Copolyester made from recycled copolyester

Abstract

A process for producing a polyester composition from recycled polyester.

Description

[Technical field]

[0001]

[0001] This disclosure relates generally to the field of polymer chemistry, and more particularly to a process for producing copolyesters from recycled polyesters and copolyesters. [Background technology]

[0002] Polyesters are often considered the most purchased and most widely used class of polymers in the world, with published global production (including recycling) recently reported to be well over 75 million tons. This level of commercial success is believed to be due in part to polyester's attractive combination of relative cost, manufacturability, and competitive performance attributes. The physical, chemical, and thermal properties of polyesters make them useful and desirable for a wide variety of end uses. Polyethylene terephthalate (PET) is one of the most popular types of polyester for many end uses. With the continued commercial success of polyesters in general, and PET in particular, efforts have been made to recover scrap materials from post-consumer, post-industrial, and other sources and reuse those materials as an alternative to basic disposal methods such as landfilling.

[0003]

[0003] In some known recycling methods, recycled PET is blended with virgin materials. This approach has been used, for example, to prepare blends of virgin poly(butylene terephthalate) ("PBT") and recycled PET to produce PBT-based products with recycled content (see, for example, U.S. Patent Application Publication No. 2009 / 0275698). However, such blends are generally immiscible and can produce relatively opaque materials. Thus, blending is not a uniformly satisfactory method to provide commercially acceptable end products with recycled content.

[0004]

[0004] Other recycling methods involve depolymerizing polyesters to form the monomer units originally used in the manufacture of the polyester. One commercially utilized method of polyester depolymerization is methanolysis, in which polyester is reacted with methanol to produce a depolymerized polyester mixture containing polyester oligomers, dimethyl terephthalate ("DMT"), and ethylene glycol ("EG"). Depending on the composition of the polyester in the methanolysis feed stream, other monomers may also be present, such as 1,4-cyclohexanedimethanol ("CHDM") and diethylene glycol. Some representative methods for the methanolysis of PET are described in U.S. Patent Nos. 3,037,050; 3,321,510; 3,776,945; 5,051,528; 5,298,530; 5,414,022; 5,432,203; 5,576,456 and 6,262,294, the contents and disclosures of which are incorporated herein by reference. Representative methanolysis methods are also described in U.S. Patent No. 5,298,530, the contents and disclosures of which are incorporated herein by reference. The '530 patent describes a process for recovering ethylene glycol and dimethyl terephthalate from scrap polyester. The process includes dissolving scrap polyester in oligomers of ethylene glycol and terephthalic acid or dimethyl terephthalate and passing superheated methanol through the mixture. The oligomers may include any low molecular weight polyester polymer of the same composition as the scrap material used as the starting component, such that the scrap polymer dissolves in the low molecular weight oligomers. Dimethyl terephthalate and ethylene glycol are recovered from the methanol vapor stream exiting the depolymerization reactor.

[0005] Another approach to depolymerizing polyesters is glycolysis, in which polyesters are reacted with glycols such as ethylene glycol or CHDM to produce a depolymerized polyester mixture. Thus, U.S. Pat. No. 4,259,478 discloses a process that includes heating the polyester in the presence of 1,4-cyclohexanedimethanol to glycolize the polymer, distilling the ethylene glycol from the glycolyzed mixture, and polycondensing the glycolyzed mixture to form a copolyester in which at least a portion of the ethylene glycol units are replaced by 1,4-cyclohexanedimethanol units. Similarly, U.S. Pat. No. 5,635,584 discloses recovered or scrap polyesters from consumers that have been reacted with glycols to produce monomers or low molecular weight oligomers by depolymerization of the polyester. The monomers or oligomers are then purified, as the case may be, using one or more steps including filtration, distillation, crystallization, and optionally adsorbent treatment or evaporation. The monomers or oligomers thus produced are particularly suitable as feedstocks for the production of acid or ester-based polyesters of packaging grade polyester materials. Because the process includes a purification step, there is no need to restrict the specifications of the recycled polyester material.

[0006] Another way to recycle scrap polyester is to introduce the scrap into a polymerization process. Thus, US Patent No. 5,559,159 discloses post-consumer recovered polyester material that is depolymerized and repolymerized to produce previously used poly(ethylene terephthalate) polyester materials and copolymers thereof, particularly bottle grade polymers containing 75% or less of the previously used material. The process involves solubilizing and depolymerizing the previously used polyester material in a transesterification and / or polymerization mixture containing dimethyl terephthalate, ethylene glycol and their transesterification products. US Patent No. 5,945,460 discloses a process for producing polyester articles that generates little or no polyester waste. The process provides for the esterification or transesterification of one or more dicarboxylic acids or their dialkyl esters, polycondensation to produce high molecular weight polyesters, and molding or shaping the polyester to produce the desired product. Scrap generated during the molding process is recycled back into the esterification or transesterification or polycondensation part of the process. Optionally, scrap can also be recycled in intermediate steps before the molding operation. US Patent No. 7,297,721 discloses a process for preparing high molecular weight crystalline PET using up to 50% post-consumer recycled PET flakes, together with purified terephthalic acid (PTA), isophthalic acid and ethylene glycol as virgin raw materials in the presence of a combination of catalysts and additives, to obtain an intermediate prepolymer heel with a low degree of polymerization, which is further subjected to autoclaving to produce an amorphous melt, followed by solid-state polymerization. Summary of the Invention [Problem to be solved by the invention]

[0007]

[0007] Nevertheless, there continues to be a need for alternative and / or improved processes for utilizing recycled copolyesters to produce high quality copolyesters. This demand for recycled content has created a need to develop new methods and new processes to capture and convert existing plastic waste streams into new plastic articles.

[0008]

[0008] The present disclosure addresses this need as well as others, which will become apparent from the following description and the appended claims. [Means for solving the problem]

[0009]

[0009] One aspect of the present disclosure is a process for preparing a copolyester from recycled copolyesters. One aspect of the present disclosure is a process for preparing a copolyester from recycled polyesters and / or recycled copolyesters.

[0010]

[0010] In one aspect, the present disclosure provides: (A) recycled polyesters and / or recycled copolyesters, the acid component of which is comprised of at least 70 mole percent terephthalic acid and the diol component of which is comprised of at least 70 mole percent ethylene glycol; or (B) recycled copolyesters the acid component of which is comprised of at least 70 mole percent terephthalic acid and the diol component of which is comprised of at least 70 mole percent of a mixture of ethylene glycol, 1,4-cyclohexanedimethanol, and diethylene glycol in a molar ratio of from 96:3:1 to 20:68:12; or (C) recycled copolyesters the acid component of which is comprised of at least 70 mole percent terephthalic acid and the diol component of which is comprised of at least 70 mole percent of a mixture of ethylene glycol, 1,4-cyclohexanedimethanol, and diethylene glycol in a molar ratio of from 96:3:1 to 20:68:12. or (D) a recycled copolyester comprising a mixture of two or more glycols comprising ethylene glycol (EG), diethylene glycol (DEG), 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), butanediol, and isosorbide, the acid component of which is at least 70 mole percent terephthalic acid and the diol component of which is at least 70 mole percent of a mixture of ethylene glycol, 1,4-cyclohexanedimethanol in a molar ratio of 3.5:96.5 to 100:0.

[0011]

[0011] The process provides fast polymerization rates and the polymers so produced can be used to produce plastics, fibers, films, shrink films, sheets, molded articles and other shaped objects with good physical properties. In one aspect, the disclosed process describes a method for converting industrial post-consumer and post-consumer waste products into high quality copolyester resins that can be used to produce new plastics with high levels of recycled content. In another aspect, the disclosed process describes a method for converting industrial post-consumer and post-consumer waste products into resins that can be used to produce high quality shrink films.

[0012] One aspect of the present disclosure is a process for producing a copolyester from a recycled copolyester, comprising: (a) 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 to form a slurry that is stirred and heated at a temperature of 150° C. or less; (b) passing the paste tank slurry to a first reaction zone; (c) introducing at least one additional glycol comprising 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), and optionally additional recycled PET, recycled PETG, recycled PCTM, and / or recycled PETM; terephthalic acid (TPA); and ethylene glycol (EG) into the first reaction zone in a molar ratio of EG:TPA of 1:1 to 4:1, and optionally adding a catalyst; (d) reacting the TPA with EG and at least one additional glycol (such as CHDM) in a first reaction zone at a melt temperature of at least 200° C. and a pressure of no more than 276 kPa (40 psi) to form a first esterification product comprising oligomers and unreacted TPA, EG, and additional glycol (such as CHDM); (e) passing the first esterification product to a second reaction zone; (f) esterifying unreacted TPA, EG and additional glycol (such as CHDM) in the first esterification product in a second reaction zone at a melt temperature of at least 200° C. and a pressure of no more than 138 kPa (20 psi) to form a second esterification product comprising a copolyester oligomer; (g) passing the second esterification product to a third reaction zone; (h) polycondensing the second esterification product in a third reaction zone, optionally in the presence of a polycondensation catalyst, to form a prepolymerization product comprising a copolyester; (i) passing the prepolymerization product through one or more termination zones; It is a process that includes:

[0013]

[0013] An aspect of the present disclosure is the process of any one of the previous aspects, further comprising 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. An aspect of the present disclosure is a method of introducing or fixing recycled content in polyester produced by the process of the previous aspect, comprising: obtaining a recycled monomer allocation or credit for at least one recycled monomer including TPA, EG, DMT, CHDM, NPG, or DEG; b. converting the recycled monomers in a synthesis process to produce polyester; c. designating at least a portion of the polyester to correspond to at least a portion of the recycled monomer allocation or credit; d. Optionally, offering for sale or selling the polyester as containing or obtained with a recycled monomer content corresponding to such designation; The method includes:

[0014]

[0014] An embodiment of the present disclosure is any one of the above-mentioned embodiments, wherein the amount of recycled polyester added to the process is 5-100% relative to the amount of TPA required. [Brief description of the drawings]

[0015] [Figure 1] 1 is a flow diagram of various processes according to the present disclosure. [Diagram 2]

[0016] FIG. 1 shows Sb catalyst levels in the final material as a function of rPET starting material input level. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016]

[0017] Surprisingly, it has been discovered that high quality copolyester resins can be produced from recycled copolyesters and / or recycled polyesters.

[0018] In one embodiment, recycled polyesters and / or copolyesters can be recovered as manufacturing scrap or post-industrial or post-consumer recycled (PCR) waste. Typically, PCR or recycled waste are articles made from polyesters or copolyesters that have been used and discarded. Today, PET is recycled by mechanical methods and incorporated into new PET bottles and other PET articles as a blend with virgin material.

[0017]

[0019] Copolyesters with recycled content and copolyesters made from recycled content include dicarboxylic acid monomer residues, diol or glycol monomer residues, and repeat units. Thus, the term "monomer residue" as used herein means a residue of a dicarboxylic acid, diol or glycol, or a hydroxycarboxylic acid. As used herein, "repeat unit" means an organic structure having two monomer residues linked through a carbonyloxy group. The copolyesters of the present disclosure contain substantially equal molar ratios of acid residues (100 mol%) and glycol residues (100 mol%), which react in substantially equal ratios such that the total moles of repeat units equal 100 mol%. Thus, the mole percentages provided in the present disclosure can be for the total moles of acid residues, the total moles of glycol residues, or the total moles of repeat units. For example, a copolyester containing 30 mol% of a monomer, which may be a dicarboxylic acid, glycol, or hydroxycarboxylic acid, relative to the total repeat units means that the copolyester contains 30 mol% of the monomer out of a total of 100 mol% of repeat units. Thus, for every 100 moles of repeat units, there are 30 moles of monomer residues. Similarly, a copolyester containing 30 mole % dicarboxylic acid monomers relative to the total acid residues means that, out of a total of 100 mole % acid residues, the polyester contains 30 mole % dicarboxylic acid monomers. Thus, in this latter case, for every 100 moles of acid residues, there are 30 moles of dicarboxylic acid monomer residues.

[0018]

[0020] The term "polyester" as used herein includes both "homopolymers" and "homopolyesters" as well as "copolyesters" and refers to synthetic polymers prepared by polycondensation of at least one diacid component containing one or more difunctional carboxylic acids with at least one glycol component containing one or more difunctional hydroxyl compounds. The term "copolyester" as used herein is intended to mean a polyester formed from the polycondensation of at least three different monomers, for example, one dicarboxylic acid and two or more glycols, or in another example, one 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, for example, glycols and diols. Alternatively, the difunctional carboxylic acid may be a hydroxycarboxylic acid, for example, p-hydroxybenzoic acid, and the difunctional hydroxyl compound may be an aromatic nucleus with two hydroxy substituents, for example, hydroquinone. The term "residue" as used herein refers to any organic structure that is incorporated into a polymer through a polycondensation reaction involving the corresponding monomers. The dicarboxylic acid residues can be derived from a dicarboxylic acid monomer or its associated acid halide, ester, salt, anhydride, or mixtures thereof. For example, in one embodiment, for the copolyesters of the present disclosure, the diacid component is provided as terephthalic acid or isophthalic acid.

[0019]

[0021] The recycled polyesters and / or copolyesters can be repolymerized into copolyesters using any polycondensation reaction conditions known in the art. They can be produced by continuous, semi-continuous, and batch mode operation and can utilize a variety of reactor types. Examples of suitable reactor types include, but are not limited to, stirred tank, continuous stirred tank, slurry, tubular, wiped film, falling film, or extrusion reactors. As used herein, the term "continuous" refers to a process in which reactants are introduced and products are withdrawn simultaneously in an uninterrupted manner. The process is advantageously operated as a continuous process for economic reasons and to develop excellent color of the polymer, since the copolyesters can deteriorate in appearance if allowed to remain in the high temperature reactor for too long.

[0020]

[0022] The copolyesters of the present disclosure are prepared by procedures known to those skilled in the art. The reaction of the diol component and the dicarboxylic acid component can be carried out using conventional copolyester polymerization conditions. For example, when preparing a copolyester by transesterification, for example from the ester form of the dicarboxylic acid component, the reaction process can include two steps. In the first step, the diol component and the dicarboxylic acid component, for example, terephthalic acid, are reacted at an elevated 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 gauge to about 414 kPa gauge (60 pounds per square inch, "psig"). The temperature of the transesterification reaction ranges from about 180° C. to about 230° C. for about 1 to about 4 hours, while the pressure ranges from about 103 kPa gauge (15 psig) to about 276 kPa gauge (40 psig). The reaction product is then heated at a higher temperature and reduced pressure to form a copolyester while eliminating the diol, which is easily volatilized under these conditions and removed from the system.

[0021]

[0023] This second step, or polycondensation step, is continued under higher vacuum and at temperatures generally ranging from about 230°C to about 350°C, or from about 250°C to about 310°C, or from about 260°C to about 290°C, for about 0.1 to about 6 hours, or from about 0.2 to about 2 hours, until a polymer with the desired degree of polymerization, as determined by inherent viscosity, is obtained. The polycondensation step can be carried out under reduced pressure ranging from about 53 kPa (400 torr) to about 0.013 kPa (0.1 torr). Stirring or suitable conditions are used in both steps to ensure sufficient heat transfer and surface renewal of the reaction mixture, as well as removal of water, excess glycol, or alcohol to promote reaction and polymerization. The reaction rates of both steps are increased by suitable catalysts, such as, for example, alkoxytitanium compounds, hydroxides and alcoholates of alkali metals, salts of organic carboxylic acids, alkyltin compounds, metal oxides, and the like. A three-step preparation procedure similar to that described in US Pat. No. 5,290,631 can also be used, particularly when a mixed monomer feed of acids and esters is used.

[0022]

[0024] To ensure completion of the reaction of the diol and dicarboxylic acid components by transesterification, it is sometimes desirable to use about 1.05 to about 2.5 moles of the diol component per mole of the dicarboxylic acid component, followed by removal of excess glycol in a subsequent step. However, those skilled in the art will appreciate that the ratio of the diol and dicarboxylic acid components is generally determined by the design of the reactor in which the reaction process occurs.

[0023]

[0025] For example, in the preparation of copolyesters by direct esterification from the acid form of a dicarboxylic acid component, a dicarboxylic acid or mixture of dicarboxylic acids is reacted with a glycol component or mixture of glycol components to produce the copolyester. The reaction is carried out at pressures of from about 7 kPa gauge (1 psig) to about 1379 kPa gauge (200 psig), or less than 689 kPa (100 psig), to produce low molecular weight linear or branched copolyester products having an average degree of polymerization of from about 1.4 to about 10. The temperature employed during the direct esterification reaction is from about 180° C. to about 280° C., or from about 220° C. to about 270° C. This low molecular weight polymer can then be polymerized by a polycondensation reaction.

[0024]

[0026] In some embodiments, 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.

[0025]

[0027] In some embodiments, copolyesters comprising the following diacids: terephthalic acid, isophthalic acid, trimellitic anhydride (or trimellitic acid), naphthalene dicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid are suitable for use in repolymerization or polymerization processes to produce new copolyesters using recycled content.

[0026]

[0028] In some embodiments, copolyesters comprising the following glycols: 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, are suitable for use in repolymerization or polymerization processes to produce new copolyesters using recycled content.

[0027]

[0029] In one embodiment, recycled waste materials including terephthalate polyesters and / or copolyesters can be used in the repolymerization process. In one embodiment, any conventionally prepared terephthalate polyester or copolyester can be used in the repolymerization process. In one embodiment, suitable terephthalate polyesters and / or copolyesters include poly(ethylene terephthalate) (PET), glycol-modified poly(ethylene terephthalate) (PETG), glycol-modified poly(cyclohexylene dimethylene terephthalate) (PCTG), poly(cyclohexylene dimethylene terephthalate) acid (PCTA), poly(butylene terephthalate) (PBT), poly(propylene terephthalate) (PPT), polytrimethylene terephthalate (PTT), polycyclohexane dimethanol terephthalate (PCT), polyethylene naphthalate (PEN), TMCD-modified poly(ethylene terephthalate) (PETM), TMCD-modified poly(cyclohexylene dimethylene terephthalate) (PCTM), and mixtures thereof. In one embodiment, the terephthalate polyester is poly(ethylene terephthalate) (PET). In one embodiment, the copolyester is PETG. In one embodiment, the copolyester is PCT. In one embodiment, the copolyester is PCTG. In one embodiment, the copolyester is PCTA. In one embodiment, the copolyester is PCTM. In one embodiment, the copolyester is PETM.

[0028]

[0030] In one embodiment, a mixture of terephthalate polyesters and copolyesters are combined and repolymerized together. In one embodiment, PET and PETG are combined and repolymerized together. In one embodiment, PET and PETM are combined and repolymerized together. In one embodiment, PET and PCT are combined and repolymerized together. In one embodiment, PET and PCTA are combined and repolymerized together. In one embodiment, PET and PCTG are combined and repolymerized together. In one embodiment, PET and PCTM are combined and repolymerized together. In one embodiment, PET and PETG and PETM are combined and repolymerized together. In one embodiment, PET and PETG and PCTM are combined and repolymerized together. In one embodiment, PET, PETG, PCTM and PETM are combined and repolymerized together.

[0029]

[0031] In one embodiment, copolyesters suitable for use in the present disclosure are prepared from monomers such as, for example, 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).

[0030]

[0032] One embodiment of the present disclosure relates to a process for preparing copolyesters having high levels of recycled content obtained by repolymerizing scrap or post-consumer polyesters, including terephthalate-containing polyesters (e.g., PET) and / or copolyesters (e.g., PETG), with water or alcohol or glycol, as well as a process for preparing copolyesters using recycled monomers that contain a high mole percentage of recycled monomer residues.

[0031]

[0033] In one aspect of the disclosure, the high molecular weight copolyester contains a glycol component and a diacid component, where the glycol component is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, dimethyl 1,4-cyclohexanedicarboxylate, trans-dimethyl 1,4-cyclohexanedicarboxylate, 1,6-hexanediol, p-xylene glycol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethylcyclobutanediol, and the like. The diacid components include dimethyl terephthalate, terephthalic acid, isophthalic acid (IPA), trimellitic anhydride (or trimellitic acid), salts of 5-(sulfo)isophthalic acid (SIPA), naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and mixtures thereof; when a depolymerization aid, or a solvent such as water, alcohol, or excess glycol, is introduced under conditions in which a reversible transesterification reaction can occur, then depolymerization by hydrolysis, alcoholysis, or glycolysis occurs to reduce the chain length (molecular weight) of the polymer. With sufficient amounts of solvent, the reaction will proceed to a point where the mixture consists primarily of diesters of the monomers, glycols, and acid components. In one embodiment, the glycols of 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, dimethyl 1,4-cyclohexanedicarboxylate, trans-dimethyl 1,4-cyclohexanedicarboxylate, 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 glycols of the mixture include 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. In one embodiment, the glycols of the mixture include ethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, and mixtures thereof. These recycled monomers can then be used to prepare copolyesters containing a high mole percentage of recycled monomer residues.

[0032]

[0034] The present invention relates to recycled polyethylene terephthalate (PET) and recycled glycol modified polyethylene terephthalate copolyesters (PETG), particularly processes that utilize post-consumer waste materials in the production of linear, high molecular weight copolyesters. There is an increasing demand to use higher amounts of recycled materials in plastic articles. This demand for recycled content has created a need to develop new methods and processes to capture and convert existing plastic waste streams into new plastic articles. Reclamation of PETG waste materials is of particular interest. In recent years, legislation has been attempted to separate recycled glycol modified PET (PETG) waste products from recycled polyethylene terephthalate (PET) waste products bearing a Resin Identification Code (RIC) 1 due to problems experienced during the treatment stream of these combined wastes. Additionally, there is a large amount of currently unrecycled PETG that can be reclaimed and converted into new plastic articles. In particular, shrinkable films made with PETG contain inks and other contaminants that must be removed from the recycling stream to produce high quality, clear recycled PET (rPET). Additionally, medical packaging is largely made from PETG, a material that currently has no recycling stream. The present invention provides a process that utilizes recycled PETG, and recycled PETG in combination with PET, as a reactive intermediate in the production of copolyesters useful in the production of extruded and injection molded products, such as shrink films, fibers, durable consumer goods, and other shaped and shaped articles.

[0033]

[0035] Today, there are very well-defined large-scale mechanical recycling processes where polyethylene terephthalate (PET) articles are regenerated and converted into semi-crystalline recycled PET (rPET) for further incorporation 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 improve the clarity, improve the toughness, and reduce the crystallinity of PET. These glycol-modified materials are usually called glycol-modified PET or PETG. Even though 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. New methods must be created to recover and recycle these PETG materials.

[0034]

[0036] The process described in this disclosure uses recycled PETG as a raw material feed to produce a variety of new copolyester resins. In this process, recycled PETG (rPETG) is introduced as a paste with ethylene glycol and terephthalic acid and fed to a transesterification reactor early in the manufacturing process to produce new copolyesters. During the process, the added glycol breaks down the rPETG into its original acid and glycol residues, the starting materials, new glycol and acid are added, and the mixture is then esterified and polymerized to produce new copolyesters. This process has the advantage of using recycled PETG as a feedstock without the need for further purification of the acid and glycol produced. Additionally, this process is advantageous because it provides a way to use rPETG that currently does not have a mechanical recycling stream and would therefore be placed in a landfill.

[0035]

[0037] In addition, rPETG (or rPCTG, or rPCTM, or rPETM, or rPCTA, or rPCTG, or rPCT) contains two or more higher value monomers, such as CHDM, TMCD, DEG, and NPG, that are not present in rPET. The PETG product produced from this process performs similarly to virgin PETG and can be used in the exact same applications without sacrificing any performance with the addition of recycled material. Traditionally, rPETG is blended with virgin materials to form physical blends. These blends often lose performance, either in terms of mechanical properties, or in terms of color and appearance, and are less usable in the same applications as the virgin material.

[0036]

[0038] It has become commercially desirable to use previously used, particularly post-consumer, PET in the synthesis of new PET for producing water and carbonated beverage bottles. Several chemical processing techniques are known to facilitate the reclamation and recycling of previously used polyester materials. These techniques are used to depolymerize recycled polyester materials, which reduces the polyester material to monomeric and / or oligomeric components. The monomeric and / or oligomeric components can then be repolymerized to produce recycled polyester materials.

[0037]

[0039] One known depolymerization technique is to subject recycled PET to methanolysis. According to the methanolysis approach, rPET is reacted with methanol to produce dimethyl terephthalate (DMT) and ethylene glycol (EG). DMT and EG can be easily purified and then used to produce PET containing recycled polyester material. However, most conventional commercial PET manufacturing facilities around the world are designed to use either terephthalic acid (TPA), and although some smaller facilities use DMT, most are not designed to use both TPA and DMT as monomer feedstocks. Thus, additional processing is generally required to convert DMT to TPA, which is required as a feedstock for many such facilities, and in either case, further purification of glycol and DMT / TPA is required.

[0038]

[0040] Another known depolymerization technique is hydrolysis, which reacts recycled PET with water to depolymerize rPET into TPA and EG. However, certain types of contaminants commonly present in recycled PET are known to be very difficult and expensive to remove from TPA. Moreover, in facilities designed to use DMT as a feedstock, TPA must be converted to DMT, requiring further purification of glycols and DMT / TPA.

[0039]

[0041] Glycolysis can also be used for the depolymerization of recycled PET. Glycolysis occurs when rPET reacts with EG, thus producing bis-(2-hydroxyethyl terephthalate) (BHET) and / or its oligomers. Glycolysis has several significant advantages over methanolysis or hydrolysis, primarily because BHET can be used as a feedstock for DMT- or TPA-based PET manufacturing processes without major improvements to the manufacturing facility or further purification. Another significant advantage offered by the glycolysis technique is that removal of glycol from the depolymerization solvent is not required.

[0040]

[0042] Previously known glycolysis processes include the independent complete glycolysis of post-consumer recovered rPET and the subsequent addition of a portion of the glycolysis products to a polycondensation process. Such a glycolysis process is described in U.S. Pat. No. 5,223,544. Such processes require high pressure and a large excess of ethylene glycol. These requirements reduce the efficiency of the reactor by decreasing its potential production capacity.

[0041]

[0043] It has been found that these glycolysis processes typically require high temperatures and a large excess of EG to solubilize the polyester molecule so that it can then be broken down into its constituent parts, such as BHET and its oligomers. High temperatures and excess EG result in the production of large amounts of diethylene glycol as a by-product. The diethylene glycol thus produced cannot be easily removed from the BHET, and therefore, when BHET is then used to produce recycled PET, the resulting PET product has an excessive diethylene glycol content, making the polymer unacceptable for many commercial applications.

[0042]

[0044] Other known processes, including glycolysis, require a heel of BHET oligomers with a degree of polymerization greater than 10 to be retained in the reactor at the end of the reaction run to solubilize post-consumer recovered rPET, which is insoluble in most solvents. These procedures are described in U.S. Patent No. 4,609,680. Thus, there remains a clear need in the art for a glycolysis process that can efficiently handle post-consumer recovered rPET that has been previously used in the production of new packaging grade PET.

[0043]

[0045] The present disclosure provides solutions to the problems discussed above. In particular, the process of the present disclosure provides an efficient and economical procedure for producing packaging grade polyester products utilizing recycled polyester and / or recycled copolyesters, including recycled PET, recycled PETG, recycled PETM, and recycled PCTM or mixtures of these materials.

[0044]

[0046] In one embodiment, the viscosity of the material in the paste zone and the viscosity of the material leaving the paste zone are reduced much more with rPETG (and rPCTM or blends with rPET) than with rPET alone. In one embodiment, TPA dissolves more quickly in rPET than EG alone. In one embodiment, TPA can dissolve even more quickly in rPETG, rPETM or rPCTM.

[0045]

[0047] In one embodiment, the TPA is completely replaced with recycled polyester or copolyester.

[0048] In one embodiment, compositional control of the final polyester product is achieved by the combination of recycle feedstock and components added to the first reaction zone.

[0046]

[0049] In one embodiment of the present disclosure, copolyesters are produced in two main stages. The first stage reacts the starting materials to form monomers and / or oligomers. If the starting materials entering the first stage contain acid end groups, such as TPA or isophthalic acid, the first stage is called esterification. The esterification stage can be a single step or can be split into multiple steps. The second stage further reacts the monomers and / or oligomers to form the final copolyester product. The second stage is generally called the polycondensation stage. The polycondensation stage can be a single step or can be split into a pre-polycondensation (or prepolymerization) step and a final (or end) polycondensation step.

[0047]

[0050] FIG. 1 shows a process flow diagram for producing polyesters or copolyesters such as PETG according to various embodiments of the present disclosure. Although the flow diagram (FIG. 1) shows the reaction zones as separate vessels, typically continuous stirred tank reactors (CSTRs), the vessels can be integrated units having multiple esterification zones with appropriate partitioning and control. Similarly, although the reaction zones are shown as separate vessels, typically wipe-film or thin-film type CSTRs, the vessels can be connected to one or more integrated units having multiple polycondensation zones with appropriate partitioning and control. Various other types of esterification and polycondensation reaction vessels and reactor configurations are known in the art and can be adapted for use according to the present disclosure.

[0048]

[0051] With reference to FIG. 1, in one embodiment, a paste composed of EG and TPA in a 2:1 molar ratio was fed to a location labeled Paste Tank along with the recycled copolyester and / or polyester. Additional EG was fed to the first reaction zone or reactor 1, and other glycols such as CHDM, TMCD, NPG, and DEG could also be fed to the first reaction zone at the same location based on the targeted final composition of the copolyester, and optionally additional recycled materials could be added. In one embodiment, these feedstocks could be added separately and / or directly to the first reaction zone. In some embodiments, the recycled copolyester and / or polyester is fed to at least one of the following locations: paste tank, zone #1, zone #2, or termination zone. In some embodiments, the recycled copolyester and / or polyester is fed to one or more of the following locations: paste tank, zone #1, zone #2, or termination zone.

[0049]

[0052] The reaction mixture in the first reaction zone is heated through a recycle loop that includes a heat exchanger. Esterification takes place in the first reaction zone to form a first esterification product that includes copolyester monomers, oligomers, or both, as well as unreacted TPA, EG, and other glycols, such as CHDM, TMCD, NPG, or DEG. The reaction product of the first reaction zone is then passed to a second reaction zone. Further esterification takes place in the second reaction zone to form a second esterification product that includes additional copolyester monomers, oligomers, or both.

[0050]

[0053] In some embodiments, the average chain length of the monomers and / or oligomers exiting the esterification stage can be less than 25, 1-20, or 5-15.

[0054] In one embodiment, the second reaction zone is optional. In some embodiments, the product passes from the first reaction zone to a third reaction zone.

[0051]

[0055] The reaction product of the second reaction zone is then passed to a third reaction zone. In some embodiments, polycondensation occurs in the third reaction zone, optionally in the presence of a polycondensation catalyst, to form a prepolymerization product comprising copolyester oligomers. In some embodiments, polycondensation occurs in the third reaction zone without the need for a polycondensation catalyst to form a prepolymerization product comprising copolyester oligomers. In some embodiments, catalyst residues remaining from the recycled copolyester and polyester are sufficient to act as polycondensation catalysts. In some embodiments, the third reaction zone converts monomers exiting the esterification stage to oligomers having average chain lengths in the range of 2 to 40, 5 to 35, or 10 to 30.

[0052]

[0056] The prepolymerization product then passes to one or more reaction zones or termination zones. Additional polycondensation optionally occurs in the termination zone in the presence of a polycondensation catalyst to form a copolyester having a desired average chain length or IV. The copolyester is then recovered from the termination zone for further processing, such as forming pellets via an extruder coupled to an underwater pelletizer.

[0053]

[0057] In one embodiment, the temperature of the paste tank is between 120-180°C.

[0058] In one embodiment, the temperature of the glycolysis and transesterification reaction zone is between 200-300°C.

[0054]

[0059] In one embodiment, the reacting step is carried out at a melt temperature of at least 253° C., at least 255° C., or at least 257° C. In one embodiment, the reacting step is additionally or alternatively carried out at a melt temperature of 290° C. or less, 285° C. or less, 280° C. or less, 275° C. or less, 270° C. or less, or 265° C. or less. In various embodiments, the reacting step is carried out at a melt temperature of 250-270° C., or 257-265° C.

[0055]

[0060] In one embodiment, the reacting step is carried out at a pressure of 172-276 kPa (25-40 psi), or 207-276 kPa (30-40 psig).

[0061] In one embodiment, the esterification step is carried out at a melt temperature of at least 253° C., at least 255° C., or at least 257° C. In one embodiment, additionally or alternatively, the esterification step is carried out at a melt temperature of 290° C. or less, 285° C. or less, 280° C. or less, 275° C. or less, 270° C. or less, or 265° C. or less. In various embodiments, the esterification step is carried out at a melt temperature of 250-270° C., or 257-265° C.

[0056]

[0062] In one embodiment, the esterifying step (d) is carried out at a pressure of from 55 to 138 kPag (8 to 20 psig).

[0063] In one embodiment, the average residence time of the reactants in the reacting 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 reacting step is 30 to 40 minutes.

[0057]

[0064] In one embodiment, the average residence time of the reactants in the esterifying 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 esterifying step (d) is 30 to 40 minutes.

[0058]

[0065] In various embodiments, the overall molar ratio of EG:TPA introduced into the process ranges from 2.3:1 to 3.0:1.

[0066] In various embodiments, the overall molar ratio of EG:TPA introduced into the process ranges from 2.3:1 to 2.71:1.

[0059]

[0067] The temperature, pressure, and average residence time of the reacting step in the first reaction zone are as described above.

[0068] In various embodiments, the reacting step in the first reaction zone is carried out at a melt temperature of 250-270° C. and a pressure of 172-276 kPa (25-40 psi).

[0060]

[0069] In various embodiments, the reacting step in the first reaction zone is carried out at a melt temperature of 257-265° C. and a pressure of 207-276 kPa (30-40 psi).

[0061]

[0070] The temperature, pressure, and average residence time of the esterifying step in the second reaction zone can be as described above.

[0071] In various embodiments, the esterifying step in the second reaction zone is carried out at a melt temperature of 250-270° C. and a pressure of 55-138 kPa (8-20 psi).

[0062]

[0072] In various embodiments, the esterifying step in the second reaction zone is carried out at a melt temperature of 257-265° C. and a pressure of 55-138 kPa (8-20 psi).

[0063]

[0073] The polycondensation catalysts useful in the process of the present disclosure are not particularly limited. Examples of such catalysts include titanium-based compounds, antimony-based compounds, and germanium-based compounds. Titanium catalysts are very efficient and give high polycondensation rates at low catalyst levels. The polycondensation catalyst can be added during the esterification stage or during the polycondensation stage. In one embodiment, the polycondensation catalyst is added with the feed to the first reaction zone. In one embodiment, the catalyst is added in the range of 1 to 500 ppm based on the weight of the copolyester. In one embodiment, in the case of titanium, the catalyst can be added in the range of 1 to 50 ppm based on the weight of the copolyester.

[0064]

[0074] In one embodiment, the catalyst selection is influenced by the catalyst derived from the recycled feedstock. A particular catalyst advantage is achieved by the combination of catalyst from the feedstock and catalyst added to the first and second reaction zones. Likely catalysts derived from rPET include Sb and Li / Al. Catalysts derived from rPETG can be Ti, Co, Ge, and Sb. Catalysts derived from rPETM and rPCTM include Co.

[0065]

[0075] In some embodiments, phosphorus compounds are often added along with the catalyst to improve thermal stability. Phosphorus compounds useful as thermal stabilizers include phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphonous acid, and various esters and salts thereof. The esters can be alkyl, branched alkyl, substituted alkyl, difunctional alkyl, alkyl ether, aryl, and substituted aryl. In some embodiments, suitable thermal stabilizers include triphenyl phosphate Merpol A. In one embodiment, phosphorus is added in the range of 10 to 100 ppm based on the weight of the copolyester.

[0066]

[0076] In various embodiments, one or more other additives can be added to the starting materials, the copolyester, and / or the monomers / oligomers of the copolyester at one or more locations in the process. In various embodiments, suitable additives can include, for example, tri- or tetra-functional comonomers such as trimellitic anhydride, trimethylolpropane, pyromellitic dianhydride, pentaerythritol, or other polyacids or polyols; crosslinkers or other branching agents; colorants; toners; pigments; carbon black; glass fibers; fillers; impact modifiers; antioxidants; UV absorbing compounds; oxygen scavenging compounds, and the like.

[0067]

[0077] The processes according to the present disclosure are particularly suitable for use on an industrial scale, for example, in one embodiment, they can be carried out in a commercial manufacturing line capable of operating at rates of polymer from 227 to 13,600 kg / hour (500 to 30,000 lbs / hour).

[0068]

[0078] In another aspect, the present disclosure relates to copolyesters produced from the processes of the present disclosure.

[0079] According to further the aforementioned process, the new polyester product can contain ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol diol units, with the 1,4-cyclohexanedimethanol units constituting up to about 25 mole percent of the total diol units and the diethylene glycol constituting up to 15 mole percent of the total diol units. In this case, the 1,4-cyclohexanedimethanol and diethylene glycol units can be added directly to a portion of the ethylene glycol component in the first reaction mixture or derived from a portion of a post-consumer recovered poly(ethylene terephthalate) or glycol modified poly(ethylene terephthalate) flake material.

[0069]

[0080] In various embodiments, the copolyester comprises: (a) a diacid component comprising 60 to 100 mole percent of the residues of terephthalic acid, isophthalic acid, or a mixture thereof; and (b) a diol component containing 0 to 96.5 mol % of ethylene glycol residues and 3.5 to 100 mol % of 1,4-cyclohexanedimethanol residues. Including, The diacid component here is based on 100 mole % of the total diacid residues in the copolyester, and the diol component here is based on 100 mole % of the total diol residues in the copolyester.

[0070]

[0081] In various embodiments, the copolyester comprises: (a) a diacid component comprising 90 to 100 mole percent of the residues of terephthalic acid; and (b) a diol component containing 50 to 96.5 mol % of ethylene glycol residues and 3.5 to 50 mol % of 1,4-cyclohexanedimethanol residues. Including, The diacid component here is based on 100 mole % of the total diacid residues in the copolyester, and the diol component is based on 100 mole % of the total diol residues in the copolyester.

[0071]

[0082] In various embodiments, the copolyester comprises: (a) a diacid component comprising 90 to 100 mole percent of the residues of terephthalic acid; and (b) a diol component containing 0 to 50 mol % of ethylene glycol residues and 50 to 100 mol % of 1,4-cyclohexanedimethanol residues. Including, The diacid component here is based on 100 mole % of the total diacid residues in the copolyester, and the diol component here is based on 100 mole % of the total diol residues in the copolyester.

[0072]

[0083] In various embodiments, the copolyester comprises: (a) a diacid component comprising 60 to 100 mole percent of the residues of terephthalic acid; and (b) a diol component containing 65 to 85 mol % of ethylene glycol residues and 25 to 35 mol % of 1,4-cyclohexanedimethanol residues. Including, The diacid component here is based on 100 mole % of the total diacid residues in the copolyester, and the diol component here is based on 100 mole % of the total diol residues in the copolyester.

[0073]

[0084] In various embodiments, the copolyester has an inherent viscosity of 0.4 to 1.5 dL / g, or 0.5 to 1.2 dL / g, or 0.6 to 0.9 dL / g.

[0085] In various other embodiments, the copolyester comprises: (a) a diacid component comprising 100 mole percent residues of terephthalic acid, residues of isophthalic acid, or a mixture thereof; (b) a diol component comprising 0 to 96.5 mole percent of residues of ethylene glycol, 3.5 to 100 mole percent of residues of 1,4-cyclohexanedimethanol, and 0 to 0.4 mole percent of residues of trimellitic anhydride; Including, wherein the copolyester has an inherent viscosity (IV) of 0.4 to 1.5 dL / g; All weight percentages are based on the total weight of the copolyester; The diacid component is for 100 mole % of the total diacid residues in the copolyester, and the diol component is for 100 mole % of the total diol residues in the copolyester.

[0074]

[0086] In one embodiment, the present disclosure includes an article of manufacture or a shaped object comprising a shrink film of any of the shrink film embodiments of the present disclosure. In another embodiment, the present disclosure includes an article of manufacture or a shaped object comprising an oriented film of any of the oriented film embodiments of the present disclosure.

[0075]

[0087] In certain embodiments, the present disclosure includes shrink films applied to, but not limited to, containers, plastic bottles, glass bottles, packaging, batteries, hot-fill containers, and / or industrial articles or other applications. In one embodiment, the present disclosure includes oriented films applied to, but not limited to, containers, packaging, plastic bottles, glass bottles, photo substrates such as paper, batteries, hot-fill containers, and / or industrial articles or other applications.

[0076]

[0088] In certain embodiments of the present disclosure, the shrink films of the present disclosure can be formed into a label or sleeve, which can then be applied to the wall of a container, an article of manufacture such as a battery, or over a sheet or film.

[0077]

[0089] The oriented film or shrink film of the present disclosure can be applied to shaped objects such as sheets, films, tubes, bottles, etc., and is generally used in various packaging applications. For example, films and sheets made from polymers such as polyolefins, polystyrene, poly(vinyl chloride), polyester, polylactic acid (PLA), etc. are frequently used to make shrink labels for plastic beverage or food containers. For example, the shrink film of the present disclosure can be used in many packaging applications where the shrink film applied to the shaped object exhibits properties such as good printability, high opacity, higher shrink force, good touch, and good stiffness.

[0078]

[0090] The combination of improved shrink properties and improved toughness should offer new commercial options including, but not limited to, shrink films or other applications applied to containers, plastic bottles, glass bottles, packaging, batteries, hot fill containers, and / or industrial articles.

[0079]

[0091] Additionally, the materials of the present disclosure can be extruded into sheets, which can be further thermoformed into three-dimensional articles. The materials of the present disclosure can be converted into molded articles, films, shrink films, oriented films, blow molded articles, and blown film articles.

[0080]

[0092] The present disclosure includes, and expressly contemplates and discloses, any and all combinations of the embodiments, features, properties, parameters, and / or ranges set forth herein, i.e., the subject matter of the present disclosure may be defined by any combination of the embodiments, features, properties, parameters, and / or ranges set forth herein.

[0081]

[0093] Any process / method, apparatus, compound, composition, embodiment, or component of the present disclosure may be modified by the transitional terms "comprising," "consisting essentially of," "consisting of," or variations of these terms.

[0082]

[0094] As used herein, the indefinite articles "a" and "an" refer to one or more, unless the context clearly indicates otherwise. Similarly, the singular form of a noun includes its plural and vice versa, unless the context clearly indicates otherwise.

[0083]

[0095] While efforts have been made to be accurate, numerical values ​​and numerical ranges described herein should be considered approximate unless otherwise indicated by the context. These values ​​and ranges may vary from their stated numbers depending on the desired properties sought to be obtained by the present disclosure as well as variations due to standard deviations found in measurement techniques. Moreover, the ranges described herein are intended to include, and are specifically contemplated to include, all subranges and values ​​within the stated ranges. For example, a range of 50-100 is intended to include all values ​​within the range, including subranges such as 60-90, 70-80, etc.

[0084]

[0096] Any two numbers of the same characteristic or parameter reported in the examples can be used to define a range, which can be rounded to the nearest thousandth, hundredth, tenth, whole number, tens, hundreds, or thousands to define the range.

[0085]

[0097] The contents of all documents cited herein, including patents and non-patent literature, are incorporated herein by reference in their entirety. To the extent that any incorporated content conflicts with the disclosure of this specification, the disclosure of this specification shall take precedence over the incorporated content.

[0086]

[0098] The present disclosure can be further illustrated by the following examples, however, it should be understood that these examples are included for illustrative purposes only and are not intended to limit the scope of the disclosure. EXAMPLES

[0087] Laboratory scale process results:

[0099] General procedure: A mixture of 53.16g PTA, 62.21g EG, 2.97g DEG, 11.52g CHDM, and 18.86g rPET was placed in a 500 milliliter flask equipped with a nitrogen inlet, metal stirrer, and a short distillation column. Additionally, 0.14ml of Ti catalyst solution (targeting 16ppm Ti) and 1ml of Mn solution (targeting 45ppm Mn) were added to the flask. The flask was placed in a Wood's metal bath already heated to 200°C. The stirring speed was set to 200 RPM at the beginning of the experiment. The contents of the flask were heated at 200°C for 60 minutes, then the temperature was gradually increased to 250°C over 300 minutes. The stirrer was then slowed to 100 rpm, and the reaction mixture was heated to 270°C in 20 minutes while a vacuum was gradually applied to 0.4 torr. The temperature was then increased to 278°C over 20 minutes, the stirring reduced to 60 rpm, and the mixture held under these conditions for 120 minutes. After this hold, the mixture was returned to atmospheric pressure and removed from the heat. The polymer was then removed from the flask for analysis. Example 1 was carried out using 100% replacement of TPA with rPET. Example 2 was carried out with 20% rPET replacement of TPA.

[0088] [000100] In one aspect of the disclosure, if the feed of rPET is reasonably constant, the amount of Sb and other residual catalyst and additives can be predictable as shown in Figure 2. In some embodiments, Figure 2 shows that the amount of antimony to be added to the system can be balanced based on the amount of rPET fed to the process. For example, if one desires 100 ppm Sb in the final product, one can feed 60% rPET to the process, or feed 20% rPET and add 60 ppm Sb to the system. Laboratory resin characterization:

[0089] [Table 1]

[0090] [000101] The resins produced in both cases were similar with respect to all essential performance criteria. Both materials had similar color, IV, and composition regardless of the amount of rPET added. Pilot plant process results: [000102] Resin samples (A1 and A2) were produced by adding 7.3 wt% recycled PET to a reactor containing 45.7 wt% ethylene glycol, 0.7 wt% diethylene glycol, 9.8 wt% cyclohexanedimethanol, and 36.4 wt% terephthalic acid. Ti catalyst was added at 30 ppm. The glycol to acid ratio was 3.3, with ethylene glycol and cyclohexanedimethanol used to make up the excess. The reaction mixture was held at 250-255°C and 172-207 kPag (25-30 psig) for 3-3.5 hours. Phosphorus was added at 21 ppm, then the reaction mixture was heated to 270°C and stirred under vacuum until the target melt viscosity was reached.

[0091] [000103] A control resin sample (B) was made using the same process except that no rPET or DEG was added to the reaction mixture and 50 ppm Ti catalyst was used. 44.1 wt% ethylene glycol, 10.5 wt% cyclohexanedimethanol, and 45.5 wt% terephthalic acid were charged to the reactor. The glycol to acid ratio was 2.9, with ethylene glycol and cyclohexanedimethanol used to make up the excess. The CHDM excess was the same as the previous sample, but the EG excess was reduced.

[0092] [000104] The characterization of the resins is set forth in the table below. Pilot plant resin characterization:

[0093] [Table 2]

[0094] [000105] Resin Examples A1 and A2 were combined to create Resin A. Resins A and B were dried in a desiccant drier at 60°C for 4-6 hours. Films having a thickness of 10 mils (250 microns) were then extruded using a 6.4 cm (2.5 inch) Davis and Standard extruder. Once extruded, the films were cut and stretched on a Bruckner Karo 4 tenter frame to a final thickness of 50 microns. The films were stretched at a ratio of 5:1 with a stretch rate of 100% / sec and a stretch temperature of 5-15 degrees Celsius above the Tg of the extruded film. Characterization of the shrinkable films produced by this process is described in the table below. Examples A and B: Shrinkable films made from resin compositions made from rPET

[0095] [Table 3]

[0096] [000106] Resins A and B had very similar compositions, IVs, and colors. Shrinkable films made with the resins also had 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 made from it. Commercial scale process: [000107] To demonstrate the utility of the present invention, resin samples were also produced in a commercial manufacturing facility.

[0097] [000108] In a commercial scale process, 5% recycled PET was added to a slurry tank along with terephthalic acid and ethylene glycol. The slurry tank was agitated for over 30 minutes to allow for adequate mixing. This slurry was then added to reaction zone 1 along with catalyst, additional ethylene glycol, diethylene glycol, and cyclohexanediol. This mixture was stirred for 242 + kPag(35 +The reaction was continued at above 235°C for at least 1 hour under a pressure of 100 psig (1000 psi) to simultaneously depolymerize the PET and react the monomers. The monomers and oligomers from reaction zone 1 were then passed to reaction zone 2 where they were further reacted while removing additional glycol but maintaining the reaction temperature. The material was passed to reaction zone 3 for termination under higher temperature and deeper vacuum conditions. Characterization of the final product, Example C, is shown in the table below in comparison to another copolyester resin, Example D, having the same composition and also made in a commercial process without the addition of rPET. Characterization of commercial process resins:

[0098] [Table 4]

[0099] [000109] Resins C and D were dried in a desiccant dryer at 60°C for 4-6 hours. Films having a thickness of 10 mils (250 microns) were then extruded using a 6.4 cm (2.5 inch) Davis and Standard extruder. Once extruded, the films were cut and stretched on a Bruckner Karo 4 tenter frame to a final thickness of 50 microns. The films were stretched at a ratio of 5:1 with a stretch rate of 100% / sec and a stretch temperature of 5-15 degrees Celsius above the Tg of the extruded film. Characterization of the shrinkable films produced by this process is described in the table below. Examples C and D: Shrinkable films made from resin compositions made from rPET

[0100] [Table 5]

[0101] [000110] Resins C and D had very similar composition, IV, and color. Shrinkable films made with the resins also had 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 made from the resin.

[0102] [000111] The present disclosure has been described in detail with particular reference to certain embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the disclosure. The present invention includes the following embodiments. [1] A process for producing a polyester composition from recycled polyester, comprising: (a) introducing recycled polyester, including terephthalic acid (TPA); and ethylene glycol (EG); and one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, recycled PCTG, recycled PCTM, or recycled PETM, into a paste tank to form a slurry that is stirred and heated at a temperature of 150° C. or less; (b) passing the paste tank slurry to a first reaction zone; (c) introducing at least one additional glycol comprising 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), diethylene glycol (DEG) or isosorbide, and optionally adding additional recycled polyester comprising one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, recycled PCTG, recycled PCTM or recycled PETM; optionally adding additional terephthalic acid (TPA); and ethylene glycol (EG) in a molar ratio of total glycol:TPA of 1:1 to 4:1 into the first reaction zone, optionally in the presence of an esterification catalyst and / or stabilizer; (d) reacting the TPA and EG and the recycled polyester with at least one additional glycol in a first reaction zone at a melt temperature of at least 175° C. to form an esterification product comprising oligomers and unreacted TPA, EG, and additional glycol; (e) optionally passing the esterification product from the first zone to a second reaction zone; (f) further reacting the esterification product from the first zone, optionally in a second reaction zone, at a melt temperature of at least 200° C., optionally in the presence of an esterification catalyst and / or stabilizer, and optionally adding additional glycols comprising one or more of CHDM, NPG, TMCD, DEG or isosorbide and / or additional recycled polyesters comprising one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, recycled PCTG, recycled PCTM or recycled PETM to form an esterification product comprising polyester oligomers; (g) passing the resulting esterification product from the one or more reaction zones to a third reaction zone; (h) polycondensing the resulting esterification product in a third reaction zone, optionally in the presence of a polycondensation catalyst and / or stabilizer, and optionally adding additional recycled polyesters comprising one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, recycled PCTG, recycled PCTM, or recycled PETM to form a polymerization product comprising polyester; The process includes: [2] The process of [1], wherein step (d) is carried out at a melt temperature of at least 240°C; or wherein step (d) is carried out at a melt temperature of at least 250°C and a pressure of 207 kPa (30 psig) or less. [3] The process of [1], wherein step (f) is carried out at a melt temperature of at least 240°C. [4] The process of [1], wherein the esterification catalyst comprises one or more of Mn, Ti, Zn, Co, Ge or Al. [5] The process of [1], wherein the polycondensation catalyst comprises one or more of Sn, Sb, Ti, Li / Al, Al, Ge, Pb, Zn, Co, Bi, Cd, Ca, or Ni. [6] The process of [1], wherein the polyester has an inherent viscosity of 0.4 to 1.2 dL / g; or the polyester has an inherent viscosity of 0.5 to 0.9 dL / g. [7] the polyester comprises 19 to 96.5 mol % ethylene glycol and 3.5 to 81 mol % 1,4-cyclohexanedimethanol based on the total diol residues in the polyester; or the polyester comprises 50 to 90 mole % ethylene glycol and 10 to 50 mole % 1,4-cyclohexanedimethanol based on the total diol residues in the polyester; or the polyester comprises 65 to 75 mole percent ethylene glycol and 25 to 35 mole percent 1,4-cyclohexanedimethanol based on the total diol residues in the polyester; or the polyester comprises, based on the total diol residues in the polyester, 60 to 70 mole percent ethylene glycol, 20 to 25 mole percent 1,4-cyclohexanedimethanol, and 10 to 15 mole percent diethylene glycol; or the polyester comprises, based on the total diol residues in the polyester, 75 to 93 mole percent ethylene glycol and 5 to 15 mole percent neopentyl glycol, and 2 to 10 mole percent diethylene glycol; or The polyester comprises 65 to 92 mole % ethylene glycol, 1 to 10 mole % 1,4-cyclohexanedimethanol, 5 to 15 mole % neopentyl glycol, and 2 to 10 mole % diethylene glycol, based on the total diol residues in the polyester; The process described in [1]. [8] Polyester is (a) a diacid component comprising 90 to 100 mole percent terephthalic acid; and (b) a diol component containing 65 to 75 mol % of ethylene glycol and 25 to 35 mol % of 1,4-cyclohexanedimethanol residues. Including, wherein the diacid component is based on 100 mole % of the total diacid residues in the polyester, and the diol component is based on 100 mole % of the total diol residues in the polyester; The process described in [1]. [9] the polyester comprises 50 mol % to 99.99 mol % of 1,4-cyclohexanedimethanol, 0.01 mol % to 50 mol % of ethylene glycol, and 70 mol % to 100 mol % of terephthalic acid, based on a total of 100 mol % of acid residues and a total of 100 mol % of diol residues; or the polyester comprises 80 mol % to 99.99 mol % 1,4-cyclohexanedimethanol, 0.01 mol % to 20 mol % ethylene glycol, and 70 mol % to 100 mol % terephthalic acid, based on a total of 100 mol % acid residues and a total of 100 mol % diol residues; the polyester comprises 90 mol % to 99.99 mol % of the residues of 1,4-cyclohexanedimethanol, 0.01 mol % to 10 mol % of the residues of ethylene glycol, and 70 mol % to 100 mol % of the residues of terephthalic acid, based on a total of 100 mol % of acid residues and a total of 100 mol % of diol residues; the polyester comprises 95 mol % to 99.99 mol % of the residues of 1,4-cyclohexanedimethanol, 0.01 mol % to 10 mol % of the residues of ethylene glycol, 90 mol % to 100 mol % of the residues of terephthalic acid, and 0.01 to 10 mol % of the residues of isophthalic acid, based on a total of 100 mol % of the acid residues and a total of 100 mol % of the diol residues; the polyester comprises from 20 mol % to less than 50 mol % of residues of 1,4-cyclohexanedimethanol, from greater than 50 mol % to 80 mol % of residues of ethylene glycol, and from 70 mol % to 100 mol % of residues of terephthalic acid, based on a total of 100 mol % of acid residues and a total of 100 mol % of diol residues; The process described in [1].

[10] Polyester is (a)(i) about 70 to about 100 mole percent terephthalic acid residues, and (ii) from about 0 to about 30 mole % of aromatic and / or aliphatic dicarboxylic acid residues having 20 or fewer carbon atoms; a dicarboxylic acid component comprising: (b)(i) from about 0 to about 40 mole % of 2,2-dimethylpropane-1,3-diol (neopentyl glycol or NPG) residues; (ii) from about 0 to about 100 mole % 1,4-cyclohexanedimethanol (CHDM) residues; (iii) from about 0 to about 45 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues; (iv) from about 0 to about 40 mole percent diethylene glycol (DEG) residues, whether or not formed in situ; A glycol component comprising: The remaining glycol component is (v) residues of ethylene glycol, and (vi) optionally, 0-10 mole % of the residue of at least one other modifying glycol; Glycol components including Including,

[0026] The process of [1], wherein the total mole % of the dicarboxylic acid components is 100 mole % and the total mole % of the glycol components is 100 mole %.

[11] The process of [1], wherein the polyester comprises at least about 90 mole percent terephthalic acid, and about 59 to about 77.5 mole percent ethylene glycol, and about 15 to about 28 mole percent 1,4-cyclohexanedimethanol (CHDM), and about 7.5 to about 13 mole percent diethylene glycol (DEG), wherein the diacid component is based on 100 mole percent and the diol component is based on 100 mole percent.

[12] A shrinkable film, a voided film, a molded article, a thermoformable article, an extruded film or sheet, a blown film, an extrusion blow molded article comprising a polyester produced by the process described in [1].

[13] A method for introducing or fixing recycled content in polyester produced by the process according to [1], comprising the steps of: Obtaining a recycled monomer allocation or credit for at least one recycled monomer including TPA, EG, DMT, CHDM, NPG, TMCD, or DEG; b. converting recycled monomers to produce polyester in a synthesis process; c. designating at least a portion of the polyester to correspond to at least a portion of the recycled monomer allocation or credit; and optionally d. offering for sale or selling the polyester as containing or obtained with a recycled monomer content corresponding to such designation; A method comprising:

[14] The process according to any one of [1] to

[11] , wherein the amount of recycled polyester added to the process is 5 to 100% relative to the amount of TPA required.

[15] The process of any of [1] to

[11] , or

[14] , further comprising the step of adding a catalyst or additive via the addition of recycled polyester, wherein the catalyst or additive is a component of the recycled polyester, such as Sb, Ti, Co, Mn, Li, Al, P.

Claims

1. 1. A process for producing a polyester composition from recycled polyester, comprising: (a) introducing into a paste tank recycled polyester including terephthalic acid (TPA); and ethylene glycol (EG); and one or more of recycled PET, recycled glycol modified poly(ethylene terephthalate) (PETG), recycled polycyclohexane dimethanol terephthalate (PCT), recycled poly(cyclohexylene dimethylene terephthalate) acid (PCTA), recycled glycol modified poly(cyclohexylene dimethylene terephthalate) (PCTG), recycled TMCD modified poly(cyclohexylene dimethylene terephthalate) (PCTM) or recycled TMCD modified poly(ethylene terephthalate) (PETM) into a paste tank to form a slurry that is stirred and heated at a temperature of 150° C. or less; (b) passing the paste tank slurry to a first reaction zone; (c) introducing at least one additional glycol comprising 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), diethylene glycol (DEG) or isosorbide, and optionally adding additional recycled polyester comprising one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, recycled PCTG, recycled PCTM or recycled PETM; optionally adding additional terephthalic acid (TPA); and ethylene glycol (EG) in a molar ratio of total glycol:TPA of 1:1 to 4:1 into the first reaction zone, optionally in the presence of an esterification catalyst and / or stabilizer; (d) reacting the TPA and EG and the recycled polyester with at least one additional glycol in a first reaction zone at a melt temperature of at least 175° C. to form an esterification product comprising oligomers and unreacted TPA, EG, and additional glycol; (e) optionally passing the esterification product from the first zone to a second reaction zone; (f) further reacting the esterification product from the first zone, optionally in a second reaction zone, at a melt temperature of at least 200° C., optionally in the presence of an esterification catalyst and / or stabilizer, and optionally adding additional glycols comprising one or more of CHDM, NPG, TMCD, DEG or isosorbide and / or additional recycled polyesters comprising one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, recycled PCTG, recycled PCTM or recycled PETM to form an esterification product comprising polyester oligomers; (g) passing the resulting esterification product from the one or more reaction zones to a third reaction zone; (h) polycondensing the resulting esterification product in a third reaction zone, optionally in the presence of a polycondensation catalyst and / or stabilizer, and optionally adding additional recycled polyester comprising one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, recycled PCTG, recycled PCTM, or recycled PETM to form a polymerization product comprising polyester; The process includes:

2. 10. The process of claim 1, wherein step (d) is carried out at a melt temperature of at least 240°C; or step (d) is carried out at a melt temperature of at least 250°C and a pressure of 207 kPa (30 psig) or less.

3. 2. The process of claim 1, wherein step (f) is carried out at a melt temperature of at least 240°C.

4. 2. The process of claim 1, wherein the esterification catalyst comprises one or more of Mn, Ti, Zn, Co, Ge, or Al.

5. 2. The process of claim 1, wherein the polycondensation catalyst comprises one or more of Sn, Sb, Ti, Li / Al, Al, Ge, Pb, Zn, Co, Bi, Cd, Ca, or Ni.

6. 10. The process of claim 1, wherein the polyester has an inherent viscosity of 0.4 to 1.2 dL / g; or the polyester has an inherent viscosity of 0.5 to 0.9 dL / g.

7. the polyester comprises from 19 to 96.5 mole percent ethylene glycol and from 3.5 to 81 mole percent 1,4-cyclohexanedimethanol, based on the total diol residues in the polyester; or the polyester comprises, based on the total diol residues in the polyester, 60 to 70 mole percent ethylene glycol and 20 to 25 mole percent 1,4-cyclohexanedimethanol and 10 to 15% diethylene glycol; or the polyester comprises, based on the total diol residues in the polyester, 75 to 93 mole percent ethylene glycol and 5 to 15 mole percent neopentyl glycol, and 2 to 10 mole percent diethylene glycol; or the polyester comprises, based on the total diol residues in the polyester, 65 to 92 mole % ethylene glycol, 1 to 10 mole % 1,4-cyclohexanedimethanol and 5 to 15 mole % neopentyl glycol, and 2 to 10% diethylene glycol; 2. The process of claim 1.

8. Polyester is (a) a diacid component comprising 90 to 100 mole percent terephthalic acid; and (b) a diol component comprising 65 to 75 mole % of ethylene glycol and 25 to 35 mole % of the residues of 1,4-cyclohexanedimethanol. Including, wherein the diacid component is based on 100 mole % of the total diacid residues in the polyester, and the diol component is based on 100 mole % of the total diol residues in the polyester; 2. The process of claim 1.

9. the polyester comprises 50 mol % to 99.99 mol % 1,4-cyclohexanedimethanol, 0.01 mol % to 50 mol % ethylene glycol, and 70 mol % to 100 mol % terephthalic acid, based on a total of 100 mol % acid residues and a total of 100 mol % diol residues; or the polyester comprises from 95 mol % to 99.99 mol % of the residues of 1,4-cyclohexanedimethanol, from 0.01 mol % to 10 mol % of the residues of ethylene glycol, from 90 mol % to 100 mol % of the residues of terephthalic acid, and from 0.01 to 10 mol % of the residues of isophthalic acid, based on a total of 100 mol % of the acid residues and a total of 100 mol % of the diol residues; or the polyester comprises from 20 mol % to less than 50 mol % of the residues of 1,4-cyclohexanedimethanol, from greater than 50 mol % to 80 mol % of the residues of ethylene glycol, and from 70 mol % to 100 mol % of the residues of terephthalic acid, based on a total of 100 mol % of the acid residues and a total of 100 mol % of the diol residues; 2. The process of claim 1.

10. Polyester is (a)(i) 70 to 100 mole percent terephthalic acid residues, and (ii) 0 to 30 mole % of aromatic and / or aliphatic dicarboxylic acid residues having 20 or fewer carbon atoms. A dicarboxylic acid component comprising: (b)(i) 0 to 40 mole % of 2,2-dimethylpropane-1,3-diol (neopentyl glycol or NPG) residues; (ii) 0 to 100 mole % of 1,4-cyclohexanedimethanol (CHDM) residues; (iii) 0 to 45 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues; (iv) 0 to 40 mole percent diethylene glycol (DEG) residues, whether or not formed in situ; A glycol component comprising: The remaining glycol component is (v) the residue of ethylene glycol, and (vi) optionally, 0 to 10 mole % of the residue of at least one other modifying glycol; Glycol components including Including, 2. The process of claim 1 , wherein the total mole percent of the dicarboxylic acid components is 100 mole percent and the total mole percent of the glycol components is 100 mole percent.

11. 2. The process of claim 1, wherein the polyester comprises at least 90 mol % terephthalic acid, and 59-77.5 mol % ethylene glycol, and 15-28 mol % 1,4-cyclohexanedimethanol (CHDM), and 7.5-13 mol % diethylene glycol (DEG), where 90 mol % is based on 100 mol % total diacid residues in the polyester, and 59-77.5 mol %, 15-28 mol %, and 7.5-13 mol % are based on 100 mol % total diol residues in the polyester.

12. 13. A method for introducing or anchoring recycled content in polyester produced by the process of claim 1, comprising the steps of: a. obtaining a recycle monomer distribution for at least one recycle monomer comprising TPA, EG, DMT, CHDM, NPG, TMCD or DEG; b. converting recycled monomers to produce polyester in a synthesis process; c. designating at least a portion of the polyester to correspond to at least a portion of the recycled monomer allocation; and optionally d. offering for sale or selling the polyester as containing or obtained with a recycled monomer content corresponding to such designation; A method comprising:

13. The process according to any one of claims 1 to 11, wherein the amount of recycled polyester added to the process is from 5 to 100% with respect to the amount of TPA required.

14. 14. The process of any one of claims 1 to 11 or claim 13, further comprising the step of adding an esterification catalyst, polycondensation catalyst, or additive via the addition of recycled polyester, wherein the esterification catalyst, polycondensation catalyst, or additive is a component of the recycled polyester, such as Sb, Ti, Co, Mn, Li, Al, P.

Images