WO2014131701A1 - Additifs de stabilisation de polymères contre l'hydrolyse - Google Patents

Additifs de stabilisation de polymères contre l'hydrolyse Download PDF

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Publication number
WO2014131701A1
WO2014131701A1 PCT/EP2014/053426 EP2014053426W WO2014131701A1 WO 2014131701 A1 WO2014131701 A1 WO 2014131701A1 EP 2014053426 W EP2014053426 W EP 2014053426W WO 2014131701 A1 WO2014131701 A1 WO 2014131701A1
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WO
WIPO (PCT)
Prior art keywords
copolymers
monomers
polymers
alkoxysilane
mol
Prior art date
Application number
PCT/EP2014/053426
Other languages
German (de)
English (en)
Inventor
Laurence Pottie
Theo SMIT
Arno Lange
Collin G. Moore
Simone Schillo
Volker Frenz
Roelof Van Der Meer
Original Assignee
Basf Se
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 Basf Se filed Critical Basf Se
Publication of WO2014131701A1 publication Critical patent/WO2014131701A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
    • C08L43/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to the use of copolymers (C) containing at least one epoxy group and at least one alkoxysilane group as stabilizers for polymers (P). Furthermore, the invention relates to methods for stabilizing polymers against hydrolysis by adding copolymers (C). Further objects of the invention are selected copolymers (C) and mixtures containing copolymers (C).
  • WO 2012/032005 A1 describes terpolymers obtainable by copolymerization of electron-deficient olefins, olefins which carry only hydrogen atoms and / or carbon atoms with no electron-withdrawing substituents on their olefinic double bond and alkoxyvinylsilanes and derivatives of such terpolymers obtainable by modification or crosslinking. No.
  • 5,354,802 describes blow molding resin compositions comprising 0.2 to 10 parts by weight of a styrene copolymer containing 40 to 97% by weight of styrene, 60 to 3% by weight of a glycidyl ester of an alpha, beta-unsaturated acid and 0 to 50% by weight of other vinylic compounds monomers.
  • No. 6,984,694 B2 describes the use of copolymers containing epoxy-functionalized (meth) acrylic acid monomers, styrene and / or (meth) acrylic acid monomers as chain extenders.
  • US 4,393,156 and US 4,393,158 describe the use of epoxy silanes and certain epoxy siloxanes for the hydrolysis stabilization of polyester carbonates or aromatic polycarbonates. However, the epoxy-siloxanes described therein are not copolymers containing epoxy and alkoxysilane groups.
  • carbodiimides such as Stabaxol I, from RheinChemie
  • Monomeric carbodiimides are also known as hydrolysis stabilizers, for example from US Pat. No. 5,439,952.
  • toxic by-products such as phenylisocyanates often arise.
  • Polymers for example polycondensation polymers such as polyesters, are often degraded by hydrolysis at elevated temperatures. Such conditions occur, for example, when processing the polymers under heat with the simultaneous presence of moisture. Hydrolysis of the polymers leads to a reduction in the molecular weight and a decrease in the melt viscosity while affecting the mechanical properties of the polymers. These effects severely limit the applicability of such hydrolysable polymers and moreover require a great deal of drying effort before the polymers are processed.
  • the object of the present invention was therefore to provide stabilizers for polymers which lead to a reduction in the degradation and a reduction in the hydrolysis.
  • Another object of the present invention was to provide hydrolysis stabilizers which have no toxic by-products.
  • These objects have been achieved by the use of copolymers (C) containing at least one epoxy group and at least one alkoxysilane group as stabilizers for polymers (P), preferably containing at least two epoxy groups and two alkoxysilane groups.
  • the copolymers (C) are preferably used as hydrolysis stabilizers or acid scavengers.
  • Alkoxysilane groups in the context of the present invention are understood to mean groups of the general formula (I):
  • R, R 2 independently of one another, the same or different, H, Ci-C 20 alkyl, C 2 -C 2 -alkenyl, C 2 -C 2 o-alkynyl, C 3 -C 5 cycloalkyl, H, Ci-C 2 o preferably alkyl.
  • Epoxy groups in the context of the present invention are understood to mean groups of the general formula (II):
  • R 3 , R 4 , R 5 independently of one another, identical or different,
  • C 1 -C 20 -alkyl C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, C 3 -C 5 -cycloalkyl, preferably H, C 1 -C 4 -alkyl.
  • Expressions of the form C a -Cb designate in the context of this invention chemical compounds or substituents with a certain number of carbon atoms.
  • the number of carbon atoms can be chosen from the entire range from a to b, including a and b, a is at least 1 and b is always greater than a.
  • Further specification of the chemical compounds or substituents is made by expressions of the form C a -Cb-V.
  • V here stands for a chemical compound class or substituent class, for example for alkyl compounds or alkyl substituents.
  • C 1 -C 20 -alkyl straight-chain or branched hydrocarbon radicals having up to 20 carbon atoms, for example C 1 -C 10 -alkyl or C 2 -C 20 -alkyl, preferably C 1 -C 10 -alkyl, for example C 1 -C 3 -alkyl, such as methyl , Ethyl, propyl, isopropyl, or C 4 -C 6 -alkyl, n-butyl, sec-butyl, tert-butyl, 1, 1-dimethylethyl, pentyl, 2-methylbutyl, 1, 1-dimethylpropyl, 1, 2 Dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 2-methylpentyl, 3-methyl-pentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,
  • C 2 -C 2 -alkenyl unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 20 carbon atoms and a double bond in any position, for example C 2 -Cio- alkenyl or Cn-C 2 o-alkenyl, preferably C 2 -Cio- Alkenyl, such as C 2 -C 4 alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1 -propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, or Cs-C6 alkenyl, such as 1 - Pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-
  • C 2 -C 20 -alkynyl straight-chain or branched hydrocarbon groups having 2 to 20 carbon atoms and a triple bond in any position, for example C 2 -C 10 -alkynyl or C 2 -C 20 -alkynyl, preferably C 2 -C 10 -alkynyl, such as C 2 -C 4 -alkynyl, as described above Ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, or C 5 -C 7 -alkynyl, such as 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1, 1-dimethyl-2- prop
  • Aryl a mono- to trinuclear aromatic ring system containing 6 to 14 carbon ring members, e.g. As phenyl, naphthyl or anthracenyl, preferably a mono- to binuclear, more preferably a mononuclear aromatic ring system.
  • the symbol " * " denotes the valency for all chemical compounds via which one chemical group is attached to another chemical group.
  • the copolymers (C) are obtained by polymerization of monomers, these monomers comprising those which
  • R 1 , R 2 independently of one another, the same or different, H,
  • R 3 , R 4 , R 5 independently of one another, identical or different,
  • C 1 -C 20 -alkyl C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, C 3 -C 5 -cycloalkyl, preferably H, C 1 -C 4 -alkyl,
  • R 7 , R 8 , R 9 independently, the same or different, H,
  • Ci-C 20 alkyl C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 5 cycloalkyl, H, Ci-C 2 o preferably alkyl, more preferably H, Ci-C 4 alkyl,
  • R 6 is a single bond, C 1 -C 20 -alkylene, -C (O) O-R 10 -,
  • At least 10% of the monomers of the copolymers (C) preferably contain epoxy groups, particularly preferably at least 20%, very particularly preferably at least 30%, in particular at least 40%. Further preferably, at least 10% of the monomers of the copolymers (C) contain alkoxy silane groups, particularly preferably at least 20%, very particularly preferably at least 30%, in particular at least 40%.
  • the monomers of the copolymers (C) are selected from glycidyl acrylate, glycidyl methacrylate, styrene, vinyltriethoxysilanes, methacryloxypropyltrimethoxysilane, methacryloxypropyltris (2-propoxy) silane, methyl methacrylate, butyl acrylate, 2 Ethylhexylacrylate, 2-propylhexylacrylate and alpha-methylstyrene.
  • exactly two, three or four monomers are selected from which the copolymers (C) consist. Further monomers are then not present in the copolymer (C) in this case.
  • the exactly two monomers are preferably glycidyl methacrylate and vinyltriethoxysilane.
  • glycidyl methacrylate and vinyltriethoxysilane are in a molar ratio in the range of 10 to 90 to 90 to 10, preferably from 20 to 80 to 80 to 20, particularly preferably from 30 to 70 to 70 to 30, most preferably from 40 to 60 to 60 used up to 40.
  • the exactly two monomers are glycidyl methacrylate and methacryloxypropyltrimethoxysilane.
  • glycidyl methacrylate and methacryloxypropyl trimethoxysilane in a molar ratio in the range of 10 to 90 to 90 to 10, preferably from 20 to 80 to 80 to 20, particularly preferably from 30 to 70 to 70 to 30, most preferably from 40 to 60 to 60 to 40 used.
  • the exactly four monomers are glycidyl acrylate, styrene, methyl methacrylate and methacryloxypropyltrimethoxysilane.
  • glycidyl acrylate and methacryloxypropyltrimethoxysilane are used in a molar ratio in the range of 0.01 to 10.
  • the copolymers (C) preferably have a weight average molecular weight Mw in the range from 100 to 50,000 g / mol, preferably from 2,400 to 20,000, particularly preferably from 3500 to 13,000.
  • the copolymers (C) are prepared by methods known to the skilled person from the prior art, as described, for example, in WO 2012/098063 A1 or WO 2012/044981 A2.
  • the polymers (P) are polycondensates or polyaddition products.
  • the polymers (P) are preferably selected from the group of polyesters, polyamides, polyurethanes, polycarbonates and their copolymers.
  • the polymers (P) are selected from polyethylene terephthalates (PET), polybutylene terephthalates (PBT), polyethylene naphthalate (PEN), polycarbonate (PC), acrylonitrile-butadiene-styrene copolymer (ABS), biodegradable aliphatic-aromatic copolyesters, biopolymers and Polyamide 6 (PA6).
  • PET polyethylene terephthalates
  • PBT polybutylene terephthalates
  • PEN polyethylene naphthalate
  • PC polycarbonate
  • ABS acrylonitrile-butadiene-styrene copolymer
  • PA6 Polyamide 6
  • Another object of the invention is a process for the stabilization of polymers (P) against hydrolysis, characterized in that the polymers (P) an effective amount of copolymers (C) is added.
  • the copolymers (C) are preferably added in an amount of from 0.01 to 10% by weight, based on the total amount of polymer (P) and copolymer (C).
  • copolymers (C) to the polymers (P) is carried out by methods known to those skilled in the art. In particular, the addition takes place by extrusion or compounding.
  • copolymers (C) consisting of
  • (c) from 0 to 95 mol%, at least one of (a) and (b) different monomer, preferably from 40 to 93 mol%, particularly preferably from 55 to 75 mol% where the proportion of monomers (a) , (b) and (c) is 100 mol% in total.
  • copolymers (C) are made
  • copolymers (C) from 0 to 95 mole% styrene and / or methyl methacrylate, preferably from 0 to 50.
  • the copolymers (C) are prepared according to the procedures described above for the copolymers (C).
  • a further subject of the invention are mixtures comprising copolymers (C) and polymers (P), where the polymers (P) are preferably polycondensates or polyaddition products.
  • the copolymers (C) are contained in the mixtures in an amount of 0.01 to 10 wt .-%.
  • the polymers (P) are preferably selected from the group of polyesters, polyamides, polyurethanes, polycarbonates and their copolymers.
  • polymers (P) in this case PET, PBT, PEN, PC, ABS, biodegradable aliphatic-aromatic copolyesters, biopolymers or PA6.
  • the preparation of the mixtures is carried out by methods known to those skilled in the art. In particular, the addition is effected by extrusion or compounding.
  • the present invention provides copolymers (C) for stabilizing polymers which cause a decrease in the melt viscosity of polymers and, because of their polymeric structure, are less toxic to handle, incorporate and use as a stabilizer.
  • copolymers (C) used in the present invention show excellent properties.
  • the invention is explained in more detail by the examples without the examples restricting the subject matter of the invention.
  • VTEOS vinyltriethoxysilane
  • GMA glycidyl methacrylate
  • a copolymer of glycidyl methacrylate (GMA), methyl methacrylate (MMA), styrene (ST) and methacryloxypropyltrimethoxysilane (TMSMA) was prepared according to the methods of WO
  • Data in mol .-% are based on the total amount of monomers.
  • PET Polyethylene terephthalate
  • the PET had a low concentration of carboxylic end groups (about 21 mmol / kg).
  • the acid numbers are obtained by titration of the respective PET solution in the solvent mixture of chloroform / cresol.
  • the stabilizers (copolymers (C)) were coextruded with the PET in various concentrations at a temperature of 260 ° C.
  • the resulting films were then exposed to elevated temperatures (1-10 ° C) and high humidity (100%) and stored for a period of two or five days (2d, 5d).
  • the degradation of the polymer was determined by measuring the viscosity number (VZ) and / or the acid end group concentration of the PET before and after storage.
  • VZ measurements (units in mg / l) were carried out with the aid of a micro Ubbelohde capillary viscometer using as solvent a 1: 1 mixture of phenol and o-dichlorobenzene.
  • In% by weight are based on the total amount of stabilizer and PET.
  • the copolymers (C) stabilize the PET against hydrolytic degradation. Compared with the Stabaxol results, although increased concentrations of acid groups but surprisingly good stabilization of the viscosity properties.

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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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne l'utilisation de copolymères (C) contenant au moins un groupe époxyde et au moins un groupe alcoxysilane comme agents de stabilisation de polymères (P). En règle générale, les copolymères (C) sont obtenus par polymérisation de monomères. Les monomères en question comprennent des monomères qui contiennent des groupes époxyde ou des groupes alcoxysilane ou des groupes époxyde et alcoxysilane ou qui peuvent être mis à réagir pendant ou après la polymérisation et qui, après cette réaction, contiennent des groupes époxyde ou des groupes alcoxysilane ou des groupes époxyde et alcoxysilane. L'invention concerne en outre un procédé de stabilisation de polymères (P) contre l'hydrolyse, caractérisé en ce que l'on ajoute aux polymères (P) une quantité efficace de copolymères (C). Elle concerne également des copolymères (C') constitués de compositions spécifiques de monomères contenant au moins un groupe époxyde et au moins un groupe alcoxysilane ainsi que, facultativement, d'autres monomères. Enfin l'invention concerne des mélanges contenant des copolymères (C') et des polymères (P).
PCT/EP2014/053426 2013-02-27 2014-02-21 Additifs de stabilisation de polymères contre l'hydrolyse WO2014131701A1 (fr)

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EP13156928.7 2013-02-27
EP13156928 2013-02-27

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017194337A1 (fr) 2016-05-13 2017-11-16 Sabic Global Technologies B.V. Polymères à base de polyester ayant une plus grande stabilité hydrolytique

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3542585A (en) * 1968-02-23 1970-11-24 Dow Corning Method for adhering acrylate finishes to silicone impregnated leather and resulting article
GB1441367A (en) * 1973-05-26 1976-06-30 Bayer Ag Filled aromatic polycabonates with improved properties
US3988287A (en) * 1974-02-09 1976-10-26 Teijin Limited Polyamide compositions
US4393158A (en) 1981-07-20 1983-07-12 General Electric Company Hydrolytically stable polycarbonate compositions
US4393156A (en) 1981-07-20 1983-07-12 General Electric Company Hydrolytically stable polyester-carbonate compositions
US5354802A (en) 1993-02-11 1994-10-11 Polyplastics Co., Ltd. Resin composition for blow molding and blow molded item made therefrom
US5439952A (en) 1993-12-21 1995-08-08 The Thompson Minwax Company Self-curing coating composition exhibiting reduced discoloration upon storage
US6177519B1 (en) 1999-03-02 2001-01-23 Exxon Chemical Patents, Inc. Silane grafted copolymers of an isomonoolefin and a vinyl aromatic monomer
US6194597B1 (en) 1999-04-15 2001-02-27 Dow Corning Corporation Living cationic polymers prepared from silyl-functional aromatic initiators
US6984694B2 (en) 2002-02-01 2006-01-10 Johnson Polymer, Llc Oligomeric chain extenders for processing, post-processing and recycling of condensation polymers, synthesis, compositions and applications
WO2012032005A1 (fr) 2010-09-07 2012-03-15 Basf Se Terpolymère à base d'oléfines déficitaires en électrons, d'oléfines sans substituants accepteurs d'électrons et d'alcoxyvinylsilanes
WO2012044981A2 (fr) 2010-10-01 2012-04-05 Basf Se Oligomères méthacryliques styréniques
WO2012098063A1 (fr) 2011-01-18 2012-07-26 Basf Se Polyamides stables à l'hydrolyse

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3542585A (en) * 1968-02-23 1970-11-24 Dow Corning Method for adhering acrylate finishes to silicone impregnated leather and resulting article
GB1441367A (en) * 1973-05-26 1976-06-30 Bayer Ag Filled aromatic polycabonates with improved properties
US3988287A (en) * 1974-02-09 1976-10-26 Teijin Limited Polyamide compositions
US4393158A (en) 1981-07-20 1983-07-12 General Electric Company Hydrolytically stable polycarbonate compositions
US4393156A (en) 1981-07-20 1983-07-12 General Electric Company Hydrolytically stable polyester-carbonate compositions
US5354802A (en) 1993-02-11 1994-10-11 Polyplastics Co., Ltd. Resin composition for blow molding and blow molded item made therefrom
US5439952A (en) 1993-12-21 1995-08-08 The Thompson Minwax Company Self-curing coating composition exhibiting reduced discoloration upon storage
US6177519B1 (en) 1999-03-02 2001-01-23 Exxon Chemical Patents, Inc. Silane grafted copolymers of an isomonoolefin and a vinyl aromatic monomer
US6194597B1 (en) 1999-04-15 2001-02-27 Dow Corning Corporation Living cationic polymers prepared from silyl-functional aromatic initiators
US6984694B2 (en) 2002-02-01 2006-01-10 Johnson Polymer, Llc Oligomeric chain extenders for processing, post-processing and recycling of condensation polymers, synthesis, compositions and applications
WO2012032005A1 (fr) 2010-09-07 2012-03-15 Basf Se Terpolymère à base d'oléfines déficitaires en électrons, d'oléfines sans substituants accepteurs d'électrons et d'alcoxyvinylsilanes
WO2012044981A2 (fr) 2010-10-01 2012-04-05 Basf Se Oligomères méthacryliques styréniques
WO2012098063A1 (fr) 2011-01-18 2012-07-26 Basf Se Polyamides stables à l'hydrolyse

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017194337A1 (fr) 2016-05-13 2017-11-16 Sabic Global Technologies B.V. Polymères à base de polyester ayant une plus grande stabilité hydrolytique

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