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WO2025193589A1 - Procédé de recyclage de polyester hautement résistant à la chaleur - Google Patents

Procédé de recyclage de polyester hautement résistant à la chaleur

Info

Publication number
WO2025193589A1
WO2025193589A1 PCT/US2025/019137 US2025019137W WO2025193589A1 WO 2025193589 A1 WO2025193589 A1 WO 2025193589A1 US 2025019137 W US2025019137 W US 2025019137W WO 2025193589 A1 WO2025193589 A1 WO 2025193589A1
Authority
WO
WIPO (PCT)
Prior art keywords
mole
residues
polyester
copolyester
glycol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2025/019137
Other languages
English (en)
Inventor
Brandon Philippe GINDT
Emmett Dudley Crawford
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Chemical Co
Original Assignee
Eastman Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eastman Chemical Co filed Critical Eastman Chemical Co
Publication of WO2025193589A1 publication Critical patent/WO2025193589A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/04—Disintegrating plastics, e.g. by milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/0026—Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting
    • B29B17/0042—Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting for shaping parts, e.g. multilayered parts with at least one layer containing regenerated plastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • This invention belongs to the field of polymer-based resins useful for forming articles intended for high heat resistance applications.
  • the articles are reusable, clear, dishwasher safe articles that are intrinsically recyclable.
  • Plastics are a preferred material for making articles/devices that are useful for food contact applications, e.g., food service/storage/preparation items that are reusable and dishwasher safe, based on the relative efficiency of molding articles of various shapes and designs. For example, food or beverage articles that will come into contact with food are often manufactured by molding plastic parts that form such articles.
  • plastics used in food and beverage applications that can be mechanically recycled can be reprocessed via solid-stating to both rebuild IV lost to thermal processing and decontaminate the recycled material to help achieve food contact requirements.
  • plastics e.g., PET
  • dish washer safe there is a need for plastic materials that have sufficient heat resistance to be reusable and dish washer safe, that are easily formed into articles, and that can also be mechanically recycled.
  • amorphous articles molded from certain copolyester plastics have sufficient heat resistance to be reusable and dish washer safe and can be mechanically recycled for subsequent use to remake such amorphous articles.
  • such articles can be useful as containers and/or other articles or devices that will contact food and can be reused by cleaning, e.g., in a dishwasher, and reusing the cleaned article numerous times.
  • such articles can be made from compositions of copolyesters that have a glass transition temperature (Tg) exceeding 85 0 C, or 90 0 C, or 95 0 C, and that can be mechanically recycled, e.g., using assets intended for recycling PET which decontaminate and increase IV.
  • Tg glass transition temperature
  • amorphous shaped articles e.g., optically clear articles, can be prepared from copolyester plastic materials that have sufficient heat resistance to provide dish washer safe articles and that can be mechanically recycled, including having the ability to rebuild inherent viscosity (IV) of the copolyester in the recycle process.
  • a process for producing a melt processible composition from polyester waste comprising: a) mechanically comminuting the polyester waste, b) optionally, granulating the comminuted polyester waste, c) crystallizing and solid-state polymerizing the comminuted or granulated polyester under conditions to provide a reformed polyester, and d) optionally, granulating the reformed polyester; wherein granulating step b) and/or d) is performed to provide a melt processible composition in a form that can be easily molded into an article; and wherein the polyester waste comprises at least one copolyester that comprises: (a) a dicarboxylic acid component comprising: i) 75 to 100 mole% of terephthalic acid residues; and ii) 0 to 25 mole% of modifying dicarboxylic acid residues; (b) a glycol component comprising: i) 0 to 100
  • step c) is carried out under conditions sufficient to increase the IV of the polyester and reduce or eliminate contaminants from the polyester, resulting in the reformed copolyester.
  • the modifying glycol comprises cyclic diol residues having a 3 to 5 member cyclic structure and/or having a bicyclic structure with each individual ring in the bicyclic structure having 3 to 5 members.
  • the at least one copolyester comprises: (a) a dicarboxylic acid component comprising: i) 90 to 100 mole % of terephthalic acid residues; (b) a glycol component comprising: i) 1 to 25, or 1 to 20, mole % of cyclic diol residues having a 3 to 5 member cyclic structure or having a bicyclic structure with each individual ring in the bicyclic structure having 3 to 5 members; and ii) 75 to 99, or 80 to 99, mole % of 1,4-cyclohexanedimethanol residues, wherein the total mole % of the dicarboxylic acid component is 100 mole %, and the total mole % of the glycol component is 100 mole %.
  • the at least one copolyester comprises: (a) a dicarboxylic acid component comprising: i) 90 to 100 mole % of terephthalic acid residues; (b) a glycol component comprising: i) 1 to 25, or 1 to 20, mole % of cyclic diol residues having a 3 to 5 member cyclic structure or having a bicyclic structure with each individual ring in the bicyclic structure having 3 to 5 members; and ii) 75 to 99, or 80 to 99, mole % of ethylene glycol residues, wherein the total mole % of the dicarboxylic acid component is 100 mole %, and the total mole % of the glycol component is 100 mole %.
  • the at least one copolyester comprises: (a) a dicarboxylic acid component comprising: i) 90 to 100 mole % of terephthalic acid residues; (b) a glycol component comprising: i) 1 to 25, or 1 to 20, mole % of cyclic diol residues having a 3 to 5 member cyclic structure or having a bicyclic structure with each individual ring in the bicyclic structure having 3 to 5 members; ii) 40 to 94, or 50 to 94, mole % of 1,4-cyclohexanedimethanol residues, and iii) 5 to 40, or 5 to 30, mole% of ethylene glycol residues, wherein the total mole % of the dicarboxylic acid component is 100 mole %, and the total mole % of the glycol component is 100 mole %.
  • the cyclic diol is 2,2,4,4-tetramethyl-1,3- cyclobutanediol (TMCD) and the glycol component comprises 1 to 20, or 5 to 20, mole % TMCD residues.
  • the cyclic diol is isosorbide and the glycol component comprises 1 to 20, or 5 to 20, mole % of isosorbide resides.
  • the at least one copolyester (contained in the polyester waste) has a Tg greater than 85 o C or greater than 90 o C, or in the range from 90 o C to 115 o C.
  • the dicarboxylic acid component comprises: i) 98 to 100 mole% of terephthalic acid residues; and ii) 0 to 2 mole% of isophthalic acid residues [0018] In other embodiments, the dicarboxylic acid component comprises 100 mole% terephthalic acid residues.
  • the glycol component comprises: i) 1 to 25 mole% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues; and ii) 75 to 99 mole% of ethylene glycol (EG) residues.
  • the glycol component comprises: i) 1 to 25 mole% of isosorbide (ISB) residues; ii) 40 to 94 mole% of 1,4-cyclohexanedimethanol (CHDM) residues; and iii) 5 to 40 mole% of ethylene glycol (EG) residues.
  • ISB isosorbide
  • CHDM 1,4-cyclohexanedimethanol
  • EG ethylene glycol
  • the copolyester composition has a crystallization half time from 3 to 30 minutes, or greater than 3 to 30 minutes, or 5 to 30 minutes, or greater than 5 minutes to 30 minutes, or 5.5 minutes to 30 minutes, or 3 to 20 minutes, or greater than 3 to 20 minutes, or 5 to 20 minutes, or greater than 5 minutes to 20 minutes, or 5.5 minutes to 20 minutes, or 3 to 10 minutes, or greater than 3 to 10 minutes, or 5 to 10 minutes, or greater than 5 minutes to 10 minutes, or 5.5 minutes to 10 minutes.
  • it is directed to a shaped article that comprises the melt processible composition (that contains the recycled copolyester).
  • the melt processible composition comprises a reformed polyester, wherein the reformed polyester comprises a copolyester having the same acid and diol residue composition as the at least one copolyester (contained in the polyester waste), a Tg of at least 90 0 C, or at least 95 0 C, or at least 100 0 C, and an inherent viscosity is 0.60 to 1.00, or 0.70 to 1.00 dL/g, or 0.70 to 0.95 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25oC.
  • the shaped articles or components thereof can be chosen from injection molded articles, extrusion molded articles, rotational molded articles, compression molded articles, blow molded articles, injection blow molded articles, injection stretch blow molded articles, extrusion blow molded articles, sheet or film extrusion articles, profile extrusion articles, gas assist molding articles, structural foam molded articles, or thermoformed articles.
  • the shaped article is chosen from transparent articles, see-through articles, thin-walled articles, technical articles (e.g., articles having a complex design), articles having high design specifications, intricate design articles, containers for holding food or beverage items, that require high heat resistance, e.g., higher heat resistance than PET and that are dish washer safe.
  • the copolyester composition further comprises at least one property chosen from: tensile modulus of greater than 1400 MPa as measured according to ASTM D638 using a 3.2 mm thick bar that has been subjected to 50% relative humidity for 40 hours at 23 o C; a notched izod impact strength of greater than 600, or 700, or 800, or 900, or 1000 J/m as measured according to ASTM D256 at 23C using a 3.2 mm thick bar that has been subjected to 50% relative humidity for 40 hours at 23 o C; a tensile stress at yield of at least 40 MPa, measured according to ASTM D638; a transmission of at least 70 measured according to ASTM D1003 using a 3.2 mm plaque after injection molding at a barrel set point of 249 o C and a mold temperature of 80 o C; a ⁇ E value of less than 25, using a 3.2 mm plaque after injection molding with a barrel temperature of 249 o C and
  • the polymer-based resin comprises at least 2, or at least 3 of the listed properties.
  • the melt processible composition comprises at least one reformed copolyester (i.e., reformed according to the process described herein) which comprises: (a) a dicarboxylic acid component comprising: i) 70 to 100 mole % of terephthalic acid residues; (b) a glycol component comprising: i) 1 to 25, or 1 to 20, mole % of cyclic diol residues having a 3 to 5 member cyclic structure or cyclic diol resides having a bicyclic structure with each individual ring in the bicyclic structure having 3 to 5 members; ii) 0 to 99 mole % of 1,4-cyclohexanedimethanol residues; and iii) 0 to 99 mole % of ethylene glycol residues, with the proviso that the glycol component comprises
  • the glycol component (of the reformed polyester) comprises 75 to 99, or 80 to 99, mole % of 1,4- cyclohexanedimethanol residues. In embodiments, the glycol component (of the reformed polyester) comprises 75 to 99, or 80 to 99, mole % of ethylene glycol residues.
  • the copolyester composition comprises a copolyester which comprises a glycol component chosen from: (1) 5 to 20 mole % of the cyclic diol residues and 55 to 95 mole % of the 1,4- cyclohexanedimethanol residues; or (2) 8 to 20 mole % of the cyclic diol residues and 55 to 92 mole % of the 1,4-cyclohexanedimethanol residues; or (3) 10 to 20 mole % of the cyclic diol residues and 55 to 90 mole % of the 1,4- cyclohexanedimethanol residues.
  • a copolyester which comprises a glycol component chosen from: (1) 5 to 20 mole % of the cyclic diol residues and 55 to 95 mole % of the 1,4- cyclohexanedimethanol residues; or (2) 8 to 20 mole % of the cyclic diol residues and 55 to 92 mole % of the 1,4
  • the cyclic diol can be an aliphatic cyclic diol or an aromatic cyclic diol. In embodiments, the cyclic diol can be an alicyclic diol. In embodiments, the cyclic diol is a cyclobutane diol, isosorbide, or combinations thereof. In one embodiment, the cyclic diol is a cyclobutane diol. In one embodiment, the cyclobutane diol is 2,2,4,4-tetramethyl-1,3- cyclobutanediol (TMCD). In one embodiment, the alicyclic diol is isosorbide.
  • TMCD 2,2,4,4-tetramethyl-1,3- cyclobutanediol
  • the reformed copolyester is amorphous. In other embodiments, the reformed copolyester is semi-crystalline.
  • at least one copolyester is a reactor grade polyester prepared by a process that includes a transesterification reaction of reaction mixture that includes all the monomers for the intended (monomeric) residues to be included in the copolyester.
  • a copolyester intended to include residues of TPA, CHDM and TMCD is prepared by a transesterification reaction that includes each of these monomers.
  • the reactor grade polyester is amorphous.
  • the at least one copolyester is a melt blend polyester prepared by a process that includes melt blending at least two different starting polyesters to provide a final copolyester that includes the monomeric residues contained in starting polyesters.
  • a PCTA copolyester containing residues of TPA, IPA and CHDM is melt blended with a PCT modified with residues of TMCD (PCTM) copolyester containing residues of TPA, CHDM and TMCD to provide a final copolyester having residues of TPA, IPA, CHDM and TMCD.
  • PCTM TMCD
  • a PCT copolyester containing residues of TPA and CHDM is melt blended with a PCTM copolyester containing residues of TPA, CHDM and TMCD to provide a final copolyester having residues of TPA, CHDM and TMCD (where the TMCD is in an amount less than the starting PCTM copolyester).
  • a PET polyester containing residues of TPA and EG is melt blended with a PETM copolyester containing residues of TPA, EG and TMCD to provide a final copolyester having residues of TPA, EG and TMCD (where the TMCD is in an amount less than the starting PETM copolyester).
  • the melt blended copolyester has residues in (net) amounts according to any of the embodiments for the copolyester (as described herein).
  • PCTM can be a PCT modified with less than 50 mole% TMCD residues, based on the total glycols.
  • the melt blended copolyester is subjected to solid stating to increase the inherent viscosity (IV) of the copolyester.
  • the solid stated copolyester has an IV according to any of the embodiments for the copolyester (as described herein).
  • a method for improving the ability to mechanically recycle a PCT polyester comprising: (1) providing Polyester A that comprises: (a) a dicarboxylic acid component comprising: i) 95 to 100 mole % of terephthalic acid residues; and ii) 0 to 5 mole% of isophthalic acid residues; and (b) a glycol component comprising: i) 95 to 100 mole % of 1,4-cyclohexanedimethanol residues, wherein the total mole % of the dicarboxylic acid component is 100 mole %, and the total mole % of the glycol component is 100 mole %; (2) combining Polyester A with Polyester B, wherein Polyester B is included in an amount sufficient to improve the mechanical recycling processing of the combination of Polyesters A and B compared to that of Polyester A, wherein Polyester B comprises: (a) a dicarboxylic acid component comprising: i) 70 to 100 mole
  • the blended polyester composition comprises: (a) a dicarboxylic acid component comprising: i) 70 to 100 net mole % of terephthalic acid residues; (b) a glycol component comprising: i) 1 to 25 net mole % of cyclic diol residues having a 3 to 5 member cyclic structure or cyclic diol resides having a bicyclic structure with each individual ring in the bicyclic structure having 3 to 5 members; and ii) 75 to 99 net mole % of 1,4-cyclohexanedimethanol residues, wherein the total net mole % of the dicarboxylic acid component is 100 mole %, and the total net mole % of the glycol component is 100 mole %; and wherein the inherent viscosity is 0.70 to 1.2 dL/g as determined in 60/40 (wt/wt) phenol/
  • Polyester B comprises: (a) a dicarboxylic acid component comprising: i) 100 mole % of terephthalic acid residues; (b) a glycol component comprising: i) 20 to 25 mole %, or 30 to 40 mole %, of 2,2,4,4- tetramethyl-1,3-cyclobutanediol residues resides; and ii) 75 to 80 mole %, or 60 to 70 mole %, of 1,4- cyclohexanedimethanol residues.
  • Polyester B comprises: (a) a dicarboxylic acid component comprising: i) 100 mole % of terephthalic acid residues; (b) a glycol component comprising: i) 10 to 35 mole %, or 15 to 35 mole %, or 15 to 25 mole %, of isosorbide resides; ii) 40 to 80 mole %, or 50 to 75 mole %, 60 to 75 mole%, of 1,4-cyclohexanedimethanol residues; and iii) 5 to 30 mole %, or 7 to 25 mole %, or 8 to 16 mole%, of ethylene glycol residues.
  • a dicarboxylic acid component comprising: i) 100 mole % of terephthalic acid residues
  • a glycol component comprising: i) 10 to 35 mole %, or 15 to 35 mole %, or 15 to 25 mole %, of isosorbide resides; ii) 40 to 80 mo
  • Polyester A comprises: (a) a dicarboxylic acid component comprising: i) 100 mole % of terephthalic acid residues; and (b) a glycol component comprising: i) 100 mole % of 1,4-cyclohexanedimethanol residues.
  • Polyester B is included in an amount to provide a weight ratio of Polyester A:B in a range from 90:10 to 50:50, or 90:10 to 60:40, or 90:10 to 65:35, or 85:15 to 50:50, or 85:15 to 60:40, or 85:15 to 65:35, or 80:20 to 50:50, or 80:20 to 60:40, or 80:20 to 65:35, or 80:20 to 70:30.
  • blending step (3) comprise melt blending Polyester A and Polyester B.
  • the blended polyester composition has a higher crystallization half-time.
  • the blended polyester composition builds IV faster during solid-state polymerization compared to Polyester A.
  • DETAILED DESCRIPTION [0040]
  • it is directed to a process for producing a melt processible composition from polyester waste, the process comprising: a) mechanically comminuting the polyester waste, b) optionally, granulating the comminuted polyester waste, c) crystallizing and solid-state polymerizing the comminuted or granulated polyester under conditions to provide a reformed polyester, and d) optionally, granulating the reformed polyester; wherein granulating step b) and/or d) is performed to provide a melt processible composition in a form that can be easily molded into an article; and wherein the polyester waste comprises at least one copolyester as described herein.
  • the polyester waste is subjected to a separation step.
  • the separation step is a step of separating and recovering a comminuted material having a copolyester rich fraction (i.e., high content of the at least one copolyester (described herein)) from a fraction having a low content of the at least one copolyester.
  • Examples of the separation step include a method of separating and sorting comminuted matter by electrostatic separation treatment using naturally occurring friction or attraction force caused by an electric charge generated on the surface by charging treatment described below, and a specific gravity sorting method using a difference in specific gravity of various materials.
  • the separation efficiency of the copolyester rich stream can be increased by performing the selection.
  • Specific examples of specific gravity sorting include wind sorting in which comminuted matter is sorted by wind power, methods in which the comminuted matter is immersed in a liquid such as water and sorted by the difference in specific gravity of the comminuted matter relative to the liquid, and methods in which comminuted matter having different specific gravity is separated and sorted by applying a constant vibration to the comminuted matter.
  • Wind selection for example, can be achieved by a method in which crushed matter impinged on an air stream generated by a spinning body has a large specific gravity or bulk specific gravity and naturally falls under its own weight in a spinning body device for generating an air stream; Examples thereof include a device for fractionating and recovering by means of a device having a small specific gravity or bulk specific gravity and being rolled up by an air stream, but any known device may be used.
  • Wind power sorting may be performed before comminuting or after comminuting, but is preferably performed before granulation described below. This is because the resin is more likely to be wound up by an air stream before granulation. Also, if the resin structure is ground into a powder, wind sorting can be difficult or inefficient.
  • the comminuting step may be performed between the primary comminuting and the secondary comminuting.
  • wind sorting for example, in addition to separating and removing labels and the like applied to multi-layer containers and the like, a portion of any non-copolyester resin may also be removed.
  • the copolyester rich fraction in the comminuted material may have higher specific gravity and bulk specific gravity then the other fraction, and therefore, in this step, the comminuted material that naturally falls under its own weight is recovered and supplied to the next step.
  • the comminuted material obtained after the separation step can be further processed in the washing step, crystallization step, solid-state polymerization step, and the like described below, but the non-copolyester content in the copolyester rich fraction, which is the final product, is substantially determined in the separation step.
  • the non-copolyester content in the comminuted material after the separation step is such that the resulting recycled copolyester product has excellent color and clarity.
  • a washing step will be carried out.
  • the method according to an embodiment of the present invention may further include a washing step of washing the used article in order to remove contents or the like adhering to the container or the like.
  • the comminuting step When performed after comminuting, the comminuting step may be performed before or after the separation step, but the pulverization step may be performed before any of granulation, crystallization, and solid-state polymerization is performed.
  • the washing step may be performed before the comminuting step, or may be performed simultaneously with the comminuting step using a wet comminuting step that simultaneously performs washing and comminuting.
  • a drying step may be performed after the washing step.
  • Sieving the comminuted matter makes it possible to reduce the non-uniformity of the thermal history that the comminuted matter receives in a subsequent process.
  • the sieving step is preferably performed simultaneously with the washing step described above or prior to the washing step, for example, the comminuted material may be sprayed onto the sieve, the comminuted material remaining on the sieve may be immersed in a liquid, or the comminuted material remaining on the sieve may be washed by dripping a liquid onto the comminuted material remaining on the sieve.
  • the removal of the fine powder by sieving may also be performed in the specific gravity sorting step described above.
  • the method for producing a reclaimed copolyester product according to the present invention includes a solid phase polymerization step for the purpose of removing volatile impurities contained in the polyester waste and improving the moldability of an intended article by increasing the molecular weight (or IV) of the used polyester.
  • a solid phase polymerization step for the purpose of removing volatile impurities contained in the polyester waste and improving the moldability of an intended article by increasing the molecular weight (or IV) of the used polyester.
  • the quality of the obtained recycled copolyester is improved, and the copolyester resin can be reused.
  • a solid- state polymerization step the molecular weight of the recycled copolyester is improved, forming processability is improved, and a container (or other article) using the recycled copolyester can have sufficient strength.
  • the solid- state polymerization step is ordinarily preferably performed after the separation step or the washing step. Since the impurity content is low after having undergone the separation step, or the washing step, degradation is less likely to occur even when heated by solid-state polymerization, and a high-quality recycled copolyester product is likely to be obtained.
  • the solid- state polymerization may be performed on a product pelletized by a granulation step described below, or, when the comminuted material is in a coarse form having a flake shape or the like, the solid-state polymerization may be performed on a coarse comminuted material having a flake shape or the like.
  • the coarse material and impurities are not melt-kneaded or subjected to a granulation step (e.g., as described below), so that the impurities that have undergone discoloration degradation after the solid-sate polymerization may be removed by a color selector or the like.
  • the solid-state polymerization is performed by maintaining the material temperature at a temperature of at least the melting point of the copolyester minus 55 °C and at most the melting point of the copolyester minus 5 °C for a certain period of time.
  • the material temperature refers to a temperature sensed by a thermocouple, a temperature sensor, or the like that can come into contact with the material directly or indirectly via a highly thermally conductive structural material or the like.
  • the upper limit temperature of the material during the solid- state polymerization to (the melting point of the copolyester resin-5 °C)
  • melting of the copolyester is prevented, and working efficiency is prevented from decreasing due to the copolyester adhering to the device (e.g., vessel) surface.
  • the lower limit temperature of the solid phase polymerization material is (the melting point of the copolyester resin-55 °C) or higher, a sufficient polymerization rate can be obtained, and impurities represented by e.g., acetaldehyde, can be efficiently removed, making it easier to obtain desired physical properties.
  • the lower limit temperature of the solid-state polymerization is preferably (melting point of the copolyester resin-35 °C) or higher.
  • the upper limit temperature of the solid-state polymerization is preferably not greater than the melting point of the copolyester - 10 °C.
  • the solid-state polymerization is performed at a vacuum of 1.5torr or less, or 0.6torr or less, or 0.2torr or less.
  • the "degree of vacuum” referred to herein refers to a value of a pressure in the apparatus that is held for a certain period of time after the material temperature reaches a predetermined temperature, and then does not reach a higher pressure until the internal temperature becomes less than a certain value, e.g., the melting point of the copolyester - 55°C, due to cooling.
  • the concentration of oxygen remaining in the solid-state polymerization apparatus is preferably reduced.
  • the oxygen concentration in the system is preferably 400 ppm or less, or 170 ppm or less.
  • the oxygen concentration assumed to remain in the system can be roughly calculated by the following calculation equation in which the oxygen concentration fraction in air is 20.9 % in terms of volume ratio.
  • X (Y/760) ⁇ (20.9/100)
  • X is the converted value of trace oxygen concentration in the system in the solid-state polymerization under vacuum
  • Y is the degree of vacuum (torr) in the system.
  • the oxygen concentration can be further lowered than the above formula by performing solid-state polymerization by replacing the inside of the system with an inert gas such as nitrogen in advance and then reducing pressure.
  • solid phase apparatuses for performing solid phase polymerization include tumbler type apparatuses equipped with a heating jacket, drying silo type apparatuses equipped with inert gas flow equipment, and crystallizing apparatuses and reactors provided with stirring blades and discharge screws inside, but any know apparatus can be used.
  • the heating time of the solid-state polymerization is determined appropriately based on the equipment and other conditions, but it is sufficient that the heating time be such that the copolyester has sufficient physical properties. In embodiments, it is preferable to continue until the intrinsic viscosity (IV) of the copolyester becomes 0.60 to 1.00, more preferably 0.71 to 0.90, and even more preferably 0.75 to 0.85.
  • the inventors of the present invention found that the rate of increase in intrinsic viscosity of the copolyester is increased by performing solid-state polymerization of a copolyester having a certain range of crystallization half-life. As a result, it is possible to reduce the heating time of solid-state polymerization to a shorter time, and furthermore, to obtain a recycled copolyester having sufficient intrinsic viscosity, high heat resistance (e.g., high Tg or HDT) and a low amount of impurities (resulting in good color and clarity). [0052] In embodiments, the recycled copolyester containing material is subjected to a granulation step.
  • the method includes a step of granulating the comminuted polyester material in order to obtain a product form that can be easily molded.
  • the granulation step may be performed before or after the solid-state polymerization, as long as the final form becomes pellets.
  • the comminuted material can be plasticized and granulated by melt blending.
  • the granulating device include a single-screw extruder, a twin-screw extruder, and a multi-screw extruder, however, any known granulator can be used.
  • the granulated form can suitably be cylindrical, pillow, spherical, or elliptical.
  • a crystallization step can be performed prior to the solid-state polymerization to avoid fusing of comminuted materials together or adhering to the inner surface of the solid-state polymerization (or other) device/apparatus.
  • the crystallization step may be performed after a granulation step. In the crystallization step, it is particularly important to crystallize the surface of the material in order to prevent fusion bonding and adhesion.
  • the copolyester containing material is held under constant heating, and specifically, heated at temperature in a range from 100 to 230 °C.
  • heat treatment may be performed after a fixed amount of water (or solvent) is added in order to promote crystallization of the surface.
  • the method of the present invention can include any of the following steps 1) to 4), and, in embodiments, performed in the stated order; however, the method is not particularly limited as long as the method includes a comminuting step, a separation step, and a solid- state polymerization step.
  • a sieving step may be performed immediately before or simultaneously with each washing step, or may be performed simultaneously with the comminuting step.
  • operations such as sorting according to the appearance of the container/article and the like, removing associated components to the article, e.g., a label, cap, or cap ring, cleaning the contents or deposits, and the like may be performed to the waste (or end-of-life) article prior to the following steps: 1) comminuting step, separation step, washing step, drying step, granulation step, crystallization step, solid-state polymerization; 2) comminuting step, washing step, drying step, separation step, granulation step, crystallization step, solid-state polymerization; 3) comminuting step, separating, washing, crystallizing, solid-state polymerizing, granulating, crystallizing; and 4) comminuting, washing, drying, separating, crystallizing, solid- state polymerizing, granulating, crystallizing.
  • the melt processible composition containing the recycled copolyester can be obtained by the above production method, and contains the copolyester as a main component.
  • the copolyester (as described herein) has high temperature resistance compared to PET, i.e., has sufficient heat resistance to be reusable and dish washer safe, but can be recycled and reformed using assets typically used for PET.
  • the recycled melt processible composition may have the same shape as a comminuted waste polyester such as a flake or a powder, but is preferably formed into a pellet shape by a granulation step, e.g., as described herein, and may be molded into other shapes such as a plate shape, container shape, bottle shape, or other drinkware, having good appearance, e.g., good color and clarity.
  • the color tone (b *) of a 2 mm thick plaque of the reclaimed copolyester product is preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less.
  • the inherent viscosity of the reclaimed copolyester product is preferably such that the difference between the inherent viscosity of the reclaimed copolyester product that has been subjected to solid- state polymerization and the inherent viscosity of the waste copolyester is at least 5 % higher.
  • the recycled copolyester contained in the melt processible composition can be reused as is as a resin raw material for molding various molded products by passing through the recycling step including the solid- state polymerization step of the present invention, but deterioration in quality such as yellowing can be reduced by diluting appropriately with new (or virgin) copolyester resin.
  • This diluted product can also be used as a resin raw material for molding various molded products.
  • the recycled copolyester is preferably a raw material of the same type of molded product as the resin structure supplied to the manufacturing method of the present invention, and it is more preferable that the resin structure supplied to the manufacturing method be a reusable food contact article that is dish washer safe, but has reached an end-of-life condition, and that the recycled copolyester product be a raw material of the same reusable food contact article.
  • the melt processible composition that comprises the recycled copolyester also has at least one of the following properties chosen from: tensile modulus of greater than 1400 MPa as measured according to ASTM D638 using a 3.2 mm thick bar that has been subjected to 50% relative humidity for 40 hours at 23 o C; a notched izod impact strength of greater than 700, or 800, or 900, or 1000 J/m as measured according to ASTM D256 at 23C using a 3.2 mm thick bar that has been subjected to 50% relative humidity for 40 hours at 23 o C; a tensile stress at yield of at least 40 MPa, measured according to ASTM D638; a transmission of at least 88 measured according to ASTM D1003 using a 3.2 mm plaque after injection molding at a barrel set point of 249 o C and a mold temperature of 80 o C; a ⁇ E value of less than 25, using a 3.2 mm plaque after injection molding with a barrel temperature of 249
  • the polymer-based resin has at least 2, or at least 3 of the listed properties.
  • the term “polyester,” as used herein, is intended to include “copolyesters” and is understood to mean a synthetic polymer prepared by the reaction of one or more difunctional carboxylic acids and/or multifunctional carboxylic acids with one or more difunctional hydroxyl compounds and/or multifunctional hydroxyl compounds.
  • the difunctional carboxylic acid can be a dicarboxylic acid
  • the difunctional hydroxyl compound can be a dihydric alcohol such as, for example, glycols and diols.
  • glycol as used in this application includes, but is not limited to, diols, glycols, and/or multifunctional hydroxyl compounds, for example, branching agents.
  • the difunctional carboxylic acid may be a hydroxy carboxylic acid such as, for example, p-hydroxybenzoic acid
  • the difunctional hydroxyl compound may be an aromatic nucleus bearing 2 hydroxyl substituents such as, for example, hydroquinone.
  • reduce as used herein, means any organic structure incorporated into a polymer through a polycondensation and/or an esterification reaction from the corresponding monomer.
  • the term “repeating unit,” as used herein, means an organic structure having a dicarboxylic acid residue and a diol residue bonded through a carbonyloxy group.
  • the dicarboxylic acid residues may be derived from a dicarboxylic acid monomer or its associated acid halides, esters, salts, anhydrides, or mixtures thereof.
  • dicarboxylic acid is intended to include dicarboxylic acids and any derivative of a dicarboxylic acid, including its associated acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof, useful in a reaction process with a diol to make polyester.
  • the term “diacid” includes multifunctional acids, for example, branching agents.
  • terephthalic acid is intended to include terephthalic acid itself and residues thereof as well as any derivative of terephthalic acid, including its associated acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof or residues thereof useful in a reaction process with a diol to make polyester.
  • terephthalic acid may be used as the starting material.
  • dimethyl terephthalate may be used as the starting material.
  • mixtures of terephthalic acid and dimethyl terephthalate may be used as the starting material and/or as an intermediate material.
  • at least a portion of the terephthalic acid or dimethyl terephthalate used as a starting material has recycle content derived directly or indirectly from recycle waste.
  • the recycle content can be obtained from waste plastic that contains terephthalic acid residues, e.g., recovered monomers obtained through a solvolysis (e.g., methanolysis) process.
  • the terephthalic acid residues present in the polyester contains at least 50 mole%, or at least 75 mole%, or 100 mole% recycle content.
  • the dicarboxylic acid component of the polyester comprises monomer residues having at least 50 mole% recycle content, or at least 75 mole% recycle content, or 100 mole% recycle content.
  • the polyester includes a diol component that comprises CHDM and/or TMCD and/or EG residues.
  • at least a portion of the CHDM and/or TMCD and/or EG used as a starting material has recycle content derived directly or indirectly from recycle waste.
  • the recycle content can be obtained from waste plastic that contains CHDM and/or TMCD and/or EG residues, e.g., recovered monomers obtained through a solvolysis (e.g., methanolysis) process.
  • the CHDM and/or TMCD and/or EG residues present in the Polyester contains at least 50 mole%, or at least 75 mole%, or 100 mole% recycle content.
  • the glycol component of the Polyester comprises monomer residues having at least 50 mole% recycle content, or at least 75 mole% recycle content, or 100 mole% recycle content.
  • the polyester (as described herein) can have (or include) a recycle content that is provided by chemical recycling where waste material is broken down into small molecules that are then used to make the polyester, e.g., a waste stream (e.g., containing waste plastic) is gasified to produce syngas and the syngas is then utilized in one or more reaction schemes to produce the polyester.
  • a recycle content polyester can also be provided that has (or includes) recycle content using a mass balance approach. In a mass balance approach, a recycle content value is determined and then applied or associated with the polyester.
  • a “recycle content value” is a unit of measure representative of a quantity of material having its origin in recycled waste, e.g., recycled plastic.
  • the particular recycle content value can be determined by a mass balance approach or a mass ratio or percentage or any other unit of measure and can be determined according to any system for tracking, allocating, and/or crediting recycle content among various compositions.
  • a recycle content value can be deducted from a recycle content inventory and applied to a product or composition (e.g., the polyester) to attribute recycle content to the product or composition (e.g., the polyester).
  • a recycle content value can come from waste material (e.g., mixed waste plastic) and can be applied to the polyester based on a mass balance approach that takes into account the stoichiometry and efficiencies of the processes used to make the polyester.
  • the recycled content in the polyester can be at least partially derived from recycled polyester of the same type, providing a circular recycling solution.
  • the circular recycling solution can include determining recycle content value (or credits) for waste polyester of the same type and applying at least a portion of such recycle value or credit to the new polyester (e.g., by a mass balance approach), or can be a closed loop process for providing a recycle polyester where at least a portion of the feedstock utilized in the process/reaction scheme to make the polyester is obtained from the same polyester type.
  • the closed loop process is based on chemical recycling and not mechanical recycling.
  • the closed loop can include end of life vapor delivery articles being used as feedstock to provide recycle content to renewed vapor delivery articles containing recycle content polyester compositions (as described herein).
  • a closed loop process is differentiated from an open loop process in that the renewed articles made in an open loop process are different from the end of life articles recycled as a feedstock material.
  • the match between recycled articles and renewed material made in a closed loop system does not have to be compositionally identical, e.g., the recycled articles can have a different polymer formulation but have a similar based polyester with the same types of monomer residues.
  • the process to provide recycle content can be operated as a closed loop process and an open loop process simultaneously.
  • the polyester composition used to make the articles contains at least 10, or at least 15, or at least 20, or at least 25, or at least 30, or at least 40, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or 100 wt% recycle content, by any of the methods (or combinations of methods) for providing recycle content described herein.
  • the polyester composition can include content sourced from renewable sources, such as bio-based materials.
  • the bio-based material is isosorbide.
  • the polyester contains both recycle content and bio-based (or other renewable source) content.
  • the mole percentages provided in the present disclosure may be based on the total moles of acid residues, the total moles of diol residues, or the total moles of repeating units.
  • a polyester containing 4 mole% isophthalic acid based on the total acid residues, means the polyester contains 4 mole% isophthalic acid residues out of a total of 100 mole% acid residues.
  • a polyester containing 15 mole% 2,2,4,4- tetramethyl-1,3-cyclobutanediol means the polyester contains 15 mole% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues out of a total of 100 mole% diol residues.
  • the Tg of the polyesters useful in the invention can be at least one of the following ranges: 95 to 115°C; 95 to 110°C; 95 to 105°C; 95 to 100°C; 100 to 115°C; 100 to 110°C; 100 to 105°C; 105 to 115°C; 105 to 110°C; and 110 to 115°C.
  • the reformed copolyester comprises at least one copolyester which comprises: (a) a dicarboxylic acid component comprising: i) 70 to 100 mole % of terephthalic acid residues; (b) a glycol component comprising: i) 1 to 25 mole % of cyclic diol residues having a 3 to 5 member cyclic structure or cyclic diol resides having a bicyclic structure with each individual ring in the bicyclic structure having 3 to 5 members; and ii) 0 to 99 mole % of 1,4-cyclohexanedimethanol residues; and iii) 0 to 99 mole % of ethylene glycol residues, with the proviso that the glycol component comprises at least 40 mole % of 1,4-cyclohexanedimethanol or ethylene glycol residues, wherein the total mole % of the dicarboxylic acid component is 100 mole %, and the total
  • the glycol component (of the reformed polyester and/or at least one copolyester) comprises 75 to 99, or 80 to 99, mole % of 1,4- cyclohexanedimethanol residues. In embodiments, the glycol component (of the reformed polyester and/or at least one copolyester) comprises 75 to 99, or 80 to 99, mole % of ethylene glycol residues.
  • the reformed polyester and/or at least one copolyester comprises a glycol component chosen from: (1) 1 to 20 mole % of the cyclic diol residues and 55 to 99 mole % of the 1,4-cyclohexanedimethanol residues; or (2) 1 to 15 mole % of the cyclic diol residues and 55 to 99 mole % of the 1,4-cyclohexanedimethanol residues; or (3) 1 to 10 mole % of the cyclic diol residues and 55 to 99 mole % of the 1,4-cyclohexanedimethanol residues.
  • a glycol component chosen from: (1) 1 to 20 mole % of the cyclic diol residues and 55 to 99 mole % of the 1,4-cyclohexanedimethanol residues; or (2) 1 to 15 mole % of the cyclic diol residues and 55 to 99 mole % of the 1,4-cyclohexanedimethanol residues; or
  • the glycol component for the polyesters can include but is not limited to at least one of the following combinations of ranges: 12 to 18 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 82 to 88 mole % 1,4-cyclohexanedimethanol; 13 to 17 mole % 2,2,4,4-tetramethyl-1,3- cyclobutanediol and 83 to 87 mole % 1,4-cyclohexanedimethanol; and 14 to 16 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 84 to 86 mole % 1,4- cyclohexanedimethanol.
  • the copolyesters can contain less than 15 mole % ethylene glycol residues, such as, for example, 0.01 to less than 15 mole % ethylene glycol residues.
  • the polyesters useful in the invention contain less than 10 mole %, or less than 5 mole %, or less than 4 mole %, or less than 2 mole %, or less than 1 mole % ethylene glycol residues, such as, for example, 0.01 to less than 10 mole %, or 0.01 to less than 5 mole %, or 0.01 to less than 4 mole %, or 0.01 to less than 2 mole %, or 0.01 to less than 1 mole %, ethylene glycol residues.
  • the copolyesters useful in the invention contain no ethylene glycol residues.
  • the glycol component for the polyesters can include but is not limited to at least one of the following combinations of ranges: 1 to 20 mole % isosorbide, 60 to 98 mole % 1,4-cyclohexanedimethanol, and 1 to 20 mole% EG; 1 to 18 mole % isosorbide, 64 to 98 mole % 1,4- cyclohexanedimethanol, and 1 to 18 mole% EG; 1 to 16 mole % isosorbide, 68 to 98 mole % 1,4-cyclohexanedimethanol, and 1 to 16 mole% EG; 5 to 20 mole % isosorbide, 60 to 90 mole % 1,4-cyclohexanedimethanol, and 5 to 20 mole% EG; 5 to 18 mole % isosorbide, 64 to 90 mole % 1,4-cyclohexanedimethanol, and 5 to 20 mole% EG; 5 to 18 mole % isosorbide, 64
  • the polyesters can include a copolyester comprising: (a) diacid residues comprising from about 90 to 100 mole percent of TPA residues and from 0 to about 10 mole percent IPA residues; and (b) diol residues comprising at least 75 mole percent of EG residues and up to 25 mole percent of TMCD residues, wherein the copolyester comprises a total of 100 mole percent diacid residues and a total of 100 mole percent diol residues.
  • the copolyester comprises: a) a dicarboxylic acid component comprising: (i) 90 to 100 mole% terephthalic acid residues; and (ii) about 0 to about 10 mole % of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a glycol component comprising: (i) about 5 to about 20 mole % 2,2,4,4-tetramethyl-1,3- cyclobutanediol (TMCD) residues; and (ii) about 80 to about 95 mole % ethylene glycol residues; and wherein the total mole % of the dicarboxylic acid component is 100 mole %, and wherein the total mole % of the glycol component is 100 mole %.
  • a dicarboxylic acid component comprising: (i) 90 to 100 mole% terephthalic acid residues; and (ii) about 0 to about 10 mole % of aromatic and/
  • the inherent viscosity (IV) of such polyester is from 0.50 to 0.8 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at 25°C; and wherein the L* color values for the polyester is 90 or greater, as determined by the L*a*b* color system measured following ASTM D 6290-98 and ASTM E308- 99, performed on polymer granules ground to pass a 1 mm sieve.
  • the L* color values for the polyester is greater than 90, as determined by the L*a*b* color system measured following ASTM D 6290-98 and ASTM E308-99, performed on polymer granules ground to pass a 1 mm sieve.
  • the glycol component of the copolyester comprises: (i) about 5 to about 18 mole % 2,2,4,4-tetramethyl-1,3- cyclobutanediol (TMCD) residues and (ii) about 82 to about 95 mole % ethylene glycol residues; or (i) about 5 to about 16 mole % 2,2,4,4-tetramethyl-1,3- cyclobutanediol (TMCD) residues and (ii) about 84 to about 95 mole % ethylene glycol residues; or (i) about 10 to about 20 mole % 2,2,4,4-tetramethyl-1,3- cyclobutanediol (TMCD) residues and (ii) about 80 to about 90 mole % ethylene glycol residues; or (i) about 10 to about 18 mole % 2,2,4,4-tetramethyl-1,3- cyclobutanediol (TMCD) residues and
  • the reformed polyesters useful in the invention may exhibit at least one of the following inherent viscosities as determined in 60/40 (wt/wt) phenol/ tetrachloroethane at a concentration of 0.5 g/100 ml at 25oC: 0.65 to 1.2 dL/g; 0.65 to 1.1 dL/g; 0.65 to 1 dL/g; 0.65 to less than 1 dL/g; 0.65 to 0.98 dL/g; 0.65 to 0.95 dL/g; 0.65 to 0.90 dL/g; 0.65 to 0.85 dL/g; 0.65 to 0.80 dL/g; 0.65 to 0.75 dL/g; 0.65 to less than 0.75 dL/g; 0.65 to 0.72 dL/g; 0.65 to 0.70 dL/g; or 0.65 to less than 0.70 dL/g; 0.70 to 1.2 dL/g; 0.70 to 1.1
  • polyester compositions of the invention can possess at least one of the inherent viscosity ranges described herein and at least one of the monomer ranges for the compositions described herein unless otherwise stated. It is also contemplated that the polyester compositions of the invention can possess at least one of the Tg ranges described herein and at least one of the monomer ranges for the compositions described herein unless otherwise stated. It is also contemplated that the polyester compositions of the invention can possess at least one of the Tg ranges described herein, at least one of the inherent viscosity ranges described herein, and at least one of the monomer ranges for the compositions described herein unless otherwise stated.
  • the molar ratio of cis/trans 2,2,4,4- tetramethyl-1,3-cyclobutanediol can vary from the pure form of each or mixtures thereof.
  • the molar percentages for cis and/or trans 2,2,4,4-tetramethyl-1,3-cyclobutanediol are greater than 50 mole % cis and less than 50 mole % trans; or greater than 55 mole % cis and less than 45 mole % trans; or 30 to 70 mole % cis and 70 to 30 % trans; or 40 to 60 mole % cis and 60 to 40 mole % trans; or 50 to 70 mole % trans and 50 to 30 mole % cis; or 50 to 70 mole % cis and 50 to 30 % trans or 60 to 70 mole % cis and 30 to 40 mole % trans; or greater than 70 mole % cis and less than 30 mo
  • terephthalic acid, or an ester thereof such as, for example, dimethyl terephthalate, or a mixture of terephthalic acid and an ester thereof, makes up most or all of the dicarboxylic acid component used to form the polyesters useful in the invention.
  • terephthalic acid residues can make up a portion or all of the dicarboxylic acid component used to form the present polyester at a concentration of at least 70 mole %, such as at least 80 mole %, at least 90 mole%, at least 95 mole%, at least 99 mole%, or, in one preferred embodiment (e.g., reactor grade), 100 mole %.
  • polyesters with higher amounts of terephthalic acid can be used in order to produce higher impact strength properties.
  • the terms "terephthalic acid” and "dimethyl terephthalate are used interchangeably herein.
  • dimethyl terephthalate is part or all of the dicarboxylic acid component used to make the polyesters useful in the present invention. In all embodiments, ranges of from 70 to 100 mole %; or 80 to 100 mole %; or 90 to 100 mole %; or 99 to 100 mole %; or 100 mole % terephthalic acid and/or dimethyl terephthalate and/or mixtures thereof may be used.
  • the dicarboxylic acid component of the polyesters useful in the invention can comprise up to 25 mole %, up to 20 mole %, up to 10 mole %, up to 5 mole %, or less than 5 mole%, or up to 3 mole%, or up to 2 mole%, or up to 1 mole % of one or more modifying aromatic dicarboxylic acids.
  • the polyester contains 0 mole % modifying aromatic dicarboxylic acids.
  • the amount of one or more modifying aromatic dicarboxylic acids can range from any of these preceding endpoint values including, for example, from 0.01 to 25 mole %, from 0.01 to 20 mole %, from 0.01 to 10 mole %, from 0.01 to 5 mole %, from 0.01 to less than 5 mole %, from 0.01 to 4 mole %, from 0.01 to 3 mole %, from 0.01 to 2 mole %, or from 0.01 to 1 mole % of one or more modifying aromatic dicarboxylic acids.
  • the amount of one or more modifying aromatic dicarboxylic acids can range from 1 to 5 mole %, from 1 to less than 5 mole %, from 1 to 4 mole %, from 1 to 3 mole %, from 1 to 2 mole %, or from 1.5 to 5 mole %, from 1.5 to less than 5 mole %, from 1.5 to 4 mole %, from 1.5 to 3.5 mole %, from 1.5 to 3 mole %, from 1.5 to 2.5 mole %, from 1.5 to 2 mole %, or from 2 to 5 mole %, from 2 to less than 5 mole %, from 2 to 4 mole %, from 2 to 3.5 mole %, from 2 to 3 mole %, from 2 to 2.5 mole %, or from 2.5 to 5 mole %, from 2.5 to less than 5 mole %, from 2.5 to 4 mole %, from 2.5 to 3.5 mole %, from 2.5 to 3 mole %, from 3 to 5 mole %, from 3 to 5 mole
  • modifying aromatic dicarboxylic acids that may be used in the present invention include but are not limited to those having up to 20 carbon atoms, and that can be linear, para-oriented, or symmetrical.
  • modifying aromatic dicarboxylic acids which may be used in this invention 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'-stilbenedicarboxylic acid, and esters thereof.
  • the modifying dicarboxylic acid is furan dicarboxylic acid.
  • isophthalic acid is the modifying aromatic dicarboxylic acid.
  • the preferred embodiment of the invention is for 100% of the dicarboxylic acid component based on terephthalic acid residues.
  • the carboxylic acid component of the polyesters useful in the invention can be further modified with up to 10 mole %, such as up to 5 mole % or up to 1 mole % of one or more aliphatic dicarboxylic acids containing 2-16 carbon atoms, such as, for example, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic and dodecanedioic dicarboxylic acids.
  • Certain embodiments can also comprise 0.01 or more mole %, such as 0.1 or more mole %, 1 or more mole %, 5 or more mole %, or 10 or more mole % of one or more modifying aliphatic dicarboxylic acids.
  • the polyester contains 0 mole % modifying aliphatic dicarboxylic acids.
  • the amount of one or more modifying aliphatic dicarboxylic acids can range from any of these preceding endpoint values including, for example, from 0.01 to 10 mole % and from 0.1 to 10 mole %.
  • the total mole % of the dicarboxylic acid component is 100 mole %.
  • esters of terephthalic acid and the other modifying dicarboxylic acids or their corresponding esters and/or salts may be used instead of the dicarboxylic acids.
  • Suitable examples of dicarboxylic acid esters include, but are not limited to, the dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, and diphenyl esters.
  • the esters are chosen from at least one of the following: methyl, ethyl, propyl, isopropyl, and phenyl esters.
  • the 1,4-cyclohexanedimethanol may be cis, trans, or a mixture thereof, for example, a cis/trans ratio of 60:40 to 40:60.
  • the trans-1,4-cyclohexanedimethanol can be present in the amount of 60 to 80 mole %.
  • the glycol component of the polyester portion of the polyester compositions useful in the invention can contain 14 mole % or less of one or more additional modifying glycols which are not 2,2,4,4-tetramethyl-1,3-cyclobutanediol or 1,4- cyclohexanedimethanol; in another embodiment, the polyesters useful in the invention can contain 10 mole % or less of one or more modifying glycols. In another embodiment, the polyesters useful in the invention can contain 5 mole % or less of one or more modifying glycols. In another embodiment, the polyesters useful in the invention can contain 3 mole % or less of one or more modifying glycols.
  • the polyesters useful in the invention may contain 0 mole % modifying glycols. Certain embodiments can also contain 0.01 or more mole %, such as 0.1 or more mole %, 1 or more mole %, 5 or more mole %, or 10 or more mole % of one or more modifying glycols. Thus, if present, it is contemplated that the amount of one or more modifying glycols can range from any of these preceding endpoint values including, for example, from 0.1 to 10 mole %.
  • modifying glycols useful in the polyesters useful in the invention refer to diols other than 2,2,4,4- tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol and may contain 2 to 16 carbon atoms.
  • Suitable modifying glycols include, but are not limited to, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3- propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, p-xylene glycol, isosorbide or mixtures thereof.
  • the modifying glycol is ethylene glycol.
  • the modifying glycols include but are not limited to 1,3-propanediol and/or 1,4-butanediol.
  • ethylene glycol is excluded as a modifying diol.
  • 1,3-propanediol and 1,4-butanediol are excluded as modifying diols.
  • 2,2-dimethyl-1,3-propanediol is excluded as a modifying diol.
  • the polyesters described herein can comprise from 0 to 10 mole percent, for example, from 0.01 to 5 mole percent, from 0.01 to 1 mole percent, from 0.05 to 5 mole percent, from 0.05 to 1 mole percent, or from 0.1 to 0.7 mole percent, or 0.1 to 0.5 mole percent, based the total mole percentages of either the diol or diacid residues; respectively, of one or more residues of a branching monomer, also referred to herein as a branching agent, having 3 or more carboxyl substituents, hydroxyl substituents, or a combination thereof.
  • the branching monomer or agent may be added prior to and/or during and/or after the polymerization of the polyester.
  • the polyester(s) useful in the invention can thus be linear or branched.
  • the branching monomer or agent may be added prior to and/or during and/or after the polymerization.
  • branching monomers include, but are not limited to, multifunctional acids or multifunctional alcohols such as trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, glycerol, pentaerythritol, citric acid, tartaric acid, 3-hydroxyglutaric acid and the like.
  • the branching monomer residues can comprise 0.1 to 0.7 mole percent of one or more residues chosen from at least one of the following: trimellitic anhydride, pyromellitic dianhydride, glycerol, sorbitol, 1,2,6- hexanetriol, pentaerythritol, trimethylolethane, and/or trimesic acid.
  • the branching monomer may be added to the polyester reaction mixture or blended with the polyester in the form of a concentrate as described, for example, in U.S. Patent Nos. 5,654,347 and 5,696,176, whose disclosure regarding branching monomers is incorporated herein by reference.
  • the polyesters described herein can be made by processes known from the literature such as, for example, by processes in homogenous solution, by transesterification processes in the melt, and by two phase interfacial processes. Suitable methods include, but are not limited to, the steps of reacting one or more dicarboxylic acids with one or more glycols at a temperature of 100°C to 315°C at a pressure of 0.1 to 760 mm Hg for a time sufficient to form a polyester. See U.S. Patent No. 3,772,405 for methods of producing polyesters, the disclosure regarding such methods is hereby incorporated herein by reference.
  • the polyesters described herein can also be prepared by reactive melt blending and extrusion of two polyesters.
  • a polyester containing 100% terephthalic acid residues; 10 mole% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and 90 mole% 1,4- cyclohexanedimethanol can be prepared by reactive melt blending and extrusion of equal amounts of a polyester containing 100 mole% terephthalic residues and 100% 1,4-cyclohexanedimethanol with another polyester containing 100 mole% terephthalic residues; 80 mole % 1,4- cyclohexanedimethanol residues, and 20 mole% 2,2,4,4-tetramethyl-1,3- cyclobutanediol residues.
  • the reformed and/or at least one copolyester is a melt blend polyester prepared by a process that includes melt blending at least two different starting polyesters to provide a final copolyester that includes the monomeric residues contained in starting polyesters.
  • a PCTA copolyester containing residues of TPA, IPA and CHDM is melt blended with a PCTM copolyester containing residues of TPA, CHDM and TMCD to provide a final copolyester having residues of TPA, IPA, CHDM and TMCD.
  • a PCT copolyester containing residues of TPA and CHDM is melt blended with a PCTM copolyester containing residues of TPA, CHDM and TMCD to provide a final copolyester having residues of TPA, CHDM and TMCD (where the TMCD is in an amount less than the starting PCTM copolyester).
  • a PCT copolyester containing residues of TPA and CHDM is melt blended with an Isosorbide copolyester containing residues of TPA, CHDM, Isosorbide and EG to provide a final copolyester having residues of TPA, CHDM, Isosorbide and EG (where the Isosorbide and EG are in amounts less than the starting Isosorbide copolyester).
  • the melt blended copolyester has residues in (net) amounts according to any of the embodiments for the copolyester (as described herein)
  • the polyesters described herein, prepared in a reactor or by melt blending/extrusion can subsequently be crystallized if needed and solid stated by techniques known in the art to further increase the IV.
  • the article made from copolyester composition can be amorphous.
  • amorphous means a crystallinity or less than 1%.
  • the article made from copolyester composition can be semi-crystalline, e.g., by crystallizing with heat.
  • the article of the invention has a crystallinity of from 1 to 40%, or 1 to 35%, or 1 to 30%, or 5 to 40%, or 5 to 35%, or 5 to 30%, or 10 to 40%, or 10 to 35%, or 10 to 30%.
  • the article made from the copolyester composition can have strain induced crystallinity. Strain induced crystallization refers to a phenomenon in which an initially amorphous solid material undergoes a phase transformation in which some amorphous domains are converted to crystalline domains due to the application of strain. This phenomenon has important effects in strength and fatigue properties.
  • the article of the invention has a strain induced crystallinity of from 1 to 40%, or 1 to 35%, or 1 to 30%, or 5 to 40%, or 5 to 35%, or 5 to 30%, or 10 to 40%, or 10 to 35%, or 10 to 30%, when stretched at a temperature above the Tg of the polyester, e.g., during molding or forming processes, such as stretch blow molding.
  • the article is a clear semi-crystalline article comprising a copolyester that has a crystallization half-time of less than 25 minutes but greater than about 5 minutes.
  • the copolyester has a crystallization half-time from about 5 minutes to 20 minutes, or 5 minutes to 15 minutes, or 5 minutes to 10 minutes.
  • the article of the invention can comprise the polyester of the invention having a melting temperature (Tm) from 260°C to 300°C.
  • the polyester useful in this invention may also contain from 0.01 to 25% by weight or 0.01 to 20% by weight or 0.01 to 15% by weight or 0.01 to 10% by weight or 0.01 to 5% by weight of the total weight of the polyester composition of common additives such as colorants, dyes, mold release agents, reheat additives, flame retardants, plasticizers, stabilizers, including but not limited to, UV stabilizers, thermal stabilizers and/or reaction products thereof, fillers, and impact modifiers.
  • common additives such as colorants, dyes, mold release agents, reheat additives, flame retardants, plasticizers, stabilizers, including but not limited to, UV stabilizers, thermal stabilizers and/or reaction products thereof, fillers, and impact modifiers.
  • Examples of typical commercially available impact modifiers well known in the art and useful in this invention include, but are not limited to, ethylene/propylene terpolymers; functionalized polyolefins, such as those containing methyl acrylate and/or glycidyl methacrylate; styrene-based block copolymeric impact modifiers; and various acrylic core/shell type impact modifiers.
  • UV additives can be incorporated into articles of manufacture through addition to the bulk, through application of a hard coat, or through coextrusion of a cap layer. Residues of such additives are also contemplated as part of the polyester composition.
  • the polyesters described herein can comprise at least one chain extender.
  • Suitable chain extenders include, but are not limited to, multifunctional (including, but not limited to, bifunctional) isocyanates, multifunctional epoxides, including for example, epoxylated novolacs, and phenoxy resins.
  • chain extenders may be added at the end of the polymerization process or after the polymerization process. If added after the polymerization process, chain extenders can be incorporated by compounding or by addition during conversion processes such as injection molding or extrusion.
  • the amount of chain extender used can vary depending on the specific monomer composition used and the physical properties desired but is generally about 0.1 percent by weight to about 10 percent by weight, preferably about 0.1 to about 5 percent by weight, based on the total weight of the polyester.
  • Thermal stabilizers are compounds that stabilize polyesters during polyester manufacture and/or post polymerization including, but not limited to, phosphorous compounds including but not limited to phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphonous acid, and various esters and salts thereof. These can be present in the polyester compositions described herein.
  • the esters can be alkyl, branched alkyl, substituted alkyl, difunctional alkyl, alkyl ethers, aryl, and substituted aryl.
  • the number of ester groups present in the particular phosphorous compound can vary from zero up to the maximum allowable based on the number of hydroxyl groups present on the thermal stabilizer used.
  • thermo stabilizer is intended to include the reaction products thereof.
  • reaction product as used in connection with the thermal stabilizers of the invention refers to any product of a polycondensation or esterification reaction between the thermal stabilizer and any of the monomers used in making the polyester as well as the product of a polycondensation or esterification reaction between the catalyst and any other type of additive.
  • Reinforcing materials may be useful in the compositions of this invention.
  • the reinforcing materials may include, but are not limited to, carbon filaments, silicates, mica, clay, talc, titanium dioxide, Wollastonite, glass flakes, glass beads and fibers, and polymeric fibers and combinations thereof.
  • the reinforcing materials are glass, such as, fibrous glass filaments, mixtures of glass and talc, glass and mica, and glass and polymeric fibers.
  • the articles can include, but are not limited to, injection blow molded articles, injection stretch blow molded articles, extrusion blow molded articles, extrusion stretch blow molded articles, calendered articles, compression molded articles, and solution casted articles. Methods of making the articles of manufacture, include, but are not limited to, extrusion blow molding, extrusion stretch blow molding, injection blow molding, injection stretch blow molding, calendering, compression molding, and solution casting.
  • the melt processible composition has a notched izod impact strength of at least 800 J/m, or at least 900 J/m, as measured according to ASTM D256 using a 3.2 mm thick bar hat has been subjected to 50% relative humidity for 48 hours at 23 o C. In certain embodiments, the melt processible composition has a notched izod impact strength of at least 1000 J/m, or at least 1050 J/m, as measured according to ASTM D256 using a 3.2 mm thick bar that has been subjected to 50% relative humidity for 48 hours at 23 o C.
  • the melt processible composition has a ⁇ E value of less than 25, or less than 20, or less than 15, or less than 14, or less than 13, or less than 12, or less than 11, or less than 10, or less than 9, or less than 8, or less than 7, or less than 6, or less than 5, using a 3.2 mm plaque after injection molding with a barrel temperature of 249 o C and a mold temperature of 80 o C, wherein ⁇ E is determined by the following equation: ((L* - 100) 2 + (a* - 0) 2 + (b* -0) 2 ) 1/2 , where the L*, a*, and b* color components were measured according to ASTM E1348.
  • the melt processible composition has a ⁇ E value in the range from 2 to 25, or from 2 to 20, or from 2 to 15, or from 2 to 14, or from 2 to 13, or from 2 to 12, or from 2 to 11, or from 2 to 10, or from 2 to 9, or from 2 to 8, or from 2 to 7, or from 2 to 6, or from 2 to 5, using a 3.2 mm plaque after injection molding with a barrel temperature of 249 o C and a mold temperature of 80 o C, wherein ⁇ E is determined by the following equation: ((L* - 100) 2 + (a* - 0) 2 + (b* -0) 2 ) 1/2 , where the L*, a*, and b* color components were measured according to ASTM E1348.
  • the melt processible composition has an L* color of at least 85, or at least 86, or at least 87, or at least 88, or at least 89, or at least 90, or at least 91, or at least 92, or at least 93, or at least 94, or at least 95, measured according to ASTM E1348 using a 3.2 mm plaque after injection molding with a barrel temperature of 249 o C and a mold temperature of 80 o C.
  • the melt processible composition has an L* color in the range from 85 to 98, or from 85 to 97, or from 85 to 96, or from 85 to 95, measured according to ASTM E1348 using a 3.2 mm plaque after injection molding with a barrel temperature of 249 o C and a mold temperature of 80 o C.
  • the melt processible composition has a b* value is less than 15, or less than 12, or less than 10, or less than 9, or less than 8, or less than 7, or less than 6, or less than 5, or less than 4, measured according to ASTM E1348 using a 3.2 mm plaque after injection molding with a barrel temperature of 249 o C and a mold temperature of 80 o C.
  • the polymer-based resin has a b* color in the range from 0 to 15, or from 0 to 10, or from 0 to 8, or from 0 to 5, measured according to ASTM E1348 using a 3.2 mm plaque after injection molding with a barrel temperature of 249 o C and a mold temperature of 80 o C.
  • ASTM E1348 using a 3.2 mm plaque after injection molding with a barrel temperature of 249 o C and a mold temperature of 80 o C.
  • it is directed to shaped articles.
  • the shaped articles are not continuously extruded films that are infinite (or continuous) in one direction and fixed in width and thickness in the other two directions, as would be the case in a rolled film.
  • a film or sheet can be converted into a shaped article, e.g., by thermoforming into a three-dimensional object, such as a cup or bowl.
  • the shaped article is not a film or is not a sheet.
  • the shaped articles can be chosen from injection molded articles, extrusion molded articles, rotational molded articles, compression molded articles, blow molded articles, injection blow molded articles, injection stretch blow molded articles, extrusion blow molded articles, sheet or film extrusion articles, profile extrusion articles, gas assist molding articles, structural foam molded articles, or thermoformed articles.
  • the shaped article is chosen from transparent articles, see-through articles, thin-walled articles, technical articles (e.g., articles having a complex design), articles having high design specifications, intricate design articles, containers, wearable articles, household articles, general consumer products, packaging articles, medical articles, high touch articles, or components thereof, where the article has high heat resistance (as discussed herein).
  • the melt processible composition can be primary molded into forms such as pellets, plates, or parisons, and can then be secondary molded into articles, e.g., conduits, tubes, thin-wall vessels, or thick- wall vessels, containers, or other food storage or handling articles.
  • Test Methods Properties disclosed herein requiring a test method can be determined as follows: Test Methods [00117] Properties disclosed throughout this application can be determined according to the test methods described herein. Samples were (or can be) evaluated using standard ASTM test methods with any special conditions noted below.
  • the inherent viscosity of the polyesters was determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C (according to ASTM D4603).
  • the glycol content was determined by proton nuclear magnetic resonance (NMR) spectroscopy. All NMR spectra were recorded on a JEOL Eclipse Plus 600MHz nuclear magnetic resonance spectrometer using either chloroform-trifluoroacetic acid (70-30 volume/volume).
  • T max is defined as the temperature required to melt the crystalline domains of the sample (if crystalline domains are present).
  • the T max reported in the examples below represents the temperature at which each sample was heated to condition the sample prior to crystallization half time measurement.
  • the Tmax temperature is dependent on composition and is typically different for each polyester. For example, PCT may need to be heated to some temperature greater than 290°C to melt the crystalline domains.
  • DSC Differential scanning calorimetry
  • the sample weight in the range of 8 to 12 mg, was measured and recorded. Samples were first heated (1 st heating scan) from 0 to 320 °C at 20 °C/min, followed by cooling to 0 °C at 20 °C/min (cooling scan), and then heated again from 0 to 320 °C at 20 °C min. Various thermal parameters were measured and recorded. ⁇ H cc (cal/g) is the heat of crystallization measured from the cooling scan. Tcc is the crystallization peak temperature on the cooling scan. Tg is the glass transition temperature measured from 2 nd heating scan. Tm is the melting point measured during the 2 nd heating scan.
  • ⁇ Hch1 (cal/g) is the heat of crystallization measured during the 1 st heating scan.
  • ⁇ Hm1 (cal/g) is the heat of melting measured during the 1 st heating scan.
  • the percent crystallinity formed during cooling is calculated by equation (1), assuming a specific heat of fusion of 29 cal/g (based on unmodified PCT). The peak temperature in the crystallization exotherm (Tcc) occurs at 227°C for unmodified PCT.
  • the percentage of strain induced crystallinity ( ⁇ c ) was determined by equation (2) from the first heating scan of films evaluated in a DSC.
  • the abbreviation "wt" means "weight”.
  • Example 1 –Copolyester Resins Two different co-polyester resins were prepared via melt polymerization using a tin-based catalyst from monomers that included dimethyl terephthalate (DMT), 1,4-cyclohexanedimethanol (CHDM) and 2,2,4,4- tetramethyl-1,3-cyclobutanediol (TMCD).
  • DMT dimethyl terephthalate
  • CHDM 1,4-cyclohexanedimethanol
  • TMCD 2,2,4,4- tetramethyl-1,3-cyclobutanediol
  • the resulting resins were formed into cylindrical pellets having an average length of about 4-5mm and an average diameter of about 2-3mm_.
  • the resins each had an acid component that included 100 mole% terephthalic acid residues contributed by the DMT.
  • the target TMCD residue mole% for Resins 1 and 2 were 14 and 16 mole%, respectively.
  • the actual glycol composition, residual Sn (from the catalyst) and properties of the co-polyester resins are listed below in Table 1. Table 1.
  • Co-polyester Resins Example 2 – Crystalizing and Solid-State Polymerizing [00127] The pellets for each resin were first subjected to a thermal crystallization step to form a crystalline layer on the surface of the particles to prevent sticking and agglomeration during the solid-sate polymerization process. The thermal crystallization process was performed by heating pellets from example 1 in an oven at 135°C for 3 hours. The pellets turned from clear to opaque and remained free flowing. [00128] The crystallized pellets for each resin were subjected to a solid- state polymerization (SSP) process where the pellets were held at a temperature of 225°C for a specified time to increase the IV of the resin.
  • SSP solid- state polymerization
  • Crystallized resin from example 1 was loaded into a solid-state polymerization apparatus consisting of 6 sample chambers.
  • the sample ports were charged with 20g of resin and purged with nitrogen and vacuum was applied to reduce pressure down to 1 torr.
  • the sample ports were then inserted into a 225°C heating block and one sample port was removed every 4 hours.
  • the IV was measured as a function of time at 4 hour intervals. The results are listed below in Table 2. Table 2. IV Over Time [00130] A review of Table 3 reveals that the IV increased for both resins over time.
  • Example 3 Test Plaques Test Plaque Production
  • Pellets of each resin from Example 1 were injection molded to form standard test plaques 1.0 inch x 1.0 inch x 0.125 inch (2.5 cm x 2.5 cm x 0.3 cm). Molding was done on a BOY 22A injection molding machine equipped with a double color plaque mold. Material was dried in a 65°C oven prior to molding. Material was molded with a barrel temperature of roughly 270°C, mold temperature of 55°C and a cycle time of 25s.
  • Example 4 – Optical Properties of Molded Plaques Test Results Haze and Transmittance (%) [00132] Haze and Transmittance data was measure using a Gardner Haze-gard plus, using ASTM D1003 as a method.
  • the grinding was performed by cooling color plaques in liquid nitrogen for at least 30 minutes followed by fracturing color plaques with a hydraulic press. Fragments were then retreated with liquid nitrogen passed through a Wiley Mill with a 6mm screen.
  • the ground powder for each resin was first subjected to a thermal crystallization step similar to Example 2.
  • the crystallized powder for each resin was then subjected to a solid-state polymerization (SSP) process similar to Example 2 except the SSP process was terminated after 14 hours.
  • the solid-stated Resin 1 powder had an IV of 0.75 dL/g and the solid-stated Resin 2 powder had an IV of 0.63 dL/g.
  • Example 6 Test Plaques and Optical Properties of Re-molded Plaques
  • Test plaques were made from the solid-stated resin powders similar to Example 3 and optical properties were measured for the remolded plaques similar to Example 4.
  • the results of haze and transmittance testing, color testing and IV of the Resin (after re-molding) is listed below in Table 4.
  • Table 4. Color, Haze and Transmittance [00139] A review of Table 4 reveals that the IV dropped for each resin after being subjected to the plaque molding process. For both resins: L*, a* and %T, decreased; and b* and % haze increased, compared to the plaques produced from the initial (or virgin) resins.

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Abstract

L'invention concerne un procédé de production d'une composition pouvant être traitée à l'état fondu à partir de déchets de polyester, le procédé comprenant : (i) le broyage mécanique des déchets de polyester, (ii) éventuellement, la granulation des déchets de polyester broyés, (iii) la cristallisation et la polymérisation à l'état solide du polyester broyé ou granulé dans des conditions permettant d'obtenir un polyester reformé, et (iv) éventuellement, la granulation du polyester reformé, les déchets de polyester comprenant un copolyester ayant une résistance à la chaleur supérieure à celle du PET.
PCT/US2025/019137 2024-03-11 2025-03-10 Procédé de recyclage de polyester hautement résistant à la chaleur Pending WO2025193589A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3772405A (en) 1972-02-02 1973-11-13 Eastman Kodak Co Process for preparing aromatic diester containing copolyesters and products obtained thereby
US5654347A (en) 1993-10-04 1997-08-05 Eastman Chemical Company Concentrates for improving polyester compositions and method of making same
US5696176A (en) 1995-09-22 1997-12-09 Eastman Chemical Company Foamable polyester compositions having a low level of unreacted branching agent
US20060287496A1 (en) * 2005-06-17 2006-12-21 Crawford Emmett D Polyester compositions comprising minimal amounts of cyclobutanediol
EP2329856B1 (fr) * 2003-04-29 2019-07-24 Eastman Chemical Company Récipients contenant des compositions polyester, qui contiennent du cyclobutanediol
WO2023091540A1 (fr) * 2021-11-22 2023-05-25 Eastman Chemical Company Articles en copolyesters recyclables avec charnières vivantes
KR102599800B1 (ko) * 2021-10-12 2023-11-08 이경희 폐pet를 활용한 고품위 리싸이클 pet 칩의 제조방법

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3772405A (en) 1972-02-02 1973-11-13 Eastman Kodak Co Process for preparing aromatic diester containing copolyesters and products obtained thereby
US5654347A (en) 1993-10-04 1997-08-05 Eastman Chemical Company Concentrates for improving polyester compositions and method of making same
US5696176A (en) 1995-09-22 1997-12-09 Eastman Chemical Company Foamable polyester compositions having a low level of unreacted branching agent
EP2329856B1 (fr) * 2003-04-29 2019-07-24 Eastman Chemical Company Récipients contenant des compositions polyester, qui contiennent du cyclobutanediol
US20060287496A1 (en) * 2005-06-17 2006-12-21 Crawford Emmett D Polyester compositions comprising minimal amounts of cyclobutanediol
KR102599800B1 (ko) * 2021-10-12 2023-11-08 이경희 폐pet를 활용한 고품위 리싸이클 pet 칩의 제조방법
WO2023091540A1 (fr) * 2021-11-22 2023-05-25 Eastman Chemical Company Articles en copolyesters recyclables avec charnières vivantes

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