WO2024089105A1 - Polyester à stabilité de couleur améliorée - Google Patents

Polyester à stabilité de couleur améliorée Download PDF

Info

Publication number
WO2024089105A1
WO2024089105A1 PCT/EP2023/079784 EP2023079784W WO2024089105A1 WO 2024089105 A1 WO2024089105 A1 WO 2024089105A1 EP 2023079784 W EP2023079784 W EP 2023079784W WO 2024089105 A1 WO2024089105 A1 WO 2024089105A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
antioxidant
furandicarboxylate
polymer
weight
Prior art date
Application number
PCT/EP2023/079784
Other languages
English (en)
Inventor
Hendawy ELFEKI
Matheus Adrianus Dam
Original Assignee
Furanix Technologies B.V.
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 Furanix Technologies B.V. filed Critical Furanix Technologies B.V.
Publication of WO2024089105A1 publication Critical patent/WO2024089105A1/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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/329—Phosphorus containing acids

Definitions

  • the present invention relates to a process for the preparation of poly(ethylene 2,5- furandicarboxylate) polymer from polyethylene 2,5- furandicarboxylate) prepolymer.
  • FDCA 2,5-Furandicarboxylic acid
  • PEF plant-based polyester poly (ethylene-2, 5- furandicarboxylate)
  • FDCA is typically obtained by oxidation of molecules having furan moieties, e.g. 5- hydroxymethylfurfural (5-HMF) and the corresponding 5-HMF esters or 5-HMF ethers, that are typically obtained from plant-based sugars, e.g. by sugar dehydration.
  • furan moieties e.g. 5- hydroxymethylfurfural (5-HMF)
  • 5-HMF esters or 5-HMF ethers that are typically obtained from plant-based sugars, e.g. by sugar dehydration.
  • a broad variety of oxidation processes is known from the prior art comprising e.g. enzymatic and metal catalysed processes such as described in W02010/132740 and WO2011/043660.
  • thermo-oxidative degradation reactions As described in the article “Effect of additives on the thermal and thermos-oxidative stability of poly (ethylene furanoate) biobased polyester” by Zoi Terzopoulou et al., Thermochimica Acta 686 (2020) 178549. It is described that the thermo- oxidative degradation was affected by the catalyst type used. It is common practice to add thermal stabilizers during the synthesis or the processing of thermoplastic polyesters. The article of Thermochimica Acta describes the addition of a commercial phenolic antioxidant (Irganox 1098) and addition of phosphorus-containing thermal stabilizers during PEF synthesis with the use of antimony catalyst.
  • Irganox 1098 commercial phenolic antioxidant
  • phosphorus-containing thermal stabilizers during PEF synthesis with the use of antimony catalyst.
  • the primary objective of the present invention was to provide a composition comprising poly(ethylene 2,5- furandicarboxylate) polymer having improved colour stability especially having good colour after melt processing.
  • Colour itself is subjective and is influenced by the wavelength and intensity of light that is reflected.
  • the colour of polymer particles is additionally influenced by crystal size and the presence of optical brighteners. Precipitated polymer particles tend to be fine and thereby appear to have good colour. To objectively assess the colour, it is to be assessed by the absorption of yellow light, specifically 400 nm, of a solution of the polymer per se.
  • Colour stability is especially relevant when exposing PEF to elevated temperatures in particular in the presence of oxygen such as can occur during melt processing including recycling.
  • CN 108586717 was the use of bio-based polyesters to reduce static electricity and electrostatic discharge.
  • a bio-based and permanent static dissipative polymer was obtained by esterifying a mix of furan dicarboxylic acid, terephthalic acid and isophthalic acid with ethylene glycol followed by condensation polymerisation in the presence of inorganic salt, catalyst and stabiliser.
  • CN 108727575 teaches the use of a titanium-silicon-cobalt composite catalyst in combination with ester formed by reacting FDCA and an aliphatic diol referred to as guide, in the preparation of FDCA based copolyesters to reduce side-reactions.
  • the copolyesters are based on a variety of diols and additional diacids besides FDCA.
  • the copolyester is based on terephthalic acid, FDCA, ethylene glycol and propylene glycol (Example 1), FDCA, azelaic acid, sebacic acid, butanediol and heptanediol (Example 6) or FDCA, pimelic acid, heptanediol and pentanediol (Example 12) or FDCA, succinic acid, hexanediol and decanediol (Example 15) or FDCA, isophthalic acid, propylene glycol and hexanediol (Example 16) or FDCA, terephthalic acid, propylene glycol and butanediol (Example 17).
  • CN 109054007 aims to provide bio-furan dicarboxylic acid polyester having excellent gas barrier properties by reacting furan dicarboxylic acid with a glycol selected from the group consisting of 2-methyl-1 ,3-propanediol, 2,2-dimethyl-1 ,3-propanediol, 2-methyl-2- ethyl-1,3-propanediol, 2-methyl-2-propyl-1 ,3-propanediol, 2-ethyl-2-butyl-1 ,3-propanediol, 2- ethyl-2-pentyl-1 ,3-propanediol and 2-ethyl-2-hexyl-1 ,3-propanediol.
  • a glycol selected from the group consisting of 2-methyl-1 ,3-propanediol, 2,2-dimethyl-1 ,3-propanediol, 2-methyl-2- ethyl-1,3-
  • WO 2022/043500 and WO 2022/043501 describe processes in which germanium catalyst was found to allow preparation of polyester comprising 2,5-furandicarboxylate units having a high molecular weight and good optical properties such as a low absorbance of 400 nm light.
  • the starting compositions of these processes can comprise typical stabilizers that are known from the prior art such as phosphorous containing compounds and hindered phenolic compounds.
  • the present invention relates to a process for the preparation of a composition comprising poly(ethylene 2,5-furandicarboxylate) polymer wherein the process comprises (a) preparing or providing polyethylene 2,5-furandicarboxylate) prepolymer, and (b) subjecting the prepolymer to polycondensation at reduced pressure in the presence of a polycondensation catalyst to obtain the polymer, which polycondensation is carried out in the presence of both antioxidant and phosphoric acid.
  • the present invention further relates to a composition
  • a composition comprising poly(ethylene 2,5- furandicarboxylate) polymer and of from 5 to 5000 parts per million by weight (ppmw) of antioxidant, based of weight of antioxidant on weight of total composition, and of from 2 to 2000 ppmw phosphoric acid, based on weight of phosphor on weight of total composition.
  • ppmw parts per million by weight
  • the present invention relates to a process comprising melt processing a composition comprising polyethylene 2,5-furandicarboxylate) polymer obtainable by a process according to the present invention and/or a poly(ethylene 2,5-furandicarboxylate) composition according to the present invention more specifically in the presence of oxygen.
  • a reduced increase in A_400 absorption after melt processing was observed for such PEF polymer.
  • the antioxidant preferably comprises a primary antioxidant selected from the group consisting of compounds comprising hindered phenols and compounds comprising phenols substituted with propionic acid and/or propionate.
  • Hindered phenols are phenols with one or more bulky functional groups preferably tertiary butyl.
  • the antioxidant consists of both a primary and a secondary antioxidant.
  • the secondary antioxidant preferably is selected from the group consisting of phosphor(lll) containing compounds and compounds containing a benzyl group.
  • Compounds can contain functional groups which make that these can be considered to be both a primary and a secondary antioxidant. In such case, the compound is considered a primary antioxidant.
  • the antioxidant preferably comprises a compound comprising hindered phenol. More preferably, the antioxidant consists of compounds comprising hindered phenol.
  • An especially preferred antioxidant was found to be a compound comprising hindered phenol and cinnamic acid and/or cinnamate, especially tetrakis methylene (3,5-di-t-butyl-4-hydroxy- hydrocinnamate)methane. The latter compound is commercially available from Dover Chemical Corporation as Dovernox 10.
  • the amount of antioxidant preferably is of from 1 to 10,000, more specifically of from 5 to 5000 parts per million by weight (ppmw), based of weight of antioxidant on weight of total composition.
  • the amount of phosphoric acid preferably is from 1 to 5000, more specifically of from 2 to 5000, more specifically of from 2 to 2000, more specifically of from 2 to 1000 ppmw of phosphoric acid, more specifically 5 to 500 ppmw, based on weight of phosphor on weight of total composition.
  • Phosphoric acid can be added as such or as a compound which is converted into phosphoric acid during preparation of the polyester composition.
  • Poly(ethylene 2,5-furandicarboxylate) contains ethylene moieties and 2,5- furandicarboxylate moieties. It may also contain a limited amount of other diacids and diol residues such as oligomers of ethylene glycol namely diethylene glycol and triethylene glycol. The amount of other diol or diacid residues is suitably at most 10 mol%, based on the molar amount of 2,5-furandicarboxylate moieties.
  • Poly(ethylene 2,5- furandicarboxylate) polymer also is referred to as polyester.
  • the poly(ethylene-2,5-furandicarboxylate) polymer prepared by the present process suitably has a relatively high melting point.
  • the melting point of the poly(ethylene-2,5- furandicarboxylate) is typically influenced by the presence of comonomers other than ethylene glycol and 2,5-furandicarboxylic acid, if any, or by its crystallinity. Suitable melting points of the poly(ethylene-2,5-furandicarboxylate) tend to be at least 215°C.
  • the melting point of the poly(ethylene-2,5-furandicarboxylate) may be as high as 245 °C.
  • the melting point of a polymer is easily determined by Differential Scanning Calorimetry (DSC) and measured at the top of the endothermic peak.
  • the ISO 11357-3 standard describes such a melting determination.
  • the polyester composition according to the present invention suitably has a melting point of at least 215 °C, more specifically of from 215 to 245 °C measured by DSC according to ISO 1357-3 standard.
  • Poly(ethylene 2,5-furandicarboxylate) prepolymer can be prepared from a starting composition comprising 2,5-furandicarboxylic acid, or its ester, and ethylene glycol.
  • the esterification of a diol compound with an acid compound is a reaction that is well known to the skilled person.
  • a method for its preparation for example has been described in WO 2015/137804.
  • the 2,5-furandicarboxylic acid or its ester and the ethylene glycol preferably constitute 90 % or more, preferably 95 % or more, most preferably 98 % or more of the starting composition by weight.
  • the poly(ethylene 2,5-furandicarboxylate) prepolymer is prepared from a starting compostion containing ethylene glycol and furandicarboxylic acid and/or its ester as sole monomors, more preferably ethylene glycol and furandicarboxylic acid as sole monomers.
  • the prepolymer preferably is prepared from the sole monomers ethylene glycol and furandicarboxylic acid and/or its ester, more preferably from the sole monomers ethylene glycol and furandicarboxylic acid.
  • further compounds which can become part of the PEF polymer, such as chain extenders are absent from the starting composition.
  • the chemical constitution of the prepolymer and polyester also depend on the molar ratio of the starting materials used in the starting composition.
  • the poly(ethylene 2,5-furandicarboxylate) prepolymer is prepared from 2,5-furandicarboxylic acid and ethylene glycol wherein the molar ratio of 2,5- furandicarboxylic acid to ethylene glycol in the starting mixture is of from 1 : 1.01 to 1 : 1.15.
  • esterification of the starting composition comprising ethylene glycol and FDCA or its ester preferably is conducted at a temperature in the range of 180 to 260 °C, preferably 185 to 240 °C, more preferably 190 to 230 °C.
  • the esterification is conducted at a pressure in the range of 40 to 400 kPa, preferably 50 to 150 kPa, more preferably 60 to 110 kPa.
  • the esterification is typically conducted for a time in the range of 30 to 480 min, preferably 60 to 360 min, more preferably 120 to 300 min, most preferably 180 to 240 min.
  • the polycondensation catalyst is already present during preparation of the prepolymer.
  • the prepolymer of step (a) preferably is prepared in the presence of antioxidant. It is possible that phosphoric acid also is present during preparation of the prepolymer depending on the further compounds which are present such as the polycondensation catalyst and if so, what polycondensation catalyst.
  • the preparation of prepolymer preferably is carried out in the presence of suppressant for suppressing ether formation between the aliphatic diol molecules.
  • the suppressant preferably is selected from the group consisting of amines and lithium hydroxide.
  • a variety of amines can be used such as primary amines, secondary amines or tertiary amines.
  • the suppressant preferably is selected from the group consisting of primary amines, secondary amines, tertiary amines and lithium hydroxide, preferably selected from the group consisting of primary amines, tertiary amines and lithium hydroxide, more preferably selected from the group consisting of 2-(diethylamino)ethanol (Et2NEtOH), N,N-dimethyldodecylamine (Me2NDodec), 3-aminocrotonic acid ester with butanediol (ACAEBD) and lithium hydroxide, most preferably selected from the group consisting of 2-(diethylamino)ethanol and N,N- dimethyldodecylamine. It can be preferred that the suppressant is lithium hydroxide.
  • the concentration of the suppressant in the starting composition is in the range of 5 to 1300 ppm, preferably 20 to 700 ppm, more preferably 30 to 450 ppm, by weight with respect of the weight of the starting composition.
  • Starting composition to be subjected to esterification conditions to produce prepolymer in step (a) preferably comprises ethylene glycol and FDCA and/or its ester, antioxidant and suppressant and optionally phosphoric acid and/or polycondensation catalyst.
  • the prepolymer is contacted with a polycondensation catalyst during the polycondensation of step (b).
  • a polycondensation catalyst already can be added to the starting composition as their presence does not deteriorate the preparation of prepolymer.
  • germanium containing polycondensation catalyst is present at preparation of the prepolymer, it is preferred that the phosphoric acid is added after preparation of the prepolymer. Especially good polyester is obtained by the present process if phosphoric acid is added to germanium polycondensation catalyst containing prepolymer.
  • Polycondensation is used for producing polyethylene 2,5-furandicarboxylate) polymer by forming additional ester moieties between the compounds of the prepolymer by means of esterification and transesterification, wherein e.g. water and/or aliphatic diol are released in the condensation process, and are typically removed from the reaction due to the elevated temperatures and reduced pressures used during polycondensation.
  • the polycondensation may be conducted in one or more steps and could suitably be operated as either batch, semi-continuous or continuous processes.
  • step a) e.g. a prepolycondensation step.
  • a pre-polycondensation step is typically conducted at a pressure lower than applied in esterification and can be used to remove the most volatile components, such as free diol and other low molecular weight compounds, before reducing the pressure even further to begin polycondensation.
  • the prepolymer of step (a) is subjected to step (b) without addition of further compounds other than polycondensation catalyst, antioxidant and/or phosphoric acid more specifically as described herein.
  • the polycondensation preferably is conducted at a temperature in the range of 240 to 300 °C, preferably 260 to 290 °C, more preferably 265 to 285 °C.
  • the polycondensation is conducted at reduced pressure in the range of 0.05 to 100 kPa, preferably 0.05 to 10 kPa, more preferably 0.1 to 1 kPa while the polycondensation is typically conducted for a time in the range of 10 to 260 min, preferably 30 to 190 min, more preferably 60 to 120 min.
  • the polycondensation catalyst can contain metals such as aluminium, antimony, tin and germanium. Suitable polycondensation catalysts have been described for example in WO2022/136332, WO 2022/043500 and WO 2022/043501.
  • the polycondensation catalyst contains germanium.
  • Germanium polycondensation catalyst can be present in the catalyst system as the metal or as the cation.
  • Preferred is a process wherein the germanium containing catalyst is selected from the group consisting of germanium oxide and germanium salts, preferably selected from the group of organic germanium salts and germanium oxide.
  • an organic germanium salt comprises a salt of a germanium cation and at least one kind of hydrocarbon anion.
  • the germanium containing catalyst consists of germanium oxide.
  • the concentration of the germanium containing catalyst in step (b), calculated as the metal per se preferably is in the range of 10 to 1000 ppm, preferably 30 to 500 ppm, more preferably 50 to 300 ppm, most preferably 70 to 150 ppm, by weight with respect of the weight of the prepolymer. Therefore, the compositions of the present invention preferably comprise an amount of germanium, calculated as the metal per se, in the range of from 5 to 5000 ppmw, more specifically 10 to 1000 ppm, preferably 30 to 500 ppm, more preferably 50 to 300 ppm, most preferably 70 to 150 ppm, by weight with respect of total weight of composition.
  • PEF polymer after polycondensation has a number average molecular weight of 20 kg/mol or more, preferably 25 kg/mol or more, preferably 30 kg/mol or more.
  • the number average molecular weight is determined through the use of gel permeation chromatography (GPC) with hexafluorisopropanol with 0.05 M potassium trifluoroacetate as eluent and calibrated using polymethylmethacrylate standard.
  • the melting temperature of PEF polymer is typically in the range of 190 to 230°C.
  • the process of the present invention further comprises melt processing of the product of step (b) optionally after the product of step (b) has been subjected to solid state polymerization as described below.
  • Melt processing of such polymer generally involves a temperature of at least 200 °C, more specifically at least 210 °C, more specifically at least 220 °C, more specifically at least 230 °C.
  • the melt processing involves a temperature ranging from 240 to 310°C, in particular from 240 to 300 °C, to ensure that the composition is in a molten state and has the desired viscosity.
  • the temperature can be at most 290 °C, more specifically at most 280 °C.
  • Melt processing tends to be applied in recycling of polymer and in the manufacture of fibers and packaging including films and containers.
  • the compositions of the present invention are suitable for use in such melt processing or may have been subjected to such melt processing.
  • steps can comprise a step of crystallizing the polymer for obtaining a crystallized polymer and subjecting the crystallized polymer to a solid-state polymerization for increasing the molecular weight. Therefore, it can be preferred that the process further comprises the steps: c) crystallizing the PEF polymer obtained in step b) to obtain a crystallized or semicrystallized polymer, and d) subjecting the crystallized polymer produced in step c) to a solid state polymerization for increasing the molecular weight.
  • Such solid state polymerization can be conducted at an elevated temperature in the range of Tm - 80 °C to Tm - 20 °C, preferably Tm - 60 °C to Tm - 25 °C, more preferably Tm - 60 °C to Tm - 30 °C, wherein Tm is the melting point of the PEF polymer in °C, wherein the solid state polymerization is preferably conducted at an elevated temperature in the range of 160 to 240 °C, more preferably 170 to 220 °C, most preferably 180 to 210 °C.
  • the melting point of a polymer is easily determined by DSC and measured at the top of the endothermic peak.
  • the ISO11357-3 standard describes such a melting determination.
  • the crystallization preferably is conducted at an elevated temperature in the range of 100 to 200 °C, preferably 120 to 180 °C, more preferably 140 to 160 °C.
  • the crystallization preferably is conducted for a time in the range of 0.5 to 48 h, preferably 1 to 6 h, wherein step d) is conducted directly after step c) without cooling the polyester comprising 2,5-furandicarboxylate units below 50 °C.
  • the crystallization preferably is conducted at or near ambient pressure or, less preferred, at reduced pressure of less than 100 kPa or less than 10 kPa.
  • the solid state polymerization preferably is conducted under inert gas atmosphere, preferably nitrogen, helium, neon or argon atmosphere. It is preferred that the crystallized or semi-crystallized PEF polymer obtained in step c) is granulated to obtain a degree of granulation in the range of 20 to 180 pellets per g, preferably 40 to 140 pellets per g.
  • Solid state polymerization can produce PEF polymer having a number average molecular weight of 30 kg/mol or more, preferably 45 kg/mol or more, more preferably 60 kg/mol or more.
  • the FDCA used in the experiments comprised less than 500 ppm FCA.
  • a starting composition comprising ethylene glycol and 2,5-furandicarboxylic acid in a molar ratio of 1.21 to 1 in combination with 210 ppm tetraethylammonium hydroxide DEG suppressant (TEAOH) was subjected to esterification at 220 °C and at atmospheric pressure. Additionally, 200 ppm of GeC>2 (calculated as amount of Ge metal) polycondensation catalyst was added as a solution of 200 ppm of GeO2 in 75 ml water.
  • TEAOH tetraethylammonium hydroxide DEG suppressant
  • the primary phenolic antioxidant Dovernox 10 was obtained from Dover Chemical Corporation and is tetrakis methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)methane.
  • the secondary antioxidant Irgafos 168 was obtained from BASF and is tris(2,4-di-tert.- butylphenyl)phosphite.
  • the antioxidant ADK STAB A611 was obtained from Adeka and is a mixture of primary hindered phenolic antioxidant and secondary phosphite.
  • the hindered phenolic antioxidant is benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-2,2-bis[[3-[3,5-bis91 ,1- dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]methyl]-1,3-propanediyl ester.
  • the phosphite is phenol, 2.4-bis(1 , 1 -dimethylethyl)-, phosphite (3:1).
  • the mixture was subjected to prepolycondensation at a temperature of 260 °C during 20 minutes and polycondensation for 75 min at 260°C followed by solid state polymerization.
  • the resins obtained after polycondensation were crystallized under a nitrogen flow of 175 ml/min at a temperature of 150 °C before being subjected to solid state polymerization for 24 hours under nitrogen atmosphere at a temperature of 200 °C.
  • the average diameter of the particles subjected to solid state polymerization was 0.6 to 2.0 mm. After solid state polymerization, the fraction having a particle size of 1.4 to 2.0 mm was isolated and used for analytics.
  • A_400 is the absorbance of a 30 mg/mL solution of polyester in a dichloromethane:hexafluoroisopropanol 8:2 (vol/vol) mixture in a 2.5 cm diameter circular vial measured at 400 nm.
  • the data measured for the 2.5 cm diameter vial can be converted to a customary 1 cm equivalent path length by dividing the measured data by 2.5.
  • Samples of polymer subsequently were heated to a temperature of 260 °C in closed vials for 30 minutes to determine the A_400 absorption increase in the presence of oxygen.
  • the A_400 absorption of all samples was assessed as described above.

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

L'invention concerne un procédé de préparation d'une composition comprenant un polymère de poly(éthylène 2,5-furandicarboxylate) qui comprend la polycondensation d'un prépolymère de poly(éthylène 2,5-furandicarboxylate) en présence à la fois d'un antioxydant et d'acide phosphorique ; une composition comprenant un polymère de poly(éthylène 2,5-furandicarboxylate), constituée de 5 à 5000 ppm en poids d'antioxydant, sur la base du poids de l'antioxydant sur le poids de la composition totale, et de 2 à 2000 ppm en poids d'acide phosphorique, sur la base du poids du phosphore sur le poids de la composition totale.
PCT/EP2023/079784 2022-10-26 2023-10-25 Polyester à stabilité de couleur améliorée WO2024089105A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP22203954.7 2022-10-26
EP22203954 2022-10-26

Publications (1)

Publication Number Publication Date
WO2024089105A1 true WO2024089105A1 (fr) 2024-05-02

Family

ID=84043880

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2023/079784 WO2024089105A1 (fr) 2022-10-26 2023-10-25 Polyester à stabilité de couleur améliorée

Country Status (1)

Country Link
WO (1) WO2024089105A1 (fr)

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100174044A1 (en) 2008-02-20 2010-07-08 Canon Kabushiki Kaisha Polyester resin, method of producing the same, composition for molded article and molded article
WO2010132740A2 (fr) 2009-05-14 2010-11-18 Archer Daniels Midland Company Oxydation de composés de furfural
WO2011043660A2 (fr) 2009-10-07 2011-04-14 Furanix Technologies B.V. Procédé de préparation d'acide 2,5-furandicarboxylique et de ses esters
WO2013120989A2 (fr) 2012-02-17 2013-08-22 Uhde Inventa-Fischer Gmbh Procédé de préparation d'un polyester ou copolyester hétéroaromatique de poids moléculaire élevé
WO2015137804A1 (fr) 2014-03-11 2015-09-17 Furanix Technologies B.V. Procédé de préparation d'un polyester dans des conditions définies d'estérification
EP3116934A1 (fr) 2014-03-11 2017-01-18 Furanix Technologies B.V. Polyester et procede de preparation d'un tel polyester
EP3116932A1 (fr) 2014-03-11 2017-01-18 Furanix Technologies B.V. Polyester et son procédé de préparation
CN108586717A (zh) 2018-05-18 2018-09-28 广东轻工职业技术学院 一种生物基静电耗散聚酯及其制备方法
CN108727575A (zh) 2018-05-21 2018-11-02 东华大学 一种生物基2,5-呋喃二甲酸基共聚酯的制备方法
CN109054007A (zh) 2018-08-30 2018-12-21 中国科学院宁波材料技术与工程研究所 生物基呋喃二甲酸聚酯及其制备方法
US20210130311A1 (en) 2018-06-18 2021-05-06 Archer Daniels Midland Company Color stabilization of monomers and other reactants for forming bio-based polymers
WO2022043500A1 (fr) 2020-08-27 2022-03-03 Furanix Technologies B.V. Procédé de production d'un polyester comprenant des motifs 2,5-furanedicarboxylate
WO2022136332A1 (fr) 2020-12-23 2022-06-30 Furanix Technologies B.V. Procédé de production d'un polyester comprenant des motifs 2,5-furandicarboxylate

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100174044A1 (en) 2008-02-20 2010-07-08 Canon Kabushiki Kaisha Polyester resin, method of producing the same, composition for molded article and molded article
WO2010132740A2 (fr) 2009-05-14 2010-11-18 Archer Daniels Midland Company Oxydation de composés de furfural
WO2011043660A2 (fr) 2009-10-07 2011-04-14 Furanix Technologies B.V. Procédé de préparation d'acide 2,5-furandicarboxylique et de ses esters
WO2013120989A2 (fr) 2012-02-17 2013-08-22 Uhde Inventa-Fischer Gmbh Procédé de préparation d'un polyester ou copolyester hétéroaromatique de poids moléculaire élevé
WO2015137804A1 (fr) 2014-03-11 2015-09-17 Furanix Technologies B.V. Procédé de préparation d'un polyester dans des conditions définies d'estérification
EP3116934A1 (fr) 2014-03-11 2017-01-18 Furanix Technologies B.V. Polyester et procede de preparation d'un tel polyester
EP3116932A1 (fr) 2014-03-11 2017-01-18 Furanix Technologies B.V. Polyester et son procédé de préparation
CN108586717B (zh) * 2018-05-18 2019-03-19 广东轻工职业技术学院 一种生物基静电耗散聚酯及其制备方法
CN108586717A (zh) 2018-05-18 2018-09-28 广东轻工职业技术学院 一种生物基静电耗散聚酯及其制备方法
CN108727575A (zh) 2018-05-21 2018-11-02 东华大学 一种生物基2,5-呋喃二甲酸基共聚酯的制备方法
CN108727575B (zh) * 2018-05-21 2020-04-17 东华大学 一种生物基2,5-呋喃二甲酸基共聚酯的制备方法
US20210130311A1 (en) 2018-06-18 2021-05-06 Archer Daniels Midland Company Color stabilization of monomers and other reactants for forming bio-based polymers
CN109054007A (zh) 2018-08-30 2018-12-21 中国科学院宁波材料技术与工程研究所 生物基呋喃二甲酸聚酯及其制备方法
WO2022043500A1 (fr) 2020-08-27 2022-03-03 Furanix Technologies B.V. Procédé de production d'un polyester comprenant des motifs 2,5-furanedicarboxylate
WO2022043501A1 (fr) 2020-08-27 2022-03-03 Furanix Technologies B.V. Préparation de polyester comprenant des unités 2,5-furanedicarboxylate avec un catalyseur au germanium
WO2022136332A1 (fr) 2020-12-23 2022-06-30 Furanix Technologies B.V. Procédé de production d'un polyester comprenant des motifs 2,5-furandicarboxylate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZOI TERZOPOULOU ET AL.: "Effect of additives on the thermal and thermos-oxidative stability of poly (ethylene furanoate) biobased polyester", THERMOCHIMICA ACTA, vol. 686, 2020, pages 178549, XP086088327, DOI: 10.1016/j.tca.2020.178549

Similar Documents

Publication Publication Date Title
EP2478031B1 (fr) Résine de polyester et procédé de préparation
EP1535945B1 (fr) Procede de fabrication de resines de polyester
US10087305B2 (en) Nucleated crystallization of poly(trimethylene-2,5-furandicarboxylate) (PTF) and articles made therefrom
EP2820063B1 (fr) Poly(butylène-co-adipate téréphtalate), procédé de fabrication et ses utilisations
US5852164A (en) Polyester, process for producing the same and molding product therefrom
EP1838770A1 (fr) Procedes de production de polymeres poly(ethylene-co-isosorbide) tereephthalate de faible couleur
EP3184572A9 (fr) Polymère biodégradable transparent
AU2016226485A1 (en) Bio-based copolyester or copolyethylene terephthalate
KR101875597B1 (ko) 폴리에스테르 카보네이트 공중합체 및 그 제조방법
EP0711315A1 (fr) Procede de preparation de polymeres de poly(ethylene-2,6-naphtalene dicarboxylate) hydrolytiquement stables
WO2024089105A1 (fr) Polyester à stabilité de couleur améliorée
JP2008239744A (ja) ポリエステル樹脂
KR102533557B1 (ko) 폴리에스테르 수지 조성물
KR102210711B1 (ko) 무수당 알코올과 무수당 알코올-알킬렌 글리콜을 포함하는 생분해성 공중합 폴리에스테르 수지 및 이의 제조 방법
CN110520459B (zh) 使用锌催化剂制备聚(呋喃二甲酸三亚甲酯)的方法
JP4010022B2 (ja) 脂肪族ポリエステルカーボネート及びその製造方法
CN115397885A (zh) 共聚聚酯树脂、成型品、热收缩性膜及纤维
JP2021155497A (ja) ポリエステル樹脂
KR102589193B1 (ko) 무수당 알코올과 무수당 알코올계 폴리카보네이트 디올을 포함하는 생분해성 공중합 폴리에스테르 수지 및 이의 제조 방법, 및 이를 포함하는 성형품
JP6300266B2 (ja) 共重合ポリエステル樹脂及びその中空容器
KR102589197B1 (ko) 무수당 알코올계 폴리카보네이트 디올을 포함하는 생분해성 공중합 폴리에스테르 수지 및 이의 제조 방법, 및 이를 포함하는 성형품
JP7494450B2 (ja) ポリエステル
KR102200880B1 (ko) 향상된 충격강도와 높은 내열도를 가진 바이오매스 유래 고분자 수지 조성물 및 그 제조방법
JP6705287B2 (ja) ポリエステル樹脂
KR101768321B1 (ko) 바이오 매스 유래 폴리카보네이트 수지 제조 및 이를 이용한 성형품

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23798390

Country of ref document: EP

Kind code of ref document: A1