[go: up one dir, main page]

WO2001021680A1 - Technique d'ajustage des proprietes de rechauffe de resines de polyester - Google Patents

Technique d'ajustage des proprietes de rechauffe de resines de polyester Download PDF

Info

Publication number
WO2001021680A1
WO2001021680A1 PCT/US2000/025858 US0025858W WO0121680A1 WO 2001021680 A1 WO2001021680 A1 WO 2001021680A1 US 0025858 W US0025858 W US 0025858W WO 0121680 A1 WO0121680 A1 WO 0121680A1
Authority
WO
WIPO (PCT)
Prior art keywords
antimony
ppm
oxygen
inert gas
reheat
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.)
Ceased
Application number
PCT/US2000/025858
Other languages
English (en)
Inventor
David Anthony Harrison
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and 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 EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of WO2001021680A1 publication Critical patent/WO2001021680A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • 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
    • 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
    • C08G63/88—Post-polymerisation treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00—Indexing scheme relating to blow-moulding
    • B29C2949/07—Preforms or parisons characterised by their configuration
    • B29C2949/0715—Preforms or parisons characterised by their configuration the preform having one end closed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/06—Injection blow-moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/712—Containers; Packaging elements or accessories, Packages
    • 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
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C08G63/86—Germanium, antimony, or compounds thereof
    • C08G63/866—Antimony or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0875—Antimony

Definitions

  • the present invention relates to a process for preparing polyester resins which exhibit desirable reheat properties, and, more particularly, the present invention relates to a method for precisely adjusting the reheat properties of a polyester resin over a wide range without having to materially change the resin composition.
  • U.S. Patent Nos. 5,419,936 and 5,529,744 describe a method for reducing the reheat time of polyester resins by introducing between 3 parts per million (ppm) and 300 ppm by weight of fine metal particles into the resin matrix during synthesis.
  • the metal particles are selected based on their ability to intrinsically absorb radiation in the wavelength region 500 ran to 2000 n , which is the wavelength region emitted by most commercially available quartz infra-red lamps used for reheat purposes.
  • the metal particles are sufficiently fine for them not to be visible to the eye, and they have a range of sizes such that absorption of radiation can occur over a relatively wide part of the wavelength range.
  • the amount of metal particles present in the resin composition as it is to be used in forming bottles from bottle preforms is a balance between the desired reduction in reheat time for the polymer, i.e., the preform, and the amount of haze that is acceptable in a given end use.
  • the concentration of contaminants, e.g., metal particles can contribute to an unacceptably high haze level. It has been found that antimony metal particles at concentrations of from 3 ppm to 300 ppm can produce satisfactory reheat times for poly(ethylene terephthalate) [PET] compositions.
  • the antimony metal particles are derived from antimony trioxide (antimony (III) oxide), i.e., a reducible form of antimony, and the PET polymer includes a suitable reducing agent. Reaction between the metal compound and the reducing agent during processing of the polymer leads to formation of the metal distributed generally throughout the polymer.
  • the quantity of reducing agent to be used must be determined by experimentation and operating experience.
  • the present invention is an improvement in a continuous process for producing a PET resin from a PET prepolymer which contains a concentration of finely divided antimony metal particles.
  • the process comprises introducing the PET prepolymer into a moving bed reaction zone while contacting the prepolymer within the reaction zone with a heated inert gas.
  • the improvement according to the invention comprises simultaneously introducing into the reaction zone and contacting the PET prepolymer with a predetermined concentration of oxygen in the range of from 10 ppm up to 350 ppm, based on the volume of inert gas, whereby to selectively convert a portion of the finely divided antimony particles to antimony trioxide.
  • the invention is a method for adjusting the reheat rate of a solid state polymerized linear polyester, e.g., PET, which contains a beginning concentration of finely divided antimony particles.
  • the method comprises contacting the linear polyester in the solid state in the presence of a heated inert gas with an amount of oxygen in the range of from 10 to 350 parts per million, based on the volume of inert gas, whereby a predetermined portion of the beginning concentration of antimony is converted to antimony trioxide.
  • the selection of oxygen level allows for the production of a PET composition having a range of reheat rates without changing the recipe, i.e., the specification, of the polymer composition.
  • the practice of adjusting of the reheat rate of the polymer by changing a single easily controlled parameter in the solid phase portion of the process is much simpler to carry out than changing the prepolymer composition.
  • the invention reduces the amount of intermediate reheat material that is normally produced when changing from one reheat grade of resin to another because the prepolymer composition can remain unchanged.
  • the present invention resides in the discovery that it is possible to control the infra-red absorption properties of commercially produced PET resins which contain finely divided antimony metal particles by exposing the PET prepolymer to controlled levels of oxygen during the solid-state polymerization stage of the production process.
  • PET is produced on a continuous basis at commercial rates by reacting a glycol with a dicarboxylic acid, as the free acid or its dimethyl ester, to produce a prepolymer compound which is then polycondensed to produce the polyester.
  • a reducible antimony metal compound usually in the form of antimony trioxide, is
  • the object of the process is to add only sufficient reducing agent to reduce only a proportion of the antimony trioxide such that the antimony metal concentration thereby produced imparts the desired level of reheat to the resin. Complete reduction of all the antimony trioxide leads to a resin which is too dark and which does not have satisfactory color for use in PET bottles.
  • the degree of reduction and hence the proportion of the antimony trioxide that is converted to antimony metal particles is a complex function of the oligomeric composition of the prepolymer, reducing agent concentration and point at which the reducing agent is added to the prepolymer. It follows that the prepolymer composition which leads to a specific reheat rate for the final polymer is unique for each route of manufacture. The composition must therefore be carefully formulated for each individual process, such as in the illustration given in Example 2 below.
  • the molecular weight of the prepolymer which is typically in the range of from 0.55 to 0.65 dl/g, is further increased by solid state polymerization to a value typically in the range of from 0.75 to 0.85 dl/g as required for commercial application.
  • the prepolymer is first crystallized in one or more stages at temperatures in the range 120° to 180°C in either air or an inert atmosphere. At the outset the resin is heated in an agitated reactor to prevent the amorphous chip from sticking before it has crystallized. Secondary crystallization stages may then be employed to raise the crystallinity of the resin to the desired level prior to the reaction stage of the process.
  • the precrystallized prepolymer is processed in one or more moving bed reactors at higher temperatures, typically in the range of from 200°-230°C, in an atmosphere of hot inert gas in order to raise the molecular weight of the final polymer to the desired level.
  • the inert gas used is nitrogen. Oxygen levels in the nitrogen stream are normally maintained at the lowest possible levels during this stage to minimize the problem of oxidative degradation, which can restrict the rate at which the polymerization reaction proceeds and lead to color formation (e.g., yellowing) in the resin.
  • the invention it is now possible to employ a single recipe for the PET prepolymer composition which contains an excess of antimony metal, yet have the capability to produce a wide range of reheat grades of resin without having to change the polymer recipe by controlling the oxygen level at precise, higher than normal levels during the solid state polymerization process.
  • the oxygen level in the inert gas used in the solid state polymerization step can be set at any predetermined value over a range of from 10 ppm up to 350 ppm whereby the desired concentration of antimony metal is oxidized.
  • Re-oxidized antimony particles i.e., those which are converted to antimony trioxide, do not absorb infrared radiation. Exposure of the prepolymer to as little as 10 ppm of oxygen during solid state polymerization has produced a measurable effect in terms of reheat time.
  • a 1 kilogram sample quantity of "fast reheat" amorphous base PET prepolymer chip was crystallized by heating for 4 hours in an air oven at 130°C.
  • the 1 kilogram sample of crystallized chip was then heated as a static column in a glass tube with a porous sintered glass base, through which heated nitrogen as the inert gas was passed at a flow rate of 40 liters/min in order to polymerize the chip in the solid state.
  • the nitrogen was heated by first being passed through a glass coil inside a glass vapor bath jacket containing a boiling liquid with the same boiling point as the required solid state polymerization reaction temperature.
  • the oxygen level in the nitrogen was precisely controlled by feeding gas from a 200 bar (20 X 10 3 kPa) cylinder of "Beta standard" purity 5% oxygen in nitrogen (Air Products) into a pure nitrogen stream via precisely calibrated flowmeters to give an inert gas/oxygen mixture with the desired level of oxygen.
  • the chip was heated in this way, at selected temperatures and selected oxygen levels, for between 4 and 8 hours.
  • the temperatures used were between 192°C and 215°C, and the oxygen amounts added to the nitrogen stream were between 10 and 350 parts per million.
  • the final polymerized polymers were injection molded into 10 cm diameter x 4 mm thick circular plaques on which reheat, infra-red absorption, color and haze was measured. Reheat was measured on a scale of values based on a standard preform reheat test (E. I. du Pont de Nemours and Company, Standard Test Method for Minimum Blowing Time Test No. MST 116). The test compares the minimum blowing time required to produce a clear PET bottle.
  • the blowing time required for a test sample is compared with that for a "zero seconds reheat" standard polymer. The difference is quoted as the "reheat" of the test sample.
  • the reheat values observed at different oxygen levels at a solid state polymerization temperature of 215°C are shown in the table below.
  • EXAMPLE 2 Commercial Plant Scale Amorphous base polymer with the desired composition was produced by a commercial continuous melt process in which terephthalic acid and ethyiene glycol were reacted in three separate stages.
  • the first was the esterification stage in an "Esterifier" vessel, in which terephthalic acid and ethyiene glycol in the form of a slurry of molar ratio of about 2 to 1 reacted to form monomer, low molecular oligomer and water. This was carried out at 280°-290°C and atmospheric pressure, during which excess glycol and the water produced during the reaction were distilled off.
  • the monomer and oligomer was continuously fed to the second part of the process, the pre-polymerization stage in the "Upflow Pre-polymerizer” (UFPP).
  • UFPP Upflow Pre-polymerizer
  • the oligomer was reacted under intermediate vacuum at 280°-295°C to increase the degree of polymerization of the oligomer to produce the "pre-polymer”.
  • Low pressure in the UFPP removed excess glycol and glycol generated during the polymerization reaction.
  • color modifiers and stabilizer compounds were injected into the monomer/oligomer.
  • phosphoric acid (H3PO4) and phosphorous acid (H3PO3) stabilizers both at levels of 80 ppm in the final polymer, were injected in the form of solutions in diethylene glycol.
  • cobalt acetate color modifier (160 ppm) and antimony trioxide polycondensation catalyst (270 ppm) were added in the form of solutions in ethyiene glycol.
  • the molten prepolymer was continuously fed from the UFPP to the third and final stage, the "Finisher", in which the prepolymer was reacted to form an intermediate molecular weight polymer under high vacuum at 285°-300°C.
  • the vessel contained a wiped-wall agitator which drives the highly viscous polymer melt through the vessel.
  • the vacuum removed glycol generated during the polymerization reaction.
  • the molten polymer finally passed through filters before being extruded through die-heads to form laces which were quenched and then chopped into chips.
  • the polymer had an intrinsic viscosity (IN) of 0.58-0.62 dl/g.
  • the amorphous base chip was then solid state polymerized in a continuous commercial production plant process to raise the viscosity to the desired level of the final product.
  • the process involved subjecting the intermediate MW polymer to a precrystallization stage, a crystallization stage, a preheating stage and a final solid state polymerization stage, in which the chip passed from stage to stage in a continuous flow with a throughput of between 10 and 15 tons of product per hour.
  • the amorphous polymer was precrystallized by heating it at a temperature of 160°C for about 20 minutes in an air atmosphere in a fluidized reactor vessel with an inventory of about 4 tons of material.
  • the crystallinity of the chip was raised by heating the chip to a temperature of about 175°C for between 5 and 10 minutes in an air atmosphere in a second fluidized reactor with an inventory of 1 to 2 tons.
  • the IV and temperature of the chip was raised further by heating the chip to a temperature of about 215°C and holding it for 4 hours in a plug-flow "preheater" vessel under a recirculated nitrogen atmosphere and an inventory of 70 tons of material.
  • the IV was raised from about 0.58-0.62 dl/g to about 0.68 dl/g.
  • the chip was heated in a vertical plug-flow solid state polymerization reactor at 205°C to 210°C and held at that temperature for about 15 hours in a recirculating nitrogen atmosphere and an inventory of about 150 tons of polymer in order to achieve the desired final intrinsic viscosity.
  • the IV was raised from about 0.68 dl/g to about 0.82 dl/g.
  • the nitrogen stream was recirculated through the preheater to the solid state polymerization reactor and then back to the preheater via firstly a platinum bed catalyst "regeneration" unit in which oxygen and organic rich off-gases in the gas stream were combusted to CO 2 , and: secondly via a dehumidification unit containing a molecular sieve desiccant material to remove moisture from the gas stream.
  • the regeneration and dehumidification units were located between the preheater and the solid state polymerization reactor.
  • the regeneration process was controlled by feeding a small and precisely controlled excess quantity of oxygen into the unit to ensure adequate combustion.
  • An oxygen level meter of the "Orbisphere" type was located between the regeneration and dehumidification units. Measurements from this meter were continuously taken and, via a feedback loop, used to automatically control the valve which inputs the excess oxygen to the combustion process such that consistent oxygen levels were maintained in the gas stream.
  • the oxygen in the recirculated gas stream is precisely controlled at 16-20 parts per million.
  • the prepolymer composition described above leads to a final polymer with a reheat of minus 12 to minus 14 seconds according to the MST 116 preform reheat scale.
  • the level of oxygen in the nitrogen stream was deliberately increased by adjusting the control loop between the oxygen meter to supply less excess oxygen input to the regeneration unit. In this way less combustion took place and hence the resulting oxygen level in the gas stream could be increased and precisely controlled.
  • 190 ppm oxygen was found to give a final product with a significantly reduced reheat, minus 4 to minus 6 seconds, with the same prepolymer composition.
  • the product can be used in applications in which faster reheat is not a necessity and offers no commercial advantage.
  • the polymer has lower haze and a lighter color than the faster reheat product, both of which are of commercial advantage in some applications.

Landscapes

  • 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 technique d'ajustage précis des propriétés de réchauffe de résines de polyester qui renferment des particules finement divisées d'antimoine en tant qu'absorbant des infrarouges sur une vaste plage, sans qu'il faille modifier concrètement la composition de la résine de polyester. Cette technique consiste à mettre ladite résine à l'état solide en contact avec une certaine dose d'oxygène en présence d'un gaz inerte chauffé.
PCT/US2000/025858 1999-09-21 2000-09-21 Technique d'ajustage des proprietes de rechauffe de resines de polyester Ceased WO2001021680A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US40002799A 1999-09-21 1999-09-21
US09/400,027 1999-09-21

Publications (1)

Publication Number Publication Date
WO2001021680A1 true WO2001021680A1 (fr) 2001-03-29

Family

ID=23581932

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2000/025858 Ceased WO2001021680A1 (fr) 1999-09-21 2000-09-21 Technique d'ajustage des proprietes de rechauffe de resines de polyester

Country Status (2)

Country Link
DZ (1) DZ3093A1 (fr)
WO (1) WO2001021680A1 (fr)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004058853A1 (fr) * 2002-12-30 2004-07-15 Plastic Systems S.P.A. Procede de polymerisation de resines de polyester a l'etat solide, en particulier de terephtalate de polyethylene, et appareil fonctionnant selon ce procede
WO2004104080A1 (fr) * 2003-05-21 2004-12-02 Wellman, Inc. Resines de polyester a cristallisation lente
WO2006028757A3 (fr) * 2004-09-03 2006-04-27 Eastman Chem Co Compositions de polymeres et copolymeres de polyester, contenant des particules metalliques de tungstene
US7094863B2 (en) 2003-05-21 2006-08-22 Wellman, Inc. Polyester preforms useful for enhanced heat-set bottles
US7189777B2 (en) 2003-06-09 2007-03-13 Eastman Chemical Company Compositions and method for improving reheat rate of PET using activated carbon
US7300967B2 (en) 2004-11-12 2007-11-27 Eastman Chemical Company Polyester polymer and copolymer compositions containing metallic titanium particles
US7368523B2 (en) 2004-11-12 2008-05-06 Eastman Chemical Company Polyester polymer and copolymer compositions containing titanium nitride particles
US7541407B2 (en) 2004-05-27 2009-06-02 Eastman Chemical Company Process for adding methine UV light absorbers to PET prepared by direct esterification
US7662880B2 (en) 2004-09-03 2010-02-16 Eastman Chemical Company Polyester polymer and copolymer compositions containing metallic nickel particles
US7745512B2 (en) 2005-09-16 2010-06-29 Eastman Chemical Company Polyester polymer and copolymer compositions containing carbon-coated iron particles
US7776942B2 (en) 2005-09-16 2010-08-17 Eastman Chemical Company Polyester polymer and copolymer compositions containing particles of titanium nitride and carbon-coated iron
WO2012170351A3 (fr) * 2011-06-10 2013-04-11 Invista Technologies S.A R.L. Systèmes de pré-polymérisateur à courant vertical (ufpp) à chute de pression variable et procédés correspondants
US8791225B2 (en) 2008-06-06 2014-07-29 Dak Americas Mississippi Inc. Titanium-nitride catalyzed polyester
US8987408B2 (en) 2005-06-16 2015-03-24 Grupo Petrotemex, S.A. De C.V. High intrinsic viscosity melt phase polyester polymers with acceptable acetaldehyde generation rates
US9267007B2 (en) 2005-09-16 2016-02-23 Grupo Petrotemex, S.A. De C.V. Method for addition of additives into a polymer melt

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3497477A (en) * 1969-06-02 1970-02-24 Eastman Kodak Co Process for removing metallic antimony from polyester prepolymers
EP0429311A2 (fr) * 1989-11-24 1991-05-29 Imperial Chemical Industries Plc Bouteilles de polyester
EP0693356A2 (fr) * 1990-06-15 1996-01-24 Imperial Chemical Industries Plc Objets en polyester

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3497477A (en) * 1969-06-02 1970-02-24 Eastman Kodak Co Process for removing metallic antimony from polyester prepolymers
EP0429311A2 (fr) * 1989-11-24 1991-05-29 Imperial Chemical Industries Plc Bouteilles de polyester
US5419936A (en) * 1989-11-24 1995-05-30 Ici Chemical Industries Plc Polyester bottles
EP0693356A2 (fr) * 1990-06-15 1996-01-24 Imperial Chemical Industries Plc Objets en polyester

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004058853A1 (fr) * 2002-12-30 2004-07-15 Plastic Systems S.P.A. Procede de polymerisation de resines de polyester a l'etat solide, en particulier de terephtalate de polyethylene, et appareil fonctionnant selon ce procede
WO2004104080A1 (fr) * 2003-05-21 2004-12-02 Wellman, Inc. Resines de polyester a cristallisation lente
US7094863B2 (en) 2003-05-21 2006-08-22 Wellman, Inc. Polyester preforms useful for enhanced heat-set bottles
US7129317B2 (en) 2003-05-21 2006-10-31 Wellman, Inc. Slow-crystallizing polyester resins
US7189777B2 (en) 2003-06-09 2007-03-13 Eastman Chemical Company Compositions and method for improving reheat rate of PET using activated carbon
US7541407B2 (en) 2004-05-27 2009-06-02 Eastman Chemical Company Process for adding methine UV light absorbers to PET prepared by direct esterification
WO2006028757A3 (fr) * 2004-09-03 2006-04-27 Eastman Chem Co Compositions de polymeres et copolymeres de polyester, contenant des particules metalliques de tungstene
US7662880B2 (en) 2004-09-03 2010-02-16 Eastman Chemical Company Polyester polymer and copolymer compositions containing metallic nickel particles
US7439294B2 (en) 2004-11-12 2008-10-21 Eastman Chemical Company Polyester polymer and copolymer compositions containing metallic titanium particles
US7368523B2 (en) 2004-11-12 2008-05-06 Eastman Chemical Company Polyester polymer and copolymer compositions containing titanium nitride particles
US7300967B2 (en) 2004-11-12 2007-11-27 Eastman Chemical Company Polyester polymer and copolymer compositions containing metallic titanium particles
US8039577B2 (en) 2004-11-12 2011-10-18 Grupo Petrotemex, S.A. De C.V. Polyester polymer and copolymer compositions containing titanium nitride particles
US8987408B2 (en) 2005-06-16 2015-03-24 Grupo Petrotemex, S.A. De C.V. High intrinsic viscosity melt phase polyester polymers with acceptable acetaldehyde generation rates
US7745512B2 (en) 2005-09-16 2010-06-29 Eastman Chemical Company Polyester polymer and copolymer compositions containing carbon-coated iron particles
US7776942B2 (en) 2005-09-16 2010-08-17 Eastman Chemical Company Polyester polymer and copolymer compositions containing particles of titanium nitride and carbon-coated iron
US9267007B2 (en) 2005-09-16 2016-02-23 Grupo Petrotemex, S.A. De C.V. Method for addition of additives into a polymer melt
US8791225B2 (en) 2008-06-06 2014-07-29 Dak Americas Mississippi Inc. Titanium-nitride catalyzed polyester
WO2012170351A3 (fr) * 2011-06-10 2013-04-11 Invista Technologies S.A R.L. Systèmes de pré-polymérisateur à courant vertical (ufpp) à chute de pression variable et procédés correspondants

Also Published As

Publication number Publication date
DZ3093A1 (fr) 2004-06-20

Similar Documents

Publication Publication Date Title
US6803082B2 (en) Methods for the late introduction of additives into polyethylene terephthalate
WO2001021680A1 (fr) Technique d'ajustage des proprietes de rechauffe de resines de polyester
EP1639034B2 (fr) Resines de polyester a cristallisation lente
US6569991B2 (en) Methods of post-polymerization extruder injection in polyethylene terephthalate production
KR840000282B1 (ko) 고분자량 폴리에스테르의 제조방법
US6590069B2 (en) Methods of post-polymerization extruder injection in condensation polymer production
US4609721A (en) Process for making molding grade polyethylene terephthalate
US6573359B2 (en) Methods of post-polymerization injection in condensation polymer production
US20110257357A1 (en) Apparatus for heat treatment of polyester particle and method of multistage solid-phase polycondensation of polyester particle
EP0389948B1 (fr) Procédé de préparation de polyéthylène théréphthalate
JP2004143442A (ja) ポリエステル樹脂の製造方法
US7262263B2 (en) Method and apparatus for producing solid-state polycondensed polyesters
WO2004013203A1 (fr) Resine polyester et son procede de production
EP1939237A1 (fr) Procédé de production de polyester
US4446303A (en) Process for preparing high molecular weight polyesters
US3718621A (en) Solid state polymerization process
EP1262514B1 (fr) Méthode pour diminuer la concentration d'oligomères cycliques dans les polyesters
KR20160047218A (ko) 부산물의 함량이 낮은 폴리(트리메틸렌 테레프탈레이트)의 연속 제조 방법
JP5444803B2 (ja) ポリエチレンテレフタレートの製造方法
JP4784213B2 (ja) ポリエステルの製造方法
KR20070108385A (ko) 폴리에스테르의 연속적 제조 방법, 폴리에스테르예비중합체 입상체 및 폴리에스테르
KR101159844B1 (ko) 티탄 화합물을 촉매로 사용하는 결정성 폴리에스테르의 제조방법
JP4784216B2 (ja) ポリエチレンテレフタレートの製造方法
JPH11106491A (ja) ポリエステル樹脂、それから成るシート状物及び中空成形体
JPH10204165A (ja) ポリエチレンナフタレート共重合体、及びその製造方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): BR CA CN ID IN JP KR MX SG TR VN ZA

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP