EP2356180A1 - Polymer blends comprising alkoxysilane-terminated polymers - Google Patents

Polymer blends comprising alkoxysilane-terminated polymers

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Publication number
EP2356180A1
EP2356180A1 EP09771355A EP09771355A EP2356180A1 EP 2356180 A1 EP2356180 A1 EP 2356180A1 EP 09771355 A EP09771355 A EP 09771355A EP 09771355 A EP09771355 A EP 09771355A EP 2356180 A1 EP2356180 A1 EP 2356180A1
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EP
European Patent Office
Prior art keywords
parts
blend
alkyl
carbon atoms
optionally
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP09771355A
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German (de)
French (fr)
Inventor
Wolfgang Ziche
Andreas Bauer
Volker Stanjek
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Wacker Chemie AG
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Wacker Chemie AG
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Publication of EP2356180A1 publication Critical patent/EP2356180A1/en
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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00Compositions of unspecified macromolecular compounds
    • C08L101/02Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/10Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/14Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/16Catalysts
    • C08G18/18Catalysts containing secondary or tertiary amines or salts thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42Block-or graft-polymers containing polysiloxane sequences
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages

Definitions

  • This invention relates to blends (M) containing methyl dialkoxysilylmethyl or trialkoxysilylmethyl-terminated polymers prepared from these blends
  • Alkoxysilane groups and their structure are formed mainly by long-chain polymers (thermoplastics), relatively wide-meshed three-dimensional networks (elastomers) or highly crosslinked systems (thermosets).
  • silantermm striv polymer systems can be both the properties of the uncrosslinked polymers or polymer-containing mixtures (viscosity, melting point, Losigeen etc.) and the properties of the finished crosslinked materials (hardness, elasticity, tensile strength, elongation at break, heat resistance etc.) set almost arbitrarily. Consequently, the possibilities of substitution of such silane-degraded polymer systems are correspondingly diverse. Thus, they can be used, for example, for the production of elastomers, sealants, adhesives, elastic adhesive systems, hard and soft foams, a wide variety of coating systems or for impression compounds. These products can be applied in any form, such as brushing, spraying, pouring, pressing, filling, etc.
  • the adhesion profile is often improved or optimized by the addition of organofunctional silanes as adhesion promoters.
  • silanes with primary amino groups such as 3-aminopropyltrimethoxysilane lead here to a significant improvement in the adhesion properties, which is why this silane is almost included in all adhesives and sealants based on silane-terminated polymers.
  • the application of such silanes is state of the art and in various combinations
  • sealants In addition to a good adhesion adhesives but above all sealants must also have a very good elasticity. Not only the stretching plays a role, but also the relaxation after stretching or compression. These are usually measured as compression set, creep behavior or as restoring behavior. For example, ISO 11600 requires a provision of over 60% or even 70% for elastic sealants.
  • the elastic behavior is often due to the formulation, but also by the nature of the silane-crosslinking base polymers certainly.
  • Organic silane-crosslinking polymers especially those with difunctional end groups on the polymer, often show insufficient repulsion.
  • the wording is decisive for the properties.
  • US 6576733 describes a way to improve the recovery by a particular catalyst system, but containing tin.
  • the use of branched polymers causes an increase in the network density and thus an improvement in the elasticity.
  • the disadvantage here associated with the branching reduction of chain lengths between two network points, which usually leads to a significant deterioration of the mechanical properties, in particular the elongation at break but also the tear strength.
  • Aminoalkylalkoxysilanes in combination with epoxy-functional silanes to improve the recovery Disadvantages here are the increase of the modulus and the deterioration of the adhesion.
  • a particularly interesting type among the silane-terminated polymers is characterized in that the reactive alkoxysilyl groups are separated from an adjacent heteroatom only by a methylene spacer. These so-called ⁇ -alkoylsilylmethyl end groups have a particularly high reactivity to atmospheric moisture.
  • Corresponding polymers are described, for example, in WO 03/014226. For sufficiently fast curing, these polymers require no or only very small amounts of toxicologically critical tin catalysts and, if desired, can achieve significantly higher curing speeds. In this respect, the use of such ⁇ -alkoylsilylterminierter prepolymers is usually particularly desirable.
  • the object of the invention is therefore to provide blends based on ⁇ TM silane-crosslinking polymers which have a high recovery in the cured state after stretching.
  • the invention relates to mixing (M) containing
  • L is a divalent linking group selected from -O-, -S-,
  • R 1 and R 4 independently of one another are hydrocarbon radicals having 1-6 carbon atoms or ⁇ -oxaalkyl-alkyl radicals having a total of 2 20 carbon atoms,
  • R ⁇ is hydrogen, an optionally halogen-substituted cyclic, linear or branched C] _ to C ⁇ ß-alkyl or alkenyl radical or a Cg to C] _g ⁇ aryl radical and x is 2 or 3,
  • the mixture (M) contains less than 2 parts of one or more compounds having a primary amine function and less than 0.2 part of one or more tin-containing catalysts.
  • L is preferably -O-CO-N (R 2 ) -N (R 2 ) -CO-NH-, -NH-CO-N (R 2 ) -, and -N (R 2 J -CO-N (R 2 ) -, more preferably -O-CO-N (R 2 ), especially -O-CO-NH.
  • x is preferably 3.
  • R - * -, R ⁇ and R ⁇ are alkyl radicals such as the methyl TM, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert. Butyl, n-pentyl, isopentyl, neo-pentyl, tert.
  • -Pentyl radical hexyl radicals such as the n-hexyl radical, heptyl radicals such as the n-heptyl radical, octyl radicals such as the n-octyl radical and iso-octyl radicals such as the 2, 2, 4-trimethylpentyl radical, nonyl radicals such as the n-nonyl radical, decyl radicals such as the n-decyl radical, dodecyl radicals such as the n-dodecyl radical; Alkenyl radicals, such as the vinyl and the
  • Cycloalkyl radicals such as cyclopentyl, cyclohexyl, cycloheptyl radicals and methylcyclohexyl radicals
  • Aryl radicals such as the phenyl and the naphthyl radical
  • Alkaryl radicals such as o-, m-, p-tolyl radicals, xylyl radicals and ethylphenyl radicals
  • Aralkyl radicals such as the benzyl radical, the ⁇ - and the ß-phenylethyl radical.
  • the radicals R ⁇ and R ⁇ are preferably hydrocarbon radicals having 1 to 6 carbon atoms, in particular an alkyl radical having 1 to 4 carbon atoms.
  • R 2 particularly preferably represents a methyl radical
  • R 1 particularly preferably represents methyl or ethyl radicals.
  • the radical R 1 is preferably hydrogen or a hydrocarbon radical having 1 to 6 carbon atoms, more preferably hydrogen, an alkyl radical having 1 to 4 carbon atoms, in particular hydrogen.
  • the blend (M) contains less than 1 part, more preferably less than 0.5 part - especially less than 0.2 part - of one or more compounds having primary amine functionality. Most preferably, the blend (M) is free of any compounds having primary amine functionality.
  • the blend (M) contains less than 0.1 parts, more preferably less than 0.05 parts - especially less than 0.02 parts - of one or more tin catalysts, most preferably the blend (M) is free of any tin-containing catalysts.
  • the invention is based on the surprising finding that compounds with primary amine function in the provision
  • the blends (M) according to the invention are preferably characterized in that molded articles (F) which consist of the cured blend (M) after a 24-hour elongation of 30% exhibit a repulsion to DIN 53504 of more than 60%, preferably more than 65%, and more preferably more than 70%.
  • the main chains of the alkoxysilane-terminated polymers (A) that can be used may be branched or unbranched.
  • the middle chain lengths can be arbitrarily adjusted according to the respective desired properties of both the uncrosslinked mixture and the cured mass. They can be composed of different building blocks, usually these are polysiloxanes, polysiloxane-urea / urethane copolymers, polyurethanes, polyureas, polyethers, polyesters, polyacrylates and methacrylates, polycarbonates, polystyrenes, polyamides, polyvinyl esters or polyolefins such as polyethylene, polybutadiene, ethylene Olefin copolymers or styrene-butadiene copolymers. Of course, any mixtures or combinations of polymers with different main chains can be used.
  • silane derivatives of the general formula (1) a large number of possibilities are known. Especially:
  • the prepolymer (Al) itself consists of several building blocks (All, A12 ). It is not absolutely necessary that these building blocks (All, A12 ... ⁇ first, the prepolymer (Al) is prepared r which is then reacted with the Sila ⁇ (A2) to the finished polymer (A). Thus, a reversal of the reaction steps is also possible here, in which one or more building blocks (All, A12...) Are first reacted with the silane (A2), and the compounds thus obtained are only subsequently reacted with the remaining building blocks (All, A12. ..) are converted to the finished polymer (A).
  • prepolymers (Al) consisting of building blocks All, and A12 are OH, NR TM or NCO-terminated polyurethanes and polyureas, which can be prepared from polyisocyanates (building block All) and polyols (building block A12).
  • a silane (A2) is used, which is selected from silanes of the general formulas (3)
  • the concentrations of all participating in felliche reaction steps isocyanate groups and all isocyanate-reactive groups and the reaction conditions are preferably selected so that react in the course of the polymer synthesis all isocyanate groups.
  • the finished polymer (A) is thus preferably isocyanate-free.
  • prepolymers (Al) are polyesters, polycarbonates, polyester carbonates (eg those commercially available under the name “Desmophen 1700" and “Desmophen C-200” from Bayer AG, Germany), polybutenylenes and polybutadienylenes (eg Such êtlich obtainable under the name “Poly bd ® R-45 HTLO” by the company. Sartonaer Co., Inc., USA or "Kraton TM Liquid L-2203" by the company. Kraton Polymers US LL C).
  • prepolymers (Al) for preparing prepolymers (A) are polyesters, polyethers and polyurethanes.
  • Particularly preferred examples of prepolymers (Al) are divalent polyethers of the general formula (4)
  • R ⁇ may be identical or different and optionally substituted hydrocarbon radicals, preferably methylene, ethylene and 1, 2-propylene radicals, and ⁇ t is an integer from 1 to 600, preferably 50 to
  • prepolymers (Al) of the general formula (4) are commercially available under the name "Acclaim 12200", “Acclaim 18000” (both Bayer AG, Germany), “Alcupol 12041LM” from Repsol, Spain and “Poly L 220-10 from Arch Chemicals, USA),
  • the proportion of alkoxysilane-terminated polymers (A) is preferably 10-70% by weight, more preferably 15-50% by weight, in particular 20-40% by weight.
  • the innovative blends (M) contain besides the
  • Prepolymer (A) preferably one or more secondary or tertiary amines (B) as a curing catalyst (K).
  • secondary or tertiary ammoalkoxysilanes such as 3- (N-cyclohexylamino) -propyltrimethoxysilane, 3- (N-cyclo TM hexylamino) -propyltriethoxysilane, 3- (N-phenylamino) -propyl- trimethoxysilane, 3- (N-phenylammo) -propyltnethoxysilane, trimethylammonium, tributylamm, 1, 4-diazabicyclo [2,2,2] octane, N, N-bis (3tf, N-dimethyl-2-ammoethyl) -methylamine, N, N ⁇ dimethylcyclohexylamine, N, N-dimethylphenylamm, N-ethylmorpho
  • inventive mixtures (M) in addition to the prepolymers (A) one or more secondary or tertiary Ammoalkyl alkoxysilanes (KS) as a curing catalyst (K).
  • KS secondary or tertiary Ammoalkyl alkoxysilanes
  • Preferred ammoalkylalkoxysilanes are those of the general formula (5)
  • R 1, R ' is hydrogen or an alkyl, cycloalkyl, alkenyl or aryl radical having 1-10 carbon atoms which may optionally be substituted by halogen atoms and / or organic functions,
  • R *> is an alkyl, cycloalkyl, alkenyl or aryl radical having 1-10 carbon atoms, which may optionally be substituted by halogen atoms and / or organic functions
  • r is a bivalent alkyl, cycloalkyl, alkenyl or aryl radical having 1-10 carbon atoms , which may optionally be substituted by halogen atoms, and all other variables have the meanings given above.
  • R ⁇ > is preferably a hydrogen atom or an alkyl, cycloalkyl or aryl group having 1-10 carbon atoms, more preferably a hydrogen atom or a
  • R *> preferably represents an alkyl, cycloalkyl or aryl radical having 1-10
  • Carbon atoms, with phenyl radicals, cyclohexyl radicals or alkyl radicals having 1-8 carbon atoms are particularly preferred.
  • ⁇ 7 is preferably hydrogen.
  • KS ominoalkyl-alkoxysilanes
  • R 3 is methyl
  • R ⁇ , R6 is hydrogen, R *> cyclohexyl or phenyl.
  • the proportion of aminoalkylalkoxysilane (KS) is preferably 0.1-10% by weight, more preferably 0.1-5% by weight, in particular 0.2-3% by weight. based on the total weight of the mixture.
  • the novel polymer blends (M) may comprise further condensation catalysts (K), for example titanate esters, such as tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetraacetylacetonate titanate or even acid catalysts, such as phosphoric acid or phosphoric acid esters, toluenesulfonic acids, mineral acids.
  • K condensation catalysts
  • titanate esters such as tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetraacetylacetonate titanate
  • acid catalysts such as phosphoric acid or phosphoric acid esters, toluenesulfonic acids, mineral acids.
  • the various catalysts can be used both in pure form and as mixtures.
  • These further condensation catalysts are preferably used in concentrations of 0.01-10% by weight, more preferably 0.1-2 % By weight, based on the total weight of the blend, of the polymer blends (M).
  • the blends (M) according to the invention may also contain tin compounds, such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin acetylacetonate, dibutyltin oxide or corresponding dioctyltin compounds within the above-indicated concentration limits as curing catalysts (K).
  • the blends (M) according to the invention are preferably tin-free.
  • the blends (M) according to the invention may also contain primary amines, in particular primary osilminosilanes such as 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane, within the above-indicated concentration limits as curing catalysts (K).
  • primary osilminosilanes such as 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane
  • the blends (M) according to the invention are free of primary amines.
  • the polymer blends according to the invention preferably further comprise fillers (F), for example calcium carbonates in the form of natural ground chalks, ground and coated crayons, precipitated crayons, precipitated and coated crayons, clay minerals, bentonites, kaolins, talc, titanium dioxides, aluminum oxides, aluminum trihydrate,
  • fillers for example calcium carbonates in the form of natural ground chalks, ground and coated crayons, precipitated crayons, precipitated and coated crayons, clay minerals, bentonites, kaolins, talc, titanium dioxides, aluminum oxides, aluminum trihydrate,
  • the fillers (F) are preferably added to the polymer blends (M) in concentrations of 10-70% by weight, more preferably 30-60% by weight, based on the total weight of the blend.
  • the novel polymer blends (M) may contain, in addition to the optionally used as catalyst (K) silanes (including the silanes (KS) according to the formula (5)) also further silanes (S) with or without additional organofunction.
  • silanes including the silanes (KS) according to the formula (5)
  • S further silanes with or without additional organofunction.
  • These are preferably water scavengers and / or silane crosslinkers, for example alkylsilanes such as methyltrimethoxysilane, vinylsilanes such as vinyltrimethoxy, vinyltriethoxy, Vxnylmethyldimethoxysilan or organofunctional silanes such as O-Methylcarbamatomethyl methyldiraethoxysilane, O-Methylcarbamatomethyl-trimethoxysilane, 0 TM Ethylcarbarnatomethyl ⁇ methyldiethoxysilane, O-ethylcarbamat
  • the water scavengers and / or Silanvernetzer serving silanes (S) are preferably in concentrations of 0.1 to 10 wt .-%, particularly preferably 0.5 to 2 wt .-%, based on the total weight of the mixture, the Polymerabmischungen (M) added.
  • silanes (S) as well as the silanes used as catalyst (K) can simultaneously serve as adhesion promoters (H).
  • the blends (M) according to the invention may of course also contain further adhesion promoters (H).
  • the novel polymer blends may contain plasticizers (W), for example phthalate esters, such as Dioctyl phthalate, Dusooctylphthalat, Diundecylphthalat, Adipmsaureester, such as Dioctyladipat, benzoic acid esters, glycol esters, phosphoric acid esters, sulfonic acid esters, polyesters, polyethers, polystyrenes, polybutadienes, polyisobutenes, paraffinic hydrocarbons, higher, branched hydrocarbons, etc.
  • W plasticizers
  • W plasticizers
  • phthalate esters such as Dioctyl phthalate, Dusooctylphthalat, Diundecylphthalat, Adipmsaureester, such as Dioctyladipat
  • benzoic acid esters glycol esters, phosphoric acid esters, sulfonic acid esters, polyesters, polyethers,
  • the plasticizers (W) are preferably added to the polymer blends (M) in concentrations of up to 40% by weight, based on the total weight of the blend.
  • the polymer mixtures (M) according to the invention may also contain thixotropic agents, for example hydrophilic pyrogenic silicic acids, coated fumed silicas, precipitated silicas, polyamide monoxide, hydrogenated ricinols, stearate salts or precipitated chalks. Also, the above fillers can be used to adjust the flow properties.
  • thixotropic agents for example hydrophilic pyrogenic silicic acids, coated fumed silicas, precipitated silicas, polyamide monoxide, hydrogenated ricinols, stearate salts or precipitated chalks.
  • the above fillers can be used to adjust the flow properties.
  • the thixotropic agents are preferably added in concentrations of 1-5 wt .-%, based on the total weight of the blend, the polymer blends (M).
  • inventive polymer blends can furthermore light stabilizers r such as so-called HALS stabilizers,
  • Fungicides flame retardants, pigments, etc., as they are known for use m conventional alkoxy-crosslinking emkomponentigen compositions.
  • the above additives are preferably used.
  • a mixture of polymer (A) and filler is first prepared, and then aminoalkylalkoxysilane (BS) is added.
  • Shaped bodies (F) e.g. Adhesive joints which can be produced by curing the mixtures (M) according to the invention are likewise provided by the invention.
  • the moldings (F) preferably have a 30% elongation after a 24-hour stretch
  • novel polymer blends are available for countless different backgrounds such as e.g. mineral substrates, metals, plastics, glass, ceramics, painted surfaces, etc. suitable.
  • Comparative Example Ib is prepared analogously, but aminopropyltrimethoxysilane (GENIOSIL® GF96 - Wacker Chemie AG) is used instead of cyclohexylaminomethyltriethoxysilane.
  • GENIOSIL® GF96 - Wacker Chemie AG aminopropyltrimethoxysilane
  • 35 g of a silane-terminated polyether obtainable from EP 1.534.940 B from Acclaim Polyol 18200S (Bayer Material Science AG) and isocyanatomethyltriethoxysilane are mixed in a Speedmixer from Hauschild (D-59065 Hamm) at 25 ° C. with 25 g of PPG 2000 ( Dow Chemical) and 3 g of methylcarbamatotrimethoxysilane, available under the name GENIOSIL® XL63 (Wacker Chemie AG), mixed for 2 minutes at 200 rpm. Thereafter, 1.50 g of a hydrophilic.
  • Fumed silica HDK® N20 (170-230 m 2 / g) (Wacker Chemie AG) is stirred until it is homogeneously distributed. Subsequently 60.4 g of chalk Carbital HOS (Imerys) are introduced and the filler digested with stirring for one minute at 600 U / min. After incorporation of the chalk, 0.1 g of cyclohexylaminomethyltriethoxysilane (GENIOSIL® XL926 - Wacker Chemie AG) is distributed for 1 minute at 200 rpm. Homogenized for 2 minutes at 600 rpm and 1 minute at 200 rpm in a partial vacuum (about 100 mbar) and stirred bubble-free.
  • the formulation is filled in 310 ml PE cartridges and stored for one day at 25 0 C.
  • Example 2b is prepared analogously, but the hydrophilic, fumed silica HDK® H15 (170-230 m 2 / g, Wacker Chemie AG) is used instead of the HDK® N20.
  • Formulations with a silanten ⁇ in capable of methylene-Dimethoxysilylend phenomenon (alpha-dimethoxy) 35 g of a silantermln capable polyether, available after EP 1.534.940 B from Acclaim Polyol 12200S ⁇ Bayer Material Science) and isocyanatomethyldimethoxysilane in a Speedmixer Fa. Hauschild (D-59065 Hamm) at 25 ° C. with 25 g of PPG 2000 (from Dow Chemical) and 3 g of methylcarbamatotrimethoxysilane, available under the name GENIOSIL® XL63 (Wacker Chemie AG), for 2 minutes at 200 rpm.
  • GENIOSIL® XL63 Wang Chemie AG
  • the formulation is filled in 310 ml PE cartridges and stored for one day at 25 0 C.
  • Comparative Example 3b is prepared analogously, but aminopropyltrimethoxysilane (GENIOSIL ⁇ GF96 - Wacker Chemie AG) is used instead of cyclohexylaminomethyl-triethoxysilane.
  • GENIOSIL ⁇ GF96 - Wacker Chemie AG aminopropyltrimethoxysilane

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a blend (M), comprising A) 100 parts of an alkoxysilylmethyl-terminated polymer (A) with at least one end group of the general formula (1) -L- (CH2) -SiR2 3-x(OR1) x (1), with L being a double-bond linking group selected from -O-, -S-, -(R3)N-, -O-CO-N(R3)-, -N(R3)-CO-O-, -N(R3)-CO-NH-, -NH-CO-N(R3)-, -N (R3) -CO-N (R3), R1 and R2 are independently hydrocarbon radicals with 1-6 carbon atoms or ?-oxaalkyl-alkyl radicals with a total of 2-20 carbon atoms, R3 is hydrogen, an optionally halogen-substituted cyclic, linear or branched C1 to C18-alkyl or alkenyl radical or a C6- to C18-aryl radical, and x is 2 or 3, B) 0.01 to 10 parts of a curing catalyst (K) that accelerates the curing of the blend (M) in the presence of air humidity, C) 0 to 1000 parts of one or more fillers (F), D) 0 to 50 parts of one or more monomeric silanes (S) as water traps and silane cross-linkers, E) 0 to 200 parts of one or more plasticizers (W) and F) 0 to 50 parts of one or more adhesion promoters (H) and F) optionally other additives, wherein the blend (M) comprises less than 2 parts of one or more compounds with a primary amine function and less than 0.2 parts of one or more catalyst that contains tin.

Description

Alkoxysilanterminxerte Polymere enthaltende PolymerabmischungenAlkoxysilane-terminated polymer blends containing polymer
Dxe Erfindung betrifft Abmischungen (M) , die methyl- dialkoxysilylmethyl- oder trialkoxysilylmethyltermimerte Polymere enthalten, aus diesen Abmischungen hergestellteThis invention relates to blends (M) containing methyl dialkoxysilylmethyl or trialkoxysilylmethyl-terminated polymers prepared from these blends
Formkorper sowie den Einsatz der Abmischungen (M) zur Verklebung von Werkstucken.Formkorper and the use of blends (M) for bonding workpieces.
Polymersysteme, die über reaktive Alkoxysilylgruppen verfugen, sind seit langem bekannt. In Gegenwart von Luftfeuchtigkeit sind diese alkoxysilanterminxerten Polymere bereits beiPolymer systems that have reactive alkoxysilyl groups have long been known. In the presence of atmospheric moisture, these alkoxysilane terminated polymers are already included
Raumtemperatur in der Lage, unter Abspaltung der Alkoxygruppen miteinander zu kondensieren. Je nach Gehalt anRoom temperature able to condense with elimination of the alkoxy groups together. Depending on the salary
Alkoxysilangruppen und deren Aufbau bilden sich dabei hauptsächlich langkettige Polymere (Thermoplaste) , relativ weitmaschige dreidimensionale Netzwerke (Elastomere) oder aber hochvernetzte Systeme (Duroplaste) .Alkoxysilane groups and their structure are formed mainly by long-chain polymers (thermoplastics), relatively wide-meshed three-dimensional networks (elastomers) or highly crosslinked systems (thermosets).
Entsprechend der zahllosen Möglichkeiten zur Gestaltung von derartigen silantermmierten Polymersystemen lassen sich sowohl die Eigenschaften der unvernetzten Polymere bzw. der polymerhaltigen Mischungen (Viskosität, Schmelzpunkt, Loslichkeiten etc.) als auch die Eigenschaften der fertig vernetzten Massen (Harte, Elastizität, Zugfestigkeit, Reißdehnung, Hitzebestandigkeit etc.) nahezu beliebig einstellen. Entsprechend vielfaltig sind daher auch die Emsatzmoglichkeiten von derartigen silantermmierten Polymersystemen. So lassen sie sich beispielsweise zur Herstellung von Elastomeren, Dichtstoffen, Klebstoffen, elastischen Klebesystemen, harten und weichen Schäumen, den unterschiedlichsten Beschichtungssystemen oder für Abformmassen verwenden. Diese Produkte lassen sich m ^eder Form applizieren, wie z.B. streichen, sprühen, gießen, pressen, spachteln etc. je nach Zusammensetzung der Formulierungen. Neben der Härtung der Massen und den mechanischen Eigenschaften des Vulkanisats sind vor allem bei Anwendungen im Kleb- und Dichtstoffbereich eine gute Haftung auf unterschiedlichsten Substraten und gute elastische Eigenschaften gefordert. Formulierungen silanvernetzender Polymere zeigen hier in aller Regel sehr gute Eigenschaften.According to the countless possibilities for designing such silantermmierten polymer systems can be both the properties of the uncrosslinked polymers or polymer-containing mixtures (viscosity, melting point, Loslichkeiten etc.) and the properties of the finished crosslinked materials (hardness, elasticity, tensile strength, elongation at break, heat resistance etc.) set almost arbitrarily. Consequently, the possibilities of substitution of such silane-degraded polymer systems are correspondingly diverse. Thus, they can be used, for example, for the production of elastomers, sealants, adhesives, elastic adhesive systems, hard and soft foams, a wide variety of coating systems or for impression compounds. These products can be applied in any form, such as brushing, spraying, pouring, pressing, filling, etc. depending on the composition of the formulations. In addition to the curing of the compositions and the mechanical properties of the vulcanizate, good adhesion to a wide variety of substrates and good elastic properties are required above all in applications in the area of adhesives and sealants. As a rule, formulations of silane-crosslinking polymers show very good properties.
Das Haftungsprofil wird vielfach durch Zusatz von organofunktionellen Silanen als Haftvermittlern verbessert bzw. optimiert. Insbesondere Silane mit primären Aminogruppen wie 3- Aminopropyltrimethoxysilan führen hier zu einer deutlichen Verbesserung der Haftungseigenschaften, weshalb dieser Silantyp beinahe in sämtlichen Kleb- und Dichtstoffen auf Basis von silanterminierten Polymeren enthalten ist. Die Anwendung derartiger Silane ist Stand der Technik und in diversenThe adhesion profile is often improved or optimized by the addition of organofunctional silanes as adhesion promoters. In particular, silanes with primary amino groups such as 3-aminopropyltrimethoxysilane lead here to a significant improvement in the adhesion properties, which is why this silane is almost included in all adhesives and sealants based on silane-terminated polymers. The application of such silanes is state of the art and in various
Monographien oder Veröffentlichungen beschrieben (z.B. Silanes and other coupling agents, VoI 1-3 Editor K. L. Mittal VSP, Utrecht 1992; Silane Coupling Agents, E. P. Plueddemann 2nd Edition, Plenum Press, New York 1991) . Daneben gibt es auch noch spezielle neu entwickelte Haftvermittlersilane, wie in EP 997469 A oder EP 1216263 A beschrieben, aber auch eine Kombination von Silanen, wie in EP 1179571 A gezeigt ist oft zielführend.Monographs or publications described (eg, silane coupling agents and other, VoI 1-3 Editor KL Mittal VSP, Utrecht, 1992; Silane Coupling Agents, EP Plueddemann 2 nd Edition, Plenum Press, New York 1991). In addition, there are also special newly developed primer silanes, as described in EP 997469 A or EP 1216263 A, but also a combination of silanes, as shown in EP 1179571 A is often expedient.
Neben einer guten Haftung müssen Klebstoffe aber vor allem Dichtstoffe auch eine sehr gute Elastizität aufweisen. Dabei spielt nicht nur die Dehnung eine Rolle, sondern auch die Relaxation nach Dehnung oder Stauchung. Diese üblicherweise als Druckverformungsrest, Kriechverhalten oder als Rückstellverhalten gemessen. Beispielsweise wird in der ISO 11600 eine Rückstellung über 60 % oder sogar 70 % für elastische Dichtstoffe gefordert.In addition to a good adhesion adhesives but above all sealants must also have a very good elasticity. Not only the stretching plays a role, but also the relaxation after stretching or compression. These are usually measured as compression set, creep behavior or as restoring behavior. For example, ISO 11600 requires a provision of over 60% or even 70% for elastic sealants.
Das elastische Verhalten wird vielfach durch die Formulierung, aber auch durch die Art der silanvernetzenden Basispolymere bestimmt. Organische silanvernetzende Polymere, speziell solche mit difunktionellen Endgruppen am Polymer zeigen oft unzureichende Ruckstellungen. Hier ist die Formulierung maßgeblich für die Eigenschaften. Beispielsweise beschreibt US 6576733 eine Möglichkeit zur Verbesserung der Ruckstellung durch ein spezielles Katalysatorsystem, das jedoch zinnhaltig ist. Ferner ist bekannt, dass die Verwendung von verzweigten Polymeren eine Erhöhung der Netzwerkdichte und damit eine Verbesserung der Elastizität bewirkt. Nachteilig ist hier allerdings die mit der Verzweigung einhergehende Verringerung der Kettenlangen zwischen zwei Netzpunkten, was meist zu einer deutlichen Verschlechterung der mechanischen Eigenschaften, insbesondere der Reißdehnung aber auch der Reißfestigkeit fuhrt .The elastic behavior is often due to the formulation, but also by the nature of the silane-crosslinking base polymers certainly. Organic silane-crosslinking polymers, especially those with difunctional end groups on the polymer, often show insufficient repulsion. Here the wording is decisive for the properties. For example, US 6576733 describes a way to improve the recovery by a particular catalyst system, but containing tin. Furthermore, it is known that the use of branched polymers causes an increase in the network density and thus an improvement in the elasticity. The disadvantage here, however, associated with the branching reduction of chain lengths between two network points, which usually leads to a significant deterioration of the mechanical properties, in particular the elongation at break but also the tear strength.
DE102006022834 beschreibt die Verwendung vonDE102006022834 describes the use of
Aminoalkylalkoxysilanen in Kombination mit epoxyfunktionellen Silanen zur Verbesserung der Ruckstellung. Nachteilig sind hierbei die Erhöhung des Moduls und die Verschlechterung der Adhäsion.Aminoalkylalkoxysilanes in combination with epoxy-functional silanes to improve the recovery. Disadvantages here are the increase of the modulus and the deterioration of the adhesion.
Ein besonders interessanter Typ unter den silanterminierten Polymeren zeichnet sich dadurch aus, dass die reaktiven Alkoxysilylgruppen nur durch einen Methylenspacer von einem benachbarten Heteroatom getrennt sind. Diese sogenannten α- alkoylsilylmethyl-Endgruppen besitzt eine besonders hohe Reaktivität gegenüber Luftfeuchtigkeit. Entsprechende Polymere sind beispielsweise in WO 03/014226 beschrieben. Diese Polymere benotigen für eine hinreichend schnelle Aushärtung keine oder nur noch sehr geringe Mengen an toxikologisch kritischen Zinnkatalysatoren und können auf Wunsch wesentlich höhere Hartungsgeschwindigkeiten erreichen. Insofern ist der Einsatz derartiger α-alkoylsilylterminierter Prepolymere meist besonders erstrebenswert. Allerdings besitzen Elastomere, die aus diesem hochreaktiven α- silanvernetzenden Polymertyp herstellbar sind, im Vergleich zu Elastomeren aus herkömmlichen silanvernetzenden Polymeren, die über γ-Alkoxysilylpropylendgruppen vernetzen, den Nachteil einer deutlich geringeren, für viele Anwendungen unzureichenden Rückstellung.A particularly interesting type among the silane-terminated polymers is characterized in that the reactive alkoxysilyl groups are separated from an adjacent heteroatom only by a methylene spacer. These so-called α-alkoylsilylmethyl end groups have a particularly high reactivity to atmospheric moisture. Corresponding polymers are described, for example, in WO 03/014226. For sufficiently fast curing, these polymers require no or only very small amounts of toxicologically critical tin catalysts and, if desired, can achieve significantly higher curing speeds. In this respect, the use of such α-alkoylsilylterminierter prepolymers is usually particularly desirable. However, elastomers which can be prepared from this highly reactive α-silane-crosslinking polymer type have the disadvantage of a much lower recovery, which is inadequate for many applications, in comparison to elastomers from conventional silane-crosslinking polymers which crosslink via γ-alkoxysilylpropyl end groups.
Aufgabe der Erfindung ist es daher, Abmischungen auf Basis von α™silanvernetzenden Polymeren bereitzustellen, die in ausgehärtetem Zustand nach Dehnung eine hohe Rückstellung aufweisen.The object of the invention is therefore to provide blends based on α ™ silane-crosslinking polymers which have a high recovery in the cured state after stretching.
Gegenstand der Erfindung sind Abmischung (M) enthaltendThe invention relates to mixing (M) containing
A) 100 Teile eines alkoxysilylmethylterminierten Polymers (A) mit mindestens einer Endgruppe der allgemeinen Formel (1)A) 100 parts of an alkoxysilylmethyl-terminated polymer (A) having at least one end group of the general formula (1)
-L- (CH2) -SiR23_x (ORi)x (1),-L- (CH 2 ) -SiR 2 3_ x (ORi) x (1),
wobei L eine zweibindige Bindegruppe ausgewählt aus -O-, -S-,where L is a divalent linking group selected from -O-, -S-,
-(R3) N-, -0-CO-N(R3)-, -N(R3) -CO-O-, -N (R3) -CO-NH-,- (R 3 ) N, -O-CO-N (R 3 ) -, -N (R 3 ) -CO-O-, -N (R 3 ) -CO-NH-,
-NH-CO-N(R3)-, -N(R3) -CO-N (R3) R^ und R^ unabhängig voneinander für Kohlenwasserstoffreste mit 1-6 Kohlenstoffatomen oder ω-Oxaalkyl-alkylreste mit insgesamt 2-20 Kohlenstoffatomen,-NH-CO-N (R 3 ) -, -N (R 3 ) -CO-N (R 3 ) R 1 and R 4 independently of one another are hydrocarbon radicals having 1-6 carbon atoms or ω-oxaalkyl-alkyl radicals having a total of 2 20 carbon atoms,
R^ Wasserstoff, einen gegebenenfalls halogensubstuierten cyclischen, linearen oder verzweigten C]_ bis C^ß-Alkyl- oder Alkenylrest oder einen Cg- bis C]_g~Arylrest stehen und x 2 oder 3 bedeutet,R ^ is hydrogen, an optionally halogen-substituted cyclic, linear or branched C] _ to C ^ ß-alkyl or alkenyl radical or a Cg to C] _g ~ aryl radical and x is 2 or 3,
B) 0,01 bis 10 Teile eines Härtungskatalysator (K) der die Aushärtung der Abmischung (M) in Gegenwart von Luftfeuchtigkeit beschleunigt,B) 0.01 to 10 parts of a curing catalyst (K) which accelerates the curing of the blend (M) in the presence of atmospheric moisture,
C) 0 bis 1000 Teile eines oder mehrere Füllstoffe (F), D) 0 bis 50 Teile eines oder mehrerer monomerer Silane (S) als Wasserfänger und Silanvernetzer,C) 0 to 1000 parts of one or more fillers (F), D) 0 to 50 parts of one or more monomeric silanes (S) as water scavengers and silane crosslinkers,
E) 0 bis 200 Teile eines oder mehrerer Weichmacher (W) undE) 0 to 200 parts of one or more plasticizers (W) and
F) 0 bis 50 Teile eines oder mehrerer Haftvermittler (H) undF) 0 to 50 parts of one or more adhesion promoters (H) and
F) gegebenenfalls weitere Zusätze und Additive,F) optionally further additives and additives,
dadurch gekennzeichnet,characterized,
dass die Λbmischung (M) weniger als 2 Teile einer oder mehrerer Verbindungen mit primärer Aminfunktion und weniger als 0,2 Teile eines oder mehrerer zinnhaltigen Katalysators enthält.the mixture (M) contains less than 2 parts of one or more compounds having a primary amine function and less than 0.2 part of one or more tin-containing catalysts.
In der Formel (1) steht L vorzugsweise für -0-CO-N(R2) -N (R2) -CO-NH-, -NH-CO-N(R2)- und -N(R2J-CO-N(R2)-, besonders bevorzugt -0-CO-N(R2), insbesondere -O-CO-NH.In the formula (1), L is preferably -O-CO-N (R 2 ) -N (R 2 ) -CO-NH-, -NH-CO-N (R 2 ) -, and -N (R 2 J -CO-N (R 2 ) -, more preferably -O-CO-N (R 2 ), especially -O-CO-NH.
x ist bevorzugt 3.x is preferably 3.
Beispiele für R-*-, R^ und R^ sind Alkylreste, wie der Methyl™, Ethyl-, n-Propyl-, iso-Propyl-, n-Butyl-, iso-Butyl-, tert . - Butyl-, n~Pentyl-, iso-Pentyl-, neo~Pentyl-, tert . -Pentylrest, Hexylreste, wie der n-Hexylrest, Heptylreste, wie der n- Heptylrest, Octylreste, wie der n-Octylrest und iso-Octylreste, wie der 2, 2, 4-Trimethylpentylrest, Nonylreste, wie der n- Nonylrest, Decylreste, wie der n-Decylrest, Dodecylreste, wie der n-Dodecylrest; Alkenylreste, wie der Vinyl- und derExamples of R - * -, R ^ and R ^ are alkyl radicals such as the methyl ™, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert. Butyl, n-pentyl, isopentyl, neo-pentyl, tert. -Pentyl radical, hexyl radicals such as the n-hexyl radical, heptyl radicals such as the n-heptyl radical, octyl radicals such as the n-octyl radical and iso-octyl radicals such as the 2, 2, 4-trimethylpentyl radical, nonyl radicals such as the n-nonyl radical, decyl radicals such as the n-decyl radical, dodecyl radicals such as the n-dodecyl radical; Alkenyl radicals, such as the vinyl and the
Allylrest; Cycloalkylreste, wie Cyclopentyl-, Cyclohexyl-, Cycloheptylreste und Methylcyclohexylreste; Arylreste, wie der Phenyl- und der Naphthylrest; Alkarylreste, wie o-, m-, p- Tolylreste, Xylylreste und Ethylphenylreste; Aralkylreste, wie der Benzylrest, der α- und der ß-Phenylethylrest . Bei den Resten RΛ und R^ handelt es sich bevorzugt um Kohlenwasserstoffreste mit 1 bis 6 Kohlenstoffatomen, insbesondere um einen Alkylreste mit 1 bis 4 Kohlenstoffatomen.allyl; Cycloalkyl radicals, such as cyclopentyl, cyclohexyl, cycloheptyl radicals and methylcyclohexyl radicals; Aryl radicals, such as the phenyl and the naphthyl radical; Alkaryl radicals, such as o-, m-, p-tolyl radicals, xylyl radicals and ethylphenyl radicals; Aralkyl radicals, such as the benzyl radical, the α- and the ß-phenylethyl radical. The radicals RΛ and R ^ are preferably hydrocarbon radicals having 1 to 6 carbon atoms, in particular an alkyl radical having 1 to 4 carbon atoms.
R.2 steht besonders bevorzugt für einen Methylrest, R^ stellt besonders bevorzugt Methyl- oder Ethylreste dar.R 2 particularly preferably represents a methyl radical, R 1 particularly preferably represents methyl or ethyl radicals.
Beim Rest R^ handelt es sich bevorzugt um Wasserstoff oder einen Kohlenwasserstoffrest mit 1 bis 6 Kohlenstoffatomen, besonders bevorzugt um Wasserstoff, einen Älkylrest mit 1 bis 4 Kohlenstoffatomen, insbesondere um Wasserstoff.The radical R 1 is preferably hydrogen or a hydrocarbon radical having 1 to 6 carbon atoms, more preferably hydrogen, an alkyl radical having 1 to 4 carbon atoms, in particular hydrogen.
Vorzugsweise enthält die Abmischung (M) weniger als 1 Teil, besonders bevorzugt weniger als 0,5 Teile - insbesondere weniger als 0,2 Teile - einer oder mehrerer Verbindung mit primärer Aminfunktion . Besonders bevorzugt ist die Abmischung (M) frei von jeglichen Verbindungen mit primärer Aminfunktion.Preferably, the blend (M) contains less than 1 part, more preferably less than 0.5 part - especially less than 0.2 part - of one or more compounds having primary amine functionality. Most preferably, the blend (M) is free of any compounds having primary amine functionality.
Vorzugsweise enthält die Abmischung (M) weniger als 0,1 Teile, besonders bevorzugt weniger 0,05 Teile - insbesondere weniger als 0,02 Teile - eines oder mehrerer Zinnkatalysatoren, besonders bevorzugt ist die Abmischung (M) frei von jeglichen zinnhaltigen Katalysatoren.Preferably, the blend (M) contains less than 0.1 parts, more preferably less than 0.05 parts - especially less than 0.02 parts - of one or more tin catalysts, most preferably the blend (M) is free of any tin-containing catalysts.
Der Erfindung liegt die überraschende Erkenntnis zugrunde, dass Verbindungen mit primärer Aminfunktion die Rückstellung beiThe invention is based on the surprising finding that compounds with primary amine function in the provision
Abmischuπgen (M) auf Basis Polymeren (A) mit α-Silanfunktionen entsprechend der Formel (1) deutlich verschlechtern. Diese Erkenntnis war insofern besonders überraschend, als dass sich eine vergleichbare Verschlechterung der Rückstellung nur bei Abmischungen (M) auf Basis der α-silaπterminierten Polymeren (A) nicht aber in den seit langem bekannten und gut untersuchten Systemen auf Basis herkömmlicher γ- alkoxysilyproypl-terminierter Prepolymere zeigt. D.h. ganz offensichtlich liegt hier ein ganz neuer und bis dato unbekannter Wirkmechanismus vor, weshalb primäre Amine in dem erfindungsgemaßen System einen derartigen Effekt zeigen.Mixtures (M) based on polymers (A) with α-silane functions according to the formula (1) significantly deteriorate. This finding was particularly surprising in that a comparable deterioration of the provision only in blends (M) based on the α-silaπterminierten polymers (A) but not in the well-known and long-known systems based on conventional γ- alkoxysilyproypl-terminated Shows prepolymers. That is obviously quite a new and up to date unknown mechanism of action, which is why primary amines show such an effect in the inventive system.
Gleichzeitig ist der erfindungsgemaße Einsatz von nur geringen Mengen an primären Amine bzw. der ganzliche Verzicht auf einen Einsatz dieser Produktgruppe auch keine naheliegende Losung, weil derartige Verbindungen - insbesondere Aminosilane wie Aminopropyltrimethoxysilan, N- (2-Aminoethyl) -aminoproypl- trimethoxysilan oder N- (2-Aminoethyl) -aminoproypl- methyldimethoxysilan - typischerweise in deutlich höheren Mengen in jeder Kleb- und Dichtstoff auf Basis silanterminierter Polymere als Haftvermittler, Wasserfanger und/oder (Co-) Katalysatoren eingesetzt werden.At the same time, the use according to the invention of only small amounts of primary amines or the complete omission of use of this product group is also not an obvious solution because such compounds - in particular aminosilanes such as aminopropyltrimethoxysilane, N- (2-aminoethyl) -aminoproypl-trimethoxysilane or N- (2-aminoethyl) -aminoproypl- methyldimethoxysilane - typically used in significantly higher amounts in each adhesive and sealant based on silane-terminated polymers as adhesion promoters, water scavengers and / or (co) catalysts.
Vorzugsweise sind die erfindungsgemaßen Abmischungen (M) dadurch gekennzeichnet, dass Formkorper (F) , die aus den ausgeharteten Abmischung (M) bestehen, nach einer 24-stundigen Dehnung um 30% eine Ruckstellung nach DIN 53504 von mehr als 60%, vorzugsweise von mehr als 65% und besonders bevorzugt von mehr als 70% aufweisen.The blends (M) according to the invention are preferably characterized in that molded articles (F) which consist of the cured blend (M) after a 24-hour elongation of 30% exhibit a repulsion to DIN 53504 of more than 60%, preferably more than 65%, and more preferably more than 70%.
Die Hauptketten der einsetzbaren alkoxysilanterminierten Polymere (A) können verzweigt oder unverzweigt sein. Die mittleren Kettenlangen können beliebig entsprechend der jeweils gewünschten Eigenschaften sowohl der unvernetzten Mischung als auch der ausgeharteten Masse angepasst werden. Sie können aus unterschiedlichen Bausteinen aufgebaut sein, üblicherweise sind dies Polysiloxane, Polysiloxan-Urea/ürethan-Copolymere, Polyurethane, Polyharnstoffe, Polyether, Polyester, Polyacrylate und -methacrylate, Polycarbonate, Polystyrole, Polyamide, Polyvinylester oder Polyolefine wie z.B. Polyethylen, Polybutadien, Ethylen-Olefincopolymere oder Styrol-Butadiencopolymere. Selbstverständlich können auch beliebige Mischungen oder Kombinationen aus Polymeren mit verschiedenen Hauptketten eingesetzt werden. Zur Herstellung von Polymeren (A) mit Silanterminierungen der allgemeinen Formel (1) ist eine Vielzahl von Möglichkeiten bekannt. Insbesondere:The main chains of the alkoxysilane-terminated polymers (A) that can be used may be branched or unbranched. The middle chain lengths can be arbitrarily adjusted according to the respective desired properties of both the uncrosslinked mixture and the cured mass. They can be composed of different building blocks, usually these are polysiloxanes, polysiloxane-urea / urethane copolymers, polyurethanes, polyureas, polyethers, polyesters, polyacrylates and methacrylates, polycarbonates, polystyrenes, polyamides, polyvinyl esters or polyolefins such as polyethylene, polybutadiene, ethylene Olefin copolymers or styrene-butadiene copolymers. Of course, any mixtures or combinations of polymers with different main chains can be used. For the preparation of polymers (A) with silane derivatives of the general formula (1), a large number of possibilities are known. Especially:
* Copolymerisationen unter Beteiligung von ungesättigten Monomeren, die über Gruppen der allgemeinen Formel (1) verfugen. Beispiele für derartige Monomere waren (Meth-) Acryloyloxymethyl-trimethoxysilan, (Meth-) Acryloyloxymethyl- methyldimethoxysilan sowie die entsprechenden Ethoxysxlylverbmdungen .* Copolymerizations involving unsaturated monomers having groups of the general formula (1). Examples of such monomers were (meth) acryloyloxymethyltrimethoxysilane, (meth) acryloyloxymethylmethyldimethoxysilane and the corresponding ethoxysxlyl compounds.
• Aufpfropfung von ungesättigten Monomeren, die über Gruppen der allgemeinen Formel (1) verfugen auf Thermoplasten wie Polyethylen. Beispiele für derartige Monomere waren wiederum (Meth-) Acryloyloxymethyl-tπmethoxysilan, (Meth-) Acryl- oyloxymethyl-methyldimethoxysilan sowie die entsprechenden Ethoxysilylverbmdungen .• Grafting of unsaturated monomers having groups of the general formula (1) on thermoplastics such as polyethylene. Examples of such monomers were in turn (meth) acryloyloxymethyl-tπmethoxysilane, (meth) acrylic oyloxymethyl-methyldimethoxysilane and the corresponding Ethoxysilylverbmdungen.
• Umsetzung von Prepolymeren (Al), welche über geeignete funktionelle Gruppen verfugen, mit einem oder mehreren Organosilanen (A2) der allgemeinen Formel (2)Reaction of prepolymers (Al) which have suitable functional groups with one or more organosilanes (A2) of the general formula (2)
B- (CH2) -SiR2 3_x (OR1Jx (2)B- (CH 2 ) -SiR 2 3 _ x (OR 1 J x (2)
in der x, R-"- und R^, die oben genannten Bedeutungen aufweisen, undin the x, R - "- and R ^, which have the meanings given above, and
B eine funktionelle Gruppe darstellt, die reaktionsfähig ist gegenüber den funktionellen Gruppen der PrepolymereB represents a functional group which is reactive with the functional groups of the prepolymers
(Al) .(Al).
Ist dabei das Prepolymer (Al) dabei selbst aus mehreren Bausteinen (All, A12 ...) zusammengesetzt, so ist es nicht unbedingt erforderlich, dass aus diesen Bausteinen (All, A12 ...} zunächst das Prepolymer (Al) hergestellt wirdr welches anschließend mit dem Silaπ (A2) zum fertigen Polymer (A) umgesetzt wird. So ist hier auch eine Umkehrung der Reaktionsschritte möglich, bei dem einer oder mehrere Bausteine (All, A12 ...) zunächst mit dem Silan (A2) umgesetzt werden, und die dabei erhaltenen Verbindungen erst anschließend mit den verbleibenden Bausteinen (All, A12 ...) zum fertigen Polymer (A) umgesetzt werden.If the prepolymer (Al) itself consists of several building blocks (All, A12 ...), it is not absolutely necessary that these building blocks (All, A12 ...} first, the prepolymer (Al) is prepared r which is then reacted with the Silaπ (A2) to the finished polymer (A). Thus, a reversal of the reaction steps is also possible here, in which one or more building blocks (All, A12...) Are first reacted with the silane (A2), and the compounds thus obtained are only subsequently reacted with the remaining building blocks (All, A12. ..) are converted to the finished polymer (A).
Beispiele für Prepolymere (Al) bestehend aus Bausteinen All, und A12 sind OH-, NR™ oder NCO-terminierte Polyurethane und Polyharnstoffe, welche sich aus Polyisocyanaten (Baustein All) sowie Polyolen (Baustein A12) herstellen lassen.Examples of prepolymers (Al) consisting of building blocks All, and A12 are OH, NR ™ or NCO-terminated polyurethanes and polyureas, which can be prepared from polyisocyanates (building block All) and polyols (building block A12).
Bei einer bevorzugten Herstellungsweise der Prepolymere (A) wird ein Silan (A2) eingesetzt, das ausgewählt wird aus Silanen der allgemeinen Formeln (3)In a preferred preparation of the prepolymers (A) a silane (A2) is used, which is selected from silanes of the general formulas (3)
OCN- (CH2) -SiR23_x (OR1) x (3)OCN- (CH 2 ) -SiR 2 3 - x (OR 1 ) x (3)
wobei samtliche Variablen die oben angegebenen Bedeutungen besitzen .where all variables have the meanings given above.
Bei der Herstellung der Prepolymeren (A) sind die Konzentrationen aller an samtlichen Reaktionsschritten beteiligter Isocyanatgruppen und aller isocyanatreaktiver Gruppen sowie die Reaktionsbedingungen bevorzugt so gewählt, dass im Laufe der Polymersynthese samtliche Isocyanatgruppen abreagieren. Das fertige Polymer (A) ist somit bevorzugt isocyanatfrei .In the preparation of the prepolymers (A), the concentrations of all participating in samtliche reaction steps isocyanate groups and all isocyanate-reactive groups and the reaction conditions are preferably selected so that react in the course of the polymer synthesis all isocyanate groups. The finished polymer (A) is thus preferably isocyanate-free.
Beispiele für Prepolymere (Al) sind Polyester, Polycarbonate, Polyestercarbonate (z.B. solche kauflich erhaltlich unter der Bezeichnung "Desmophen 1700" und "Desmophen C-200" von Bayer AG, Deutschland), Polybutenylene und Polybutadienylene (z.B. solche kauflich erhaltlich unter der Bezeichnung "PoIy bd® R-45 HTLO" von der Fa. Sartonaer Co., Inc., USA oder "Kraton™ Liquid L-2203" von der Fa. Kraton Polymers US L. L. C) .Examples of prepolymers (Al) are polyesters, polycarbonates, polyester carbonates (eg those commercially available under the name "Desmophen 1700" and "Desmophen C-200" from Bayer AG, Germany), polybutenylenes and polybutadienylenes (eg Such kauflich obtainable under the name "Poly bd ® R-45 HTLO" by the company. Sartonaer Co., Inc., USA or "Kraton ™ Liquid L-2203" by the company. Kraton Polymers US LL C).
Bevorzugte Beispiele für Prepolymere (Al) zur Herstellung Prepolyraere (A) sind Polyester, Polyether und Polyurethane. Besonders bevorzugte Beispiele für Prepolymere (Al) sind zweiwertige Polyether der allgemeinen Formel (4)Preferred examples of prepolymers (Al) for preparing prepolymers (A) are polyesters, polyethers and polyurethanes. Particularly preferred examples of prepolymers (Al) are divalent polyethers of the general formula (4)
HO-(R4O)1n-H (4),HO- (R 4 O) 1n -H (4),
wobeiin which
R^ gleich oder verschieden sein kann und gegebenenfalls substituierte Kohlenwasserstoffreste, bevorzugt Methylen-, Ethylen- und 1, 2-Propylenreste, bedeutet und πt gleich einer ganzen Zahl von 1 bis 600, bevorzugt 50 bisR ^ may be identical or different and optionally substituted hydrocarbon radicals, preferably methylene, ethylene and 1, 2-propylene radicals, and πt is an integer from 1 to 600, preferably 50 to
400, ist.400, is.
Beispiele für Prepolymere (Al) der allgemeinen Formel (4) sind kauflich erhältlich unter der Bezeichnung „Acclaim 12200", „Acclaim 18000" (beide Bayer AG, Deutschland) , „Alcupol 12041LM" von Repsol, Spanien und „Poly L 220-10" von Arch Chemicals, USA) ,Examples of prepolymers (Al) of the general formula (4) are commercially available under the name "Acclaim 12200", "Acclaim 18000" (both Bayer AG, Germany), "Alcupol 12041LM" from Repsol, Spain and "Poly L 220-10 from Arch Chemicals, USA),
In den erfindungsgemaßen Polymerabmischungen (M) betragt der Anteil an alkoxysilanterminierten Polymeren (A) vorzugsweise 10-70 Gew.-%, besonders bevorzugt 15-50 Gew.-%, insbesondere 20-40 Gew.-%.In the polymer blends (M) according to the invention, the proportion of alkoxysilane-terminated polymers (A) is preferably 10-70% by weight, more preferably 15-50% by weight, in particular 20-40% by weight.
Die erfinderischen Abmischungen (M) enthalten neben denThe innovative blends (M) contain besides the
Prepolymeren (A) vorzugsweise ein oder mehrere sekundäre oder tertiäre Amine (B) als Hartungskatalysator (K) . Beispiele sind Ammoalkoxysilane mit sekundärer oder tertiärer Ammofunktion wie 3- (N-Cyclohexylamino) -propyltrimethoxysilan, 3- (N-Cyclo™ hexylamino) -propyltriethoxysilan, 3- (N-Phenylamino-) -propyl- tπmethoxysilan, 3- (N-Phenylammo) -propyltnethoxysilan, Tπethylamm, Tributylamm, 1 , 4-Diazabicyclo [2, 2, 2 } octan, N, N- Bis- (3tf,N-dimethyl-2-ammoethyl) -methylamin, N,N~Dimethylcyclo- hexylamin, N,N-Di-methylphenylamm, N-Ethyl-morpholmin .Prepolymer (A) preferably one or more secondary or tertiary amines (B) as a curing catalyst (K). Examples are secondary or tertiary ammoalkoxysilanes such as 3- (N-cyclohexylamino) -propyltrimethoxysilane, 3- (N-cyclo ™ hexylamino) -propyltriethoxysilane, 3- (N-phenylamino) -propyl- trimethoxysilane, 3- (N-phenylammo) -propyltnethoxysilane, trimethylammonium, tributylamm, 1, 4-diazabicyclo [2,2,2] octane, N, N-bis (3tf, N-dimethyl-2-ammoethyl) -methylamine, N, N ~ dimethylcyclohexylamine, N, N-dimethylphenylamm, N-ethylmorpholmin.
Besonders bevorzugt enthalten die erfinderischen Abmischungen (M) neben den Prepolymeren (A) ein oder mehrere sekundäre oder tertiäre Ammoalkyl-alkoxysilane (KS) als Hartungskatalysator (K) .Particularly preferably, the inventive mixtures (M) in addition to the prepolymers (A) one or more secondary or tertiary Ammoalkyl alkoxysilanes (KS) as a curing catalyst (K).
Bevorzugte Ammoalkyl-alkoxysilane (KS) sind solche der allgemeinen Formel (5)Preferred ammoalkylalkoxysilanes (KS) are those of the general formula (5)
(R5R6N- (CR72) -Si (R2) 3-J1(OR1) x (5) ,(R 5 R 6 N- (CR 7 2) -Si (R 2 ) 3- J 1 (OR 1 ) x (5)
in derin the
R^, R' Wasserstoff oder einen Alkyl-, Cycloalkyl-, Alkenyl- oder Arylrest mit 1-10 Kohlenstoffatomen, der gegebenenfalls mit Halogenatomen und/oder organischen Funktionen substituiert sein kann,R 1, R 'is hydrogen or an alkyl, cycloalkyl, alkenyl or aryl radical having 1-10 carbon atoms which may optionally be substituted by halogen atoms and / or organic functions,
R*> einen Alkyl-, Cycloalkyl-, Alkenyl- oder Arylrest mit 1-10 Kohlenstoffatomen, der gegebenenfalls mit Halogenatomen und/oder organischen Funktionen substituiert sein kannr ein zweibmdiger Alkyl-, Cycloalkyl-, Alkenyl- oder Arylrest mit 1-10 Kohlenstoffatomen, der gegebenenfalls mit Halogenatomen substituiert sein kann, bedeuten und alle übrigen Variablen die oben angegebenen Bedeutungen aufweisen .R *> is an alkyl, cycloalkyl, alkenyl or aryl radical having 1-10 carbon atoms, which may optionally be substituted by halogen atoms and / or organic functions r is a bivalent alkyl, cycloalkyl, alkenyl or aryl radical having 1-10 carbon atoms , which may optionally be substituted by halogen atoms, and all other variables have the meanings given above.
wobei das Ammoalkyl-alkoxysilan (KS) über keine primäre Ammofunktion verfugt. R~> steht vorzugsweise für ein Wasserstoffatom oder eine Alkyl-, Cycloalkyl- oder Arylgruppe mit 1-10 Kohlenstoffatomen, besonders bevorzugt für ein Wasserstoffatom oder einewherein the Ammoalkyl-alkoxysilane (KS) has no primary Ammofunktion. R ~> is preferably a hydrogen atom or an alkyl, cycloalkyl or aryl group having 1-10 carbon atoms, more preferably a hydrogen atom or a
Alkylgruppe mit 1-8 Kohlenstoffatomen. R*> stellt bevorzugt einen Alkyl™, Cycloalkyl- oder Arylrest mit 1-10Alkyl group with 1-8 carbon atoms. R *> preferably represents an alkyl, cycloalkyl or aryl radical having 1-10
Kohlenstoffatomen dar, wobei Phenylreste, Cyclohexylreste oder Alkylreste mit 1-8 Kohlenstoffatomen besonders bevorzugt sind. κ7 steht vorzugsweise für Wasserstoff.Carbon atoms, with phenyl radicals, cyclohexyl radicals or alkyl radicals having 1-8 carbon atoms are particularly preferred. κ7 is preferably hydrogen.
Besonders bevorzugt sind Λminoalkyl-alkoxysilane (KS) der allgemeinen Formel (5), bei denenParticular preference is given to ominoalkyl-alkoxysilanes (KS) of the general formula (5) in which
R3 Methyl ,R 3 is methyl,
R^, R6 Wasserstoff, R*> Cyclohexyl oder Phenyl bedeuten.R ^, R6 is hydrogen, R *> cyclohexyl or phenyl.
In den erfindungsgemaßen Polymerabmischungen (M) betragt der Anteil an Aminoalkyl-alkoxysilan (KS) vorzugsweise 0,1-10 Gew.™ %, besonders bevorzugt 0,1-5 Gew.-%, insbesondere 0,2-3 Gew.-% bezogen auf das Gesamtgewicht der Abmischung.In the novel polymer blends (M), the proportion of aminoalkylalkoxysilane (KS) is preferably 0.1-10% by weight, more preferably 0.1-5% by weight, in particular 0.2-3% by weight. based on the total weight of the mixture.
Die erfindungsgemaßen Polymerabmischungen (M) können weitere Kondensationskatalysatoren (K) enthalten, beispielsweise Titanatester, wie Tetrabutyltitanat, Tetrapropyltitanat, Tetraisopropyltitanat, Tetraacetylacetonat-titanat oder auch saure Katalysatoren, wie Phosphorsaure- bzw. Phosphorsaureester, Toluolsulfonsauren, Mineralsauren. Die verschiedenen Katalysatoren können sowohl in reiner Form als auch als Mischungen verwendet werden.The novel polymer blends (M) may comprise further condensation catalysts (K), for example titanate esters, such as tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetraacetylacetonate titanate or even acid catalysts, such as phosphoric acid or phosphoric acid esters, toluenesulfonic acids, mineral acids. The various catalysts can be used both in pure form and as mixtures.
Diese weiteren Kondensationskatalysatoren werden bevorzugt in Konzentrationen von 0,01-10 Gew.-%, besonders bevorzugt 0,1-2 Gew.-%, bezogen auf das Gesamtgewicht der Abmischung, den Polymerabmischungen (M) zugesetzt.These further condensation catalysts are preferably used in concentrations of 0.01-10% by weight, more preferably 0.1-2 % By weight, based on the total weight of the blend, of the polymer blends (M).
Daneben können die erfindungsgemäßen Abmischungen (M) auch noch Zinnverbindungen, wie Dibutylzinndilaurat, Dibutylzinnmaleat, Dibutylzinndiacetat, Dibutylzinndioctanoat, Dibutylzinn- acetylacetonat, Dibutytzinnoxid oder entsprechende Verbindungen des Dioctylzinn innerhalb der oben angegebenen Konzentrationsgrenzen als Härtungskatalysatoren (K) enthalten. Vorzugsweise sind die erfindungsgemäßen Abmischungen (M) jedoch zinnfrei.In addition, the blends (M) according to the invention may also contain tin compounds, such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin acetylacetonate, dibutyltin oxide or corresponding dioctyltin compounds within the above-indicated concentration limits as curing catalysts (K). However, the blends (M) according to the invention are preferably tin-free.
Des Weiteren können die erfindungsgemäßen Abmischungen (M) auch noch primäre Amine, insbesondere primäre Λminosilane wie 3- Aminopropyltrimethoxysilan oder 3-Aminopropyltriethoxysilan innerhalb der oben angegebenen Konzentrationsgrenzen als Härtungskatalysatoren (K) enthalten. Vorzugsweise sind die erfindungsgemäßen Abmischungen (M) jedoch frei von primären Aminen .Furthermore, the blends (M) according to the invention may also contain primary amines, in particular primary osilminosilanes such as 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane, within the above-indicated concentration limits as curing catalysts (K). Preferably, however, the blends (M) according to the invention are free of primary amines.
Die erfindungsgemäßen Polymerabmischungen enthalten ferner vorzugsweise Füllstoffe (F) , beispielsweise Kalciumcarbonate in Form von natürlichen gemahlenen Kreiden, gemahlenen und beschichteten Kreiden, gefällten Kreiden, gefällten und beschichteten Kreiden, Tonmineralien, Bentonite, Kaoline, Talkum, Titandioxide,- Aluminiumoxide, Aluminiumtrihydrat,The polymer blends according to the invention preferably further comprise fillers (F), for example calcium carbonates in the form of natural ground chalks, ground and coated crayons, precipitated crayons, precipitated and coated crayons, clay minerals, bentonites, kaolins, talc, titanium dioxides, aluminum oxides, aluminum trihydrate,
Magnesiumoxid, Magnesiumhydroxid, Ruße, gefällte oder pyrogene, hydrophile oder hydrophobe Kieselsäuren.Magnesium oxide, magnesium hydroxide, carbon blacks, precipitated or pyrogenic, hydrophilic or hydrophobic silicas.
Bevorzugt werden Kalciumcarbonate und gefällte oder pyrogene, hydrophile oder hydrophobe Kieselsäuren, besonders bevorzugt pyrogene, hydrophile oder hydrophobe Kieselsäuren, insbesondere pyrogene, hydrophile Kieselsäuren verwendet. Die Füllstoffe (F) werden bevorzugt in Konzentrationen von 10- 70 Gew.-%, besonders bevorzugt 30-60 Gew.~%, bezogen auf das Gesamtgewicht der Abmischung, den Polymerabmischungen (M) zugesetzt.Preference is given to using calcium carbonates and precipitated or pyrogenic, hydrophilic or hydrophobic silicic acids, more preferably pyrogenic, hydrophilic or hydrophobic silicic acids, in particular pyrogenic, hydrophilic silicic acids. The fillers (F) are preferably added to the polymer blends (M) in concentrations of 10-70% by weight, more preferably 30-60% by weight, based on the total weight of the blend.
Die erfindungsgemaßen Polymerabmischungen (M) können neben den gegebenenfalls als Katalysator (K) eingesetzten Silanen (inklusive den Silanen (KS) entsprechend der Formel (5) ) auch noch weitere Silane (S) mit oder ohne zusatzlicher Organofunktion enthalten. Diese dienen vorzugsweise als Wasserfanger und/oder Silanvernetzer, beispielsweise Alkylsilane wie Methyltrimethoxysilan, Vinylsilane wie Vinyltrimethoxy-, Vinyltriethoxy-, Vxnylmethyldimethoxysilan oder organofunktionelle Silane wie O-Methylcarbamatomethyl- methyldiraethoxysilan, O-Methylcarbamatomethyl-trimethoxysilan, 0™Ethylcarbarnatomethyl~-methyldiethoxysilan, O-Ethylcarbamato- methyl-triethoxysilan, Glycidoxypropyltrimethoxysilan etc.. Auch samtliche als Katalysatoren (K) genannten Silane können als Wasserfanger und/oder Vernetzer dienen.The novel polymer blends (M) may contain, in addition to the optionally used as catalyst (K) silanes (including the silanes (KS) according to the formula (5)) also further silanes (S) with or without additional organofunction. These are preferably water scavengers and / or silane crosslinkers, for example alkylsilanes such as methyltrimethoxysilane, vinylsilanes such as vinyltrimethoxy, vinyltriethoxy, Vxnylmethyldimethoxysilan or organofunctional silanes such as O-Methylcarbamatomethyl methyldiraethoxysilane, O-Methylcarbamatomethyl-trimethoxysilane, 0 ™ Ethylcarbarnatomethyl ~ methyldiethoxysilane, O-ethylcarbamato Methyl-triethoxysilane, glycidoxypropyltrimethoxysilane, etc. All the silanes mentioned as catalysts (K) can also serve as water scavengers and / or crosslinkers.
Die Wasserfanger und/oder Silanvernetzer dienenden Silane (S) werden bevorzugt in Konzentrationen von 0,1 - 10 Gew.-%, besonders bevorzugt 0.5-2 Gew.-%, bezogen auf das Gesamtgewicht der Abmischung, den Polymerabmischungen (M) zugesetzt.The water scavengers and / or Silanvernetzer serving silanes (S) are preferably in concentrations of 0.1 to 10 wt .-%, particularly preferably 0.5 to 2 wt .-%, based on the total weight of the mixture, the Polymerabmischungen (M) added.
Samtliche Silane (S) wie auch die als Katalysator (K) eingesetzten Silane (inklusive den Silanen (KS) entsprechend der Formel (5)) können gleichzeitig auch als Haftvermittler (H) dienen. Daneben können die erfindungsgemaßen Abmischungen (M) selbstverständlich auch weitere Haftvermittler (H) enthalten.All silanes (S) as well as the silanes used as catalyst (K) (including the silanes (KS) according to the formula (5)) can simultaneously serve as adhesion promoters (H). In addition, the blends (M) according to the invention may of course also contain further adhesion promoters (H).
Die erfindungsgemaßen Polymerabmischungen können Weichmacher (W) enthalten, beispielsweise Phthalatester, wie Dioctylphthalat, Dusooctylphthalat, Diundecylphthalat, Adipmsaureester, wie Dioctyladipat, Benzoesaureester, Glycolester, Phosphorsaureester, Sulfonsaureester, Polyester, Polyether, Polystyrole, Polybutadiene, Polyisobutene, paraffinische Kohlenwasserstoffe, höhere, verzweigte Kohlenwasserstoffe etc.The novel polymer blends may contain plasticizers (W), for example phthalate esters, such as Dioctyl phthalate, Dusooctylphthalat, Diundecylphthalat, Adipmsaureester, such as Dioctyladipat, benzoic acid esters, glycol esters, phosphoric acid esters, sulfonic acid esters, polyesters, polyethers, polystyrenes, polybutadienes, polyisobutenes, paraffinic hydrocarbons, higher, branched hydrocarbons, etc.
Die Weichmacher (W) werden bevorzugt in Konzentrationen von bis zu 40 Gew.-%, bezogen auf das Gesamtgewicht der Abmischung, den Polymerabmischungen (M) zugesetzt.The plasticizers (W) are preferably added to the polymer blends (M) in concentrations of up to 40% by weight, based on the total weight of the blend.
Die erfmdungsgemaßen Polymerabmischungen (M) können ferner Thixotropiermittel enthalten, beispielsweise hydrophile pyrogene Kieselsauren, beschichtete pyrogene Kieselsauren, gefällte Kieselsauren, Polyamidwache, hydrierte Ricmusole, Stearatsalze oder gefällte Kreiden. Auch die oben genannten Füllstoffe können zur Einstellung der Fließeigenschaften benutzt werden.The polymer mixtures (M) according to the invention may also contain thixotropic agents, for example hydrophilic pyrogenic silicic acids, coated fumed silicas, precipitated silicas, polyamide monoxide, hydrogenated ricinols, stearate salts or precipitated chalks. Also, the above fillers can be used to adjust the flow properties.
Die Thixotropiermittel werden bevorzugt in Konzentrationen von 1-5 Gew.-%, bezogen auf das Gesamtgewicht der Abmischung, den Polymerabmischungen (M) zugesetzt.The thixotropic agents are preferably added in concentrations of 1-5 wt .-%, based on the total weight of the blend, the polymer blends (M).
Die erfmdungsgemaßen Polymerabmischungen können weiterhin Lichtschutzmittelr wie sogenannte HALS-Stabilisatoren,The inventive polymer blends can furthermore light stabilizers r such as so-called HALS stabilizers,
Fungizide, Flammschutzmittel, Pigmente etc. enthalten, wie sie für den Einsatz m herkömmlichen alkoxyvernetzenden emkomponentigen Massen bekannt sind.Fungicides, flame retardants, pigments, etc., as they are known for use m conventional alkoxy-crosslinking emkomponentigen compositions.
Zur Erzeugung der jeweils gewünschten Eigenschaftsprofile sowohl der unvernetzten Polymerabmischungen als auch der ausgeharteten Massen werden vorstehende Zusätze bevorzugt eingesetzt . Vorzugsweise wird bei der Herstellung der erfindungsgemassen Polymerabmischungen (M) zuerst eine Mischung aus Polymer (A) und Füllstoff hergestellt, anschließend werden Aminoalkyl- alkoxysilan (BS) zugemischt.To produce the respective desired property profiles of both the uncrosslinked polymer blends and the cured masses, the above additives are preferably used. Preferably, in the preparation of the polymer blends (M) according to the invention, a mixture of polymer (A) and filler is first prepared, and then aminoalkylalkoxysilane (BS) is added.
Formkorper (F), wie z.B. Klebefugen, die durch Aushärtung der erfindungsgemaßen Abmischungen (M) herstellbar sind, sind ebenfalls Gegenstand der Erfindung. Die Formkorper (F) weisen vorzugsweise nach einer 24-stundigen Dehnung um 30% eineShaped bodies (F), e.g. Adhesive joints which can be produced by curing the mixtures (M) according to the invention are likewise provided by the invention. The moldings (F) preferably have a 30% elongation after a 24-hour stretch
Ruckstellung nach DIN 53504 von mehr als 60%, bevorzugt von mehr als 65% und besonders bevorzugt von mehr als 70% auf.Restocking according to DIN 53504 of more than 60%, preferably more than 65% and particularly preferably more than 70%.
Für die erfindungsgemaßen Polymerabmischungen existieren zahllose verschiedene Anwendungen im Bereich der Kleb-, Dicht- und Fugendichtstoffe, Oberflachenbeschichtungen sowie auch bei der Herstellung von Abformmassen und Formteilen.There are countless different applications in the field of adhesives, sealants and joint sealants, surface coatings as well as in the production of impression compounds and moldings for the novel polymer blends.
Dabei sind die erfindungsgemaßen Polymerabmischungen für zahllose unterschiedliche Untergrunde wie z.B. mineralische Untergründe, Metalle, Kunststoffe, Glas, Keramik, lackierte Oberflachen etc. geeignet.The novel polymer blends are available for countless different backgrounds such as e.g. mineral substrates, metals, plastics, glass, ceramics, painted surfaces, etc. suitable.
Alle vorstehenden Symbole der vorstehenden Formeln weisen ihre Bedeutungen jeweils unabhängig voneinander auf. In allen Formeln ist das Siliciumatom vierwertig.All the above symbols of the above formulas each have their meanings independently of each other. In all formulas, the silicon atom is tetravalent.
In den folgenden Beispielen sind soweit nicht anders angegeben, alle Mengen- und Prozentangaben auf das Gewicht bezogen. BeispieleIn the following examples, unless otherwise stated, all amounts and percentages are by weight. Examples
Beispiele 1Examples 1
Formulierungen mit einem silanterminierten Polyether mit Methylen-Trimethoxysilylendgruppen (alpha-Trimethoxy)Formulations with a silane-terminated polyether with methylene-trimethoxysilyl end groups (alpha-trimethoxy)
35 g eines silanterminierten Polyethers , erhaltlich nach EP 1,534,940 B aus Acclaim Polyol 12200S (Bayer Material Science AG) und Isocyanatomethyltrimethoxysilan werden in einem Speedmixer der Fa. Hauschild (D-59065 Hamm), bei ca. 25 0C mit 25 g PPG 2000 {Fa. Dow Chemical) und 3 g Methylcarbamatotrimethoxysilan, erhaltlich unter der Bezeichnung GENIOSIL® XL63 (Wacker Chemie AG) , 2 Minuten bei 200 U/min vermischt. Danach werden 1,50 g einer hydrophilen, pyrogenen Kieselsaure HDK® N20 (170 - 230 m2/g) (Wacker Chemie AG) eingerührt bis sie homogen verteilt ist. Anschließend werden 60,4 g Kreide Carbital HOS (Fa. Imerys) eingebracht und der Füllstoff unter Ruhren eine Minute bei 600 U/min aufgeschlossen. Nach Einarbeitung der Kreide werden 0,1 g Cyclohexylaminomethyl-triethoxysilan {GENIOSIL® XL926 - Wacker Chemie AG) 1 Minute bei 200 U/min verteilt. 2 Minuten bei 600 U/min und 1 Minute bei 200 U/min im Teilvakuum (ca. 100 mbar) homogenisiert und blasenfrei gerührt. Die Formulierung wird in 310 ml PE-Kartuschen abgefüllt und einen Tag bei 25 0C gelagert.35 g of a silane-terminated polyether obtainable according to EP 1,534,940 B from Acclaim Polyol 12200S (Bayer Material Science AG) and isocyanatomethyltrimethoxysilane be in a Speedmixer Fa. Hauschild (D-59065 Hamm) at about 25 0 C with 25 g PPG 2000 { Fa. Dow Chemical) and 3 g of methylcarbamatotrimethoxysilane, available under the name GENIOSIL® XL63 (Wacker Chemie AG), mixed for 2 minutes at 200 rpm. Thereafter, 1.50 g of a hydrophilic, fumed silica HDK® N20 (170-230 m 2 / g) (Wacker Chemie AG) is stirred until it is homogeneously distributed. Subsequently, 60.4 g of chalk Carbital HOS (Imerys) are introduced and the filler digested with stirring for one minute at 600 U / min. After incorporation of the chalk, 0.1 g of cyclohexylaminomethyltriethoxysilane {GENIOSIL® XL926 - Wacker Chemie AG) is distributed for 1 minute at 200 rpm. Homogenized for 2 minutes at 600 rpm and 1 minute at 200 rpm in a partial vacuum (about 100 mbar) and stirred bubble-free. The formulation is filled in 310 ml PE cartridges and stored for one day at 25 0 C.
Das Vergleichsbeispiel Ib wird analog hergestellt, allerdings wird Aminopropyltrimethoxysilan (GENIOSIL® GF96 - Wacker Chemie AG) statt des Cyclohexylaminomethyl-triethoxysilans eingesetzt. Comparative Example Ib is prepared analogously, but aminopropyltrimethoxysilane (GENIOSIL® GF96 - Wacker Chemie AG) is used instead of cyclohexylaminomethyltriethoxysilane.
Beispiele 2Examples 2
Formulierungen mit einem silanterminierten Polyether mit Methylen-Triethoxysilylendgruppen (alpha-Triethoxy)Formulations with a silane-terminated polyether with methylene-triethoxysilyl end groups (alpha-triethoxy)
35 g eines silanterminierten Polyethers , erhältlich nach EP 1,534,940 B aus Acclaim Polyol 18200S (Bayer Material Science AG) und Isocyanatomethyltriethoxysilan werden in einem Speedmixer der Fa. Hauschild (D-59065 Hamm), bei ca. 25 °C mit 25 g PPG 2000 (Fa. Dow Chemical) und 3 g Methylcarbamatotrimethoxysilan, erhältlich unter der Bezeichnung GENIOSIL® XL63 (Wacker Chemie AG) , 2 Minuten bei 200 U/min vermischt. Danach werden 1,50 g einer hydrophilen,. pyrogenen Kieselsäure HDK® N20 (170 - 230 m2/g) (Wacker Chemie AG) eingerührt bis sie homogen verteilt ist. Anschließend werden 60,4 g Kreide Carbital HOS (Fa. Imerys) eingebracht und der Füllstoff unter Rühren eine Minute bei 600 U/min aufgeschlossen. Nach Einarbeitung der Kreide werden 0,1 g Cyclohexylaminomethyl-triethoxysilan (GENIOSIL® XL926 - Wacker Chemie AG) 1 Minute bei 200 U/min verteilt. 2 Minuten bei 600 U/min und 1 Minute bei 200 U/min im Teilvakuum (ca. 100 mbar) homogenisiert und blasenfrei gerührt.35 g of a silane-terminated polyether obtainable from EP 1.534.940 B from Acclaim Polyol 18200S (Bayer Material Science AG) and isocyanatomethyltriethoxysilane are mixed in a Speedmixer from Hauschild (D-59065 Hamm) at 25 ° C. with 25 g of PPG 2000 ( Dow Chemical) and 3 g of methylcarbamatotrimethoxysilane, available under the name GENIOSIL® XL63 (Wacker Chemie AG), mixed for 2 minutes at 200 rpm. Thereafter, 1.50 g of a hydrophilic. Fumed silica HDK® N20 (170-230 m 2 / g) (Wacker Chemie AG) is stirred until it is homogeneously distributed. Subsequently 60.4 g of chalk Carbital HOS (Imerys) are introduced and the filler digested with stirring for one minute at 600 U / min. After incorporation of the chalk, 0.1 g of cyclohexylaminomethyltriethoxysilane (GENIOSIL® XL926 - Wacker Chemie AG) is distributed for 1 minute at 200 rpm. Homogenized for 2 minutes at 600 rpm and 1 minute at 200 rpm in a partial vacuum (about 100 mbar) and stirred bubble-free.
Die Formulierung wird in 310 ml PE-Kartuschen abgefüllt und einen Tag bei 25 0C gelagert.The formulation is filled in 310 ml PE cartridges and stored for one day at 25 0 C.
Das Beispiel 2b wird analog hergestellt, allerdings wird die hydrophile, pyrogene Kieselsäure HDK® H15 (170 - 230 m2/g, Wacker Chemie AG) anstelle der HDK® N20 eingesetzt.Example 2b is prepared analogously, but the hydrophilic, fumed silica HDK® H15 (170-230 m 2 / g, Wacker Chemie AG) is used instead of the HDK® N20.
Beispiele 3 Examples 3
Formulierungen mit einem silantenαinierten Polyether mit Methylen-Dimethoxysilylendgruppen (alpha-Dimethoxy) 35 g eines silantermlnierten Polyethers, erhältlich nach EP 1,534,940 B aus Acclaim Polyol 12200S {Bayer Material Science) und Isocyanatomethyldimethoxysilan werden in einem Speedmixer der Fa. Hauschild (D-59065 Hamm), bei ca. 25 0C mit 25 g PPG 2000 (Fa. Dow Chemical) und 3 g Methylcarbamatotrimethoxysilan, erhältlich unter der Bezeichnung GENIOSIL® XL63 (Wacker Chemie AG), 2 Minuten bei 200 U/min vermischt. Danach werden 1,50 g einer hydrophilen, pyrogenen Kieselsäure HDK® N20 (170 - 230 m2/g) (Wacker Chemie AG) eingerührt bis sie homogen verteilt ist. Anschließend werden 60,4 g Kreide Carbital HOS (Fa. Imerys) eingebracht und der Füllstoff unter Rühren eine Minute bei 600 U/min aufgeschlossen. Nach Einarbeitung der Kreide werden 0,1 g Cyclohexylaminomethyl-triethoxysilan (GENIOSIL® XL926 - Wacker Chemie AG) 1 Minute bei 200 U/min verteilt. 2 Minuten bei 600 U/min und 1 Minute bei 200 U/min im Teilvakuum (ca. 100 mbar} homogenisiert und blasenfrei gerührt.Formulations with a silantenαinierten polyether with methylene-Dimethoxysilylendgruppen (alpha-dimethoxy) 35 g of a silantermlnierten polyether, available after EP 1.534.940 B from Acclaim Polyol 12200S {Bayer Material Science) and isocyanatomethyldimethoxysilane in a Speedmixer Fa. Hauschild (D-59065 Hamm) at 25 ° C. with 25 g of PPG 2000 (from Dow Chemical) and 3 g of methylcarbamatotrimethoxysilane, available under the name GENIOSIL® XL63 (Wacker Chemie AG), for 2 minutes at 200 rpm. Thereafter, 1.50 g of a hydrophilic, fumed silica HDK® N20 (170-230 m 2 / g) (Wacker Chemie AG) is stirred until it is homogeneously distributed. Subsequently, 60.4 g of chalk Carbital HOS (Imerys) are introduced and the filler digested with stirring for one minute at 600 U / min. After incorporation of the chalk, 0.1 g of cyclohexylaminomethyltriethoxysilane (GENIOSIL® XL926 - Wacker Chemie AG) is distributed for 1 minute at 200 rpm. Homogenized for 2 minutes at 600 U / min and 1 minute at 200 U / min in a partial vacuum (about 100 mbar) and stirred bubble-free.
Die Formulierung wird in 310 ml PE-Kartuschen abgefüllt und einen Tag bei 25 0C gelagert.The formulation is filled in 310 ml PE cartridges and stored for one day at 25 0 C.
Das Vergleichsbeispiel 3b wird analog hergestellt, allerdings wird Aminopropyltrimethoxysilan (GENIOSIL© GF96 - Wacker Chemie AG) statt des Cyclohexylaminomethyl-triethoxysilans eingesetzt. Comparative Example 3b is prepared analogously, but aminopropyltrimethoxysilane (GENIOSIL © GF96 - Wacker Chemie AG) is used instead of cyclohexylaminomethyl-triethoxysilane.
Bestimmung der mechanischen EigenschaftenDetermination of mechanical properties
Die Proben wurden auf ausgefrasten Teflonplatten mit 2 mm Tiefe ausgestrichen und 2 Wochen bei 23 0C, 50 % rel. Luftfeuchte gehartet . Die mechanischen Eigenschaften wurden nach DIN 53504The samples were spread on gilled Teflon plates with 2 mm depth and 2 weeks at 23 0 C, 50% rel. Humidity healed. The mechanical properties were according to DIN 53504
(Zugprüfung) und DIN 53505 (Harte Shore A) bestimmt. Die(Tensile test) and DIN 53505 (Hard Shore A) determined. The
Messung der Ruckstellung erfolgte nach 2 und 4 wochigerMeasurement of the recovery took place after 2 weeks and 4 weeks
Vorlagerung der S2~Prufkorper (DIN 53504) bei 230C, 50 rel.Pre-storage of S2 ~ Prufkorper (DIN 53504) at 23 0 C, 50 rel.
Luftfeuchte. Die Prüfkörper wurden 24h um 30 % gedehnt. Die Bestimmung der Ruckstellung erfolgte nach 1 h Relaxation beiHumidity. The specimens were stretched by 30% for 24 hours. The determination of the recovery took place after 1 h relaxation
230C, 50 % rel. Luftfeuchte . 23 ° C, 50% rel. Humidity.

Claims

Patentansprüche claims
1. Abmischung (M) enthaltend A) 100 Teile eines alkoxysilylmethylterminierten Polymers (A) mit mindestens einer Endgruppe der allgemeinen Formel (1)1. Blend (M) comprising A) 100 parts of an alkoxysilylmethyl-terminated polymer (A) having at least one end group of the general formula (1)
-L- (CH2) ~SiR2 3_x(ORl)x (1),-L- (CH 2 ) SiSiR 2 3 _ x (ORI) x (1),
wobeiin which
L eine zweibindige Bindegruppe ausgewählt aus -0-, -S-,L is a divalent linking group selected from -O-, -S-,
-(R3)N-, -0-CO-N(R3)-, -N(R3) -CO-O-, -N (R3) -CO-NH-,- (R 3 ) N, -O-CO-N (R 3 ) -, -N (R 3 ) -CO-O-, -N (R 3 ) -CO-NH-,
-NH-CO-N(R3)-, -N(R3) -CO-N(R3)-NH-CO-N (R 3) -, -N (R 3) -CO-N (R 3)
R! und R.2 unabhängig voneinander für Kohlenwasserstoffreste mit 1-6 Kohlenstoffatomen oder ω-Oxaalkyl-alkylreste mit insgesamt 2-20 Kohlenstoffatomen, R3 Wasserstoff, einen gegebenenfalls halogensubstuierten cyclischen, linearen oder verzweigten Cj_ bis C]_g-Alkyl- oder Alkenylrest oder einen Cg- bis C]_ß-Arylrest stehen und x 2 oder 3 bedeutet,R! and R 2 independently of one another are hydrocarbon radicals having 1-6 carbon atoms or ω-oxaalkyl-alkyl radicals having a total of 2-20 carbon atoms, R 3 is hydrogen, an optionally halogen-substituted cyclic, linear or branched C 1 - to C] -alkyl or alkenyl radical or a Cg - to C] _ß-aryl radical and x is 2 or 3,
B) 0,01 bis 10 Teile eines Hartungskatalysator (K) der die Aushärtung der Abmischung (M) in Gegenwart von Luftfeuchtigkeit beschleunigt,B) 0.01 to 10 parts of a curing catalyst (K) which accelerates the curing of the mixture (M) in the presence of atmospheric moisture,
C) 0 bis 1000 Teile eines oder mehrere Füllstoffe (F) ,C) 0 to 1000 parts of one or more fillers (F),
D) 0 bis 50 Teile eines oder mehrerer monomerer Silane (S) als Wasserfanger und Silanvernetzer,D) 0 to 50 parts of one or more monomeric silanes (S) as water catchers and silane crosslinkers,
E) 0 bis 200 Teile exnes oder mehrerer Weichmacher (W) undE) 0 to 200 parts exnes or more plasticizers (W) and
F) 0 bis 50 Teile eines oder mehrerer Haftvermittler (H) undF) 0 to 50 parts of one or more adhesion promoters (H) and
F) gegebenenfalls weitere Zusätze und Additive, dadurch gekennzeichnet,F) optionally further additives and additives, characterized,
dass die Abmischung (M) weniger als 2 Teile einer oder mehrerer Verbindungen mit primärer Aminfunktion und weniger als 0,2 Teile eines oder mehrerer zinnhaltiger Katalysators enthalt.in that the blend (M) contains less than 2 parts of one or more compounds having a primary amine function and less than 0.2 part of one or more tin-containing catalysts.
2. Abmischung (M) nach Anspruch 1, dadurch gekennzeichnet, dass beim trialkox.ysilylmethylterminierten Polymer (A) mit mindestens einer Endgruppe der allgemeinen Formel (1) -L eine -O-CO-N (H) -Gruppe bedeutet.2. blend (M) according to claim 1, characterized in that in the trialkox.ysilylmethylterminierten polymer (A) having at least one end group of the general formula (1) -L is a -O-CO-N (H) group.
3. Abmischung (M) nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass ein oder mehrere sekundäre oder tertiäre Amine (B) als Härtungskatalysator enthalten sind3. blend (M) according to claim 1 or 2, characterized in that one or more secondary or tertiary amines (B) are included as a curing catalyst
4. Abmischung (M) nach Anspruch 3, dadurch gekennzeichnet, dass als die ein oder mehreren sekundären oder tertiären Aminen (B) , ein oder mehrere sekundäre oder tertiäre Aminoalkyl- alkoxysilane (BS) als Hartungskatalysator enthalten sxnd.4. blend (M) according to claim 3, characterized in that as the one or more secondary or tertiary amines (B), sxnd contain one or more secondary or tertiary aminoalkyl alkoxysilanes (BS) as a curing catalyst.
5. Abmischung (M) nach Anspruch 4, dadurch gekennzeichnet, dass das Aminoalkyl-alkoxysilane (BS) sind solche der allgemeinen Formel (4) sind5. blend (M) according to claim 4, characterized in that the aminoalkyl-alkoxysilanes (BS) are those of the general formula (4)
(R4R5N- (CR6 2) -Si (R3) 3-χ (OR1) χ 4) ,(R 4 R 5 N- (CR 6 2 ) -Si (R 3 ) 3-χ (OR 1 ) χ 4),
in derin the
R^ einen Alkyl-, Alkenyl- oder Arylrest mit 1-10 Kohlenstoffatomen,R 1 is an alkyl, alkenyl or aryl radical having 1-10 carbon atoms,
R4, R6 Wasserstoff oder einen Alkyl-, Cycloalkyl-, Alkenyl- oder Arylrest mit 1-10 Kohlenstoffatomen, der gegebenenfalls mit Halogenatomen und/oder organischen Funktionen substituiert sein kann,R 4 , R 6 is hydrogen or an alkyl, cycloalkyl, alkenyl or aryl radical having 1-10 carbon atoms, the optionally substituted with halogen atoms and / or organic functions,
R.5 einen Alkyl-, Cycloalkyl-, Alkenyl- oder Arylrest mit 1-10R.5 is an alkyl, cycloalkyl, alkenyl or aryl radical having 1-10
Kohlenstoffatomen, der gegebenenfalls mit Halogenatomen und/oder organischen Funktionen substituiert sein kann, ein zweibindiger Alkyl-, Cycloalkyl-, Alkenyl- oder Arylrest mit 1-10 Kohlenstoffatoraen, der gegebenenfalls mit Halogenatomen substituiert sein kann, bedeuten und x eine Zahl von 1 bis 3 darstellt,Carbon atoms which may optionally be substituted by halogen atoms and / or organic functions, a bivalent alkyl, cycloalkyl, alkenyl or aryl radical having 1-10 Kohlenstoffatoraen, which may optionally be substituted by halogen atoms, and x is a number from 1 to 3 represents,
wobei das Aminoalkyl-alkoxysilan {BS} über keine primärewherein the aminoalkyl-alkoxysilane {BS} has no primary
Aminofunktion verfügt.Amino function features.
6. Abmischung (M) nach Anspruch 5, dadurch gekennzeichnet, dass beim Aminoalkyl-alkoxysilane (BS) der allgemeinen Formel (4)6. blend (M) according to claim 5, characterized in that in the aminoalkyl-alkoxysilanes (BS) of the general formula (4)
R3 Methyl,R 3 is methyl,
R4 f R6 Wasserstoff,R 4 f R 6 is hydrogen,
R5 Cyclohexyl oder Phenyl und x 2 oder 3 bedeutet.R5 is cyclohexyl or phenyl and x is 2 or 3.
7. Formkorper, dadurch gekennzeichnet, dass er eine Abmischung nach einem oder mehreren der Ansprüche 1 bis 6 enthalt.7. Formkorper, characterized in that it contains a blend according to one or more of claims 1 to 6.
8. Formkorper nach Anspruch 7, dadurch gekennzeichnet, dass sie nach einer 24-stϋndigen Dehnung um 30% eine Rückstellung nach DIN 53504 von mehr als 70% aufweisen. 8. Shaped body according to claim 7, characterized in that they have a provision according to DIN 53504 of more than 70% after a 24-hour elongation of 30%.
EP09771355A 2008-12-11 2009-12-10 Polymer blends comprising alkoxysilane-terminated polymers Withdrawn EP2356180A1 (en)

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