WO2014131701A1 - Additives for hydrolysis stabilization of polymers - Google Patents

Additives for hydrolysis stabilization of polymers 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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Prior art keywords
copolymers
monomers
polymers
alkoxysilane
mol
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PCT/EP2014/053426
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German (de)
French (fr)
Inventor
Laurence Pottie
Theo SMIT
Arno Lange
Collin G. Moore
Simone Schillo
Volker Frenz
Roelof Van Der Meer
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Basf Se
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    • 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.

Abstract

The use of copolymers (C) containing at least one epoxy group and at least one alkoxysilane group as stabilizers for polymers (P), wherein the copolymers (C) are generally obtained by polymerizing monomers and these monomers include those which contain epoxy groups or alkoxysilane groups or epoxy and alkoxysilane groups or are converted during or after the polymerization and, after the conversion, contain epoxy groups or alkoxysilane groups or epoxy and alkoxysilane groups. Methods for stabilizing polymers (P) against hydrolysis, characterized in that an effective amount of copolymers (C) is added to the polymers (P). Copolymers (C') consisting of specific compositions of monomers containing at least one epoxy group and at least one alkoxysilane group, and optionally further monomers. Mixtures containing copolymers (C') and polymers (P).

Description

Additive zur Hydrolysestabilisierung von Polymeren  Additives for hydrolysis stabilization of polymers
Beschreibung: Die vorliegende Erfindung betrifft die Verwendung von Copolymeren (C), enthaltend mindestens eine Epoxygruppe und mindestens eine Alkoxysilangruppe, als Stabilisatoren für Polymere (P). Weiterhin betrifft die Erfindung Verfahren zur Stabilisierung von Polymeren gegen Hydrolyse durch Zugabe von Copolymeren (C). Weitere Gegenstände der Erfindung sind ausgewählte Copolymere (C) und Mischungen enthaltend Copolymere (C). Description: 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).
Weitere Ausführungsformen der vorliegenden Erfindung sind den Ansprüchen, der Beschreibung und den Beispielen zu entnehmen. Es versteht sich, dass die vorstehend genannten und die nachstehend noch zu erläuternden Merkmale des erfindungsgemäßen Gegenstandes nicht nur in der jeweils konkret angegebenen Kombination, sondern auch in anderen Kombinationen verwendbar sind, ohne den Rahmen der Erfindung zu verlassen. Bevorzugt, beziehungsweise ganz bevorzugt, sind insbesondere auch diejenigen Ausführungsformen der vorliegenden Erfindung, in denen alle Merkmale des erfindungsgemäßen Gegenstandes die bevorzugten, beziehungsweise ganz bevorzugten, Bedeutungen haben. Polymerisate mit Kohlenwasserstoffketten und Alkoxysilangruppen können vernetzen und sind damit häufig Ausgangsstoffe für Kleb- oder Dichtmassen oder für Mittel zur Oberflächenmodifikation. Further embodiments of the present invention can be taken from the claims, the description and the examples. It is understood that the features mentioned above and those yet to be explained of the subject matter according to the invention can be used not only in the particular concretely specified combination but also in other combinations without departing from the scope of the invention. In particular, those embodiments of the present invention in which all features of the article according to the invention have the preferred, or very preferred, meanings are preferred or very particularly preferred. Polymers with hydrocarbon chains and alkoxysilane groups can crosslink and are therefore often starting materials for adhesives or sealants or for agents for surface modification.
Es sind verschiedene Herstellverfahren für Polymerisate mit Kohlenwasserstoffketten und Silo- xangruppen bekannt. So wird in der US 6,177,519 B1 die Pfropfung eines Polyolefins mit einem Vinylsiloxan beschrieben. Aus der US 6,194,597 B1 ist weiterhin die Copolymerisation von Isobuten mit Silylstyrol oder Silylmethylstyrol bekannt. Various production processes for polymers with hydrocarbon chains and siloxane groups are known. For example, US Pat. No. 6,177,519 B1 describes the grafting of a polyolefin with a vinylsiloxane. The copolymerization of isobutene with silylstyrene or silylmethylstyrene is also known from US Pat. No. 6,194,597 B1.
WO 2012/032005 A1 beschreibt Terpolymerisate, erhältlich durch Copolymerisation von elekt- ronendefizienten Olefinen, Olefinen, welche an ihrer olefinischen Doppelbindung nur Wasserstoffatome und/oder Kohlenstoffatome ohne elektronenziehende Substituenten tragen und Al- koxyvinylsilanen sowie durch Modifizierung oder Vernetzung erhältliche Folgeprodukte solcher Terpolymerisate. US 5,354,802 beschreibt Harzzusammensetzungen zur Blasformung enthaltend 0,2 bis 10 Gewichtsteile eines Styrolcopolymers enthaltend 40 bis 97 Gew.-% Styrol, 60 bis 3 Gew.-% eines Glycidylesters einer alpha, beta ungesättigten Säure und 0 bis 50 Gew.-% anderer vinylischer Monomere. In der US 6,984,694 B2 wird die Verwendung von Copolymeren enthaltend epoxy- funktionalisierte (Meth)acrylsäure Monomere, Styrol und/oder (Meth)acrylsäure Monomere als Kettenverlängerer beschrieben. In der US 4,393,156 und US 4,393,158 werden die Verwendung von Epoxy-Silanen und bestimmten Epoxy-Siloxanen zur Hydrolysestabilisierung von Polyestercarbonaten oder aromatischen Polycarbonaten beschrieben. Bei den dort beschriebenen Epoxy-Siloxanen handelt es sich jedoch nicht um Copolymere enthaltend Epoxy- und Alkoxysilangruppen. 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.
Die unveröffentlichte PCT/EP2012/072489 beschreibt Mischungen enthaltend multifunktionelle Kettenverlängerer und mono- oder difunktionelle Hydrolysestabilisatoren für Polymere. Unpublished PCT / EP2012 / 072489 describes mixtures containing multifunctional chain extenders and mono- or difunctional hydrolysis stabilizers for polymers.
Zur Hydrolysestabilisierung von Polymeren werden industriell häufig Carbodiimide wie bei- spielsweise Stabaxol I, der Firma RheinChemie eingesetzt. Monomere Carbodiimide sind als Hydrolysestabilisatoren auch beispielsweise aus der US 5,439,952 bekannt. Bei ihrer Verwendung entstehen jedoch häufig toxische Nebenprodukte wie Phenylisocyanate. To stabilize the hydrolysis of polymers, carbodiimides, such as Stabaxol I, from RheinChemie, are frequently used industrially. Monomeric carbodiimides are also known as hydrolysis stabilizers, for example from US Pat. No. 5,439,952. When used, however, toxic by-products such as phenylisocyanates often arise.
Polymere, beispielsweise Polykondensationspolymer wie Polyester unterliegen bei erhöhten Temperaturen häufig einem Abbau durch Hydrolyse. Solche Bedingungen treten beispielsweise bei einer Verarbeitung der Polymere unter Wärmezufuhr bei gleichzeitigem Vorhandensein von Feuchtigkeit auf. Hydrolyse der Polymere führt zu einer Herabsetzung des Molekulargewichts und zu einer Abnahme der Schmelzviskosität unter gleichzeitiger Beeinträchtigung der mechanischen Eigenschaften der Polymere. Diese Effekte schränken die Anwendbarkeit solcher hyd- rolysierbarer Polymere stark ein und bedingen außerdem einen großen Trocknungsaufwand vor der Verarbeitung der Polymere. 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.
Aufgabe der vorliegenden Erfindung war es daher Stabilisatoren für Polymere zur Verfügung zu stellen, die zu einer Verringerung des Abbaus und einer Verminderung der Hydrolyse führen. Insbesondere war es eine Aufgabe der Erfindung eine Abnahme der Schmelzviskosität von Polymeren bei der Verarbeitung zu unterdrücken. Eine weitere Aufgabe der vorliegenden Erfindung war es Hydrolysestabilisatoren bereit zu stellen, die keine toxischen Nebenprodukte aufweisen. Diese Aufgaben wurden gelöst durch die Verwendung von Copolymeren (C), enthaltend mindestens eine Epoxygruppe und mindestens eine Alkoxysilangruppe, als Stabilisatoren für Polymere (P), bevorzugt enthaltend mindestens zwei Epoxygruppen und zwei Alkoxysilangruppen. Bevorzugt finden die Copolymere (C) Anwendung als Hydrolysestabilisatoren oder Säurefänger. 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. In particular, it was an object of the invention to suppress a decrease in the melt viscosity of polymers during processing. 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.
Unter Alkoxysilangruppen werden im Rahmen der vorliegenden Erfindung Gruppen der allgemeinen Formel (I) verstanden:
Figure imgf000003_0001
Alkoxysilane groups in the context of the present invention are understood to mean groups of the general formula (I):
Figure imgf000003_0001
mit With
n 1 , 2, 3, bevorzugt 3, n 1, 2, 3, preferably 3,
R , R2 unabhängig voneinander, gleich oder verschieden, H, Ci-C20-Alkyl, C2-C2o-Alkenyl, C2-C2o-Alkinyl, C3-Ci5-Cycloalkyl, bevorzugt H, Ci-C2o-Alkyl. 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.
Unter Epoxygruppen werden im Rahmen der vorliegenden Erfindung Gruppen der allgemei Formel (II) verstanden: Epoxy groups in the context of the present invention are understood to mean groups of the general formula (II):
Figure imgf000004_0001
Figure imgf000004_0001
mit With
R3, R4, R5 unabhängig voneinander, gleich oder verschieden, H, R 3 , R 4 , R 5 independently of one another, identical or different,
Ci-C20-Alkyl, C2-C20-Alkenyl, C2-C20-Alkinyl, C3-Ci5-Cycloalkyl, bevorzugt H, Ci-C4-Alkyl. 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.
Ausdrücke der Form Ca-Cb bezeichnen im Rahmen dieser Erfindung chemische Verbindungen oder Substituenten mit einer bestimmten Anzahl von Kohlenstoffatomen. Die Anzahl an Kohlen- stoffatomen kann aus dem gesamten Bereich von a bis b, einschließlich a und b gewählt werden, a ist mindestens 1 und b immer größer als a. Eine weitere Spezifizierung der chemischen Verbindungen oder der Substituenten erfolgt durch Ausdrücke der Form Ca-Cb-V. V steht hierbei für eine chemische Verbindungsklasse oder Substituentenklasse, beispielsweise für Alkylver- bindungen oder Alkylsubstituenten. 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.
Im Einzelnen haben die für die verschiedenen Substituenten angegebenen Sammelbegriffe folgende Bedeutung: In detail, the collective terms given for the various substituents have the following meaning:
Ci-C2o-Alkyl: geradkettige oder verzweigte Kohlenwasserstoffreste mit bis zu 20 Kohlenstoff- atomen, beispielsweise Ci-Cio-Alkyl oder Cn-C2o-Alkyl, bevorzugt Ci-Cio-Alkyl beispielsweise Ci-C3-Alkyl, wie Methyl, Ethyl, Propyl, Isopropyl, oder 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-Methyl-pentyl, 1 ,1 -Dimethylbutyl, 1 ,2- Dimethylbutyl, 1 ,3-Dimethylbutyl, 2,2-Dimethylbutyl, 2,3-Dimethylbutyl, 3,3-Dimethylbutyl, 2- Ethylbutyl, 1 ,1 ,2-Trimethylpropyl, 1 ,2,2-Trimethylpropyl, 1 -Ethyl-1 -methylpropyl, 1 -Ethyl-2- methylpropyl, oder C7-C10-Alkyl, wie Heptyl, Octyl, 2-Ethyl-hexyl, 2,4,4-Trimethylpentyl, 1 ,1 ,3,3-Tetramethylbutyl, Nonyl oder Decyl sowie deren Isomere. 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, 3-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, or C7-C10 Alkyl, such as heptyl, octyl, 2-ethyl-hexyl, 2,4,4-trimethylpentyl, 1, 1, 3,3-tetramethylbutyl, nonyl or decyl and their isomers.
C2-C2o-Alkenyl: ungesättigte, geradkettige oder verzweigte Kohlenwasserstoffreste mit 2 bis 20 Kohlenstoffatomen und einer Doppelbindung in einer beliebigen Position, beispielsweise C2-Cio- Alkenyl oder Cn-C2o-Alkenyl, bevorzugt C2-Cio-Alkenyl wie C2-C4-Alkenyl, wie 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, oder Cs-C6-Alkenyl, wie 1 - Pentenyl, 2-Pentenyl, 3-Pentenyl, 4-Pentenyl, 1 -Methyl-1 -butenyl, 2-Methyl-1 -butenyl, 3-Methyl- 1 -butenyl, 1 -Methyl-2-butenyl, 2-Methyl-2-butenyl, 3-Methyl-2-butenyl, 1 -Methyl-3-butenyl, 2- Methyl-3-butenyl, 3-Methyl-3-butenyl, 1 ,1 -Dimethyl-2-propenyl, 1 ,2-Dimethyl-1 -propenyl, 1 ,2- Dimethyl-2-propenyl, 1 -Ethyl-1 -propenyl, 1 -Ethyl-2-propenyl, 1 -Hexenyl, 2-Hexenyl, 3-Hexenyl, 4-Hexenyl, 5-Hexenyl, 1 -Methyl-1 -pentenyl, 2-Methyl-1 -pentenyl, 3-Methyl-1 -pentenyl, 4-Methyl- 1 -pentenyl, 1 -Methyl-2-pentenyl, 2-Methyl-2-pentenyl, 3-Methyl-2-pentenyl, 4-Methyl-2- pentenyl, 1 -Methyl-3-pentenyl, 2-Methyl-3-pentenyl, 3-Methyl-3-pentenyl, 4-Methyl-3-pentenyl, 1 -Methyl-4-pentenyl, 2-Methyl-4-pentenyl, 3-Methyl-4-pentenyl, 4-Methyl-4-pentenyl, 1 ,1 - Dimethyl-2-butenyl, 1 ,1 -Dimethyl-3-butenyl, 1 ,2-Dimethyl-1 -butenyl, 1 ,2-Dimethyl-2-butenyl, 1 ,2- Dimethyl-3-butenyl, 1 ,3-Dimethyl-1 -butenyl, 1 ,3-Dimethyl-2-butenyl, 1 ,3-Dimethyl-3-butenyl, 2,2- Dimethyl-3-butenyl, 2,3-Dimethyl-1 -butenyl, 2,3-Dimethyl-2-butenyl, 2,3-Dimethyl-3-butenyl, 3,3- Dimethyl-1 -butenyl, 3,3-Dimethyl-2-butenyl, 1 -Ethyl-1 -butenyl, 1 -Ethyl-2-butenyl, 1 -Ethyl-3- butenyl, 2-Ethyl-1 -butenyl, 2-Ethyl-2-butenyl, 2-Ethyl-3-butenyl, 1 ,1 ,2-Trimethyl-2-propenyl, 1 - Ethyl-1 -methyl-2-propenyl, 1 -Ethyl-2-methyl-1 -propenyl oder 1 -Ethyl-2-methyl-2-propenyl, sowie C7-Cio-Alkenyl, wie die Isomere von Heptenyl, Octenyl, Nonenyl oder Decenyl. 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-butenyl, 2-methyl 2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1, 1-dimethyl-2-propenyl, 1, 2 Dimethyl-1-propenyl, 1, 2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5- Hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1 - Methyl 4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1, 1-dimethyl-2-butenyl, 1, 1-dimethyl-3-butenyl, 1, 2-dimethyl-1-butenyl, 1, 2-dimethyl-2-butenyl, 1, 2-dimethyl-3-butenyl, 1, 3-dimethyl-1-butenyl, 1, 3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimet hyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl 1-Butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1, 1, 2 Trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl or 1-ethyl-2-methyl-2-propenyl, and C7-Cio-alkenyl, as the isomers of heptenyl, octenyl, nonenyl or decenyl.
C2-C2o-Alkinyl: geradkettige oder verzweigte Kohlenwasserstoffgruppen mit 2 bis 20 Kohlenstoffatomen und einer Dreifachbindung in einer beliebigen Position, beispielsweise C2-C10- Alkinyl oder Cn-C2o-Alkinyl, bevorzugt C2-Cio-Alkinyl wie C2-C4-Alkinyl, wie Ethinyl, 1 -Propinyl, 2-Propinyl, 1 -Butinyl, 2-Butinyl, 3-Butinyl, 1 -Me-thyl-2-propinyl, oder C5-C7-Alkinyl, wie 1 - Pentinyl, 2-Pentinyl, 3-Pentinyl, 4-Pentinyl, 1 -Methyl-2-butinyl, 1 -Me-thyl-3-butinyl, 2-Methyl-3- butinyl, 3-Methyl-1 -butinyl, 1 ,1 -Dimethyl-2-propinyl, 1 -Ethyl-2-propinyl, 1 -Hexinyl, 2-Hexinyl, 3- Hexinyl, 4-Hexinyl, 5-Hexinyl, 1 -Methyl-2-pentinyl, 1 -Methyl-3-pentinyl, 1 -Methyl-4-pentinyl, 2- Methyl-3-pentinyl, 2-Methyl-4-pentinyl, 3-Methyl-1 -pentinyl, 3-Methyl-4-pentinyl, 4-Methyl-1 - pentinyl, 4-Methyl-2-pentinyl, 1 ,1 -Dimethyl-2-butinyl, 1 ,1 -Dimethyl-3-butinyl, 1 ,2-Dimethyl-3- butinyl, 2,2-Dimethyl-3-butinyl, 3, 3-Dimethyl-1 -butinyl, 1 -Ethyl-2-butinyl, 1 -Ethyl-3-butinyl, 2- Ethyl-3-butinyl oder 1 -Ethyl-1 -methyl-2-propinyl sowie C7-C10-Alkinyl, wie die Isomere von Heptinyl, Octinyl, Noninyl, Decinyl. C3-Ci5-Cycloalkyl: monocyclische, gesättigte Kohlenwasserstoffgruppen mit 3 bis zu 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- propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl 4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2- pentynyl, 1, 1-dimethyl-2-butynyl, 1, 1-dimethyl-3-butynyl, 1, 2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3, 3-dimethyl-1 - butinyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl o the 1-ethyl-1-methyl-2-propynyl and C7-C10 alkynyl, such as the isomers of heptynyl, octynyl, nonynyl, decynyl. C3-C15-cycloalkyl: monocyclic saturated hydrocarbon groups with 3 up to
15 Kohlenstoffringgliedern, bevorzugt Cs-Cs-Cycloalkyl wie Cyclopropyl, Cyclobutyl, Cyclopen- tyl, Cyclohexyl, Cycloheptyl oder Cyclooctyl sowie ein gesättigtes oder ungesättigtes cyclisches System wie z. B. Norbornyl oder Norbenyl. Aryl: ein ein- bis dreikerniges aromatisches Ringsystem enthaltend 6 bis 14 Kohlenstoffringglieder, z. B. Phenyl, Naphthyl oder Anthracenyl, bevorzugt ein ein- bis zweikerniges, besonders bevorzugt ein einkerniges aromatisches Ringsystem.  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, e.g. As phenyl, naphthyl or anthracenyl, preferably a mono- to binuclear, more preferably a mononuclear aromatic ring system.
Das Symbol „*" kennzeichnet im Rahmen der vorliegenden Erfindung bei allen chemischen Verbindungen die Valenz über die eine chemische Gruppe an eine andere chemische Gruppe angebunden ist. In einer bevorzugten Ausführungsform der erfindungsgemäßen Verwendung werden die Copo- lymere (C) durch Polymerisation von Monomeren erhalten, wobei diese Monomere solche umfassen, die In the context of the present invention, the symbol " * " denotes the valency for all chemical compounds via which one chemical group is attached to another chemical group. In a preferred embodiment of the use according to the invention, the copolymers (C) are obtained by polymerization of monomers, these monomers comprising those which
(a) Epoxygruppen oder Alkoxysilangruppen oder Epoxy- und Alkoxysilangruppen enthal- ten oder  (a) contain epoxy groups or alkoxysilane groups or epoxy and alkoxysilane groups or
(b) während oder nach der Polymerisation umgesetzt werden und nach der Umsetzung Epoxygruppen oder Alkoxysilangruppen oder Epoxy- und Alkoxysilangruppen enthalten. Bevorzugt entsprechen solche Monomere den allgemeinen Formel (III) und (IV):  (b) are reacted during or after the polymerization and after the reaction contain epoxy groups or alkoxysilane groups or epoxy and alkoxysilane groups. Preferably, such monomers correspond to the general formula (III) and (IV):
Figure imgf000006_0001
Figure imgf000006_0001
mit With
n 1 , 2, 3, bevorzugt 3, n 1, 2, 3, preferably 3,
R1, R2 unabhängig voneinander, gleich oder verschieden, H, R 1 , R 2 independently of one another, the same or different, H,
Ci-C20-Alkyl, C2-C2o-Alkenyl, C2-C2o-Alkinyl, C3-Ci5-Cycloalkyl, bevorzugt H, Ci-C2o-Alkyl, Ci-C 20 alkyl, C 2 -C 2 -alkenyl, C 2 -C 2 o-alkynyl, C 3 -C 5 cycloalkyl, H, Ci-C preferably 2 -alkyl,
R3, R4, R5 unabhängig voneinander, gleich oder verschieden, H, R 3 , R 4 , R 5 independently of one another, identical or different,
Ci-C20-Alkyl, C2-C20-Alkenyl, C2-C20-Alkinyl, C3-Ci5-Cycloalkyl, bevorzugt H, Ci-C4-Alkyl, 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,
R7, R8, R9 unabhängig voneinander, gleich oder verschieden, H, R 7 , R 8 , R 9 independently, the same or different, H,
Ci-C20-Alkyl, C2-C20-Alkenyl, C2-C20-Alkinyl, C3-Ci5-Cycloalkyl, bevorzugt H, Ci-C2o-Alkyl, ganz bevorzugt H, Ci-C4-Alkyl, 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,
R6 Einfachbindung, Ci-C20-Alkylen, -C(0)0-R10-, R 6 is a single bond, C 1 -C 20 -alkylene, -C (O) O-R 10 -,
R10 Einfachbindung, Ci-C20-Alkylen. Bevorzugt enthalten mindestens 10% der Monomere der Copolymere (C) Epoxygruppen, besonders bevorzugt mindestens 20%, ganz besonders bevorzugt mindestens 30%, insbesondere mindestens 40%. Weiterhin bevorzugt enthalten mindestens 10% der Monomere der Copolymere (C) Alkoxy- silangruppen, besonders bevorzugt mindestens 20%, ganz besonders bevorzugt mindestens 30%, insbesondere mindestens 40%. R 10 single bond, Ci-C 20 -alkylene. 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%.
In einer bevorzugten Ausführungsform der erfindungsgemäßen Verwendung werden die Mo- nomere der Copolymere (C) gewählt aus Glycidylacrylat, Glycidylmethacrylat, Styrol, Vi- nyltriethoxysilane, Methacryloxypropyl-trimethoxysilan, Methacryloxypropyl-tris-(2-propoxy)silan, Methylmethacrylat, Butylacrylat, 2-Ethylhexylacrylat, 2-Propylhexylacrylate und alpha- Methylstyrol. Bevorzugt sind Glycidylmethacrylat, Vinyltriethoxysilan, Methacryloxypropyltrime- thoxysilan, Styrol, Methylmethacrylat. In a preferred embodiment of the use according to the invention, 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. Preference is given to glycidyl methacrylate, vinyltriethoxysilane, methacryloxypropyltrimethoxysilane, styrene, methyl methacrylate.
In einer weiteren bevorzugten Ausführungsform der erfindungsgemäßen Verwendung werden genau zwei, drei oder vier Monomere gewählt aus denen die Copolymere (C) bestehen. Weitere Monomere sind dann in diesem Fall nicht im Copolymeren (C) vorhanden. Bevorzugt handelt es sich bei den genau zwei Monomeren um Glycidylmethacrylat und Vinyltriethoxysilan handelt. Insbesondere werden hierbei Glycidylmethacrylat und Vinyltriethoxysilan in einem Molverhältnis im Bereich von 10 bis 90 zu 90 bis 10, bevorzugt von 20 bis 80 zu 80 bis 20, besonders bevorzugt von 30 bis 70 zu 70 bis 30, ganz besonders bevorzugt von 40 bis 60 zu 60 bis 40 eingesetzt. In a further preferred embodiment of the use according to the invention, 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. In particular, 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.
Weiterhin bevorzugt handelt es sich bei den genau zwei Monomeren um Glycidylmethacrylat und Methacryloxypropyltrimethoxysilan. Insbesondere werden hierbei Glycidylmethacrylat und Methacryloxypropyl trimethoxysilan in einem Molverhältnis im Bereich von 10 bis 90 zu 90 bis 10, bevorzugt von 20 bis 80 zu 80 bis 20, besonders bevorzugt von 30 bis 70 zu 70 bis 30, ganz besonders bevorzugt von 40 bis 60 zu 60 bis 40 eingesetzt. Further preferably, the exactly two monomers are glycidyl methacrylate and methacryloxypropyltrimethoxysilane. In particular, in this case 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.
Weiterhin bevorzugt handelt es sich bei den genau vier Monomeren um Glycidylacrylat, Styrol, Methylmethacrylat und Methacryloxypropyltrimethoxysilan. Insbesondere werden hierbei Glycidylacrylat und Methacryloxypropyltrimethoxysilane in einem Molverhältnis im Bereich von 0,01 bis 10 eingesetzt werden. Further preferably, the exactly four monomers are glycidyl acrylate, styrene, methyl methacrylate and methacryloxypropyltrimethoxysilane. In particular, glycidyl acrylate and methacryloxypropyltrimethoxysilane are used in a molar ratio in the range of 0.01 to 10.
Bevorzugt weisen die Copolymere (C) ein Molekulargewicht ein Gewichtsmittel Mw aus dem Bereich von 100 bis 50.000 g/mol, bevorzugt von 2.400 bis 20.000, besonders bevorzugt von 3.500 bis 13.000 auf. Die Copolymere (C) werden nach dem Fachmann aus dem Stand der Technik bekannten Verfahren hergestellt wie sie beispielsweise in der WO 2012/098063 A1 oder WO 2012/044981 A2 beschrieben sind. In einer bevorzugten Ausführungsform der erfindungsgemäßen Verwendung sind die Polymere (P) Polykondensate oder Polyadditionsprodukte. Hierbei werden die Polymere (P) bevorzugt gewählt aus der Gruppe der Polyester, Polyamide, Polyurethane, Polycarbonate und ihrer Copolymere. Insbesondere werden die Polymere (P) gewählt aus Polyethylenterephthalaten (PET), Polybutylenterephtalaten (PBT), Polyethylennaphthalat (PEN), Polycarbonat (PC), Ac- rylnitril-Butadien-Styrol-Copolymer (ABS), bioabbaubare aliphatisch-aromatische Copolyester, Biopolymere und Polyamid 6 (PA6). 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. In a preferred embodiment of the use according to the invention, the polymers (P) are polycondensates or polyaddition products. Here, the polymers (P) are preferably selected from the group of polyesters, polyamides, polyurethanes, polycarbonates and their copolymers. In particular, 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).
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Stabilisierung von Polymeren (P) gegen Hydrolyse, dadurch gekennzeichnet, dass den Polymeren (P) eine effektive Menge an Copolymeren (C) zugegeben wird. Bevorzugt werden die Copolymere (C) in einer Menge von 0,01 bis 10 Gew.-% bezogen auf die Gesamtmenge an Polymer (P) und Copolymer (C) zugegeben. 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).
Die Zugabe der Copolymere (C) zu den Polymeren (P) erfolgt durch Verfahren, die dem Fach- mann aus dem Stand der Technik bekannt sind. Insbesondere erfolgt die Zugabe durch Extru- sion oder Compounding. The addition of the 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.
Ein weiterer Gegenstand der Erfindung sind Copolymere (C) bestehend aus Another object of the invention are copolymers (C) consisting of
(a) von 4,99 bis 90 Mol-% eines Monomers enthaltend mindestens eine Epoxygruppe, bevorzugt von 5 bis 58 Mol-%, besonders bevorzugt von 10 bis 50 Mol-%, (a) from 4.99 to 90 mol% of a monomer containing at least one epoxy group, preferably from 5 to 58 mol%, particularly preferably from 10 to 50 mol%,
(b) von 0,01 bis 90 Mol-% eines Monomers enthaltend mindestens eine Alkoxysilan- gruppe, bevorzugt von 2 bis 50 Mol-%, besonders bevorzugt von 15 bis 35 Mol-%,(b) from 0.01 to 90 mol% of a monomer containing at least one alkoxysilane group, preferably from 2 to 50 mol%, particularly preferably from 15 to 35 mol%,
(c) von 0 bis 95 Mol-%, mindestens eines von (a) und (b) verschiedenen Monomers, bevorzugt von 40 bis 93 Mol-%, besonders bevorzugt von 55 bis 75 Mol-% wobei der Anteil an Monomeren (a), (b) und (c) insgesamt 100 Mol-% beträgt. (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.
Bevorzugt bestehen Copolymere (C) aus Preferably consist of copolymers (C)
(a) von 10 bis 90 Mol-% Glycidylmethacrylat,  (a) from 10 to 90 mole percent glycidyl methacrylate,
(b) von 10 bis 90 Mol-% Vinyltriethoxysilan,  (b) from 10 to 90 mole percent vinyltriethoxysilane,
(c) von 0 bis 50 Mol-% mindestens eines von (a) und (b) verschiedenen Monomers, wobei der Anteil an Monomeren (a), (b) und (c) insgesamt 100 Mol-% beträgt.  (c) from 0 to 50 mol% of at least one of (a) and (b) different monomer, wherein the proportion of monomers (a), (b) and (c) is 100 mol% in total.
Weiterhin bevorzugt bestehen Copolymere (C) aus Further preferably, copolymers (C) are made
(a) von 4,99 bis 70 Mol-% Glycidylacrylat, bevorzugt von 10 bis 50 Mol-%,  (a) from 4.99 to 70 mol% glycidyl acrylate, preferably from 10 to 50 mol%,
(b) von 0,01 bis 60 Mol-% Methacryloxypropyltrimethoxysilan, bevorzugt von 5 bis 50 (b) from 0.01 to 60 mole% of methacryloxypropyltrimethoxysilane, preferably from 5 to 50
Mol-%, Mol%
(c) von 0 bis 95 Mol-% Styrol und/oder Methylmethacrylat, bevorzugt von 0 bis 50. Die Copolymere (C) werden nach den oben für die Copolymere (C) beschriebenen Verfahren hergestellt. (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).
Ein weitere Gegenstand der Erfindung sind Mischungen enthaltend Copolymere (C) und Poly- mere (P), wobei die Polymere (P) bevorzugt Polykondensate oder Polyadditionsprodukte sind. Bevorzugt sind die Copolymere (C) in den Mischungen in einer Menge von 0,01 bis 10 Gew.-% enthalten sind. A further subject of the invention are mixtures comprising copolymers (C) and polymers (P), where the polymers (P) are preferably polycondensates or polyaddition products. Preferably, the copolymers (C) are contained in the mixtures in an amount of 0.01 to 10 wt .-%.
Weiterhin bevorzugt werden die Polymere (P) hierbei gewählt aus der Gruppe der Polyester, Polyamide, Polyurethane, Polycarbonate und ihrer Copolymere. Furthermore, the polymers (P) are preferably selected from the group of polyesters, polyamides, polyurethanes, polycarbonates and their copolymers.
Ebenfalls bevorzugt sind die Polymere (P) hierbei PET, PBT, PEN, PC, ABS, bioabbaubare aliphatisch-aromatische Copolyester, Biopolymere oder PA6. Die Herstellung der Mischungen erfolgt durch Verfahren, die dem Fachmann aus dem Stand der Technik bekannt sind. Insbesondere erfolgt die Zugabe durch Extrusion oder Compounding. Likewise preferred are the 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.
Die vorliegende Erfindung stellt Copolymere (C) zur Stabilisierung von Polymeren zur Verfügung, die eine Abnahme der Schmelzviskosität von Polymeren bewirken und auf Grund ihrer polymeren Struktur wenig toxisch bei der Handhabung, Einarbeitung und Verwendung als Stabilisator sind. Insbesondere als Hydrolysestabilisatoren für Polyadditions- und Polykondensati- onspolymere zeigen die im Rahmen der vorliegenden Erfindung verwendeten Copolymere (C) hervorragende Eigenschaften. Die Erfindung wird durch die Beispiele näher erläutert ohne dass die Beispiele den Gegenstand der Erfindung einschränken. 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. Especially as hydrolysis stabilizers for polyaddition and polycondensation polymers, the 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.
Beispiele: Beispiel 1 : Examples: Example 1
Ein Copolymer aus Vinyltriethoxysilan (VTEOS) und Glycidylmethacrylat (GMA) wurde gemäß den Verfahren aus WO 2012/098063 A1 mit Hilfe von radikalischer Polymerisation hergestellt. Die Herstellung erfolgte in (26 Gew.-% bezogen auf die gesamte Reaktionslösung) Toluol als Lösungsmittel bei einer Temperatur von 120°C. Das Molverhältnis zwischen VTEOS und GMA betrug etwa 1 :1 (152.8 g VTEOS und 1 13.8 g GMA). Tert-butylperoxibenzoat (2.6 mol-% bezogen auf die Menge an Monomeren) wurde als Radikalinitiator eingesetzt. Die Reaktionszeit betrug 6 Stunden. Eine trübe, viskose Polymerlösung wurde erhalten. Schematische Darstellung des linearen Copolymeren aus Beispiel 1 : A copolymer of vinyltriethoxysilane (VTEOS) and glycidyl methacrylate (GMA) was prepared according to the methods of WO 2012/098063 A1 by means of radical polymerization. The preparation was carried out in (26 wt .-% based on the total reaction solution) of toluene as a solvent at a temperature of 120 ° C. The molar ratio between VTEOS and GMA was about 1: 1 (152.8 g VTEOS and 1.13.8 g GMA). Tert-butyl peroxibenzoate (2.6 mol% based on the amount of monomers) was used as a radical initiator. The reaction time was 6 hours. A cloudy, viscous polymer solution was obtained. Schematic representation of the linear copolymer of Example 1:
Figure imgf000010_0001
Figure imgf000010_0001
Beispiel 2: Example 2:
Ein Copolymer aus Glycidylmethacrylat (GMA), Metylmetacrylat (MMA), Styrol (ST) und Me- thacryloxypropyltrimethoxysilan (TMSMA) wurde gemäß den Verfahren aus der WO A copolymer of glycidyl methacrylate (GMA), methyl methacrylate (MMA), styrene (ST) and methacryloxypropyltrimethoxysilane (TMSMA) was prepared according to the methods of WO
2012/044981 A2 mit Hilfe einer Hochtemperaurpolymerisation hergestellt. Die Herstellung erfolgte gemäß Beispiel 15 der WO 2012/044981 A2. Das Molverhältnis der Monomere ist in Ta- belle 1 beschrieben. 2012/044981 A2 produced by means of a Hochtemperaurpolymerisation. The preparation was carried out according to Example 15 of WO 2012/044981 A2. The molar ratio of the monomers is described in Table 1.
Schematische Darstellung des Copolymeren aus Beispiel 2: Schematic representation of the copolymer from Example 2:
Figure imgf000010_0002
Tabelle 1 :
Figure imgf000010_0002
Table 1 :
Mol.-% Mol.-% Mol.% Mol.% Mol.% Mol.%
Molekulargewicht, Mol.% ST  Molecular weight, mol.% ST
Beispiel GMA im TMSMA im MMA im  Example GMA in TMSMA in MMA in
Mn (g/mol) im Zulauf  Mn (g / mol) in the feed
Zulauf Zulauf Zulauf  Inlet inlet inlet
2a 2400 27.96 5.24 65.6 1 .2  2a 2400 27.96 5.24 65.6 1 .2
2b 2500 18.99 5.1 74.74 1 .17  2b 2500 18.99 5.1 74.74 1 .17
2c 2800 10.42 4.95 83.48 1 .15  2c 2800 10.42 4.95 83.48 1 .15
Angaben in Mol.-% sind bezogen auf die Gesamtstoffmenge an Monomeren. Data in mol .-% are based on the total amount of monomers.
Beispiel 3: Polyethylenterephthalat (PET) für die Herstellung von biaxial orientierten Folien wurde von der Fa. Mitsubishi Polyester Film GmbH, Wiesbaden bezogen. Das PET wies eine geringe Konzentration an carboxylischen Endgruppen auf (ca. 21 mmol/kg). Die Säurezahlen werden durch Titration der jeweiligen PET-Lösung im Lösungsmittelgemisch aus Chloroform/Kresol erhalten. Die Stabilisatoren (Copolymere (C)) wurden in verschiedenen Konzentrationen bei einer Temperatur von 260°C mit dem PET gemeinsam extrudiert. Example 3: Polyethylene terephthalate (PET) for the production of biaxially oriented films was purchased from Mitsubishi Polyester Film GmbH, Wiesbaden. 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.
Die so entstandenen Folien wurden dann erhöhten Temperaturen (1 10°C) und hoher Luftfeuchtigkeit (100 %) ausgesetzt und für einen Zeitraum von zwei bzw. fünf Tagen (2d, 5d) gelagert. 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).
Der Abbau des Polymers wurde durch Messung der Viskositätszahl (VZ) und/oder der Säure- Endgruppenkonzentration des PET vor und nach der Lagerung bestimmt. Die VZ Messungen (Einheiten in mg/l) wurden mit Hilfe eines Mikro-Ubbelohde Kapillarviskosimeters durchgeführt wobei als Lösungsmittel eine 1 :1 Mischung von Phenol und o-Dichlorbenzol eingesetzt wurde. 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.
Als Referenz (REF 1 , REF 2 und REF IND) dienen, soweit nichts anderes angegeben ist, jeweils die Polymere, die ohne Stabilisatoren extrudiert wurden. The references (REF 1, REF 2 and REF IND), unless stated otherwise, are in each case the polymers which have been extruded without stabilizers.
Als Vergleichsexperiment (IND REF) wurde das industriell häufig eingesetzte Stabaxol I (Rhein Chemie) ebenfalls in PET eingearbeitet. Tabelle 2: As a comparative experiment (IND REF), Stabaxol I (Rhein Chemie), which is frequently used industrially, was also incorporated in PET. Table 2:
Zugabe Konzentration der Säu¬Addition Concentration of Säu¬
VZ (mg/l) VZ (mg / l)
Stabilisaregruppen (mg/kg)  Stabilizer groups (mg / kg)
Beispiel Stabilisator  Example stabilizer
tor (Gew.- O d 2 d 5 d O d 2 d 5 d gate (weight O d 2 d 5 d O d 2 d 5 d
%) %)
REF 1 - 0 21 34 - 70  REF 1 - 0 21 34 - 70
3a Beispiel 1 0.2 20 33 75 58  3a Example 1 0.2 20 33 75 58
3b Beispiel 1 0.6 14 26 73 59  3b Example 1 0.6 14 26 73 59
REF 2 - 0 29 67 129 64 42 31 REF 2 - 0 29 67 129 64 42 31
3c Beispiel 2a 0.6 28 50 99 68 52 383c Example 2a 0.6 28 50 99 68 52 38
3d Beispiel 2a 1 21 36 84 77 62 463d example 2a 1 21 36 84 77 62 46
3e Beispiel 2b 0.6 32 58 1 18 66 72 703e Example 2b 0.6 32 58 1 18 66 72 70
3f Beispiel 2b 1 30 61 1 13 72 49 353f example 2b 1 30 61 1 13 72 49 35
3g Beispiel 2c 0.6 32 61 1 16 64 49 343g Example 2c 0.6 32 61 1 16 64 49 34
3h Beispiel 2c 1 32 53 105 66 50 353h Example 2c 1 32 53 105 66 50 35
REF IND - 0 22 48 100 67 51 37REF IND - 0 22 48 100 67 51 37
IND REF 1 Stabaxol I 0.6 9 18 59 68 62 46IND REF 1 Stabaxol I 0.6 9 18 59 68 62 46
IND REF 2 Stabaxol I 1 3 5 19 69 68 62 IND REF 2 Stabaxol I 1 3 5 19 69 68 62
Angaben in Gew.-% sind bezogen auf die Gesamtmenge an Stabilisator und PET. In% by weight are based on the total amount of stabilizer and PET.
Wie aus Tabelle 2 ersichtlich führen die Copolymere (C) zu einer Stabilisierung des PET gegen hydrolytischen Abbau. Verglichen mit den Stabaxol-Resultaten ergeben sich zwar erhöhte Konzentrationen an Säuregruppen aber überraschender Weise dennoch eine gute Stabilisierung der Viskositätseigenschaften. As shown in Table 2, 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.

Claims

Patentansprüche: claims:
1 . Verwendung von Copolymeren (C), enthaltend mindestens eine Epoxygruppe und mindestens eine Alkoxysilangruppe, als Stabilisatoren für Polymere (P). 1 . Use of copolymers (C) containing at least one epoxy group and at least one alkoxysilane group as stabilizers for polymers (P).
2. Verwendung nach Anspruch 1 , wobei die Copolymere (C) durch Polymerisation von Monomeren erhalten werden und diese Monomere solche umfassen, die 2. Use according to claim 1, wherein the copolymers (C) are obtained by polymerization of monomers and these monomers include those which
(a) Epoxygruppen oder Alkoxysilangruppen oder Epoxy- und Alkoxysilangruppen enthalten oder  (a) contain epoxy groups or alkoxysilane groups or epoxy and alkoxysilane groups or
(b) während oder nach der Polymerisation umgesetzt werden und nach der Umsetzung (b) are reacted during or after the polymerization and after the reaction
Epoxygruppen oder Alkoxysilangruppen oder Epoxy- und Alkoxysilangruppen enthalten. Contain epoxy groups or alkoxysilane or epoxy and alkoxysilane.
3. Verwendung nach Anspruch 1 oder 2, wobei mindestens 10% der Monomere der Copoly- mere Epoxygruppen enthalten. 3. Use according to claim 1 or 2, wherein at least 10% of the monomers of the copolymers contain epoxy groups.
4. Verwendung nach den Ansprüchen 1 bis 3, wobei mindestens 10% der Monomere der Copolymere Alkoxysilangruppen enthalten. 4. Use according to claims 1 to 3, wherein at least 10% of the monomers of the copolymers contain alkoxysilane groups.
5. Verwendung nach den Ansprüchen 1 bis 4, wobei die Monomere gewählt werden aus Gly- cidylacrylat, Glycidylmethacrylat, Styrol, Vinyltriethoxysilane, Methacryloxypropyl- trimethoxysilan, Methacryloxypropyl-tris-(2-propoxy)silan, Methylmethacrylat, Butylacrylat, 2- Ethylhexylacrylat, 2-Propylhexylacrylate, alpha-Methylstyrol. 5. Use according to claims 1 to 4, wherein the monomers are selected from glycidyl acrylate, glycidyl methacrylate, styrene, vinyltriethoxysilanes, methacryloxypropyl trimethoxysilane, methacryloxypropyl tris (2-propoxy) silane, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, 2 -Propylhexylacrylate, alpha-methylstyrene.
6. Verwendung nach den Ansprüchen 1 bis 5, wobei genau zwei, drei oder vier Monomere gewählt werden. 6. Use according to claims 1 to 5, wherein exactly two, three or four monomers are selected.
7. Verwendung nach Anspruch 6, wobei es sich bei den genau zwei Monomeren um Glycidylmethacrylat und Vinyltriethoxysilan handelt. 7. Use according to claim 6, wherein the exactly two monomers are glycidyl methacrylate and vinyltriethoxysilane.
8. Verwendung nach Anspruch 6, wobei es sich bei den genau zwei Monomeren um Glycidylmethacrylat und Methacryloxypropyltrimethoxysilan handelt. 8. Use according to claim 6, wherein the exactly two monomers are glycidyl methacrylate and methacryloxypropyltrimethoxysilane.
9. Verwendung nach Anspruch 6, wobei es sich bei den genau vier Monomeren um Gly- cidylacrylat, Styrol, Methylmethacrylat und Methacryloxypropyltrimethoxysilan handelt. 9. Use according to claim 6, wherein the exactly four monomers are glycidyl acrylate, styrene, methyl methacrylate and methacryloxypropyltrimethoxysilane.
10. Verwendung nach den Ansprüchen 1 bis 9, wobei die Polymere (P) Polykondensate oder Polyadditionsprodukte sind. 10. Use according to claims 1 to 9, wherein the polymers (P) are polycondensates or polyaddition products.
1 1 . Verfahren zur Stabilisierung von Polymeren (P) gegen Hydrolyse, dadurch gekennzeichnet, dass den Polymeren (P) eine effektive Menge an Copolymeren (C) gemäß den Ansprüchen 1 bis 10 zugegeben wird. 1 1. Process for the stabilization of polymers (P) against hydrolysis, characterized in that an effective amount of copolymers (C) according to claims 1 to 10 is added to the polymers (P).
12. Copolymere (C) bestehend aus 12. Copolymers (C) consisting of
(a) von 4,99 bis 90 Mol-% eines Monomers enthaltend mindestens eine Epoxygruppe, (a) from 4.99 to 90 mol% of a monomer containing at least one epoxy group,
(b) von 0,01 bis 90 Mol-% eines Monomers enthaltend mindestens eine Alkoxysilan- gruppe, (b) from 0.01 to 90 mol% of a monomer containing at least one alkoxysilane group,
(c) 0 bis 95 Mol-% mindestens eines von (a) und (b) verschiedenen Monomers, wobei der Anteil an Monomeren (a), (b) und (c) insgesamt 100 Mol-% beträgt.  (C) 0 to 95 mol% of at least one of (a) and (b) different monomer, wherein the proportion of monomers (a), (b) and (c) is 100 mol% in total.
13. Copolymere (C) nach Anspruch 12, bestehend aus 13. Copolymers (C) according to claim 12, consisting of
(a) von 10 bis 90 Mol-% Glycidylmethacrylat,  (a) from 10 to 90 mole percent glycidyl methacrylate,
(b) von 10 bis 90 Mol-% Vinyltriethoxysilan,  (b) from 10 to 90 mole percent vinyltriethoxysilane,
(c) von 0 bis 50 Mol-% mindestens eines von (a) und (b) verschiedenen Monomers, wobei der Anteil an Monomeren (a), (b) und (c) insgesamt 100 Mol-% beträgt.  (c) from 0 to 50 mol% of at least one of (a) and (b) different monomer, wherein the proportion of monomers (a), (b) and (c) is 100 mol% in total.
14. Copolymere (C) nach Anspruch 12 bestehend aus 14. Copolymers (C) according to claim 12 consisting of
(a) von 4,99 bis 70 Mol-% Glycidylacrylat,  (a) from 4.99 to 70 mole percent glycidyl acrylate,
(b) von 0,01 bis 60 Mol-% Methacryloxypropyltrimethoxysilan,  (b) from 0.01 to 60 mole% of methacryloxypropyltrimethoxysilane,
(c) von 0 bis 95 Mol-% Styrol und/oder Methylmethacrylat.  (c) from 0 to 95 mole percent styrene and / or methyl methacrylate.
15. Mischungen enthaltend Copolymere (C) gemäß den Ansprüchen 12 bis 14 und Polymere (P)- 15. Mixtures comprising copolymers (C) according to claims 12 to 14 and polymers (P) -
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