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WO2009053998A2 - Catalyseur pour la production de polyester - Google Patents

Catalyseur pour la production de polyester Download PDF

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Publication number
WO2009053998A2
WO2009053998A2 PCT/IN2008/000456 IN2008000456W WO2009053998A2 WO 2009053998 A2 WO2009053998 A2 WO 2009053998A2 IN 2008000456 W IN2008000456 W IN 2008000456W WO 2009053998 A2 WO2009053998 A2 WO 2009053998A2
Authority
WO
WIPO (PCT)
Prior art keywords
polyester
catalyst system
range
ppm
antimony
Prior art date
Application number
PCT/IN2008/000456
Other languages
English (en)
Other versions
WO2009053998A3 (fr
Inventor
Vikas Madhusudan Nadkarni
Sheeram Ashok Wadekar
Rajan Dubey
Sanjai Kesanwani
Anil Kumar Satpathy
Original Assignee
Reliance Industries Limited
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 Reliance Industries Limited filed Critical Reliance Industries Limited
Publication of WO2009053998A2 publication Critical patent/WO2009053998A2/fr
Publication of WO2009053998A3 publication Critical patent/WO2009053998A3/fr

Links

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
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • 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

Definitions

  • the invention relates to a catalyst system comprising an antimony compound and an alkali metal salt of paratoluene sulphonic acid for the synthesis of polyester resins.
  • the invention also relates to the process for polyester synthesis, to the polyester and to the articles prepared thereof .
  • Polyesters such as polyethylene terephthalate (PET) are used in large quantities in the manufacture of textile fibers, packaging films and containers. Typically, such polyesters are synthesized by a catalysed two stage reaction. In the first stage, esterification reaction is carried out between a dicarboxylic acid and a polyol. The esterification reaction is followed by melt polymerization wherein the ester formed in the first stage undergoes polycondensation resulting in a polyester. Often the polyester obtained after melt polymerisation is further subjected to solid state polymerisation.
  • PET polyethylene terephthalate
  • the invention provides a catalyst system comprising an antimony compound and an alkali metal salt of paratoluene sulphonic acid for the synthesis of polyester.
  • polyester as used herein, is intended to include “copolyesters” and is understood to mean a synthetic polymer prepared by the polycondensation of one or more difunctional carboxylic acids with one or more difunctional hydroxyl compounds.
  • low viscosity polyester is intended to mean polyester having intrinsic viscosity in the range of 0.20 dl/g to 0.65 dl/g.
  • the invention provides a catalyst system for polyester synthesis, the catalyst system comprising at least 50 ppm of antimony wherein the antimony is present in the form of a compound and at least 10 ppm of an alkali metal salt of paratoluene sulphonic acid.
  • the invention provides a catalyst system for polyester synthesis comprising antimony present in an amount ranging from 50 to 1500 ppm and an alkali metal salt of paratoluene sulphonic acid present in an amount ranging from 10 to 500 ppm wherein the antimony is present in the form of a compound.
  • the invention provides a catalyst system for polyester synthesis comprising antimony present in an amount ranging from 50 to 1500 ppm and an alkali metal salt of paratoluene sulphonic acid present in an amount ranging from 10 to 500 ppm wherein the antimony is present in the form of a compound and the alkali metal salt is a sodium salt or a potassium salt.
  • the invention provides a process for synthesis of a polyester resin in the presence of a catalyst system comprising antimony present in an amount ranging from 50 to 1500 ppm, the antimony being present in the form of a compound and an alkali metal salt of paratoluene sulphonic acid present in an amount ranging from 10 to 500 ppm, the process comprising esterifying at least one organic dicarboxylic acid with a polyol at a temperature in the range of 250°C to 290 0 C to obtain a carboxylic acid ester and melt polymerizing the acid ester at temperature in the range of 260°C to 300°C to obtain a low viscosity polyester.
  • a catalyst system comprising antimony present in an amount ranging from 50 to 1500 ppm, the antimony being present in the form of a compound and an alkali metal salt of paratoluene sulphonic acid present in an amount ranging from 10 to 500 ppm
  • the process comprising esterifying at least one organic dicarboxy
  • the invention provides a polyester having an intrinsic viscosity in the range of 0.20 to 0.45 dl/g
  • the invention provides a polyester having an intrinsic viscosity in the range of 0.45 to 0.65 dl/g.
  • the invention provides a polyester having an intrinsic viscosity in the range of 0.70 to 1.20 dl/g.
  • the invention provides films, fibers, filaments and yarns prepared from the polyester.
  • the invention provides a process for synthesis of a polyester resin in the presence of catalyst system comprising antimony present in an amount ranging from 50 to 1500 ppm wherein the antimony is present in the form of a compound and an alkali metal salt of paratoluene sulphonic acid present in an amount ranging from 10 to 500 ppm, the process comprising esterifying at least one dicarboxylic acid with a polyol at a temperature in the range of 250°C to 290°C to obtain a carboxylic acid ester, melt polymerizing the acid ester at temperature in the range of 26O 0 C to 300°C to obtain a low viscosity polyester and reacting the low viscosity polyester in the solid state at a temperature in the range of 200 0 C to 24O 0 C to form a polyester having intrinsic viscosity in the range of 0.70 to 1.20 dl/g
  • the invention provides shaped articles prepared from the polyester.
  • the invention provides a catalyst system comprising an antimony compound and an alkali metal salt of paratoluene sulphonic acid.
  • the total metal content of the catalyst system is in the range of 10 ppm to 1000 ppm.
  • the catalyst system has a metal content in the range of 100 to 400 ppm.
  • an antimony compound in combination with a sodium or potassium salt of the paratoluene sulphonic acid is used in the catalyst system.
  • the invention also provides a process for synthesis of polyester resins in the presence of the catalyst system. Usually, the process is carried out in two stages resulting in a low molecular weight polyester. In the first stage an organic dicarboxylic acid is reacted with polyol at around 250°celsius to 290°celsius to obtain an acid ester.
  • the organic dicarboxylic acid used in the esterification stage is selected from the group consisting of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, 4,4'-biphenyl dicarboxylic or any suitable dicarboxylic acids or derivatives thereof.
  • the polyol used is selected from monoethylene glycol, diethylene glycol, Methylene glycol, propylene glycol, dipropylene glycol, butylenes glycol, 1 ,4-cyclohexane diol or any other suitable polyol.
  • the first stage reaction results in carboxylic acid ester which is melt polymerised at around 260°C to 300°C to obtain a low viscosity polyester.
  • the intrinsic viscosity of the polyester formed after melt polymerization is in the range of 0.20 dl/g to 0.65 dl/g.
  • the melt polymerization yields polyester having different intrinsic viscosities.
  • a polyester having intrinsic viscosity of around 0.60 dl/g is obtained.
  • a polyester having intrinsic viscosity of around 0.26 dl/g is obtained.
  • the low viscosity polyesters can be crystalline, semicrystalline or amorphous.
  • the low viscosity polyester is either used directly in the manufacture of films, fibers or filaments or is further polymersied in the solid state to form higher molecular weight polyester. After melt polymerization the low viscosity polyester is either drained and cut into granular form or is passed through an orifice to form droplets on a steel conveyor belt of a particle former.
  • the catalyst system is added at any stage during esterification or melt polymerization but before particle former stage or before solid state polymerization.
  • the solid state polymerization is catalysed by the catalyst system used in the melt polymerization stage.
  • the solid state polymerization usually results in polyester having intrinsic viscosity in the range of 0.70 to 1.20 dl/g.
  • the polyester may be linear or branched and may be a homo-polyester and may contain co-monomers upto 10 wt%.
  • the catalyst system used in the process of the invention can be used either in the supported or unsupported form.
  • the polyester resins synthesized by the process of the invention can be used for the manufacture of articles such as preforms, molded parts, containers, fibers or filaments, films or sheets or technical yarn in various sizes and shapes.
  • the polymerization process can be a continuous process or a batch process.
  • the resin can also be combined with additives to impart specific functional characteristics.
  • the invention is further illustrated by way of the following examples. In the examples, the melt polymerization synthesis of polyester resin having intrinsic viscosity around 0.26 dl/g is carried out at atmospheric pressure under nitrogen flow. Consequently, the reactivity or the catalyst activity is measured in terms of the amount of nitrogen gas that flows into the reactor at a fixed nitrogen gas temperature.
  • the catalyst activity and reactivity during the synthesis of polyester resins of higher viscosity is measured in terms of the residence time.
  • the residence time is measured as the time required to obtain a polyester of desired intrinsic viscosity from the beginning of polymerisation reaction Example 1:
  • polyester having intrinsic viscosity of around 0.60 dl/g using the catalyst system comprising antimony trioxide and sodium para toluene sulphonate
  • the oligomer obtained was then subjected to polycondensation in the presence of Cobalt acetate based on 25 ppm cobalt and phosphoric acid based on 25 ppm as phosphorous at temperature of 285 0 C to obtain the prepolymer having IV up to 0.60 dl/g. After achieving desired prepolymer IV, the polyester was drained and cut in a granular form for further processing.
  • Example 2 Example 2:
  • polyester having intrinsic viscosity of around 0.26 dl/g using the catalyst system comprising antimony trioxide and sodium para toluene sulphonate
  • terephthalic acid and monoethylene glycol were charged in 1 :2 molar ratio.
  • 2 wt % Isophthalic acid and 1.5 wt % diethyl ene glycol (DEG) were added.
  • the esterification reaction was carried out at 280°C.
  • Sodium para-toluene sulfonate having 200ppm based on sodium was added at the end of esterification reaction.
  • the oligomer obtained was polymerized at 290°C to raise the IV up to 0.26 dl/g in presence of about 290ppm of antimony as a catalyst and 15 ppm phosphorous as a thermal stabilizer.
  • a static mixer was put after every injection nozzle for adding any suitable additive, co-monomer for better dispersion.
  • the low IV prepolymer melt was then passed through the 1.5 mm diameter orifice to form droplets on a continuous moving steel belt of particle former. These droplets were then crystallized on the particle former maintained at a temperature between 110 to 16O 0 C and then collected for carrying out solid-state polymerization.
  • Crystalline prepolymer having IV of 0.26 dl/g obtained in the example 2 and 4 was solid-state polymerized under inert atmosphere to raise the IV up to 0.76 dl/g.
  • the solid-state polymerization reaction was carried out at 235°C of nitrogen gas temperature. After achieving desired IV, the reaction terminated and polymer drained and collected.
  • Example 7 Manufacture of performs and bottles
  • Resin produced by SSP process was used for producing preforms using 2 cavity Arburg injection moulding machine (Model: Allrounder 420C). Before moulding, resins were dried for 6 hrs at 175°C in a dryer. Preform weight was 48g. Processing temperatures were in the range of 280 - 300°C and the cycle time was 34.5 seconds. These preforms were then used for producing bottles having volume of 1.5L. Bottles were produced using SIDEL SBOl single cavity blow moulding machine. Blowing temperature was maintained at 105 0 C.
  • melt polymerization (polycondensation) activity of the catalyst system of the invention is compared with antimony trioxide alone as catalyst in Table 1.
  • Table 1 Comparison of activity of the catalyst system comprising antimony trioxide and sodium para toluene sulphonate with antimony trioxide alone as catalyst during polycondensation of ester to achieve an intrinsic viscosity (IV) of 0.60 dl/g
  • Table 2 Comparison of activity of the catalyst system comprising antimony trioxide and sodium para toluene sulphonate with antimony trioxide alone as catalyst during polycondensation of ester to achieve an intrinsic viscosity of 0.26 dl/g
  • Table 4 Comparison of activity of the catalyst system comprising antimony trioxide and sodium para toluene sulphonate with antimony trioxide catalyst during solid state polymerization of low viscosity polymers formed in examples 2 and 4
  • Polyester of comparable intrinsic viscosity (0.767 dl/g) is obtained at a lower residence time (12 hours) by using the catalyst system of the invention.
  • the catalyst system of the invention exhibits improved activity that enables synthesis of polyester with high productivity and throughput.
  • the synthesis is more efficient and cost effective.
  • the reaction temperatures can be kept low to avoid unwanted side reactions.

Landscapes

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

Abstract

La présente invention a pour objet un système de catalyseur pour la synthèse de polyester, le système de catalyseur comprenant au moins 10 ppm d'un sel de métal alcalin de l'acide paratoluène sulfonique et au moins 50 ppm d'antimoine. La présente invention concerne également un procédé pour la synthèse de polyester, le polyester et les articles préparés à partir de celui-ci.
PCT/IN2008/000456 2007-07-16 2008-07-16 Catalyseur pour la production de polyester WO2009053998A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN1352/MUM/2007 2007-07-16
IN1352MU2007 2007-07-16

Publications (2)

Publication Number Publication Date
WO2009053998A2 true WO2009053998A2 (fr) 2009-04-30
WO2009053998A3 WO2009053998A3 (fr) 2009-07-02

Family

ID=40580201

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IN2008/000456 WO2009053998A2 (fr) 2007-07-16 2008-07-16 Catalyseur pour la production de polyester

Country Status (1)

Country Link
WO (1) WO2009053998A2 (fr)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4835247A (en) * 1988-08-08 1989-05-30 The Goodyear Tire & Rubber Company Process for the synthesis of a copolyester adhesive resin
JPH08245778A (ja) * 1995-03-13 1996-09-24 Nippon Ester Co Ltd コポリエステルの製造法

Also Published As

Publication number Publication date
WO2009053998A3 (fr) 2009-07-02

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