG:TPA introduced into the process is in the range of 2.3:1 to 3.0:1.

[0248] In various embodiments, the overall molar ratio of EG:TPA introduced into the process is in the range of 2.3:1 to 2.71:1.

[0225]

[0249] The temperature, pressure, and average residence time of the reaction process in the first reaction area are as described above.

[0250] In various embodiments, the reaction process in the first reaction area is carried out at a melting temperature of 250-270°C and a pressure of 25-40 psi.

[0226]

[0251] In various embodiments, the reaction process in the first reaction area is carried out at a melting temperature of 257–265°C and a pressure of 30–40 psi.

[0252] The temperature, pressure, and average residence time for the esterification step in the second reaction zone may be as described above.

[0227]

[0253] In various embodiments, the esterification step in the second reaction area is carried out at a melting temperature of 250-270°C and a pressure of 8-20 psi.

[0254] In various embodiments, the esterification step in the second reaction zone is carried out at a melting temperature of 257–265°C and a pressure of 8–20 psi.

[0228]

[0255] The polycondensation catalysts useful in the processes of this disclosure are not particularly limited. Examples of such catalysts include titanium compounds, antimony compounds, and germanium compounds. Titanium catalysts are highly efficient and provide a fast polycondensation rate at low catalyst concentrations. The polycondensation catalyst may be added either during the esterification step or during the polycondensation step. In one embodiment, the catalyst is added to the first reaction area along with the feed material. In one embodiment, the catalyst is added in the range of 1 to 500 ppm based on the weight of the copolymerized polyester. In one embodiment, in the case of titanium, the catalyst may be added in the range of 1 to 50 ppm based on the weight of the copolymerized polyester.

[0229]

[0256] In one embodiment, the selection of catalyst is influenced by the catalyst derived from the recycled raw materials. The advantages of a particular catalyst are achieved through the combination of the catalyst from the raw materials and the catalyst added to the first and second reaction zones. Catalysts likely to be obtained from rPET include Sb and Li / Al. Catalysts obtained from rPETG may include Ti, Co, Ge, and Sb. Catalysts obtained from rPETM and rPCTM include Co.

[0230]

[0257] In some embodiments, phosphorus compounds are often added along with the catalyst to improve thermal stability. Useful phosphorus compounds as thermal stabilizers include phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphonic acid, and various esters and salts thereof. The esters may be alkyl, branched alkyl, substituted alkyl, difunctional alkyl, alkyl ether, aryl, and substituted aryl. In some embodiments, a suitable thermal stabilizer is Merpol A, which is triphenyl phosphate. In one embodiment, phosphorus is added in the range of 10 to 100 ppm based on the weight of the copolymerized polyester.

[0231]

[0258] In various embodiments, one or more other additives may be added to the starting material, copolymerized polyester, and / or copolymerized polyester monomer / oligomer at one or more positions in the process. Suitable additives in various embodiments include, for example, trifunctional or tetrafunctional comonomers such as trimellitic anhydride, trimethylolpropane, pyromellitic dianhydride, pentaerythritol, or other polyacids or polyols; crosslinking agents or other branching agents; colorants; toners; pigments; carbon black; glass fibers; fillers; impact modifiers; antioxidants; UV absorbing compounds; deoxygenating compounds, and the like.

[0232]

[0259] The processes described herein are particularly well suited for use on an industrial scale. For example, in one embodiment, these processes may be carried out on a commercial production line capable of operating the polymer at a rate of 500 to 30,000 pounds per hour.

[0233]

[0260] In another aspect, the disclosure relates to copolymerized polyesters produced from the processes of the disclosure.

[0261] Furthermore, according to the process described above, the new polyester product may also contain ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol diol units, the 1,4-cyclohexanedimethanol units accounting for up to approximately 25 mol% of the total diol units, and the diethylene glycol accounting for up to approximately 15 mol% of the total diol units. In this case, the 1,4-cyclohexanedimethanol units and diethylene glycol units may be directly added to a portion of the ethylene glycol component in the first reaction mixture, or they may be derived from a portion of the flaked polyethylene terephthalate or glycol-modified polyethylene terephthalate material after consumption.

[0234]

[0262] In various embodiments, the copolymerized polyester is (a) Diacid components containing 60-100 mol% terephthalic acid residues, isophthalic acid residues, or mixtures thereof; and (b) Containing a diol component comprising 0 to 96.5 mol% ethylene glycol residues and 3.5 to 100 mol% 1,4-cyclohexanedimethanol residues, Here, the diacid component is based on 100 mol% of all diacid residues in the copolymerized polyester, and the diol component is based on 100 mol% of all diol residues in the copolymerized polyester.

[0235]

[0263] In various embodiments, the copolymerized polyester is (a) Diacid components containing 90-100 mol% terephthalic acid residues; and (b) Containing a diol component comprising 50-96.5 mol% ethylene glycol residues and 3.5-50 mol% 1,4-cyclohexanedimethanol residues, Here, the diacid component is based on 100 mol% of all diacid residues in the copolymerized polyester, and the diol component is based on 100 mol% of all diol residues in the copolymerized polyester.

[0236]

[0264] In various embodiments, the copolymerized polyester is (a) Diacid components containing 90-100 mol% terephthalic acid residues; and (b) A diol component comprising 0-50 mol% ethylene glycol residues and 50-100 mol% 1,4-cyclohexanedimethanol residues, Here, the diacid component is based on 100 mol% of all diacid residues in the copolymerized polyester, and the diol component is based on 100 mol% of all diol residues in the copolymerized polyester.

[0237]

[0265] In various embodiments, the copolymerized polyester is (a) Diacid components containing 60-100 mol% terephthalic acid residues; and (b) A diol component comprising 65-85 mol% ethylene glycol residues and 25-35 mol% 1,4-cyclohexanedimethanol residues, Here, the diacid component is based on 100 mol% of all diacid residues in the copolymerized polyester, and the diol component is based on 100 mol% of all diol residues in the copolymerized polyester.

[0238]

[0266] In various embodiments, the intrinsic viscosity of the copolymerized polyester is 0.4–1.5 dL / g, 0.5–1.2 dL / g, or 0.6–0.9 dL / g.

[0267] In various other embodiments, the copolymerized polyester is (a) Diacid components comprising 100 mol% terephthalic acid residues, isophthalic acid residues, or mixtures thereof; and (b) A diol component comprising 0-96.5 mol% ethylene glycol residues, 3.5-100 mol% 1,4-cyclohexanedimethanol residues, and 0-0.4 mol% trimellitic anhydride residues, Here, the intrinsic viscosity (IV) of the copolymerized polyester is 0.4 to 1.5 dL / g. All weight percentages are based on the total weight of copolymerized polyester, and The diacid component is based on 100 mol% of all diacid residues in the copolymerized polyester, and the diol component is based on 100 mol% of all diol residues in the copolymerized polyester.

[0239]

[0268] In one embodiment, the Disclosure includes a manufactured or molded article comprising a shrink film of any embodiment of the shrink film of the Disclosure. In another embodiment, the Disclosure includes a manufactured or molded article comprising an orientation film of any embodiment of the orientation film of the Disclosure.

[0240]

[0269] In certain embodiments, the disclosure includes, but is not limited to, shrink films suitable for containers, plastic bottles, glass bottles, packaging, batteries, high-temperature filling containers, and / or industrial products or other applications. In one embodiment, the disclosure includes, but is not limited to, orientation films suitable for containers, packaging, plastic bottles, glass bottles, photographic substrates such as paper, batteries, high-temperature filling containers, and / or industrial products or other applications.

[0241]

[0270] In certain embodiments of the present disclosure, the shrink film of the present disclosure may be formed into a label or sleeve. The label or sleeve may then be affixed to a manufactured article such as the wall of a container or a battery, or onto a sheet or film.

[0242]

[0271] The orientation films or shrink films of this disclosure can be applied to molded articles such as sheets, films, tubes, and bottles, and are commonly used in a variety of packaging applications. For example, films and sheets made from polymers such as polyolefins, polystyrene, polyvinyl chloride, polyester, and polylactic acid (PLA) are frequently used in the manufacture of shrink labels for plastic beverage or food containers. For example, the shrink films of this disclosure can be used in many packaging applications, in which the shrink films applied to molded articles exhibit properties such as excellent printability, high opacity, excellent shrinkage strength, excellent texture, and high rigidity.

[0243]

[0272] The combination of improved shrinkage properties and improved toughness should provide new commercial options, including, but not limited to, shrink films suitable for containers, plastic bottles, glass bottles, packaging, batteries, high-temperature filled containers, and / or industrial products or other applications.

[0244]

[0273] Furthermore, the material of this disclosure may be extruded into a sheet, which may be further thermoformed into a three-dimensional article. The material of this disclosure may be converted into molded articles, films, shrinkable films, oriented films, blow-molded articles, and blow-film articles.

[0245]

[0274] The following embodiments further illustrate how the polyesters of the Disclosure may be manufactured and evaluated, and are intended to be purely illustrative and not to limit their scope. Unless otherwise specified, parts are parts by weight, temperatures are given in °C (Celsius) or room temperature, and pressures are atmospheric or near atmospheric.

[0246]

[0275] This disclosure includes any and all combinations of the embodiments, features, characteristics, parameters, and / or scopes described herein, and explicitly considers and discloses such combinations. That is, the subject matter of this disclosure can be defined by any combination of the embodiments, features, characteristics, parameters, and / or scopes described herein.

[0247]

[0276] Any process / method, apparatus, compound, composition, embodiment, or component of this disclosure may be modified by “contains,” “essentially consists of,” or “consists of,” or transitional phrases which are variations of those terms.

[0248]

[0277] As used herein, the indefinite articles "a" and "an" mean one or more unless explicitly indicated by the context. Similarly, the singular form of a noun includes its plural form unless explicitly indicated by the context, and vice versa.

[0249]

[0278] Although attempts have been made to increase the accuracy, the numerical values and ranges described in this specification should be considered as approximate values unless otherwise indicated in the context. These numerical values and ranges may vary from the recited numerical values depending on the desired characteristics to be obtained by the present disclosure and the variations resulting from the standard deviations found in the measurement techniques. Further, the ranges described in this specification are intended to and specifically contemplate including all sub-ranges and numerical values within the recited ranges. For example, the range of 50 to 100 is intended to include all numerical values within the range including sub-ranges such as 60 to 90, 70 to 80, etc.

[0250]

[0279] The range may be defined by any two numerical values of the same characteristic or parameter reported in the examples. Those numerical values may be rounded to the nearest thousandth, hundredth, tenth, integer, ten, hundred, or thousand for defining the range.

[0251]

[0280] The content of all documents cited in this specification, including patent documents and non-patent documents, is incorporated herein by reference in its entirety. If any incorporated subject matter conflicts with any disclosure in this specification, the disclosure in this specification shall prevail over the incorporated content.

[0252]

[0281] The present disclosure can be further illustrated by the following examples, but of course, these examples are included for illustrative purposes only and are not intended to limit the scope of the present disclosure.

Examples

[0253]

[0282] The oligomers used in these examples were prepared in batch-type testing equipment and used as is. The compositions evaluated were copolymers of terephthalic acid, ethylene glycol, 1,4-cyclohexanedimethanol, diethylene glycol, and neopentyl glycol. The concentrations of each glycol were 13 mol% for NPG, 3 mol% for 1,4-cyclohexanedimethanol, 5 mol% for diethylene glycol, with the remainder being 79 mol% ethylene glycol. Based on the weight of all glycols added, the oligomers were prepared with a molar ratio of 1.55 of all glycols to terephthalic acid.

[0254]

[0283] Each polyester sample was prepared by adding enough oligomer to produce 100 g of polyester to a 500 mL round-bottom flask. Target concentrations of titanium and antimony catalysts, along with desired concentrations of phosphorus, were added to the flask as an ethylene glycol solution. A stainless steel stirrer consisting of a 2.5-inch diameter impeller and a 1 / 4-inch diameter shaft attached to it was inserted into the flask, and then a glass polymer head was attached to the flask. The polymer head, consisting of a standard tapered 24 / 40 male connector, was connected to the reaction flask. This flask was connected to a reaction flask having side arms positioned at approximately 45° to the neck of the flask to remove volatile substances, and a glass tube section extending above the neck of the flask through which the stirring shaft passed. A Teflon® bearing tube and rubber hose were attached to the tube section through which the stirring shaft passed, and the area around the stirring shaft was vacuum-sealed. This shaft was rotated by a 1 / 8 horsepower motor connected to the shaft using a flexible "universal" joint. The sidearm was connected to a vacuum system consisting of a dry ice condenser and a vacuum pump. The pressure inside the reaction flask was controlled by flowing nitrogen into the vacuum channel. The reaction flask was heated using a molten metal bath. All reaction parameters were monitored and controlled using a distributed data acquisition and control system.

[0255]

[0284] Table 1 shows the sequence of reactions used in all cases to prepare the polyester samples included in this evaluation.

[0256]

Table 1

[0257]

[0285] Following the synthesis, each polymer was removed from the blades of the stirring shaft and ground to a small particle size sufficient to pass through a sieve with 6 mm holes in a hammer mill. All tests were carried out without further treatment of these granules.

[0258]

[0286] Table 2 below includes eight control compositions prepared with a titanium-only catalyst system and several examples of the catalyst systems of the present disclosure at various temperatures.

[0259]

Table 2

[0260]

[0287] In the data of Table 2, the average b of the control titanium-only catalyst system (25 ppm Ti; 25 ppm P) at the standard polymerization temperature (280 °C) * is shown to be about 20. However, the data of b * is improved for all catalyst systems using Ti (5 - 15 ppm) and P (5 - 50 ppm) combined with Sb (110 - 125 ppm). These results indicate that the polymers of the present invention have a lower b * i.e., lower yellowness than the control resins made with titanium alone. At the standard polymerization temperature of 280 °C, the intrinsic viscosity is equivalent, but b * is improved and lower than 20. At higher temperatures (290 °C and 300 °C), both IV and b * are improved, the intrinsic viscosity is higher, and b * is still lower than 20.

[0261]

[0288] The intrinsic viscosity of the polyester herein is measured in 60 / 40 (weight / weight) phenol / tetrachloroethane at a concentration of 0.5 g / dL at 25 °C, and the value is recorded in dL / g.

[0262]

[0289] Copolymerized polyester resin samples were prepared using the procedure described herein. In all cases, the resin samples were dried before extrusion.

[0290] Test film samples were prepared by extruding resin samples into 10 mil (250 μm) films using a 2.5-inch Davis and Standard single-screw extruder. These 10 mil films were cut and stretched to a final thickness of 50 μm using a Bruckner Karo 4-width tenter frame at a temperature 5 to 15°C higher than the glass transition temperature (Tg) of the extruded film and at a stretching ratio of approximately 5:1.

[0263]

[0291] Film samples were prepared by extruding resin samples using a widening machine and then stretching them using a commercially available widening machine (located at Marshall and Williams, a division of Parkinson Technologies). Here, the film was extruded using three layers from ABC dies, with layer B extruded from a 2.5-inch single-screw extruder and layers A and C extruded from separate 1.25-inch single-screw satellite extruders. The film was formed to a thickness of approximately 10 mil (250 μm) and then stretched to a thickness of 50 μm at a stretch ratio of 5:1. Generally, the initial thickness was 250 μm, and the final film thickness was 50 μm. The line speed was 45 fpm.

[0264]

[0292] The glycol content of the extruded film composition was measured by NMR. All NMR spectra were recorded using a JEOL Eclipse Plus 600 MHz nuclear magnetic resonance spectrometer, with chloroform-trifluoroacetic acid (70-30:vol / vol) added to the polymer for locking. The acid component of the mixed polymer used in the examples herein was 100 mol% terephthalic acid. The total mol% of the glycol component was equal to 100 mol%, and the total mol% of the acid component was equal to 100 mol%.

[0265]

[0293] The intrinsic viscosity of polyesters used herein is measured at 25°C in 60 / 40 (weight / weight) phenol / tetrachloroethane at a concentration of 0.5 g / dL, and the value is recorded in dL / g.

[0266]

[0294] In this specification, the shrinkage rate was measured by placing a 50 mm x 50 mm square film sample in water at temperatures between 65°C and 95°C in 5°C increments. The film was immersed in water for 10 seconds without restricting shrinkage in any direction, and the shrinkage (or expansion) of the film sample was measured. The shrinkage rate was calculated using the following formula.

[0267] Shrinkage rate (%) = [(50mm - length after shrinkage) / 50mm] × 100%

[0295] The shrinkage rate was measured in the direction perpendicular to the main shrinkage direction (machine direction: MD) and also in the main shrinkage direction (transverse direction: TD).

[0268]

[0296] The shrinkage force was measured in MPa units using a LabThink FST-02 heat shrinkage tester at the same temperature used to stretch the film for the examples described herein.

[0297] The tensile film properties were measured for the examples described herein using the ASTM method D882. The toughness of the film was evaluated using multiple film stretching speeds (300 mm / min and 500 mm / min).

[0269]

[0298] The glass transition temperature and the melting point of strain-induced crystals (Tg and Tm, respectively) of polyesters were measured using a Thermal Analyst Instrument TA DSC 2920 at a scanning rate of 20°C / min. Tm was measured during the first heating step of the stretched sample, and Tg was measured during the second heating step. Furthermore, the sample could be crystallized in a forced-air circulation oven at 165°C for 30 minutes and then analyzed by DSC. For all samples, the crystal melting point was typically not present during the second heating step of the DSC scanning at a heating rate of 20°C / min.

[0270]

[0299] The compatibility of materials with the recycling process is defined by procedures published by the Association of Plastic Recyclers (APR). In the case of PETG resin, the agglomeration of PET was a major issue addressed by the present invention. A laboratory process was developed to mimic this industry standard. The parameters of the experimental agglomeration test are as follows. · Combine 582 g of PET flakes with 18 g of shrink film flakes (3% film relative to the PET flakes) in their shrunk state (the film was shrunk prior to combination by immersion in water at 85 °C for 10 seconds). · Place the PET flakes + film in an aluminum dish to a depth of 1.5 inches. · Place the dish containing the flakes in a forced air circulation oven at 208 °C for 1.5 hours. · Then carefully pour out the flakes through a 0.5-inch sieve and measure the amount of flakes remaining in the dish or not passing through the sieve, and calculate the agglomeration rate (%) as a percentage of the starting weight.

[0271]

[0300] The Association of Plastic Recyclers (APR) established tests to measure whether materials are compatible with the current recycling process (important guidelines for transparent PET articles with revised or established labels and seals as of April 11, 2019; PET-CG-02). This method refers to the method for measuring the agglomeration of PET (PET flake agglomeration evaluation revised on November 16, 2018; PET-S-08). The details of this test are as follows. · Grind the label (minimum weight: 3 wt%, pre-shrunk at 85 °C for 10 seconds) and the bottle into flakes with a dimension of 1 / 4 to 1 / 2 inch to produce labeled bottle flakes. · Mix the labeled bottle flakes with unlabeled reference bottle flakes at a ratio of 50:50. · Then wet classify the sample under conditions that permit up to 1.2% of the PET to carry over with the label. · Then wash the flakes with a 0.3% Triton X-100 and 1.0% caustic alkali at 88 °C for 15 minutes. Next, the flakes are washed with water after removing all suspended particles, and then filtered to remove excess water. The thin sections are subjected to wet classification again, as in the previous attempt. Place 2 pounds (including labels) of washed flakes into a Teflon®-coated baking dish, one flake per washed sample, and add the flakes until the layer is 1.5 inches thick. Place the dish containing the slices in a circulating oven at 208°C for 1.5 hours. The thin section is cooled and then passed through a sieve with a 0.0625-inch opening. If the material passes through the sieve, it is not agglomerated, i.e., it is not too coarse to pass through the sieve. Following this test, an extrusion / pelletization and molding process was carried out to confirm the quality of the flakes.

[0272]

[0301] Modulated differential scanning calorimetry (MDSC) is a technique that measures the difference in heat flow between a sample and an inert reference as a function of time and temperature. Furthermore, it uses the same heat flux cell design as that used in conventional DSC. However, MDSC applies different heating modes (temperature states) to the sample and reference. Specifically, sinusoidal modulation (amplitude) is superimposed on the conventional linear heating or cooling gradient, creating a mode in which the average sample temperature changes continuously over time but not linearly. The net effect of applying this more complex heating mode to the sample is that it is as if two tests—one with a conventional linear (average) heating rate and another with a sinusoidal (instantaneous) heating rate—were performed simultaneously on the material. The actual speeds of these two simultaneous tests depend on three variables that can be selected by the operator. • Basic heating rate (3°C / min) • Modulation period (60 seconds) • Modulation temperature amplitude (±1°C)

[0302] The glass transition temperature and the area of ​​the melting peak were analyzed using inversion heat flow. The heat of fusion (Hf) during heating was measured as an integrated inversion heat flow signal. The heat of crystallization (Hc) during heating was integrated from the total heat flow signal. The relative crystallinity (C) of the sample was measured by subtracting the heat of fusion (Hf) from the heat of crystallization (Hc) during heating.

[0273] Examples 1-4

[0303] Copolymer polyester resins containing various glycol compositions were prepared and converted into shrinkable films using an experimental film process. The properties of the corresponding shrinkable films were then measured. The film samples were also tested for aggregation with PET flakes using an experimental aggregation test. The main performance characteristics are shown below. The films prepared in Examples 1 and 2 of the resin showed an aggregation rate of less than 1% with PET flakes. The films prepared in Examples 1, 3, and 4 of the resin exhibited excellent shrinkable film properties. Only the film prepared in Example 1 of the resin exhibited excellent shrinkable film properties and an aggregation rate of less than 1%.

[0274] [Table 3]

[0275]

[0304] Examples 5-7 Examples 5-7 of the resin were prepared, converted into shrinkable films using a commercially available width-stretching machine, and tested for suitability for PET recycling using the APR test procedure.

[0276] [Table 4]

[0277]

[0305] Examples 8-11 The resins based on Examples 8-11 were converted into shrinkable film samples, their shrinkable film properties were tested, and their aggregation with PET flakes was examined using experimental aggregation tests.

[0278] [Table 5]

[0279]

[0306] Examples 12-16 Multilayer films were fabricated using a commercially available widening machine process, and their adhesion with PET flakes was tested using experimental agglomeration tests. These films were fabricated using Example 4 as the core layer and Example 1 as the cap layer.

[0280] [Table 6]

[0281] Examples of thermoformed sheets:

[0307] Examples A, B, and C were extruded into 30 mil (750 μm) thick sheets using a 2.5-inch Davis and Standard extruder. The sheet samples were then thermoformed into a basic tray shape (dimensions: 169 mm × 136 mm × 44 mm) using an aluminum female mold designed to allow vacuum evacuation throughout the entire shape. This mold was mounted on a Hydrotrim laboratory thermoforming machine. The oven temperature and mold temperature were kept constant at 260°C and 42°C, respectively. The sheet samples were placed in the oven for various residence times, removed from the oven, immediately molded into trays, cooled, and then removed from the mold. The sheet temperature was measured using an infrared temperature sensor, which is part of the thermoforming machine, and confirmed with a portable infrared thermometer.

[0282]

[0308] The residence time was varied, starting at 15 seconds and increasing by 2 seconds each time, to determine the range of thermoforming conditions that could produce high-quality parts. By varying the residence time, the samples were heated to various temperatures before molding. The test was stopped after the residence time reached 29 seconds because Example C was very turbid and could not be considered a tray that could be used as a product. Turbidity was measured for each sample as an indicator of part quality and crystallization.

[0283]

[0309] The tray produced from Example C began to show slight turbidity after a residence time of 23 seconds. This indicates that the thermoforming range in Example C is smaller compared to Examples A and B, as Examples A and B did not show an increase in turbidity over this residence time range. The quality of the thermoformed parts is indicated by "+" for acceptable quality or "-" for poor quality. These quality ratings are based on a combination of turbidity after thermoforming and part accuracy.

[0284]

[0310] Samples of extruded sheets and thermoformed parts were evaluated for their suitability for PET recycling using an experimental agglomeration procedure. Furthermore, a preliminary crystallization process was used, as described in the APR sorting test for PET agglomeration. The results of this agglomeration test are shown below.

[0285]

[0311] Example B exhibits desirable and distinct properties, namely having a wider range of thermoforming conditions that facilitates processing, and enabling crystallization in the recycling process, thus demonstrating suitability for the PET recycling process.

[0286] [Table 7]

[0287] [Table 8]

[0288] [Table 9]

[0289] Injection molded sample:

[0312] Samples A, B, C, and Examples 1 and 3 were injection molded, and their mechanical properties were tested using standard injection molding procedures well known to those skilled in the art. The test parts were tested according to ASTM methods D638, D3763, D256, D4812, and D64. The mechanical properties of the injection-molded parts made from these reactor-grade resins are shown in Table 10.

[0290] [Table 10]

[0291]

[0313] While this disclosure has been described in detail with particular reference to its preferred embodiments, it is understood that several changes and modifications can be made within the spirit and scope of this disclosure.

[0292] Results of experimental-scale processes

[0314] General procedure: A mixture of 53.16 g PTA, 62.21 g EG, 2.97 g DEG, 11.52 g CHDM, and 18.86 g rPET was placed in a 500 mL flask equipped with a nitrogen inlet, a metal stirrer, and a short distillation column. Furthermore, 0.14 mL of Ti catalyst solution (targeting 16 ppm Ti) and 1 mL of Mn solution (targeting 45 ppm Mn) were added to the flask. The flask was placed in a Wood's metal bath preheated to 200°C. The stirring speed was set to 200 rpm at the start of the experiment. The contents of the flask were heated at 200°C for 60 minutes, and then gradually increased to 250°C over 300 minutes. The stirrer speed was then reduced to 100 rpm, and the reaction mixture was heated to 270°C over 20 minutes while gradually increasing the vacuum to 0.4 torr. The temperature was then raised to 278°C over 20 minutes, the stirring speed was reduced to 60 rpm, and the mixture was held under these conditions for 120 minutes. After this holding period, the mixture was returned to atmospheric pressure and cooled. The polymer was then removed from the flask and analyzed. In Example 1, the polymer was prepared by 100% substitution of TPA with rPET. In Example 2, the polymer was prepared by 20% substitution of TPA with rPET.

[0293]

[0315] In one aspect of this disclosure, under conditions where a moderately constant amount of rPET is supplied, the amounts of Sb and other residual catalysts and additives can be predicted as shown in Figure 3. Depending on the embodiment, Figure 3 shows the amount of antimony that needs to be added to the system to balance the amount of rPET supplied into the process. For example, if 100 ppm of Sb is to be included in the final product, 60% rPET can be supplied to the process, or if 20% rPET is supplied, 60 ppm of Sb should be added to the system.

[0294] [Table 11]

[0295]

[0316] The resins produced in both examples were similar with respect to all important performance criteria. Both materials had similar color, IV, and composition, regardless of the amount of rPET added.

[0296] Results of the test factory process

[0317] Resin samples (A1 and A2) were prepared by adding 7.3% recycled PET to a reactor containing 45.7% by weight ethylene glycol, 0.7% by weight diethylene glycol, 9.8% by weight 1,4-cyclohexanedimethanol, and 36.4% by weight terephthalic acid. A Ti catalyst was added at 30 ppm. The glycol-to-acid ratio was 3.3, with excess ethylene glycol and 1,4-cyclohexanedimethanol. The reaction mixture was heated at 250-255°C and 25-30 psig. (172~207kPaG) The mixture was held for 3 to 3.5 hours. Phosphorus was added at 21 ppm, and the reaction mixture was then heated to 270°C and stirred under vacuum until the target melt viscosity was reached.

[0297]

[0318] A control resin sample (B) was prepared using the same process, except that 50 ppm of Ti catalyst was used without adding rPET or DEG to the reaction mixture. 44.1% by weight of ethylene glycol, 10.5% by weight of 1,4-cyclohexanedimethanol, and 45.5% by weight of terephthalic acid were added to the reactor. The glycol-to-acid ratio was 2.9, and ethylene glycol and 1,4-cyclohexanedimethanol were used in excess. The excess CHDM was the same as in the sample described above, but the excess EG was reduced.

[0298]

[0319] The properties of these resins are explained in the table below.

[0299] [Table 12]

[0300]

[0320] Resin A was prepared by mixing resin examples A1 and A2. Resins A and B were dried in a 60°C dryer for 4 to 6 hours. A film with a thickness of 10 mil (250 μm) was then extruded using a 2.5-inch Davis and Standard extruder. After extrusion, the film was cut and stretched to a final thickness of 50 μm using a Bruckner Karo 4-width extruder. This film was then stretched at a ratio of 5:1, a stretching speed of 100% / second, and a stretching temperature 5 to 15°C higher than the Tg of the extruded film. The characteristics of the shrinkable film produced by this process are described in the table below.

[0301] [Table 13]

[0302]

[0321] Resins A and B were very similar in composition, IV, and color. Furthermore, the shrinkable films produced from these resins exhibited very similar performance. These results demonstrate that incorporating rPET into the resin manufacturing process does not affect the final performance of the resin or the articles produced from it.

[0303] Commercial-scale processes

[0322] The usefulness of the present invention was further demonstrated by manufacturing resin samples using commercial manufacturing equipment.

[0323] In the commercial-scale process, 5% recycled PET was added to the slurry storage tank along with terephthalic acid and ethylene glycol. The slurry storage tank was stirred for more than 30 minutes to allow for thorough mixing. This slurry was then added to reaction area 1 along with the catalyst, additional ethylene glycol, diethylene glycol, and cyclohexanediol. This mixture was reacted at 35+ psig (241 kPaG) The reaction was carried out under pressure and at over 235°C for at least 1 hour, while simultaneously depolymerizing the PET to react with the monomer. Subsequently, the monomer and oligomer from reaction area 1 were delivered to reaction area 2, where the reaction was carried out further while maintaining the reaction temperature and removing additional glycol. This material was delivered into reaction area 3, where a finishing treatment was performed under higher temperature and higher vacuum conditions. The properties of the final product, Example C, are shown in the table below in comparison with Example D, another copolymer polyester resin of the same composition produced by a commercial process without the addition of rPET.

[0304] [Table 14]

[0305]

[0324] Resins C and D were dried in a 60°C dryer for 4-6 hours. Then, a film with a thickness of 10 mil (250 μm) was extruded using a 2.5-inch Davis and Standard extruder. After extrusion, the film was cut and stretched to a final thickness of 50 μm using a Bruckner Karo 4-width extruder. This film was then stretched at a stretching speed of 100% / second and a stretching temperature 5-15°C higher than the Tg of the extruded film, in a 5:1 ratio. The characteristics of the shrinkable film produced by this process are described in the table below.

[0306] [Table 15]

[0307]

[0325] Resins C and D were very similar in composition, IV, and color. Shrink films made from these resins also exhibited very similar performance. These results demonstrate that incorporating rPET into the resin manufacturing process does not affect the final performance of the resin or the articles manufactured from it.

[0308]

[0326] While this disclosure has been described in detail with particular reference to its specific embodiments, modifications and alterations may be made within the spirit and scope of this disclosure. The embodiments are described below. Appearance 1 A process for producing a polyester composition from recycled polyester, (a) A step of introducing terephthalic acid (TPA) and ethylene glycol (EG) and recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG into a paste tank, and stirring and heating at a maximum temperature of 150°C to produce a slurry; (b) A step of delivering the slurry from the paste tank to the first reaction area; (c) In the first reaction area, in the presence of an esterification catalyst comprising a stabilizer optionally comprising a titanium compound, an antimony compound, and / or a phosphorus compound, at least one additional glycol comprising 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG), and optionally adding additional terephthalic acid (TPA) and ethylene glycol (EG) such that the molar ratio of total glycol to TPA is 1:1 to 4:1; (d) A step of reacting the TPA and EG and the recycled polyester in the first reaction area with the at least one additional glycol at a melting temperature of at least 200°C to produce a first esterification product comprising an oligomer and unreacted TPA, EG, and the additional glycol; (e) A step of delivering the first esterification product to the second reaction area; (f) In the second reaction area, the first esterification product and optionally additional glycols are further reacted at a melting temperature of at least 200°C in the presence of an esterification catalyst which optionally includes a stabilizer containing a titanium compound, an antimony compound, and / or a phosphorus compound, to produce a second esterification product containing a polyester oligomer; (g) A step of delivering the second esterification product to a third reaction area; and (h) A process comprising the step of polycondensing the second esterification product in the third reaction area in the presence of a polycondensation catalyst which optionally includes a titanium compound and an antimony compound and / or a phosphorus compound as stabilizers, to produce a polymerization product which includes a polyester. Appearance 2 A process for producing a polyester composition from recycled polyester, (a) A step of introducing terephthalic acid (TPA) and ethylene glycol (EG) and recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG into a paste tank, and stirring and heating at a maximum temperature of 150°C to produce a slurry; (b) A step of delivering the slurry from the paste tank to the first reaction area; (c) In the first reaction area, in the presence of an esterification catalyst containing a stabilizer which optionally includes a titanium compound, an antimony compound, and / or a phosphorus compound, at least one additional glycol including 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG), and optionally adding additional terephthalic acid (TPA) and ethylene glycol (EG) such that the molar ratio of total glycol to TPA is 1:1 to 4:1; (d) A step of reacting the TPA and EG and recycled polyester with the at least one additional glycol in the first reaction area at a melting temperature of at least 200°C to produce an oligomer and an esterification product comprising unreacted TPA, EG, and the additional glycol; (e) If necessary, the step of delivering the product from the first reaction area to the second reaction area; (f) If necessary, the second reaction area contains a stabilizer comprising, if necessary, a titanium compound and an antimony compound, and / or a phosphorus compound, to the product of the first area. A step of further reacting with additional glycol, optionally added in the presence of an esterification catalyst, at a melting temperature of at least 200°C to produce a second esterification product containing a polyester oligomer; (g) A step of delivering the esterification product from one or more reaction areas to a third reaction area; and (h) A process comprising the step of further reacting the product delivered from the first reaction area (or optionally the second reaction area) to the third reaction area in the presence of a polycondensation catalyst containing a stabilizer, optionally a titanium compound and an antimony compound and / or a phosphorus compound, to produce a polymerization product containing a polyester. Appearance 3 A process for producing a polyester composition from recycled polyester, (a) A step of introducing terephthalic acid (TPA) or its ester and ethylene glycol (EG) and recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG into a paste tank, and stirring and heating at a maximum temperature of 150°C to produce a slurry; (b) A step of delivering the slurry from the paste tank to the first reaction area; (c) In the first reaction area, in the presence of an esterification catalyst containing a titanium compound and an antimony compound, and / or a stabilizer containing a phosphorus compound, at least one additional glycol including 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG), and optionally adding recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, and optionally adding additional terephthalic acid (TPA) and ethylene glycol (EG) so that the molar ratio of total glycol to TPA is 1:1 to 4:1; (d) A step of reacting the TPA and EG and the recycled polyester in the first reaction area with the at least one additional glycol at a melting temperature of at least 200°C to produce a first esterification product comprising an oligomer and unreacted TPA, EG, and the additional glycol; (e) A step of delivering the first esterification product to the second reaction area; (f) In the second reaction area, additional glycols containing one or more of CHDM, NPG, or DEG as needed, and / or additional recycled polyesters containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG as needed, and further reacting the first esterification product at a melting temperature of at least 200°C in the presence of an esterification catalyst containing a stabilizer containing a titanium compound, an antimony compound, and / or a phosphorus compound as needed, to produce a second esterification product containing a polyester oligomer; (g) A step of delivering the second esterification product to a third reaction area; and (h) A process comprising the step of polycondensing the second esterification product in the third reaction area in the presence of a polycondensation catalyst which optionally includes a titanium compound and an antimony compound and / or a phosphorus compound as stabilizers, to produce a polymerization product which includes a polyester. Pattern 4 A process for producing a polyester composition from recycled polyester, (a) A step of introducing terephthalic acid (TPA) and ethylene glycol (EG) and recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG into a paste tank, and stirring and heating at a maximum temperature of 150°C to produce a slurry; (b) A step of delivering the slurry from the paste tank to the first reaction area; (c) In the first reaction area, in the presence of an esterification catalyst which optionally includes a titanium compound and an antimony compound and / or a phosphorus compound as stabilizers, 1,4-cycline A step of introducing at least one additional glycol, including hexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG), and optionally adding a recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, and optionally adding additional terephthalic acid (TPA) and ethylene glycol (EG) so that the total glycol:TPA molar ratio is 1:1 to 4:1; (d) A step of reacting the TPA and EG and the recycled polyester in the first reaction area with the at least one additional glycol at a melting temperature of at least 200°C to produce a first esterification product comprising an oligomer and unreacted TPA, EG, and the additional glycol; (e) A step of delivering the first esterification product to the second reaction area; (f) In the second reaction area, additional glycols containing one or more of CHDM, NPG, or DEG as needed, and / or additional recycled polyesters containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG as needed, and further reacting the first esterification product at a melting temperature of at least 200°C in the presence of an esterification catalyst containing a stabilizer containing a titanium compound, an antimony compound, and / or a phosphorus compound as needed, to produce a second esterification product containing a polyester oligomer; (g) A step of delivering the second esterification product to a third reaction area; and (h) A process comprising adding, if necessary, an additional recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG in the third reaction area, and polycondensing the second esterification product in the presence of a polycondensation catalyst containing a stabilizer containing a titanium compound and an antimony compound and / or a phosphorus compound to produce a polymerization product containing a polyester. Appearance 5 A process for producing a polyester composition from recycled polyester, (a) A step of introducing terephthalic acid (TPA) and ethylene glycol (EG) into a paste tank and stirring and heating at a maximum temperature of 150°C to produce a slurry; (b) A step of delivering the slurry from the paste tank to the first reaction area; (c) In the first reaction area, in the presence of an esterification catalyst containing a stabilizer which optionally includes a titanium compound, an antimony compound, and / or a phosphorus compound, at least one additional glycol including 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG); adding a recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG; and adding additional terephthalic acid (TPA) and ethylene glycol (EG) as necessary so that the molar ratio of total glycol to TPA is 1:1 to 4:1; (d) A step of reacting the TPA and EG and the recycled polyester in the first reaction area with the at least one additional glycol at a melting temperature of at least 200°C to produce a first esterification product comprising an oligomer and unreacted TPA, EG, and the additional glycol; (e) A step of delivering the first esterification product to the second reaction area; (f) In the second reaction area, additional glycols containing one or more of CHDM, NPG, or DEG as needed, and / or additional recycled polyesters containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, recycled PCTG, recycled PCTM, or recycled PETM are added, and the first esterification product is further reacted at a melting temperature of at least 200°C in the presence of an esterification catalyst containing a stabilizer containing a titanium compound and an antimony compound and / or a phosphorus compound as needed, to produce a second esterification product containing a polyester oligomer. The process of doing so; (g) A step of delivering the second esterification product to a third reaction area; and (h) A process comprising adding, if necessary, an additional recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, recycled PCTG, recycled PCTM, or recycled PETM in the third reaction area, and polycondensing the second esterification product in the presence of a polycondensation catalyst containing a stabilizer containing a titanium compound and an antimony compound and / or a phosphorus compound to produce a polymerization product containing a polyester. Appearance 6 A process for producing a polyester composition from recycled polyester, (a) A step of introducing terephthalic acid (TPA) and ethylene glycol (EG) and recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG into a paste tank, and stirring and heating at a maximum temperature of 150°C to produce a slurry; (b) A step of delivering the slurry from the paste tank to the first reaction area; (c) In the first reaction area, at least one additional glycol, including 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG), is introduced in the presence of an esterification catalyst containing a stabilizer, optionally including a titanium compound, an antimony compound, and / or a phosphorus compound; a recycled polyester, including one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, is added; and additional terephthalic acid (TPA) and ethylene glycol (EG) are added, optionally, so that the molar ratio of total glycol to TPA is 1:1 to 4:1; (d) A step of reacting the TPA and EG and the recycled polyester in the first reaction area with the at least one additional glycol at a melting temperature of at least 200°C to produce a first esterification product comprising an oligomer and unreacted TPA, EG, and the additional glycol; (e) A step of delivering the first esterification product to the second reaction area; (f) Adding an additional glycol containing one or more of CHDM, NPG, or DEG and / or an additional recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG in the second reaction area, and further reacting the first esterification product at a melting temperature of at least 200°C in the presence of an esterification catalyst which optionally contains a titanium compound, an antimony compound, and / or a phosphorus compound as a stabilizer, to produce a second esterification product containing a polyester oligomer; (g) A step of delivering the second esterification product to a third reaction area; and (h) A process comprising adding, if necessary, an additional recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG in the third reaction area, and polycondensing the second esterification product in the presence of a polycondensation catalyst containing a stabilizer containing a titanium compound and an antimony compound and / or a phosphorus compound to produce a polymerization product containing a polyester. Appearance 7 A process for producing a polyester composition from recycled polyester, (a) A step of introducing terephthalic acid (TPA) and ethylene glycol (EG) and recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG into a paste tank, and stirring and heating at a maximum temperature of 150°C to produce a slurry; (b) A step of delivering the slurry from the paste tank to the first reaction area; (c) Within the first reaction area, a titanium compound and an antimony compound, if necessary The process involves introducing at least one additional glycol, including 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG), in the presence of an esterification catalyst containing a stabilizer including a phosphorus compound, adding additional recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG as needed, and adding terephthalic acid (TPA) and ethylene glycol (EG) as needed so that the total glycol:TPA molar ratio is 1:1 to 4:1; (d) A step of reacting the TPA and EG and the recycled polyester in the first reaction area with the at least one additional glycol at a melting temperature of at least 200°C to produce a first esterification product comprising an oligomer and unreacted TPA, EG, and the additional glycol; (e) A step of delivering the first esterification product to the second reaction area; (f) In the second reaction area, additional glycols containing one or more of CHDM, NPG, or DEG as needed, and / or additional recycled polyesters containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG as needed, and further reacting the first esterification product at a melting temperature of at least 200°C in the presence of an esterification catalyst containing a stabilizer containing a titanium compound, an antimony compound, and / or a phosphorus compound as needed, to produce a second esterification product containing a polyester oligomer; (g) A step of delivering the second esterification product to a third reaction area; and (h) A process comprising adding an additional recycled polyester, comprising one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, in the third reaction area, and polycondensing the second esterification product in the presence of a polycondensation catalyst comprising a stabilizer, optionally a titanium compound and an antimony compound and / or a phosphorus compound, to produce a polymerization product comprising polyester. Appearance 8 A process for producing a polyester composition from recycled polyester, (a) A step of introducing terephthalic acid (TPA) and ethylene glycol (EG) and recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG into a paste tank, and stirring and heating at a maximum temperature of 150°C to produce a slurry; (b) A step of delivering the slurry from the paste tank to the first reaction area; (c) In the first reaction area, in the presence of an esterification catalyst containing a stabilizer which optionally includes a titanium compound, an antimony compound, and / or a phosphorus compound, at least one additional glycol including 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG); additional recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG; and optionally terephthalic acid (TPA) and ethylene glycol (EG) such that the molar ratio of total glycol to TPA is 1:1 to 4:1; (d) A step of reacting the TPA and EG and the recycled polyester in the first reaction area with the at least one additional glycol at a melting temperature of at least 200°C to produce a first esterification product comprising an oligomer and unreacted TPA, EG, and the additional glycol; (e) A step of delivering the first esterification product to the second reaction area; (f) In the second reaction area, additional glycols containing one or more of CHDM, NPG, or DEG and / or additional recycled polyesters containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG are added, and the reaction is carried out at at least 200°C in the presence of an esterification catalyst containing, if necessary, a stabilizer containing a titanium compound and an antimony compound and / or a phosphorus compound. A step of further reacting the first esterification product at the melting temperature to produce a second esterification product containing a polyester oligomer; (g) A step of delivering the second esterification product to a third reaction area; and (h) A process comprising adding an additional recycled polyester, comprising one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, in the third reaction area, and polycondensing the second esterification product in the presence of a polycondensation catalyst comprising a stabilizer, optionally a titanium compound and an antimony compound and / or a phosphorus compound, to produce a polymerization product comprising polyester. Appearance 9 The process according to any one of embodiments 1 to 8, wherein the esterification catalyst or polycondensation catalyst comprises 2 to 15 ppm of a titanium compound, 50 to 150 ppm of an antimony compound, and 0 to 90 ppm of a phosphorus-based stabilizer. Appearance 10 The process according to any one of embodiments 1 to 8, wherein the temperature of the esterification reaction is 240 to 270°C and the pressure is 5 to 50 psig, and the temperature of the polycondensation reaction is 240 to 270°C and the pressure is 5 to 50 psig. Appearance 11 The process according to any one of embodiments 1 to 8, wherein the polycondensation temperature is 255 to 275°C or 280 to 320°C. Appearance 12 The titanium compound is selected from titanium tetraalkoxides such as titanium tetraisopropoxide, titanium tetraethoxide, or titanium tetrabutoxide, or tetraalkyl titanates such as tetraisopropyl titanate, and mixtures thereof, or The antimony compound is antimony trioxide, antimony acetate, or antimony oxalate, or The process according to any one of embodiments 1 to 11, wherein the phosphorus-containing compound is a phosphate ester or phosphoric acid alcohol such as trialkyl phosphate, triphenyl phosphate, or trisnonylphenyl phosphite, or phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphonic acid, and various esters and salts thereof. Appearance 13 The process according to any one of embodiments 1 to 12, further comprising the step of dissolving the antimony compound in one of the glycols. Appearance 14 The process according to any one of embodiments 1 to 13, wherein the titanium compound and the antimony compound are added together, and the phosphorus compound is added as a separate feed. Appearance 15 The process according to any one of embodiments 1 to 14, wherein the titanium compound is dissolved in one of the glycols or in butanol. Appearance 16 A shrinkable film containing polyester, manufactured by the process described in Embodiment 1. Appearance 17 A molded article, a voided film, a thermoformable article, an extruded film or sheet, a blow-molded film, or an extruded blow-molded article, comprising polyester produced by the process described in Embodiment 1. Appearance 18 A method for introducing or forming a recyclable content in polyester produced by the process described in Embodiment 1, (a) A step of obtaining an allocation or limit for a recyclable monomer for at least one recyclable monomer, including TPA, EG, DMT, CHDM, NPG, or DEG; (b) A step of producing polyester by converting the recycled monomer within the synthesis process; (c) a step of designating at least a portion of the polyester as corresponding to at least a portion of the allocation or limit of the recycled monomer; and (d) A method comprising the step of marketing or selling the polyester, which, if necessary, contains or is obtained using the specified amount of recycled monomer. Appearance 19 The process according to any one of embodiments 1 to 18, wherein the amount of recycled polyester added to the process is 5 to 100% based on the required amount of TPA. Appearance 20 The process according to any one of embodiments 1 to 18, further comprising the step of adding a catalyst or additive via the addition of the recycled polyester, wherein the catalyst or additive is a component of the recycled polyester such as Sb, Ti, Co, Mn, Li, Al, or P.

Claims

1. A process for producing a polyester composition from recycled polyester, (a) A step of introducing terephthalic acid (TPA) and ethylene glycol (EG) and recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG into a paste tank and stirring and heating at a maximum temperature of 150°C to produce a slurry; (b) A step of delivering the slurry from the paste tank to the first reaction area; (c) In the first reaction area, in the presence of an esterification catalyst which optionally includes a stabilizer comprising a titanium compound, an antimony compound, and / or a phosphorus compound, at least one additional glycol including 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG), and optionally adding additional terephthalic acid (TPA) and ethylene glycol (EG) such that the molar ratio of total glycol to TPA is 1:1 to 4:1; (d) A step of reacting the TPA and EG and the recycled polyester in the first reaction area with the at least one additional glycol at a melting temperature of at least 200°C to produce a first esterification product comprising an oligomer and unreacted TPA, EG, and the additional glycol; (e) A step of delivering the first esterification product to the second reaction area; (f) A step of further reacting the first esterification product and optionally additional glycol in the second reaction area at a melting temperature of at least 200°C, optionally in the presence of an esterification catalyst which includes a stabilizer comprising a titanium compound, an antimony compound, and / or a phosphorus compound, to produce a second esterification product comprising a polyester oligomer; (g) A step of delivering the second esterification product to a third reaction area; and (h) A process comprising the step of polycondensing the second esterification product in the third reaction area, optionally in the presence of a polycondensation catalyst comprising a stabilizer including a titanium compound and an antimony compound and / or a phosphorus compound, to produce a polymerization product including a polyester.

2. A process for producing a polyester composition from recycled polyester, (a) A step of introducing terephthalic acid (TPA) and ethylene glycol (EG) and recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG into a paste tank and stirring and heating at a maximum temperature of 150°C to produce a slurry; (b) A step of delivering the slurry from the paste tank to the first reaction area; (c) In the first reaction area, in the presence of an esterification catalyst which optionally includes a stabilizer comprising a titanium compound, an antimony compound, and / or a phosphorus compound, at least one additional glycol including 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG), and optionally adding additional terephthalic acid (TPA) and ethylene glycol (EG) such that the molar ratio of total glycol to TPA is 1:1 to 4:1; (d) A step of reacting the TPA and EG and recycled polyester with the at least one additional glycol in the first reaction area at a melting temperature of at least 200°C to produce an oligomer and an esterification product comprising unreacted TPA, EG, and the additional glycol; (e) If necessary, the step of delivering the product from the first reaction area to the second reaction area; (f) If necessary, in the second reaction area, the product of the first area is further reacted with additional glycols, if necessary, in the presence of an esterification catalyst which optionally includes a stabilizer comprising a titanium compound, an antimony compound, and / or a phosphorus compound, at a melting temperature of at least 200°C to produce a second esterified product comprising a polyester oligomer; (g) A step of delivering the esterification product from one or more reaction areas to a third reaction area; and (h) A process comprising the step of further reacting the product delivered from the first reaction area (or optionally the second reaction area) to the third reaction area, optionally in the presence of a polycondensation catalyst comprising a stabilizer including a titanium compound and an antimony compound and / or a phosphorus compound, to produce a polymerization product including a polyester.

3. A process for producing a polyester composition from recycled polyester, (a) A step of introducing terephthalic acid (TPA) or its ester and ethylene glycol (EG) and recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG into a paste tank and stirring and heating at a maximum temperature of 150°C to produce a slurry; (b) A step of delivering the slurry from the paste tank to the first reaction area; (c) In the first reaction area, in the presence of an esterification catalyst which optionally includes a stabilizer comprising a titanium compound, an antimony compound, and / or a phosphorus compound, at least one additional glycol comprising 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG); and optionally adding recycled polyester comprising one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG; and optionally adding additional terephthalic acid (TPA) and ethylene glycol (EG) such that the molar ratio of total glycol to TPA is 1:1 to 4:1; (d) A step of reacting the TPA and EG and the recycled polyester in the first reaction area with the at least one additional glycol at a melting temperature of at least 200°C to produce a first esterification product comprising an oligomer and unreacted TPA, EG, and the additional glycol; (e) A step of delivering the first esterification product to the second reaction area; (f) In the second reaction area, additional glycols, which optionally include one or more of CHDM, NPG, or DEG, and / or additional recycled polyesters, which optionally include one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, are added, and the first esterification product is further reacted at a melting temperature of at least 200°C in the presence of an esterification catalyst, which optionally includes a stabilizer containing a titanium compound, an antimony compound, and / or a phosphorus compound, to produce a second esterification product containing a polyester oligomer; (g) A step of delivering the second esterification product to a third reaction area; and (h) A process comprising the step of polycondensing the second esterification product in the third reaction area, optionally in the presence of a polycondensation catalyst comprising a stabilizer including a titanium compound and an antimony compound and / or a phosphorus compound, to produce a polymerization product including a polyester.

4. A process for producing a polyester composition from recycled polyester, (a) A step of introducing terephthalic acid (TPA) and ethylene glycol (EG) and recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG into a paste tank and stirring and heating at a maximum temperature of 150°C to produce a slurry; (b) A step of delivering the slurry from the paste tank to the first reaction area; (c) In the first reaction area, in the presence of an esterification catalyst which optionally includes a stabilizer comprising a titanium compound, an antimony compound, and / or a phosphorus compound, at least one additional glycol comprising 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG); and optionally adding recycled polyester comprising one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG; and optionally adding additional terephthalic acid (TPA) and ethylene glycol (EG) such that the molar ratio of total glycol to TPA is 1:1 to 4:1; (d) A step of reacting the TPA and EG and the recycled polyester in the first reaction area with the at least one additional glycol at a melting temperature of at least 200°C to produce a first esterification product comprising an oligomer and unreacted TPA, EG, and the additional glycol; (e) A step of delivering the first esterification product to the second reaction area; (f) In the second reaction area, additional glycols, which optionally include one or more of CHDM, NPG, or DEG, and / or additional recycled polyesters, which optionally include one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, are added, and the first esterification product is further reacted at a melting temperature of at least 200°C in the presence of an esterification catalyst, which optionally includes a stabilizer containing a titanium compound, an antimony compound, and / or a phosphorus compound, to produce a second esterification product containing a polyester oligomer; (g) A step of delivering the second esterification product to a third reaction area; and (h) A process comprising the step of adding, if necessary, an additional recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG in the third reaction area, and polycondensing the second esterification product in the presence of a polycondensation catalyst which contains a stabilizer comprising a titanium compound and an antimony compound and / or a phosphorus compound, to produce a polymerization product containing polyester.

5. A process for producing a polyester composition from recycled polyester, (a) A step of introducing terephthalic acid (TPA) and ethylene glycol (EG) into a paste tank and stirring and heating at a maximum temperature of 150°C to produce a slurry; (b) A step of delivering the slurry from the paste tank to the first reaction area; (c) In the first reaction area, in the presence of an esterification catalyst which optionally includes a stabilizer comprising a titanium compound, an antimony compound, and / or a phosphorus compound, at least one additional glycol comprising 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG); adding recycled polyester comprising one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG; and optionally adding additional terephthalic acid (TPA) and ethylene glycol (EG) such that the molar ratio of total glycol to TPA is 1:1 to 4:1; (d) A step of reacting the TPA and EG and the recycled polyester in the first reaction area with the at least one additional glycol at a melting temperature of at least 200°C to produce a first esterification product comprising an oligomer and unreacted TPA, EG, and the additional glycol; (e) A step of delivering the first esterification product to the second reaction area; (f) In the second reaction area, additional glycols, which optionally include one or more of CHDM, NPG, or DEG, and / or additional recycled polyesters, which optionally include one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, recycled PCTG, recycled PCTM, or recycled PETM, and further reacting the first esterification product at a melting temperature of at least 200°C in the presence of an esterification catalyst, which optionally includes a stabilizer containing a titanium compound and an antimony compound and / or a phosphorus compound, to produce a second esterification product containing a polyester oligomer; (g) A step of delivering the second esterification product to a third reaction area; and (h) A process comprising the step of adding, if necessary, an additional recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, recycled PCTG, recycled PCTM, or recycled PETM in the third reaction area, and polycondensing the second esterification product in the presence of a polycondensation catalyst which contains a stabilizer comprising a titanium compound and an antimony compound and / or a phosphorus compound, to produce a polymerization product containing polyester.

6. A process for producing a polyester composition from recycled polyester, (a) A step of introducing terephthalic acid (TPA) and ethylene glycol (EG) and recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG into a paste tank and stirring and heating at a maximum temperature of 150°C to produce a slurry; (b) A step of delivering the slurry from the paste tank to the first reaction area; (c) In the first reaction area, in the presence of an esterification catalyst which optionally includes a stabilizer comprising a titanium compound, an antimony compound, and / or a phosphorus compound, an esterification catalyst comprising at least one additional glycol including 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG); adding recycled polyester comprising one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG; and optionally adding additional terephthalic acid (TPA) and ethylene glycol (EG) such that the molar ratio of total glycol to TPA is 1:1 to 4:1; (d) A step of reacting the TPA and EG and the recycled polyester in the first reaction area with the at least one additional glycol at a melting temperature of at least 200°C to produce a first esterification product comprising an oligomer and unreacted TPA, EG, and the additional glycol; (e) A step of delivering the first esterification product to the second reaction area; (f) Adding an additional glycol containing one or more of CHDM, NPG, or DEG and / or an additional recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG in the second reaction area, and further reacting the first esterification product at a melting temperature of at least 200°C in the presence of an esterification catalyst which optionally contains a stabilizer comprising a titanium compound, an antimony compound, and / or a phosphorus compound, to produce a second esterification product containing a polyester oligomer; (g) A step of delivering the second esterification product to a third reaction area; and (h) A process comprising adding, if necessary, an additional recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG in the third reaction area, and polycondensing the second esterification product in the presence of a polycondensation catalyst which contains a stabilizer comprising a titanium compound and an antimony compound and / or a phosphorus compound, to produce a polymerization product containing polyester.

7. A process for producing a polyester composition from recycled polyester, (a) A step of introducing terephthalic acid (TPA) and ethylene glycol (EG) and recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG into a paste tank and stirring and heating at a maximum temperature of 150°C to produce a slurry; (b) A step of delivering the slurry from the paste tank to the first reaction area; (c) In the first reaction area, in the presence of an esterification catalyst which optionally includes a stabilizer comprising a titanium compound, an antimony compound, and / or a phosphorus compound, at least one additional glycol comprising 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG); optionally adding additional recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG; and optionally adding terephthalic acid (TPA) and ethylene glycol (EG) such that the molar ratio of total glycol to TPA is 1:1 to 4:1; (d) A step of reacting the TPA and EG and the recycled polyester in the first reaction area with the at least one additional glycol at a melting temperature of at least 200°C to produce a first esterification product comprising an oligomer and unreacted TPA, EG, and the additional glycol; (e) A step of delivering the first esterification product to the second reaction area; (f) In the second reaction area, additional glycols, which optionally include one or more of CHDM, NPG, or DEG, and / or additional recycled polyesters, which optionally include one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, are added, and the first esterification product is further reacted at a melting temperature of at least 200°C in the presence of an esterification catalyst, which optionally includes a stabilizer containing a titanium compound, an antimony compound, and / or a phosphorus compound, to produce a second esterification product containing a polyester oligomer; (g) A step of delivering the second esterification product to a third reaction area; and (h) A process comprising adding an additional recycled polyester containing one or more recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG in the third reaction area, and polycondensing the second esterification product in the presence of a polycondensation catalyst which optionally contains a stabilizer comprising a titanium compound and an antimony compound and / or a phosphorus compound, to produce a polymerization product containing a polyester.

8. A process for producing a polyester composition from recycled polyester, (a) A step of introducing terephthalic acid (TPA) and ethylene glycol (EG) and recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG into a paste tank and stirring and heating at a maximum temperature of 150°C to produce a slurry; (b) A step of delivering the slurry from the paste tank to the first reaction area; (c) In the first reaction area, in the presence of an esterification catalyst which optionally includes a stabilizer comprising a titanium compound, an antimony compound, and / or a phosphorus compound, at least one additional glycol comprising 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG); additional recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG; and optionally adding terephthalic acid (TPA) and ethylene glycol (EG) such that the molar ratio of total glycol to TPA is 1:1 to 4:1; (d) A step of reacting the TPA and EG and the recycled polyester in the first reaction area with the at least one additional glycol at a melting temperature of at least 200°C to produce a first esterification product comprising an oligomer and unreacted TPA, EG, and the additional glycol; (e) A step of delivering the first esterification product to the second reaction area; (f) Adding an additional glycol containing one or more of CHDM, NPG, or DEG and / or an additional recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG in the second reaction area, and further reacting the first esterification product at a melting temperature of at least 200°C in the presence of an esterification catalyst which optionally contains a stabilizer comprising a titanium compound, an antimony compound, and / or a phosphorus compound, to produce a second esterification product containing a polyester oligomer; (g) A step of delivering the second esterification product to a third reaction area; and (h) A process comprising adding an additional recycled polyester containing one or more recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG in the third reaction area, and polycondensing the second esterification product in the presence of a polycondensation catalyst which optionally contains a stabilizer comprising a titanium compound and an antimony compound and / or a phosphorus compound, to produce a polymerization product containing a polyester.

9. The process according to any one of claims 1 to 8, wherein the esterification catalyst or polycondensation catalyst comprises 2 to 15 ppm of a titanium compound, 50 to 150 ppm of an antimony compound, and 0 to 90 ppm of a phosphorus-based stabilizer.

10. The process according to any one of claims 1 to 8, wherein the temperature of the esterification reaction is 240 to 270°C and the pressure is 5 to 50 psig (34.5 to 345 kPaG), and the temperature of the polycondensation reaction is 240 to 270°C and the pressure is 5 to 50 psig (34.5 to 345 kPaG).

11. The process according to any one of claims 1 to 8, wherein the polycondensation temperature is 255 to 275°C or 280 to 320°C.

12. The titanium compound is selected from titanium tetraalkoxide, or tetraalkyl titanate, and mixtures thereof, or The antimony compound is antimony trioxide, antimony acetate, or antimony oxalate, or The process according to any one of claims 1 to 11, wherein the phosphorus-containing compound is a phosphate ester or a phosphate alcohol, or phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphonic acid, and various esters and salts thereof.

13. The process according to any one of claims 1 to 12, further comprising the step of dissolving the antimony compound in one of the glycols.

14. The process according to any one of claims 1 to 13, wherein the titanium compound and the antimony compound are added together, and the phosphorus compound is added as a separate feed.

15. The process according to any one of claims 1 to 14, wherein the titanium compound is dissolved in one of the glycols or in butanol.

16. A shrinkable film containing polyester, manufactured by the process described in claim 1.

17. A molded article, a voided film, a thermoformable article, an extruded film or sheet, a blow-molded film, or an extruded blow-molded article, comprising polyester produced by the process described in claim 1.

18. A method for introducing or forming a recyclable content in polyester produced by the process described in claim 1, (a) A step of obtaining an allocation or limit for a recyclable monomer for at least one recyclable monomer, including TPA, EG, DMT, CHDM, NPG, or DEG; (b) A step of producing polyester by converting the recycled monomer in the synthesis process; (c) The step of designating at least a portion of the polyester as corresponding to at least a portion of the allocation or limit of the recycled monomer; and (d) A method comprising the step of marketing or selling the polyester, which, if necessary, contains or is obtained using the specified amount of the recycled monomer.

19. The process according to any one of claims 1 to 15, wherein the amount of recycled polyester added to the process is 5 to 100% based on the required amount of TPA.

20. The process according to any one of claims 1 to 15, further comprising the step of adding a catalyst or additive via the addition of the recycled polyester, wherein the catalyst or additive comprises Sb, Ti, Co, Mn, Li, Al, or P.

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