WO2007088074A1 - Procede de fabrication de terephtalate de polyethylene - Google Patents

Procede de fabrication de terephtalate de polyethylene Download PDF

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Publication number
WO2007088074A1
WO2007088074A1 PCT/EP2007/001274 EP2007001274W WO2007088074A1 WO 2007088074 A1 WO2007088074 A1 WO 2007088074A1 EP 2007001274 W EP2007001274 W EP 2007001274W WO 2007088074 A1 WO2007088074 A1 WO 2007088074A1
Authority
WO
WIPO (PCT)
Prior art keywords
process according
added
polycondensation
pet
phosphate ester
Prior art date
Application number
PCT/EP2007/001274
Other languages
English (en)
Inventor
Jadil Siddiqui
Munif Al-Munif
Original Assignee
Saudi Basic Industries Corporation
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 Saudi Basic Industries Corporation filed Critical Saudi Basic Industries Corporation
Publication of WO2007088074A1 publication Critical patent/WO2007088074A1/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
    • C08G63/78—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
    • 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4

Definitions

  • the present invention relates to a process for the preparation of a polyethylene terephthalate (PET) homo- or copolymer, comprising the step of reacting, utilizing an antimony containing compound as a catalyst, at least one dicarboxylic acid with at least one diol, in an esterification step and a polycondensation step, wherein the polycondensation step is conducted in a split operation using first a melt polycondensation reaction followed by a solid state polycondensation reaction.
  • PET polyethylene terephthalate
  • PET Polyethylene terephthalate
  • DMT and PTA processes or its copolymers as polyesters in general may be produced in two steps by one of two ways, called the DMT and PTA processes, or the trans-esterification and direct esterification routes, respectively.
  • the applications for PET include fibres, filaments, films, and bottle- grade chips. Modern plants are based on the PTA process and further they incorporate direct product formation (fibres and filaments, films) by extruding the melt from final polycondensation reactor.
  • the PTA process is generally used comprising in step 1 that purified terephthtalic acid is esterified with ethylene glycol to form diethylene glycol terephthalate and oligomers.
  • the diethylene glycol terephthalate is heated to carry out a melt-phase polycondensation, which may be optionally followed by a solid state polycondensation step.
  • a specific kind of catalyst is required within the process for preparing PET.
  • the catalysts that support the forward polymerization reactions also enhance the rates of degradation reactions. These degradation reactions can cause yellowing of the polymer and a reduction in molecular weight.
  • stabilizing agents such as phosphoric acid, are added to the reaction mixture.
  • US 4,123,420 discloses a process for the preparation of polyethylene terephthtalate, wherein a phosphorous-containing compound is added to the reaction mixture prior to or after the polymerisation. In that process, the polyethylene terephthalate obtained is directly extruded without carrying out a solid state polycondensation step.
  • US 5,744,572 discloses a process for the acceleration of the polycondensation of polyester made by the esterification of at least one dicarboxylic acid with at least one diol, precondensation, melt phase polycondensation and solid phase polycondensation, wherein prior to the precondensation reaction a specific phosphorous compound, carboxy phosphonic acid, is added.
  • WO 96/19520 discloses a process for the acceleration of the polycondensation of polyester comprising adding an alkyl titanate and an acidic phosphate ester.
  • This object is achieved in that during or after the esterification step an organic non-acidic phosphate ester is added to the reaction mixture in an amount equivalent with 30-150 ppm phosphor based on the weight of the PET homo- or copolymer.
  • the organic phosphoric acid ester is added when 80-90 % of carboxylic end groups are esterified.
  • the organic non-acidic phosphate ester is added after completion of the esterification step. Further alternatively, the organic non-acidic phosphate ester is added to the molten reaction mixture prior to the melt polycondensation step.
  • the organic non-acidic phosphate ester is added in an amount of about 30 to about 80 ppm, preferably about 30 to about 60 ppm, based on the PET.
  • the organic non-acidic phosphate ester is triethyl phosphate and/or tributyl phosphate, wherein triethyl phosphate is preferred.
  • the intrinsic viscosity (I.V.) of the reaction mixture after the melt polycondensation step is 0.6-0.7 dl/g as measured at 25°C of a 3:2 mixture of phenol and 1 ,2-dichlorobenzene at a concentration of about 0.5% of PET.
  • the polyester has an intrinsic viscosity after solid state polycondensation reaction of about 0.71-0.88 dl/g.
  • the process may be carried out batchwise.
  • the catalyst used is an antimony compound, suitable examples of which are antimony oxide, antimony acetate, antimony glycolates, antimony ethyleneglycoxide and mixtures thereof. No further catalyst are applied in the process according to the invention.
  • the esterification step is conducted at a temperature of 230 to 26O 0 C, preferably under nitrogen pressure and the melt polycondensation step being carried out at a temperature of 270 to 285 0 C under adequate vacuum.
  • the tricarboxylic acid is terephthalic acid, isophthalic acid, 2,6-naphthalen dicarboxylic acid and/or p-hydroxy benzoicacid, and wherein the diol is ethylenglycol and/or 1 ,4-cyclohexane dimethanol, wherein terephthalic acid and ethylenglycol are preferred.
  • At least one color correction agent such as cobalt acetate and/or bluetoner, may be added.
  • the process according to the present invention shows an increase in the rate of production of polyester, preferably polyethylene terephthalate (PET) or copolymers thereof having a high intrinsic viscosity and improved thermal properties.
  • PET polyethylene terephthalate
  • the polymers may be produced using conventional esterification and polycondensation procedures which are known in the prior art, however, the addition of the specific organic phosphoric acid ester component is essential, which has to be added during or after the esterification step, i.e. the phosphoric acid ester component is added to the reaction mixture prior to the melt polycondensation step.
  • the polycondensation is accelerated by the addition of the phosphoric acid ester component.
  • the enhancement in solid state polycondensation by the addition of the phosphoric acid ester component is significantly higher compared to the addition of phosphoric acid. So far, phosphoric acid ester has not been disclosed as enhancer of the intrinsic viscosity (I.V.) in solid state polycondensation in the prior art. Compared to the use of phosphoric acid, the addition of phosphoric acid ester decreases the solid state polycondensation time of about 30%.
  • polyethylene terephthalate homopolymer or copolymer prepared according to the inventive process shows good color values (L * , b * ) and also provide a thermally stable polymer.
  • the PET produced according to the present invention is particularly well suited for the production of beverage bottles.
  • the ester bonds of the PET may hydrolyze to form free acid which neutralizes the basic polymerization catalyst. Accordingly, adding phosphorous compounds at the wrong time can adversely affect the building up of molecular weight of the PET during polycondensation.
  • the addition of the phosphorous compound according to the present invention is carried out when the presence of water is unlikely in the reaction mixture.
  • adding the phosphoric acid ester compound after the molten monomers have been mixed and just before reaction does not result in the phosphorous ester being hydrolyzed to acid and consequent interference with the catalyst.
  • the intrinsic viscosity or I. V. is a measure of the molecular weight of the polymer and is measured by dilute solution viscometry.
  • the I.V. is influenced predominantly by polymer molecular weight, but the solvent type and the solution temperature also have an effect on its numerical value. I.V. values for the same polymer will be different if different solvents and temperatures are used. All the I.V.s here were measured in a 3:2 mixture of phenol and 1 ,2- dichlorobenzene at 25°C. The method is based on a single measurement at a single concentration. Typically, about 8-10 chips are dissolved to make a solution with a concentration of about 0.5%.
  • the I.V. was obtained from a measurement of relative viscosity for a single polymer concentration (0.5%) by using the Billmeyer equation, see F.W. Billmeyer, J. of Polymer Sci. ]V, 83 (1949).
  • the color parameters were measured with a HunterLab ColorFlex model no. 45/0, serial number CX0969.
  • the amorphous chips were used without grinding or crystallization, in the transparent state. Generally, the changes measured could also be seen by eye.
  • the L * measures lightness and varies from 100 for perfect white and 0 for black, approximately as the eye would evaluate it.
  • the color value b * measures yellowness when positive, grey when zero and blueness when negative.
  • the diethylene glycol (DEG) contained in the PET was determined by gas chromatography in the re-esterification mixture of 1 g of PET with 30 ml methanol and 50 mg/l of zinc acetate obtained in carious stainless tube at 220 0 C.
  • monoethylene glycol MEG
  • PTA terephthalic acid
  • catalyst an antimony catalyst was used, which is commonly used in the art.
  • cobalt acetate was mixed with a small portion of PTA and was added together in the reactor. Afterwards, all ingredients were mixed under nitrogen blanket for 20 minutes and a temperature of 50 0 C.
  • the reaction temperature was next increased to 23O 0 C, and the pressure was allowed to build up to 0.6-0.7 MPa.
  • the esterification reaction was maintained at this temperature for 30 minutes, while a stirrer speed was fixed at 100 rpm.
  • the temperature was then raised to 25O 0 C, and the pressure was vented to the atmosphere in short intervals. The conditions were maintained for approximately 2-3 hours until the amount of water required to reach the desired degree of conversion was collected in a receiver.
  • the phosphorous stabilizer mixed with small amount of ethylene glycol was added to the reactor, wherein as stabilizer triethyl phosphate was utilized.
  • Pre-condensation was accomplished by a gradual reduction of the pressure for 50-100 mbar (5 kPa - 10 kPa) and a simultaneous increase of the temperature to about 265 0 C within 15 minutes.
  • the pressure was further reduced to 0.5 - 1.0 mbar (0.05 - 0.1 kPa) within 30 minutes and the temperature raised to approximately 275°C.
  • the polycondensation continued to get the desired torque of the stirrer.
  • the PET was extruded from the reactor by pressurizing with nitrogen within 15 minutes.
  • the PET strand was quenched into chilled water and was further chipped into small grains.
  • the granulates were then first dried and crystallized at 170 0 C for one hour in a nitrogen stream oven. It was then solid state polycondensed (SSP) for 8 hours at a temperature of 210 0 C.
  • SSP solid state polycondensed
  • the use of triethyl phosphate results in improved intrinsic viscosities compared to the use of phosphoric acid. Further, increasing the amount of triethyl phosphate utilized (50 ppm instead of 20 ppm) results in even improved intrinsic viscosities. Polymers obtained with such intrinsic viscosities are well suited for processing them into beverage bottles. Adding more than 120 ppm of the phosphoric acid ester could not improve the results further.
  • polyethylene terephthalate polymers have been prepared containing varying amounts of the triethyl phosphate during the polycondensation. These polyethylene terephthalate chips containing various amount of triethylephosphate were treated in an oven at 230 0 C for 30 to 120 minutes.

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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

L'invention concerne un procédé de fabrication d'un homopolymère ou d'un copolymère de téréphtalate de polyéthylène (PET), comprenant une étape consistant à mettre en réaction, en utilisant un composé contenant de l'antimoine en tant que catalyseur, au moins un acide dicarboxylique avec au moins un diol, en une étape d'estérification et une étape de polycondensation, ladite étape de polycondensation étant réalisée en une opération partagée en utilisant tout d'abord une réaction de polycondensation à l'état fondu, puis une réaction de polycondensation à l'état solide, caractérisé en ce que, durant ou après l'étape d'estérification, un ester organique de phosphate non acide est ajouté au mélange réactionnel en une quantité équivalente à 30 à 150 ppm de phosphore par rapport au poids de l'homopolymère ou du copolymère.
PCT/EP2007/001274 2006-02-03 2007-01-25 Procede de fabrication de terephtalate de polyethylene WO2007088074A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP06002231.6 2006-02-03
EP06002231 2006-02-03

Publications (1)

Publication Number Publication Date
WO2007088074A1 true WO2007088074A1 (fr) 2007-08-09

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PCT/EP2007/001274 WO2007088074A1 (fr) 2006-02-03 2007-01-25 Procede de fabrication de terephtalate de polyethylene

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2143749A1 (fr) * 2008-07-12 2010-01-13 Epc Industrial Engineering GmbH Procédé de fabrication de polyester, notamment de polyester linéaire, pour fils textiles et fibres textiles ainsi que pour bouteilles et installation destinée à l'exécution du procédé
EP2268704A1 (fr) * 2008-04-15 2011-01-05 Basf Se Procédé de fabrication en continu de polyesters biodégradables

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5235027A (en) * 1991-07-30 1993-08-10 Zimmer Aktiengesellschaft Modified copolyethylene terephthalate
JPH07145233A (ja) * 1993-10-01 1995-06-06 Kanebo Ltd ポリエステル組成物
WO1996019520A1 (fr) * 1994-12-22 1996-06-27 Eastman Chemical Company Production de polyesters particulaires au moyen d'un nouveau systeme catalyseur
EP0764672A1 (fr) * 1995-04-10 1997-03-26 Mitsui Petrochemical Industries, Ltd. Procede de production de terephtalate de polyethylene
US6160085A (en) * 1998-05-06 2000-12-12 Mitsubishi Chemical Corporation Polyester and process for its production
WO2001014449A1 (fr) * 1999-08-24 2001-03-01 Eastman Chemical Company Procede de fabrication de polyesters utilisant des composes contenant du phosphore acide
KR20010061108A (ko) * 1999-12-28 2001-07-07 조 정 래 폴리에스테르 수지의 제조방법
EP1273610A1 (fr) * 2001-02-06 2003-01-08 Mitsubishi Chemical Corporation R sine de polyester et proc d de production

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5235027A (en) * 1991-07-30 1993-08-10 Zimmer Aktiengesellschaft Modified copolyethylene terephthalate
JPH07145233A (ja) * 1993-10-01 1995-06-06 Kanebo Ltd ポリエステル組成物
WO1996019520A1 (fr) * 1994-12-22 1996-06-27 Eastman Chemical Company Production de polyesters particulaires au moyen d'un nouveau systeme catalyseur
EP0764672A1 (fr) * 1995-04-10 1997-03-26 Mitsui Petrochemical Industries, Ltd. Procede de production de terephtalate de polyethylene
US6160085A (en) * 1998-05-06 2000-12-12 Mitsubishi Chemical Corporation Polyester and process for its production
WO2001014449A1 (fr) * 1999-08-24 2001-03-01 Eastman Chemical Company Procede de fabrication de polyesters utilisant des composes contenant du phosphore acide
KR20010061108A (ko) * 1999-12-28 2001-07-07 조 정 래 폴리에스테르 수지의 제조방법
EP1273610A1 (fr) * 2001-02-06 2003-01-08 Mitsubishi Chemical Corporation R sine de polyester et proc d de production

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 200229, Derwent World Patents Index; AN 2002-233721, XP002372741 *
PATENT ABSTRACTS OF JAPAN vol. 1995, no. 09 31 October 1995 (1995-10-31) *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2268704A1 (fr) * 2008-04-15 2011-01-05 Basf Se Procédé de fabrication en continu de polyesters biodégradables
EP2143749A1 (fr) * 2008-07-12 2010-01-13 Epc Industrial Engineering GmbH Procédé de fabrication de polyester, notamment de polyester linéaire, pour fils textiles et fibres textiles ainsi que pour bouteilles et installation destinée à l'exécution du procédé

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