WO1996030428A1 - Procede de preparation de polyesters - Google Patents

Procede de preparation de polyesters Download PDF

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Publication number
WO1996030428A1
WO1996030428A1 PCT/US1996/003739 US9603739W WO9630428A1 WO 1996030428 A1 WO1996030428 A1 WO 1996030428A1 US 9603739 W US9603739 W US 9603739W WO 9630428 A1 WO9630428 A1 WO 9630428A1
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WO
WIPO (PCT)
Prior art keywords
mol
solid state
cyclohexanedimethanol
ethylene glycol
prepolymer
Prior art date
Application number
PCT/US1996/003739
Other languages
English (en)
Inventor
Randy Steven Beavers
Karen Lynn Carman
Michael Lynn Cassell
Joseph Franklin Knight
Marc Alan Strand
Sara Stanley Wells
Original Assignee
Eastman Chemical Company
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 Company filed Critical Eastman Chemical Company
Priority to AU53163/96A priority Critical patent/AU5316396A/en
Publication of WO1996030428A1 publication Critical patent/WO1996030428A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/80—Solid-state polycondensation

Definitions

  • This invention relates to an improved process for making high molecular weight poly(ethylene terephthalate) copolyesters in a solid phase polymerization process.
  • the improved process involves the use of small amounts of 1,4—cyclohexanedimethanol and diethylene glycol in the copolyester composition which provides for significantly improved rates of inherent viscosity buildup.
  • PET Poly(ethylene terephthalate) (PET) polymers are useful in a wide variety of applications including fibers, molding plastics, sheeting, films and the like. For some applications such as tire cord fibers, beverage and food bottles or containers and food trays, it is necessary to use very high molecular weight poly(ethylene terephthalate) polymers. The melt viscosity of such high molecular weight PET type polymers is so high that it is not feasible or practical to make them by conventional melt phase processes.
  • U.S. 4,446,303 discloses a process for making high molecular weight PET and modified PET which involves one or more recrystallizations of the polymer incident to solid—state polycondensation reactions. These recrystallizations restore the high polycondensation activity experienced in the early stages of the reaction.
  • U.S. 4,314,928 relates to PET polymers containing up to 10 mol % of certain specified branched or unbranched C to C 10 diols which are subjected to a solid phase post—condensation reaction to provide polymers with a fast crystallization rate.
  • the patent is not concerned with diethylene glycol containing copolymers.
  • U.S. 4,849,497 describes the preparation of PET in which solid state polymerization rates are claimed to be improved by utilizing polyester prepolymers which are in the form of porous pills.
  • U.S. 4,917,845, U.S. 4,957,945 and U.S. 4,792,573 describe high molecular weight polyester resin prepared by rapid solid state polymerization from polyester prepolymer in the form of porous pills.
  • U.S. 4,217,440 describes a method for making branched polyesters. The patent does not involve solid phase polycondensation techniques.
  • U.S. 3,544,523 describes the polycondensation of PET polymer in the solid state using anticaking agents such as talc to prevent sticking during polycondensation.
  • U.S. 4,876,326 and U.S 4,755,587 describe the solid state polymerization of polyester polymers in the form of porous pills, giving high molecular weight products in a short time.
  • European Patent Application 269,583 and Italy 1,199,166 describe a fixed bed solid state polycondensation of granular polyesters after a crystallization treatment with carbon dioxide.
  • U.S 4,234,708 describes branched PET polymers containing branching agents such as pentaerythritol.
  • U.S. 4,238,593 describes PET production by solid state polymerization of prepolymer having an optimum carboxyl content.
  • U.S. 4,150,215 describes the preparation of catalyst—free high molecular weight PET by solid—state polymerization of ground low molecular weight polymer.
  • U.S. 4,165,420 describes the solid state polymerization of polyester prepolymer using discrete spherical beads of prepolymer prepared by a spray congealing process.
  • U.S. 4,154,920 describes a thermally stable PET for carbonated beverage containers obtained by solid—state polymerization of prepolymer.
  • U.S. 4,092,458 describes the preparation of polyester pellets from flakes of waste polyester film giving easily handled material for solid phase polymerization.
  • U.S. 4,069,194 describes the solid state polymerization of linear polyesters by moving a mixture of polyester granules and spherical glass particles through a heated reactor.
  • Japan Patent 18116 (1974) describes the solid phase polymerization of particulated aromatic polyesters in a rotating reactor.
  • U.S. 3,960,817 describes polyester polycondensation in the solid phase by heating the polymer in contact with an inert gas under vacuum.
  • a process for improving the rate of solid state polymerization of ethylene terephthalate polymers or copolymers comprising copolymerizing at least 80 mol % terephthalic acid or dimethyl terephthalate and at least 80 mol % ethylene glycol with 2—10 mol % diethylene glycol and 0.1—10 mol % cyclohexanedimethanol to form a prepolymer having an I.V. of 0.30 to 0.70, forming solid particles from said prepolymer, and solid state polymerizing said particles at a temperature between the glass transition temperature and melting point of said particles until a predetermined I.V. is reached.
  • the rate of change in I.V. units has been observed to be 0.015 dL/g per hour at 215°C. It has now been discovered that the rate of I.V. increase can be substantially improved by incorporating small amounts of diethylene glycol and 1,4—cyclohexane ⁇ dimethanol in the PET polymer.
  • the copolyesters can have an I.V. build—up rate twice as fast as that observed with unmodified PET polymers. Such rate increases have a significant economic impact on the manufacturing costs of high molecular weight PET polymers.
  • the polymers of this invention are made by first making a prepolymer using melt phase polycondensation techniques.
  • melt phase procedures are well known to those skilled in the art.
  • a wide range of metal based catalysts may be used and may include catalysts based on titanium, manganese, antimony, cobalt, germanium, tin and the like or mixtures of these materials.
  • the prepolymers generally have I.V. values of 0.30 dL/g to 0.70 dL/g.
  • the prepolymers are granulated or pelletized by conventional methods and these particles are then heated at 180°C to 230°C under vacuum or with an inert gas passing through the reactor bed to remove ethylene glycol that diffuses out of the pellets or granules.
  • diethylene glycol and 1,4—cyclohexanedimethanol could be incorporated in PET polymers to provide solid state polymerization rate increases.
  • Diethylene glycol concentrations in the copolyesters generally range from 1.5 to 10 mol % while preferred concentrations are 2 to 7 mol %.
  • concentrations of 1,4—cyclohexane ⁇ dimethanol include 0.1 to 10 mol % with a preferred range of 0.5 to 5 mol %.
  • concentrations of diethylene glycol and 1,4—cyclohexanedimethanol are not desirable because this decreases the softening point of the polymer which makes it difficult to solid state the copolymers without the pellets sticking in the solid state polymerization bed.
  • Either the cis, trans or cis trans isomer mixtures of 1,4—cyclohexanedimethanol may be used. It is also possible to use the 1,3— or 1,2—cyclohexanedimethanol isomers instead of 1,4—cyclohexanedimethanol.
  • diethylene glycol and cyclohexanedimethanol it is also possible to have small amounts of other glycols present such as 1,4—butanediol, 1,6-hexanediol, neopentyl glycol and the like. In such cases, the amount of comonomer glycol must be limited so that the crystallinity of the PET copolyester is not eliminated.
  • 1,4—butanediol, 1,6-hexanediol, neopentyl glycol and the like the amount of comonomer glycol must be limited so that the crystallinity of the PET copolyester is not eliminated.
  • terephthalic acid and esterify it with ethylene glycol, 1,4—cyclohexanedimethanol and diethylene glycol prior to the melt phase polycondensation reaction 1,4—cyclohexanedimethanol and diethylene glycol prior to the melt phase polycondensation reaction.
  • dialkyl terephthalate ester such as dimethyl terephthalate
  • transesterify it with the glycol moieties prior to the melt phase polycondensation reaction Small amounts of other dibasic acids or their esters may be used if desired. For example, up to 10 mol % of other acids such as succinic, adipic, suberic, isophthalic, naphthalene— dicarboxylic, cyclohexanedicarboxylic and the like may be used.
  • branched copolyesters containing up to 1.0 mol % of suitable branching agents may be made by the process of this invention.
  • Useful branching agents include tricarboxylic acids or ester forming derivatives thereof such as trimellitic (1,2,4—benzenetricarboxylie) acid and anhydride, hemimellitic (1,2,3—benzenetricarboxylic) acid and anhydride, trimesic (1,3,5-benzenetricarboxylic) acid and tricarballyic (1,2,3-propanetricarboxylic) acid.
  • any tricarboxylic residue containing 6 to 9 carbon atoms may be used.
  • the trifunctional residue also may be derived from an aliphatic triol containing 3 to 8 carbon atoms such as glycerin, trimethylolethane and trimethylolpropane.
  • the amount of the trifunctional monomer residue present in the copolyester preferably is in the range of 0.05 to 0.25 mol %.
  • the preferred trifunctional monomer residues are residues of benzenetricarboxylic acids (including anhydrides) , especially trimellitic acid or anhydride.
  • copolyesters of this invention are frequently used as produced in the form of fibers or in molded or extruded shapes
  • additives frequently used in polymers may also be present. These additives may include dyes, colorants, pigments, fillers, stabilizers, molding agents and the like.
  • Example 1 Branched PET Copolyester Containing 3.1 Mol % of 1.4-Cyclohexanedimethanol and 5.3 Mol % of Diethylene Glvcol —
  • 96.81 g (0.50 mole) of dimethyl terephthalate, 58.28 g (0.94 mole) of ethylene glycol, 2.52 g (0.018 mole) of a 30/70 cis trans mixture of 1,4—cyclo— hexanedimethanol, 1.33 g (0.013 mole) of diethylene glycol, 0.19 g (0.001 mole) of trimellitic anhydride, 0.17 mL of a solution of titanium tetraisopropoxide in 1-butanol which is 1.12 wt vol % titanium, 1.50 mL of a solution of manganese acetate in acetic acid and ethylene glycol which is 0.49 wt/vol % manganese,
  • Example 2 PET Copolyester Containing 3.7 Mol % of 1.4—Cyclohexane Dimethanol and 4.2 Mol % of Diethylene Glycol —
  • Example 3 PET Copolyester Containing 3.5 Mol % of 1.4—Cvclohexane Dimethanol and 6.4 Mol % of Diethylene Glvcol -
  • dimethyl terephthalate 58.28 g (0.94 mole) of ethylene glycol
  • 2.52 g 0.018 mole
  • diethylene glycol 0.17 mL of a solution of titanium tetraisopropoxide in 1—butanol which is 1.12 wt/vol % titanium
  • 1.80 L a solution of antimony acetate in ethylene glycol which is 1.23 w
  • Example 4 Branched PET Copolyester Containing 0.7 Mol % of 1.4-Cyclohexanedimethanol and 5.7 Mol % of Diethylene Glycol -
  • 96.80 g (0.50 mole) of dimethyl terephthalate, 58.90 g (0.95 mole) of ethylene glycol, 0.36 g (0.003 mole) of a 30/70 cis/trans mixture of 1,4—cyclohexanedimethanol, 2.39 g (0.023 mole) diethylene glycol, 0.19 g (0.001 mole) trimellitic anhydride, 0.17 mL of a solution of titanium tetraisopropoxide in 1-butanol which is 1.12 wt/vol % titanium, 1.50 mL of a solution of manganese acetate in acetic acid and ethylene glycol which is 0.49 wt/vol % manganese, 1.80 L of
  • Example 5 PET Copolyester Containing 3.6 Mol % of 1.4—Cvclohexane Dimethanol and 1.4 Mol % of Diethylene Glycol — To a 500 mL single neck flask are charged
  • the copolyesters in this report were characterized by the following methods: Inherent Viscosity (I.V.) — a 0.5 g sample of polymer was dissolved in a 60/40 mixture of phenol tetrachloroethane. The I.V. was determined at 25°C.
  • I.V. Inherent Viscosity
  • Mol % Glycols The mol % glycols were determined by gas chromatography.
  • Mol % Brancher The concentration of trimellitic anhydride (TMA) was determined by liquid chromatography.
  • Examples 6-14 Preparation of PET Copolyesters in a Continuous Melt Phase Reactor Process - Copolyesters containing 0.0 to 7.9 mol % of 1,4—cyclohexane ⁇ dimethanol, 1.0 to 8.4 mol % of diethylene glycol and 0.20 ⁇ 0.03 mol % of trimellitic anhydride are prepared in a continuous reactor. To the first ester exchange reactor is continuously fed molten dimethyl terephthalate, ethylene glycol, and the catalyst components in ethylene glycol. Ester interchange begins in the first reactor which is maintained at 190—210°C under a positive pressure of 40 psi.
  • the reaction mixture is forced by differential pressure through additional ester exchange reactors and the temperature is increased up to 250°C, while the pressure is reduced to 7 psi.
  • an ethylene glycol ester of trimellitic acid and the additional catalysts are added to the product stream and the mixture of monomer and low molecular weight oligomers are pumped into a prepolymer reactor.
  • the temperature is 255°C and the pressure is reduced to
  • the temperature is increased to 270°C and the pressure is decreased to 80 mm Hg.
  • the molten prepolymer is pumped into a finishing reactor where melt phase polycondensation is completed at 280°C using a pressure of ⁇ 4 mm Hg pressure.
  • the viscous copolymer is extruded through a rod die into a water bath where the material is quenched before being pelletized.
  • Copolymers from Examples 6—14 are screened to obtain a pellet diameter between 0.079 inches and 0.132 inches.
  • the copolymers are solid state polymerized for 24 hours at 205° or 215°C in a glass laboratory static bed solid state unit using 1,3—butanediol or diethyl succinate as the heat exchange solvents.
  • a nitrogen gas flow of 4 scfh is passed through the sample particle bed. Samples are taken after 0, 1, 2, 3, 4, 5, 6, 9, 12, 15, 18, 21 and 24 hours of solid state time. The inherent viscosity is measured on these samples to determine the rate of I.V. increase per hour. The results are summarized in
  • the dryer is rotated on a shaft and heated at 205°C with 4 scfm (standard cubic feet per minute) of dry nitrogen passing through the reactor to remove the ethylene glycol after it is liberated from the surface of the pellet.
  • Polymer pellets are removed every 2 hours to determine the rate of I.V. change.
  • Table 3 These results show that increasing the diethylene concentration from 1.9 mol % to 8.4 mol % and solid stating the samples in a larger scale pilot plant process gives a 54% increase in solid state polycondensation rate (Examples 15 and 19).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

Cette invention concerne un procédé permettant d'améliorer le taux de polymérisation à l'état solide de copolymères ou de polymères de téréphtalate d'éthylène, consistant à copolymériser de l'acide téréphtalique ou du téréphtalate de diméthyle et de l'éthylène glycol avec du diéthylène glycol en un pourcentage molaire de 2 à 10 % et du cyclohexanediméthanol en un pourcentage molaire de 0,1 à 10 %, ceci afin d'obtenir un prépolymère. Des particules solides sont ensuite obtenues à partir du prépolymère, lesquelles particules seront polymérisées à l'état solide à une température située entre la température de transition du verre et celle du point de fusion desdites particules, ceci jusqu'à ce que l'on atteigne un indice de viscosité intrinsèque prédéterminé.
PCT/US1996/003739 1995-03-27 1996-03-20 Procede de preparation de polyesters WO1996030428A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU53163/96A AU5316396A (en) 1995-03-27 1996-03-20 Process for preparing polyesters

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US41135695A 1995-03-27 1995-03-27
US08/411,356 1995-03-27

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WO1996030428A1 true WO1996030428A1 (fr) 1996-10-03

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AR (1) AR000405A1 (fr)
AU (1) AU5316396A (fr)
CO (1) CO4560369A1 (fr)
IL (1) IL117668A0 (fr)
TR (1) TR199600215A2 (fr)
WO (1) WO1996030428A1 (fr)
ZA (1) ZA962456B (fr)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0854160A2 (fr) * 1997-01-21 1998-07-22 Eastman Chemical Company Copolyester à transparence améliorée
WO1998049217A1 (fr) * 1997-05-01 1998-11-05 Eastman Chemical Company Procede de preparation de polyesters
WO1998058008A1 (fr) * 1997-06-19 1998-12-23 Eastman Chemical Company Copolymeres de poly(ethylene terephtalate) (pet) comportant des fragments de 1,4-cyclohexanedimethal (chdm) et d'acide isophtalique
US6197878B1 (en) 1997-08-28 2001-03-06 Eastman Chemical Company Diol latex compositions and modified condensation polymers
US6246112B1 (en) 1998-06-11 2001-06-12 Intel Corporation Interleaved signal trace routing
WO2001042334A1 (fr) * 1999-12-07 2001-06-14 Wellman, Inc. Methode de preparation de resines pour bouteilles en polyester modifie
US6329462B1 (en) 1999-06-18 2001-12-11 Eastman Chemical Company Nylon 6/silicone blends
US6340726B1 (en) 1999-03-03 2002-01-22 Eastman Chemical Company Silicone polymer diol compositions and condensation polymer/silicone polymer blends
WO2002016464A2 (fr) * 2000-08-24 2002-02-28 Milliken & Company Procede de production de materiaux thermoplastiques en polyester colore comportant des operations specifiques de solidification
US6353052B1 (en) 1999-06-18 2002-03-05 Eastman Chemical Company Amide-type polymer/silicone polymer blends and processes of making the same
US6362306B1 (en) * 1999-08-17 2002-03-26 Eastman Chemical Company Reactor grade copolyesters for shrink film applications
US6403698B1 (en) 1999-03-03 2002-06-11 Eastman Chemical Company Polyamide/emulsion polymer blends
KR100614622B1 (ko) * 2000-07-21 2006-08-21 주식회사 코오롱 폴리에스테르계 고수축 연신 필름 및 그의 제조방법
EP3130623A1 (fr) * 2009-03-03 2017-02-15 The Coca-Cola Company Conditionnement de polyéthylène téréphtalate d'origine biologique et son procédé de fabrication

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5362844A (en) * 1993-03-23 1994-11-08 Zimmer Aktiengesellschaft Continuous process for the production of polyester for food packaging
WO1996007690A1 (fr) * 1994-09-06 1996-03-14 Eastman Chemical Company Copolyesters ramifies convenant particulierement au moulage par extrusion soufflage

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5362844A (en) * 1993-03-23 1994-11-08 Zimmer Aktiengesellschaft Continuous process for the production of polyester for food packaging
WO1996007690A1 (fr) * 1994-09-06 1996-03-14 Eastman Chemical Company Copolyesters ramifies convenant particulierement au moulage par extrusion soufflage

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0854160A2 (fr) * 1997-01-21 1998-07-22 Eastman Chemical Company Copolyester à transparence améliorée
EP0854160A3 (fr) * 1997-01-21 2000-10-18 Eastman Chemical Company Copolyester à transparence améliorée
WO1998049217A1 (fr) * 1997-05-01 1998-11-05 Eastman Chemical Company Procede de preparation de polyesters
US6048957A (en) * 1997-05-01 2000-04-11 Eastman Chemical Company Process for polyesters with improved properties
WO1998058008A1 (fr) * 1997-06-19 1998-12-23 Eastman Chemical Company Copolymeres de poly(ethylene terephtalate) (pet) comportant des fragments de 1,4-cyclohexanedimethal (chdm) et d'acide isophtalique
US6103857A (en) * 1997-06-19 2000-08-15 Eastman Chemical Company Poly(ethylene terephthalate) (PET) copolymers containing both 1,4-cyclohexanedimethanol and isophthalic acid moieties
US6197878B1 (en) 1997-08-28 2001-03-06 Eastman Chemical Company Diol latex compositions and modified condensation polymers
US6417269B1 (en) 1997-08-28 2002-07-09 Eastman Chemical Company Methods of making modified condensation polymers
US6417239B1 (en) 1997-08-28 2002-07-09 Eastman Chemical Company Methods of making modified condensation polymers
US6246112B1 (en) 1998-06-11 2001-06-12 Intel Corporation Interleaved signal trace routing
US6352914B2 (en) * 1998-06-11 2002-03-05 Intel Corporation Interleaved signal trace routing
US6340726B1 (en) 1999-03-03 2002-01-22 Eastman Chemical Company Silicone polymer diol compositions and condensation polymer/silicone polymer blends
US6403698B1 (en) 1999-03-03 2002-06-11 Eastman Chemical Company Polyamide/emulsion polymer blends
US6353052B1 (en) 1999-06-18 2002-03-05 Eastman Chemical Company Amide-type polymer/silicone polymer blends and processes of making the same
US6329462B1 (en) 1999-06-18 2001-12-11 Eastman Chemical Company Nylon 6/silicone blends
US6362306B1 (en) * 1999-08-17 2002-03-26 Eastman Chemical Company Reactor grade copolyesters for shrink film applications
US6335422B2 (en) 1999-12-07 2002-01-01 Wellman, Inc. Method of preparing modified polyester bottle resins
US6284866B1 (en) 1999-12-07 2001-09-04 Wellman, Inc. Method of preparing modified polyester bottle resins
WO2001042334A1 (fr) * 1999-12-07 2001-06-14 Wellman, Inc. Methode de preparation de resines pour bouteilles en polyester modifie
KR100614622B1 (ko) * 2000-07-21 2006-08-21 주식회사 코오롱 폴리에스테르계 고수축 연신 필름 및 그의 제조방법
WO2002016464A3 (fr) * 2000-08-24 2002-05-02 Milliken & Co Procede de production de materiaux thermoplastiques en polyester colore comportant des operations specifiques de solidification
WO2002016464A2 (fr) * 2000-08-24 2002-02-28 Milliken & Company Procede de production de materiaux thermoplastiques en polyester colore comportant des operations specifiques de solidification
US6423764B1 (en) 2000-08-24 2002-07-23 Milliken & Company Method of producing colored polyester thermoplastic materials through specific solid-state procedures
EP3130623A1 (fr) * 2009-03-03 2017-02-15 The Coca-Cola Company Conditionnement de polyéthylène téréphtalate d'origine biologique et son procédé de fabrication
EP3878887A1 (fr) * 2009-03-03 2021-09-15 The Coca-Cola Company Procédé de fabrication de polyéthylène téréphtalate d'origine biologique

Also Published As

Publication number Publication date
ZA962456B (en) 1996-10-02
AU5316396A (en) 1996-10-16
CO4560369A1 (es) 1998-02-10
AR000405A1 (es) 1997-06-18
TR199600215A2 (tr) 1996-10-21
IL117668A0 (en) 1996-07-23

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