WO2013072310A1 - Additive zur hydrolysestabilisierung von polykondensaten - Google Patents

Additive zur hydrolysestabilisierung von polykondensaten Download PDF

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WO2013072310A1
WO2013072310A1 PCT/EP2012/072489 EP2012072489W WO2013072310A1 WO 2013072310 A1 WO2013072310 A1 WO 2013072310A1 EP 2012072489 W EP2012072489 W EP 2012072489W WO 2013072310 A1 WO2013072310 A1 WO 2013072310A1
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polymers
alkyl
mixture
different
independently
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PCT/EP2012/072489
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German (de)
English (en)
French (fr)
Inventor
Laurence Pottie
Theo SMIT
Simone Schillo
Volker Frenz
Roelof Van Der Meer
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Basf Se
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Priority to EP12783627.8A priority Critical patent/EP2780407A1/de
Priority to CN201280056408.XA priority patent/CN103946291A/zh
Priority to JP2014541624A priority patent/JP2014533752A/ja
Priority to KR1020147016344A priority patent/KR20140103956A/ko
Priority to IN3735CHN2014 priority patent/IN2014CN03735A/en
Publication of WO2013072310A1 publication Critical patent/WO2013072310A1/de

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    • 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
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916—Dicarboxylic acids and dihydroxy 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds

Definitions

  • the present invention relates to mixtures containing multifunctional chain extenders and mono- or difunctional hydrolysis stabilizers for polymers. Furthermore, the invention relates to mixtures of multifunctional chain extenders, mono- or difunctional hydrolysis stabilizers and polymers. Further objects of the invention are the use of the mixtures containing multifunctional chain extenders and mono- or difunctional hydrolysis stabilizers for stabilizing polymers and methods for stabilizing against molecular weight loss of polymers.
  • Chain extenders were originally developed to obtain polycondensates with high molecular weights by reactive extrusion.
  • WO 98/47940 A1 describes bifunctional caprolactam chain extenders for the preparation of high molecular weight polyesters and polyamides.
  • Multifunctional chain extenders with three or more reactive groups lead to branched structures.
  • the use of such additives in a polymer matrix therefore often leads, in addition to the chain extension, to branchings which, when processed in the melt, markedly increase the viscosity.
  • Such additives are in the US
  • 5,354,802 for use in, for example, polyesters or polyamides.
  • WO 2004/067629 A1 describes the use of chain extenders in the form of a dilution in an inert carrier plastic.
  • 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.
  • Carbodiimides are known as hydrolysis stabilizers, for example from US Pat. No. 5,439,952, EP 799843 A1 or EP 126251 1 A2. In their use, however, arise often toxic by-products such as phenyl isocyanates. To avoid problems with toxicity, oligomeric or polymeric carbodiimides are used.
  • DE 3217440 A1 describes polyethylene terephthalates having improved hydrolysis resistance, containing polycarbodlimides.
  • EP 0 507 407 A1 describes multifunctional water-dispersible crosslinking agents based on oligomeric substances containing carbodiimide and other reactive functional groups, such as heterocycles. Furthermore, aqueous dispersions, emulsions or solutions of such crosslinking agents as well as processes for the preparation of the crosslinking agents are described.
  • JP 2007023100 A2 describes the use of alkyl ketene dimers in the stabilization of aliphatic polyesters.
  • 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 hydrolyzable polymers and, moreover, require a great deal of drying 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.
  • the chain extenders (K) and the hydrolysis stabilizers (H) react with the end groups of polymers (P) in the molten or solid state of the polymers (P) to form a chemical bond.
  • the chain extenders (K) react with the end groups of polymers (P) in the molten state of the polymers (P) and the hydrolysis stabilizers (H) with the end groups of polymers (P) in the molten or solid state of the polymers (P).
  • 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 selected 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.
  • Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, particularly preferably fluorine or chlorine.
  • 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 C3-alkyl, such as methyl, ethyl, propyl, isopropyl, or C4-C6-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-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3
  • C 2 -C 20 -alkenyl unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 20 carbon atoms and one double bond in any position, for example C 2 -C 10 -alkenyl or C 2 -C 20 -alkenyl, preferably C 2 -C 10 -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-buteny
  • 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, such as 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
  • C3-C15-cycloalkyl monocyclic, saturated hydrocarbon groups having 3 to 15 carbon ring members, preferably Cs-Cs-cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl and a saturated or unsaturated cyclic system such as. B. norbornyl or norbenyl.
  • Aryl a mono- to trinuclear aromatic ring system containing 6 to 14 carbon ring members, eg. As phenyl, naphthyl or anthracenyl, preferably a mono- to binuclear, more preferably a mononuclear aromatic ring system.
  • C 1 -C 20 -alkoxy denotes a straight-chain or branched alkyl group having 1 to 20 carbon atoms (as mentioned above) which are bonded via an oxygen atom (-O-), for example C 1 -C 10 -alkoxy or C 2 -C 20 -alkoxy, preferably C 1 C10 alkyloxy, particularly preferably Ci-C3-alkoxy, such as methoxy, ethoxy, propoxy.
  • Heteroatoms are phosphorus, oxygen, nitrogen or sulfur, preferably oxygen, nitrogen or sulfur whose free valencies are optionally saturated by H atoms.
  • the chain extenders (K) are selected from the group of homopolymers and copolymers containing at least three epoxide groups, at least three aziridine groups, or at least three anhydride groups.
  • Particularly preferred chain extenders (K) are homo- or copolymers containing at least three epoxy groups. Very particular preference is given to such chain extenders (K) are copolymers containing at least three epoxy groups, in particular copolymers functionalized with epoxy groups containing styrene, (meth) acrylic acid ester monomer in polymerized form.
  • Preferred chain extenders (K) are copolymerization products of at least one monomer having at least one epoxy group and at least one styrene and / or (meth) acrylic acid ester monomer.
  • these are epoxy group-functionalized (meth) acrylic acid ester monomers in combination with non-epoxy-functionalized styrene monomers and / or
  • (meth) acrylic ester monomers refers to For the purposes of the present application, both acrylic ester monomers (acrylate monomers) and methacrylic acid ester monomers (methacrylate monomers) are included.
  • epoxy group-functionalized (meth) acrylic ester monomers examples include those containing 1,2-epoxy groups such as glycidyl acrylate and glycidyl methacrylate.
  • Other monomers functionalized with epoxy groups include allyl glycidyl ether, glycidyl methacrylate, glycidyl titanate.
  • Acrylate and methacrylate monomers that can be used in the invention include, independently of a functionalization with epoxy groups, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-hexyl acrylate, n-octyl acrylate, methyl methacrylate, ethyl methacrylate, n Propyl methacrylate, methylcyclohexyl methacrylate, isobornyl methacrylate, butyl acrylate, butyl methacrylate, iso-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, and mixtures of these.
  • Preferred non-functionalized acrylate and methacrylate include butyl acrylate, butyl methacrylate, methyl methacrylate, iso-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, and mixtures thereof.
  • Styrenic monomers that can be used in the present invention include styrene, alpha-methylstyrene, vinyltoluene, p-methylstyrene, tert-butylstyrene, o-chlorostyrene, vinylpyridines and mixtures thereof.
  • the monomers are selected from styrene or alpha-methylstyrene.
  • Particularly preferred co-polymerization products contain at least one monomer selected from glycidyl acrylate and glycidyl methacrylate and at least one monomer selected from styrene, methyl methacrylate, methyl acrylate, butyl acrylate and ethyl hexyl acrylate.
  • (Meth) acrylic ester monomer an epoxy equivalent weight (EEW) of 180 to 2800 g / mol, preferably from 190 to 1400 g / mol and particularly preferably from 200 to 700 g / mol.
  • Efn Mn / EEW
  • Efn stands for the number average of the epoxy functionality and Efw for the weight average of the epoxy functionality.
  • (Meth) acrylic acid ester monomer has a number average molecular weight (Mn) of less than 6000 g / mol, preferably from 1000 to 5000 g / mol and particularly preferably from 1500 to 4000 g / mol.
  • these co-polymerization preferably have a weight average molecular weight (Mw) of less than 25,000 g / mol, preferably from 1500 to 18000 g / mol, more preferably from 3000 to 13000 g / mol and in particular from 4000 to 8500 g / mol
  • Mw weight average molecular weight
  • the EEW values correspond to the mass of co-polymerization product having one equivalent of epoxy functionality and are determined according to ASTM D 1652-90 (Standard Test Method for Epoxy Content of Epoxy Resins (1990) Test Method B) or as described, for example, in US 6,552,144 B1 determined from the mass balance of the monomers used with epoxy groups.
  • Molecular weight distributions of the co-polymerization products are determined by gel permeation chromatography (GPC) measurements.
  • the co-polymerization products are first dissolved in tetrahydrofuran (THF) and then injected into the GPC apparatus.
  • THF tetrahydrofuran
  • RI refractive index
  • columns the PLGEL MIXED B columns can be used with a monitoring column and, among other things, determine the Mn and Mw values.
  • Co-polymerization of at least one monomer having at least one epoxy group and at least one styrene and / or (meth) acrylic acid ester monomer are commercially available, for example as Joncryle® Fa. BASF SE.
  • the hydrolysis stabilizers (H) are selected from the a. oligomeric carbodiimides of the general formula (I)
  • a 1 , A 2 independently of one another, the same or different,
  • C3-C14 cycloalkylene, arylene, B 1 , B 2 independently of one another, identical or different, heterocycles, C 1 -C 30 -alcohols, poletherols, polyesterols, amines, polyetheramines, polyesteramines, thioalcohols, polyether thiols, polyester thiols, n integer in the range from 2 to 100, preferably in the range of 2 to 50, more preferably in the range of 2 to 20,
  • Halogen preferably C 1 -C 4 -alkyl, mono- or difunctional epoxy compounds of the general formulas (IIa) or (IIb)
  • X 1 , X 2 , X 3 independently of one another, identical or different, CH 2 , O,
  • Z 2 , Z 3 independently of one another, identical or different, single bond, SiR 1 R 2 , Si (OR 1 ) R 2 , Si (OR 1 ) (OR 2 ),
  • R 1, R 2, R 3 independently of one another, identical or different, Ci-C2o-alkyl, preferably Ci-Cio-alkyl, particularly preferably Ci-C4-alkyl, in particular Ci-C2 alkyl, R 20 , R 21 , R 22 are independent of each other, identical or different, H, C 1 -C 20 -alkyl, preferably H, or
  • R 20 together with R 21 or R 22 dimethylene, trimethylene, tetramethylene to form a five-, six- or seven-membered ring system
  • R 23 , R 24 , R 25 are independent of each other, identical or different, H, C 1 -C 20 -alkyl, preferably H, or
  • R 23 together with R 24 or R 25 dimethylene, trimethylene, tetramethylene to form a five-, six- or seven-membered ring system
  • R 4 , R 42 are each, independently of one another or different, H, C 1 -C 30 -alkyl, preferably H, C 4 -C 20 -alkyl, particularly preferably H, C 6 -C 18 -alkyl,
  • R 51 R 52 independently of one another are identical or different, H, C 1 -C 30 -alkyl, preferably H, C 4 -C 20 -alkyl, particularly preferably H, C 6 -C 18 -alkyl,
  • R 6 is H, C 1 -C 20 -alkyl, aryl, C 3 -C 5 -cycloalkyl, NR 26 R 27 ,
  • R 16 is H, C 1 -C 20 -alkyl, aryl, C 3 -C 5 -cycloalkyl, halogen,
  • R 26 , R 27 independently of one another, the same or different, H,
  • R 7 , R 8 , R 9 , R 10 are independently, the same or different, H,
  • hydrolysis stabilizers (H) have no negative influence on the melt viscosity, color, turbidity or odor of polymers.
  • the hydrolysis stabilizers (H) are preferably chosen such that the melt viscosity does not increase significantly during the extrusion, preferably by less than 20%, more preferably by less than 10%, so that an adjustment of the target viscosity essentially via the addition of the chain extender (K ) is regulated.
  • Oligomeric carbodiimides c. of the general formula (I) can be as described for example in EP 0 507 407 A1 or our unpublished patent application EP
  • a general preparation process for preparing oligomeric carbodiimides containing at least one heterocyclic end group includes, for example, the reaction of a diisocyanate with a polyetherol and a heterocycle.
  • the substituents of the oligomeric carbodiimides of the general formula (I) A 1 , A 2 contain the hydrocarbon groups
  • the substituents of the carbodiimides B 1 , B 2 are selected from the group of the three- to zwoifgliedrigen, preferably three- to nine-membered, more preferably five- to seven-membered, oxygen, nitrogen and / or sulfur atoms and one or more ring-containing ring systems (heterocycles, heterocyclic end groups), such as aziridine, epoxide, thiirane, azirine, oxirene, thiirene, azetidine, oxetane, thietane, beta-lactam, beta-lactone, thiethanone, furan, pyrroline, dihydrofuran , Dihydrothiophene, pyrogen rolidine, tetrahydrofuran, tetrahydrothiophene, oxazolidine, dioxolane, oxathiolane, thiazolidine
  • Epoxy compounds b. of the general formulas (IIa) and (IIb) and their preparation are known to the skilled person from his specialist knowledge, for example from US 4,385,144, US 4,393,156 or US 4,393,158. Epoxy compounds of the general formulas (IIa) and (IIb) are commercially available.
  • Alkyl ketene dimers c. of the general formulas (III) and their preparation are known to the person skilled in the art from his specialist knowledge, for example from US Pat. No. 5,028,236 or WO 92/15746 A1. Alkylketene dimers of the general formulas (III) are commercially available.
  • Heterocycles (oxazolidinones and derivatives or isomers) d. of the general formulas (IV) and (IV) and their preparation are known to the person skilled in the art from his specialist knowledge, for example from US Pat. No. 3,770,693 or US Pat. No. 4,123,419. Heterocycles of the general formulas (IV) and (V) are commercially available.
  • the ratio between the at least one multifunctional chain extender (K) and the at least one mono- or difunctional hydrolysis stabilizer (H) in the mixture (M) can vary over a wide range, depending on the application. For example, in applications requiring a higher initial viscosity, eg PET recycling, higher amounts of chain extenders (K) are used.
  • the proportion of hydrolysis stabilizers increases accordingly.
  • the skilled person is able to set the appropriate ratio by appropriate experiments.
  • the quantitative ratio (weight) of K to H is in the range from 1: 100 to 100: 1, preferably from 1:50 to 50: 1, more preferably from 1:20 to 20: 1 and especially from 1:10 to 10: 1.
  • the polymers (P) are polycondensates or polyaddition products.
  • the polymers are preferably selected from the group of polyesters, polyamides, polyurethanes, polycarbonates, their copolymers and / or mixtures.
  • the polymers to be stabilized are selected from PET (polyethylene terephthalate), PBT (polybutylene terephthalate), PEN (polyethylene naphthalate), PC (polycarbonate), biodegradable aliphatic-aromatic copolyesters, biopolymers or PA6 (polyamide 6).
  • biodegradable aliphatic-aromatic copolyesters are poly (butylene adipate-co-terephthalates) and suitable biopolymers are in particular PLA (polylactic acid) and PHA (polyhydroxyalkanoates).
  • PLA polylactic acid
  • PHA polyhydroxyalkanoates
  • the stabilized polymers also include recycled or recycled polymers.
  • the polymers (P) comprise hydroxyl, amine, carboxy or carboxylic acid end groups, in particular carboxylic acid end groups.
  • Another object of the present invention are mixtures (MP) containing a. at least one mixture (M) described above and
  • At least one mixture (M) is added to the at least one polymer (P) in an amount of from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, in particular from 0.1 to 2
  • the incorporation of the mixtures (M) in the polymers (P) is generally carried out by mixing the ingredients. For example, mixing is carried out by methods known to those skilled in the art, such as those generally used in the addition of polymers.
  • the mixtures (M) in solid, liquid or dissolved form preferably used for the equipment of polyaddition or polycondensation polymers.
  • the mixtures (M) can be incorporated for this purpose both as a solid or liquid formulation, as well as a powder by the usual methods in the polymers. Mentioned here is, for example, the mixing of the mixtures (M) with the polymers (P) before or during an extrusion step, kneading, calendering, film, fiber extrusion or blow molding.
  • the additized polymers can be present, for example, as granules, pellets, powders, films or fibers.
  • polymer moldings containing the mixture (M) is carried out by methods known to the person skilled in the art.
  • the polymer moldings can be produced by extrusion or coextrusion, compounding, processing of granules or pellets, injection molding, blow molding or kneading.
  • the processing preferably takes place by extrusion or coextrusion into films (see Saechtling Kunststoff Taschenbuch, 28th Edition, Karl Oberbach, 2001).
  • the polymers or polymer moldings may additionally contain at least one other, often commercially available, additive, preferably selected from colorants, antioxidants, other stabilizers, e.g. Hindered amine light stabilizers (HALS), UV absorbers, nickel quenchers, metal deactivators, reinforcing agents and fillers, anti-fogging agents, biocides, acid scavengers, antistatic agents, IR absorbers for long-wave IR radiation, antiblocking agents such as SiO 2, light scatterers such as MgO or ⁇ 02, inorganic or organic reflectors (for example aluminum flakes). It is also possible to use other chain extenders or hydrolysis stabilizers not contained in the mixtures (M).
  • HALS Hindered amine light stabilizers
  • UV absorbers e.g. Hindered amine light stabilizers
  • nickel quenchers e.g., nickel quenchers, metal deactivators, reinforcing agents and fillers
  • anti-fogging agents e.g.,
  • the invention relates to the use of mixtures (M) described above as stabilizers for polymers (P) described above, in particular the use for stabilizing against molecular weight loss and / or hydrolysis.
  • Another object of the invention is a process for the stabilization of polymers (P), in particular against molecular weight loss and / or hydrolysis, wherein the polymer (P) an effective amount of mixture (M) is added.
  • the amount of (M) from 0.01 to 10% by weight, based on the total amount of polymer (P) and mixture (M), is preferably added to the polymer (P).
  • the polymer (P) in the context of the process according to the invention stabilization, the additives described in the foregoing added.
  • the present invention provides stabilizing mixtures (M) for polymers which result in a reduction in degradation and a reduction in the hydrolysis of the polymers, particularly in their processing. The invention is explained in more detail by the examples without the examples restricting the subject matter of the invention.
  • 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 additives 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.
  • 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.
  • the 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.
  • Ultradur® B4520 (BASF SE) with a viscosity number of 18 ml / g and an acid number of about 25 mmol / kg was used as the PBT matrix. Additives were added to the PBT by coextrusion and moldings were made for tensile tests. Viscosity numbers and acid end groups were determined on parts of the test specimens before and after storage at 110 ° C. and 100% atmospheric humidity.
  • Table 1 .1 compares the viscosity numbers and acid end group concentrations in comparison to the reference (Ref.). Table 1.1
  • the amount of Joncryl® is given based on the total amount of Joncryl® and polymer.
  • the concentration of acid end groups refers to the total amount of Joncryl® and polymer.
  • the Joncryle® causes a significant increase in the melt viscosity after the extrusion of the films.
  • only low levels of Joncryl® can be used (for example, 0.2% by weight of Joncryl® 4300). At these concentrations, however, the increase in acid end groups during storage is not prevented.
  • Table 1 .2 summarizes the course of the viscosity number during the storage of the films. The data are the same as in Table 1 .1. As reference (reference), however, the viscosity number of the respective sample before storage is now selected.
  • VZ PBT test specimen [mL / g] 1 18 130 -
  • Tables 2.1 and 2.2 show the stabilization of polymers such as PET and PBT against hydrolysis by the AKD of the form (III '):
  • Table 2.1 shows the effect of the AKD alone as a comparison.
  • the amount of AKD is given based on the total amount of AKD and polymer.
  • the concentration of acid end groups refers to the total amount of AKD and polymer.
  • the AKD prevents the increase in acid end groups during storage. However, the viscosity number does not increase significantly during the extrusion.
  • Table 2.2 shows a comparison of the efficiency of using AKD alone and in conjunction with the Joncryl® ADR 4300 chain extender. It can be clearly seen that its combination of hydrolysis stabilizer (H) and chain extender (H) has a synergistic effect.
  • the amount of AKD and Joncryl® ADR 4300 is given based on the total amount of AKD and / or Joncryl® ADR 4300 and polymer.
  • the acid end group concentration refers to the total amount of AKD and / or Joncryl® ADR 4300 and polymer.
  • the amount of oxazolidinone is based on the total amount of oxazolidinone and polymer.
  • the concentration of acid end groups refers to the total amount of oxazolidinone and polymer.
  • Tables 4.1 and 4.2 show the results of the extrusion of PET or PBT in the presence of an epoxysilane: 3-glycidoxypropyltriethoxysilane, which is available under the designation Geniosil® GF 82 (Wacker Chemie AG). Furthermore, the tables contain results for the use of 1, 2-epoxydecane as a hydrolysis stabilizer.
  • the concentration of acid end groups refers to the total amount of additive and polymer.
  • the concentration of additive is given based on the total amount of additive and polymer.
  • the concentration of acid end groups refers to the total amount of additive and polymer.
  • the additives in the form of a masterbatch and thereby to obtain the advantageous effect as a hydrolysis stabilizer in the end product.
  • the amount of hydrolysis stabilizer which is necessary to completely stabilize 5 kg of extruded PBT by reaction with the acid end groups (about 30 mmol / kg) is extruded in about 800 g of PBT to prepare the masterbatch.
  • the acid end group concentration of the masterbatch was determined before storage and after two days storage at 110 ° C and 100% humidity.
  • the concentration of additive is given based on the total amount of additive and polymer.
  • the concentration of acid end groups refers to the total amount of additive and polymer.
  • the monoepoxy compounds hardly increase the initial viscosity during the extrusion and can therefore advantageously be combined synergistically with chain extenders as already described above in Examples 2 and 3.
  • the concentration of additive is given based on the total amount of additive and polymer.
  • the concentration of acid end groups refers to the total amount of additive and polymer.

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PCT/EP2012/072489 2011-11-17 2012-11-13 Additive zur hydrolysestabilisierung von polykondensaten WO2013072310A1 (de)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP12783627.8A EP2780407A1 (de) 2011-11-17 2012-11-13 Additive zur hydrolysestabilisierung von polykondensaten
CN201280056408.XA CN103946291A (zh) 2011-11-17 2012-11-13 用于缩聚物的水解稳定的添加剂
JP2014541624A JP2014533752A (ja) 2011-11-17 2012-11-13 重縮合物を加水分解安定化するための添加剤
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US11001706B2 (en) 2017-02-02 2021-05-11 Toyobo Co., Ltd. Polyester resin composition, and light reflector component and light reflector including polyester resin composition
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US11795298B2 (en) 2018-03-26 2023-10-24 Toyobo Mc Corporation Polyester resin composition, light-reflector component containing same, and light reflector
EP4279529A1 (en) * 2022-05-21 2023-11-22 Ecovance Co. Ltd Biodegradable polyester resin composition
EP4279526A1 (en) * 2022-05-21 2023-11-22 Ecovance Co. Ltd Biodegradable polyester resin composition
EP4279533A1 (en) * 2022-05-21 2023-11-22 Ecovance Co. Ltd Method of preparing a biodegradable polyester resin composition

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US11001705B2 (en) 2015-12-25 2021-05-11 Toyobo Co., Ltd. Polyester resin composition, light-reflector component containing same, light reflector, and method for producing polyester resin composition
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US11713392B2 (en) 2017-02-02 2023-08-01 Toyobo Co., Ltd. Polyester resin composition, and light reflector component and light reflector including polyester resin composition
US11795298B2 (en) 2018-03-26 2023-10-24 Toyobo Mc Corporation Polyester resin composition, light-reflector component containing same, and light reflector
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EP4279529A1 (en) * 2022-05-21 2023-11-22 Ecovance Co. Ltd Biodegradable polyester resin composition
EP4279526A1 (en) * 2022-05-21 2023-11-22 Ecovance Co. Ltd Biodegradable polyester resin composition
EP4279533A1 (en) * 2022-05-21 2023-11-22 Ecovance Co. Ltd Method of preparing a biodegradable polyester resin composition
US11898004B2 (en) 2022-05-21 2024-02-13 Ecovance Co. Ltd. Biodegradable molded article and biodegradable polyester resin composition

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