EP0000349B1 - Polyurethane-modified organopolysiloxan compositions, process for preparing same and their application - Google Patents

Polyurethane-modified organopolysiloxan compositions, process for preparing same and their application Download PDF

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Publication number
EP0000349B1
EP0000349B1 EP78100257A EP78100257A EP0000349B1 EP 0000349 B1 EP0000349 B1 EP 0000349B1 EP 78100257 A EP78100257 A EP 78100257A EP 78100257 A EP78100257 A EP 78100257A EP 0000349 B1 EP0000349 B1 EP 0000349B1
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Prior art keywords
polyurethane
modified
mixture
groups
compositions
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German (de)
French (fr)
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EP0000349A1 (en
Inventor
Hans-Heinrich Dr. Moretto
Armand Dr. De Montigny
Helmut Dr. Steinberger
Hans Dr. Sattlegger
Ingrid Larking
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Bayer AG
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Bayer AG
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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
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/458—Block-or graft-polymers containing polysiloxane sequences containing polyurethane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions 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
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
    • C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences

Definitions

  • Organopolysiloxanes modified with inorganic and organic materials are known per se. So with inorganic fillers such as Silicon dioxide aerogels, diatomaceous earth, gastric esium and / or iron oxide mixed organopolysiloxanes or organopolysiloxane mixtures with additional crosslinking agents and processing aids are used in many areas. This includes e.g. the use of so-called one or two-component systems which cure under the action of moisture, the curing by the reaction of OH-functional siloxanes with crosslinking and curing catalysts, e.g. Alkyl silicates or alkyl triacyloxysilanes and water is brought about. Other known crosslinking systems are based on the reaction of Si-H-containing siloxanes with unsaturated compounds in the presence of catalytically active peroxides.
  • inorganic fillers such as Silicon dioxide aerogels, diatomaceous earth, gastric esium and / or iron oxide mixed organopoly
  • Organopolysiloxanes modified with organic materials include e.g. Block copolymers in which organopolysiloxane blocks are chemically linked to organic polymer blocks (e.g. polyethers, polycarbonates, polycarbodiimides, polyurethanes).
  • organic polymer blocks e.g. polyethers, polycarbonates, polycarbodiimides, polyurethanes.
  • Such products are described, for example, in U.S. Patents 3,402,192, U.S. Patent 3,701,815, U.S. Patent 3,189,662, DT-OS 2,445,220 and DT-OS 2,543,966. These products are generally manufactured using multi-stage processes.
  • Modified organopolysiloxane compositions have also become known, which are formed by radical polymerization of unsaturated organic monomers in organopolysiloxanes or by mixing corresponding constituents.
  • masses filled only with organic polymer particles e.g. polyolefin, polystyrene
  • Such compositions and processes for their preparation are described, for example, in the patents US Pat. No. 2,965,593 and US Pat. No. 3,627,836.
  • the polymers which have become known for filling or grafting result from one or more unsaturated monomers which are polymerizable, e.g. Ethylene, vinyl chloride or 1,3 butadiene.
  • organic polymers usually have a low temperature resistance. They transfer this unfavorable property to the resulting hardened organopolysiloxane masses. They also have unfavorable elastomer properties such as high compression set. Furthermore, the mechanical properties deteriorate significantly at elevated temperatures (e.g. tensile strength). The permanent heat resistance, which otherwise distinguishes the organopolysiloxanes, is lost.
  • organopolysiloxane compositions which, for economic and technical reasons, also meet the condition that they can be prepared without great technical outlay and without a long reaction time, and that the compositions prepared are flowable without the use of solvents and are sufficiently stable in storage.
  • the compositions After vulcanization, the compositions should cure without tack and should be distinguished from other organically modified organopolysiloxane compositions by improved mechanical properties at elevated temperature.
  • the present invention relates to ⁇ , ⁇ -dihydroxypolysiloxanes modified with polyurethane, which are characterized in that the ⁇ , ⁇ -dihydroxypolysiloxane and the polyurethane are present as distinguishable phases.
  • the polyurethane is made in a manner known per se by polyaddition of di- or polyisocyanates of the general formula where R 'represents an optionally substituted alkylene or arylene radical, preferably having up to 24 carbon atoms, on polymers containing diols or polyols or hydroxyl groups in a, (0-dihydroxypolysiloxane.
  • the improved organopolysiloxane compositions according to the present invention are thus to be regarded as polyurethane-filled organopolysiloxane mixtures which are composed of the following two phases: (i) a continuous phase of an organopolysiloxane liquid and (ii) a non-continuous phase composed of finely divided particles of a polyurethane Polymer obtained by polyaddition of the corresponding monomer or monomer mixture in the presence of the ⁇ , ⁇ -dihydroxypolysiloxane and a catalyst which accelerates the formation of polyurethane.
  • the mixtures generally contain about 3-95% by weight of polyurethane, based on the total mixture. About 40-80% by weight is preferred, particularly preferably 45-55% by weight.
  • the polyurethane-filled organopolysiloxane compositions of the present invention are prepared by intensely mixing the organopolysiloxane liquid with a di- or polyol or mixtures thereof and then adding a diisocyanate to this mixture.
  • the organopolysiloxane liquids preferred for the use according to the invention are characterized by the following formula:
  • R represents an optionally substituted alkyl, alkenyl, aryl or haloalkyl radical having up to 10 C atoms
  • R represents hydrogen, an optionally substituted alkyl, alkenyl, aryl or haloalkyl radical having up to 10 C atoms
  • X is the hydroxyl radical
  • silicone resins such as are obtainable, for example, by cohydrolysis of methyltrichlorosilane and dimethyldichlorosilane, alone or in a mixture with the organopolysiloxanes mentioned.
  • Suitable starting components according to the invention are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, as are described, for example, by W. Siefgen in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, for example ethylene diisocyanate, 1,4 Tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,3, 5-trimethyl-5-isocyanatomethyl-cyclohexane (DAS 1 202 785), 2,4- and 2,6-hexahydrotoluylene diisocyanate and any mixtures of these isomers, hexahydro-1,3- and / or
  • distillation residues containing isocyanate groups obtained in the technical production of isocyanates optionally dissolved in one or more of the aforementioned polyisocyanates. It is also possible to use any mixtures of the aforementioned polyisocyanates.
  • polyisocyanates e.g. 2,4- and 2,6-tolylene diisocyanate as well as any mixtures of these isomers (“TDI”), polyphenyl-polymethylene polyisocyanates, such as those produced by aniline-formaldehyde condensation and subsequent phosgenation (“crude MDI”) and carbodiimide groups, Polyisocyanates containing urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups (“modified polyisocyanates").
  • TDI polyisocyanates
  • polyphenyl-polymethylene polyisocyanates such as those produced by aniline-formaldehyde condensation and subsequent phosgenation
  • CAMDI aniline-formaldehyde condensation and subsequent phosgenation
  • carbodiimide groups Polyisocyanates containing urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups
  • Examples of these particularly preferred polyisocyanates are 4,4'-diphenylmethane diisocyanate liquefied by partial carbodiimidization, as described, for example, in DT-PS 1 568 501 by heating in the presence of 2.5 mol% of urea at 225 ° C. for 1-2 Hours is available or by reacting 1 mol of 4,4'-diphenylmethane diisocyanate with about 0.1-0.3 mol of di- or polypropylene glycol with a maximum molecular weight of 700 obtainable "liquefied" 4,4'-diphenylmethane diisocyanate.
  • Starting components to be used according to the invention are furthermore optionally connected solutions with at least two isocyanate-reactive hydrogen atoms with a molecular weight of generally from 62 to 10,000.
  • isocyanate-reactive hydrogen atoms with a molecular weight of generally from 62 to 10,000.
  • these are preferably polyhydroxyl compounds, in particular two to eight compounds containing hydroxyl groups, especially those with a molecular weight of 200 to 10,000, preferably 1000 to 6000, for example at least two, usually 2nd to 8, but preferably 2nd to 4, hydroxyl-containing polyesters, polyethers, polythioethers, polyacetals, polycarbonates, polyesteramides, as are known per se for the production of homogeneous and cellular polyurethanes.
  • the higher molecular weight polyhydroxyl compounds mentioned are often advantageously used in the process according to the invention in a mixture with up to 95, preferably up to 50 percent by weight, based on the total amount of polyhydroxyl compounds, of low molecular weight polyols of the molecular weight range 62-200.
  • Such low molecular weight polyols are, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol , Tripropylene glycol, glycerin, trimethylolpropane and the like.
  • the polyesters containing hydroxyl groups are, for example, reaction products of polyhydric, preferably dihydric and optionally additionally trihydric alcohols with polyhydric, preferably dihydric, carboxylic acids.
  • polyhydric preferably dihydric and optionally additionally trihydric alcohols
  • polyhydric preferably dihydric, carboxylic acids.
  • the corresponding polycarboxylic anhydrides or corresponding polycarboxylic esters of lower alcohols or mixtures thereof can also be used to produce the polyesters.
  • the polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and optionally substituted, for example by halogen atoms, and / or unsaturated.
  • Polyhydric alcohols include, for example, ethylene glycol, propylene glycol (1,2) and - (1,3), butylene glycol (1,4) and - (2,3), hexanediol (1,6), octane diol ( 1.8), neopentyl glycol, cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane), 2-methyl-1,3-propanediol, glycerin, trimethylolpropane, hexanetriol- (1,2,6), butanetriol- (1,2,4 ), Trimethylolethane, pentaerythritol, quinite, mannitol and sorbitol, methylglycoside, also diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycols, dibutylene glycol and polybutylene glycol in question.
  • the at least two, generally two to eight, preferably two to three, hydroxyl groups-containing polyethers which are suitable according to the invention are also of the type known per se and are obtained, for example, by polymerizing epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, syrene oxide or Epichlorohydrin with itself, e.g. in the presence of BF 3 , or by the addition of these epoxides, optionally in a mixture or in succession, to starting components with reactive hydrogen atoms such as alcohols or amines, e.g.
  • epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, syrene oxide or Epichlorohydrin
  • Sucrose polyethers such as are described, for example, in German publications 1 176 358 and 1 064 938, are also suitable according to the invention. In many cases, those polyethers are preferred which predominantly (up to 90% by weight, based on all OH groups present in the polyether) have primary OH groups.
  • Polyethers modified by vinyl polymers such as those produced by polymerizing styrene or acrylonitrile in the presence of polyethers (American patents 3,383,351, 3,304,273, 3,523,093, 3,110,695, German patent 1,152,536) are also suitable. also polybutadienes containing OH groups.
  • the condensation products of thiodiglycol with themselves and / or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino alcohols should be mentioned in particular.
  • the products are polythio ether, polythio ether ester, polythio ether ester amide.
  • polyacetals e.g. the compounds which can be prepared from glycols, such as diethylene glycol, triethylene glycol, 4,4'-dioxethoxy-diphenyldimethylmethane, hexanediol and formaldehyde.
  • glycols such as diethylene glycol, triethylene glycol, 4,4'-dioxethoxy-diphenyldimethylmethane, hexanediol and formaldehyde.
  • Polyacetals suitable according to the invention can also be prepared by polymerizing cyclic acetals.
  • Suitable polycarbonates containing hydroxyl groups are those of the type known per se, which e.g. by reacting diols such as propanediol (1,3), butanediol (1,4) and / or hexanediol (1,6), diethylene glycol, triethylene glycol, tetraethylene glycol with diaryl carbonates, e.g. Diphenyl carbonate or phosgene can be produced.
  • diols such as propanediol (1,3), butanediol (1,4) and / or hexanediol (1,6)
  • diethylene glycol triethylene glycol
  • tetraethylene glycol e.g. Diphenyl carbonate or phosgene
  • polyester amides and polyamides include e.g. the predominantly linear condensates obtained from polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyvalent saturated and unsaturated amino alcohols, diamines, polyamines and their mixtures.
  • Polyhydroxyl compounds which already contain urethane or urea groups and optionally modified natural polyols, such as castor oil, carbohydrates, starch, can also be used. Addition products of alkylene oxides on phenol-formaldehyde resins or also on urea-formaldehyde resins can also be used according to the invention.
  • the reactants are used in proportions which correspond to an NCO index of 70-160.
  • the NCO index 100 means the presence of equivalent amounts of isocyanate groups and active hydrogen atoms which react with these isocyanate groups in the reaction mixture).
  • catalysts are often also used.
  • Suitable catalysts to be used are those of the type known per se, e.g. tertiary amines, such as triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N-cocomorpholine, N, N, N ', N'-tetramethyl-ethylenediamine, 1,4-diaza-bicyclo- (2.2 , 2) octane, N-methyl-N'-dimethylaminoethyl-piperazine, N, N-dimethylbenzylamine, bis (N, N-diathylaminoethyl) adipate, N, N-diethylbenzylamine, pentamethyldiethylenetriamine, N, N-dimethylcyclohexylamine, N , N, N ', N'-tetramethyl-1,3-butanediamine, N, N-dimethyl
  • Tertiary amines which have hydrogen atoms active against isocyanate groups are e.g. Triethanolamine, triisopropanolamine, N-methyl-diethanolamine, N-ethyl-diethanolamine, N, N-dimethyl-ethanolamine, and their reaction products with alkylene oxides, such as propylene oxide and / or ethylene oxide.
  • Silaamines with carbon-silicon bonds may also be used as catalysts, e.g. 2,2,4-trimethyl-2-silamorpholine, 1,3-diethylaminomethyl-tetramethyl-disiloxane ..
  • Suitable catalysts are also nitrogen-containing bases such as tetraalkylammonium hydroxides, alkali metal hydroxides such as sodium hydroxide, alkali phenolates such as sodium phenolate or alkali metal alcoholates such as sodium methylate. Hexahydrotriazines can also be used as catalysts.
  • organic metal compounds in particular organic tin compounds, can also be used as catalysts.
  • tin (II) are salts of carboxylic acids such as tin (II) acetate, tin (II) octoate, tin (ll) ethyl hexoate and tin (II) laurate, and the dialkyltin salts of carboxylic acids b on , such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate or dioctyltin diacetate.
  • carboxylic acids such as tin (II) acetate, tin (II) octoate, tin (ll) ethyl hexoate and tin (II) laurate
  • dialkyltin salts of carboxylic acids b on such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate or dioctyltin diacetate
  • the catalysts are generally used in an amount between about 0.001 and 10% by weight, based on the amount of compounds having at least two isocyanate-reactive hydrogen atoms with a molecular weight of 62 to 10,000.
  • surface-active additives emulsifiers and foam stabilizers
  • the emulsifiers are e.g. the sodium salts of castor oil sulfonates or also of fatty acids or salts of fatty acids with amines such as oleic acid diethylamine or stearic acid diethanolamine.
  • Alkali or ammonium salts of sulfonic acids such as dodecylbenzenesulfonic acid or dinaphenylmethane disulfonic acid or also of fatty acids such as ricinoleic acid or of polymeric fatty acids can also be used as surface-active additives.
  • the mixtures according to the invention are stable. They are suitable for the production of molding compositions curable to elastomers.
  • the majority of the solid particles (greater than 80%) of the homo- or copolymer have an average diameter of about 0.3 to 10 microns, with some of the particles being less than 0.3 microns in diameter.
  • the polyurethane-modified polysiloxane liquids according to the invention are advantageously prepared in such a way that an ⁇ , ⁇ -dihydroxypolysiloxane is mixed with a diol, polyol or polyetherol at room temperature or elevated temperature (up to approx. 150 ° C.), the catalyst is added, and the appropriate amount of isocyanate or isocyanate mixture within a predetermined period dosed evenly and continuously.
  • the isocyanate or the isocyanate mixture is preferably added at temperatures from 60 to 120.degree.
  • the rate of isocyanate addition (about 1-8 hours - depending on the batch size) is generally controlled so that the heat of reaction released can be removed and the desired reaction temperature is kept constant.
  • the viscosity of the mixture increases considerably during the manufacturing process.
  • the extent of the viscosity increase depends on the initial viscosity of the siloxane component used, the degree of filling by the polyurethane produced and the degree of distribution of the discontinuous phase
  • the fine particle size of the polyurethane phase distributed in the organosiloxane phase depends on the stirring speed and the type of stirrer used, the reaction temperature and the viscosity of the organosiloxane phase.
  • the polyurethane-modified polysiloxanes obtained are white, mostly non-transparent, flowable and crosslinkable compositions with medium to high viscosity, which can be cured with many of the customary catalysts which are suitable for silanol condensation.
  • Suitable crosslinking agents are substances which are conventionally used for the production of one- or two-component systems. As such, for example, alkoxysilicon compounds, tetraalkoxysilanes, alkyl polysilicates and acyloxysilicon compounds come into question.
  • One- or two-component compositions based on polyurethane-polysiloxane copolymers are prepared by mixing the polyurethane-siloxane composition with the crosslinking component and, if appropriate, the fillers and / or plasticizers in a commercially available mixer or kneader.
  • a commercially available mixer or kneader for example, quartz powder, chalk or diatomaceous earth or pyrogenic Si0 2 or other finely divided metal oxides such as TiO 2 , Fe 2 O 3 can serve as fillers.
  • plasticizers can optionally be added.
  • liquid inert polydiorganosiloxanes e.g. a, w-trimethyl siloxy end-stopped polydimethyl siloxanes.
  • the water required to vulcanize the copolymers can be added to the curable copolymer compositions by atmospheric moisture or by direct mixing.
  • polyurethane-modified organopolysiloxane compositions can be used both in substance per se and as an additional component in other polymer compositions.
  • This example describes the preparation of a dispersion of 50% polyurethane based on tolylene diisocyanate and dipropylene glycol in a molar ratio of 1: 1 and 50% ⁇ . ⁇ ⁇ dihydroxypolydimethylsiloxane.
  • a mixture of 620 g of polydimethylsiloxane with terminal hydroxyl groups and a viscosity of 18000 mPa.s (20 ° C.) and 270 g of dipropylene glycol (isomer mixture) is heated to 80 ° C. and a mixture of 349.5 g of tolylene diisocyanate (isomer mixture from 80% 2,4- and 20% 2,6-tolylene diisocyanate) and 1.8 g triethylamine evenly with stirring.
  • the reaction temperature is maintained between 80 and 90 ° C during the addition period.
  • the mixture is stirred for a further hour and then cooled.
  • a mixture of 1500 g of polydimethylsiloxane from Example 1 and 804 g of dipropylene glycol is heated to 80 ° C. and a mixture of 696 g of tolylene diisocyanate from Example 1 and 3.5 g of triethylamine is added at 80 ° C. in the course of one hour with stirring.
  • the molar ratio of isocyanates of tolylene diisocyanate and hydroxyl groups of dipropylene glycol is 1: 2.
  • the mixture is stirred at 80 ° C. for 1 hour and then cooled.
  • the yellowish-white product obtained has a viscosity of 217,000 mPa.s (20 ° C).
  • a film produced and cured from this composition in accordance with Example 1 has a Shore A hardness of 43.
  • a mixture of 1500 g of polymethylsiloxane from Example 1 and 909.5 g of dipropylene glycol is heated to 80 ° C. and a mixture of 800.6 g of tolylene diisocyanate from Example 1 and 2.9 g of tri thylamine added within one hour at 80 ° C with stirring.
  • the molar ratio of isocyanate groups of tolylene diisocyanate and hydroxyl groups of dipropylene glycol is 1: 2.
  • the mixture is stirred at 80 ° C. for 1 hour and then cooled.
  • the white product obtained has a viscosity of 230,000 mPa.s (20 ° C).
  • a film produced and cured from this composition in accordance with Example 1 has a Shore A hardness of 11.
  • Example 3 If, analogously to Example 3, instead of a polydimethylsiloxane with a viscosity of 18,000 mPa.s (20 ° C.), one with a viscosity of 10,000 mPa.s (20 ° C.) is used, the resulting polyurethane-modified composition has a viscosity of 85,000 mPa .s (20 ° C).
  • a film produced from this in accordance with Example 1 has a Shore A hardness of 13.
  • a mixture of 1200 g of the product from Example 1, 600 g of the product from Example 4 and 600 g of polydimethylsiloxane from Example 1 are mixed at 70 ° C. for 2 hours.
  • the white, flowable mass obtained from it has a viscosity of 300,000 mPa.s.
  • the size of the dispersed particles was found to be about 1 to 2.5 microns.
  • composition of a cold-curing composition and the properties of the cured product are given in Example 10, Table 1 (one-component system) and Table 2 (two-component system).
  • a solution of 402 g of trimethylolpropane and 576 g of polydimethylsiloxane from Example 1 in 1150 g of dry toluene is heated from 80 ° C. and a mixture of 174 g of tolylene diisocyanate from Example 1 and 5 g of triethylemine at 80 to 100 ° C. within 2 hours with stirring admitted. After the solvent has been distilled off, a white mass is obtained which is used further in Example 8.
  • composition of a cold-curing composition and the properties of the cured product are given in Example 9, Table 1 (one-component system) and Table 2 (two-component system).
  • This example provides an overview of the composition of some cold-curing compositions and properties of the hardened products made from them.
  • a solution of 35.7 g of dipropylene glycol, 8.9 g of trimethylolpropane and 76.5 g of polymethylsiloxane from Example 1 in 150 g of dry toluene is heated to 100 ° C. and a mixture of 0.4 g of triethylamine and 31.9 within one hour g of tolylene diisocyanate added. The mixture is stirred for a further hour at 100 ° C. and then the solvent is distilled off. The residue has a viscosity of 72,000 mPa.s (20 ° C.)
  • a hardened film produced therefrom according to Example 1 has a Shore A hardness of 16.
  • a mixture of 57.9 g of tolylene diisocyanate of Example 1 and 0.3 g of triethylamine is added to a mixture of 100 g of polydimethylsiloxane from Example 1.40 g of dipropylene glycol and 2.1 g of glycerol with stirring within 0.5 Hours added. After the addition has ended, the mixture is stirred at 80 ° C. for 2 hours. A slightly yellowish, crosslinkable mass with a viscosity of 220,000 mPa.s (20 ° C.) is obtained.
  • a hardened film produced therefrom according to Example 1 has the Shore A hardness 25.
  • Example 3 The experiment in Example 3 is carried out with the difference that butene (2) diol (1,4) is used instead of dipropylene glycol.
  • a hardened film produced therefrom according to Example 1 has the Shore A hardness 17.
  • Example 3 The experiment in Example 3 is carried out with the difference that butanediol-1,4) is used instead of dipropylene glycol.
  • a hardened film produced therefrom according to Example 1 has the Shore A hardness 13.
  • Example 3 The experiment in Example 3 is carried out with the difference that propanediol- (1,3) is used instead of dipropylene glycol.
  • a white crosslinkable mass is obtained with a viscosity of 182,000 mPa.s.
  • a hardened film produced therefrom according to Example 1 has the Shore A hardness 13.
  • This example illustrates the preparation of a dispersion of 50% polyurethane based on tolylene diisocyanate and a polyester in a molar ratio of 1: 0.9 and 50% of an ⁇ , ⁇ -dihydroxypolydimethylsiloxane.
  • a mixture of 1500 g of polydimethylsiloxane from Example 1.909.5 g of dipropylene glycol and 1.5 g of ethylenediaminomethyldimethylethoxysilane is heated to 80 ° C. and stirred for 1 hour.
  • 800.6 g of tolylene diisocyanate from Example 1 are then added at 80 ° C. in the course of one hour and the mixture is stirred at the same temperature for 2 hours.
  • a white mass with a viscosity of 230,000 mPa.s (2 ⁇ ° C) is obtained.
  • a hardened film produced therefrom according to Example 1 has a Shore A hardness of 16.
  • Example 3 The experiment in Example 3 is carried out with the difference that 0.06 ml of dibutyltin dilaurate is used as the catalyst instead of the triethylamine.
  • a hardened film produced therefrom according to Example 1 has the Shore A hardness 15.

Description

Mit anorganischen und organischen Materialien modifizierte Organopolysiloxane sind an sich bekannt. So werden mit anorganischen Füllstoffen, wie z.B. Siliciumdioxid-Aerogelen, Diatomeenerde, Magenesium und/oder Eisenoxid vermischte Organopolysiloxane oder Organo-polysiloxangemische mit zusätzlichen Vernetzungsmitteln und Verarbeitungshilfsstoffen in vielen Bereichen verwendet. Dazu zählt z.B. die Verwendung von sogenannten Ein- oder Zweikomponentensystemen, die unter Einwirkung von Feuchtigkeit aushärten, wobei die Härtung durch die Reaktion von OH-funktionellen Siloxanen mit Vernetzungs- und Härtungskatalysatoren wie z.B. Alkylsilikaten oder Alkyltriacyloxysilanen sowie Wasser herbeigeführt wird. Weitere bekannte Vernetzungssysteme beruhen auf der Reaktion von Si-H-haltigen Siloxanen mit ungesättigten Verbindungen in Gegenwart katalytisch wirkender Peroxide.Organopolysiloxanes modified with inorganic and organic materials are known per se. So with inorganic fillers such as Silicon dioxide aerogels, diatomaceous earth, gastric esium and / or iron oxide mixed organopolysiloxanes or organopolysiloxane mixtures with additional crosslinking agents and processing aids are used in many areas. This includes e.g. the use of so-called one or two-component systems which cure under the action of moisture, the curing by the reaction of OH-functional siloxanes with crosslinking and curing catalysts, e.g. Alkyl silicates or alkyl triacyloxysilanes and water is brought about. Other known crosslinking systems are based on the reaction of Si-H-containing siloxanes with unsaturated compounds in the presence of catalytically active peroxides.

Die bereits erwähnten anorganischen und organischen Modifizierungsmittel verleihen den damit entstehenden Organopolysiloxan-Massen unterschiedliche Eigenschaften. Zu den mit organischen Materialien, meist Polymeren, modifizierten Organopolysiloxanen gehören z.B. Blockcopolymere, in denen Organopolysiloxanblöcke mit organischen Polymerblöcken (z.B. Polyäthern, Polycarbonaten, Polycarbodiimiden, Polyurethanen) chemisch verknüpft sind. Derartige Produkte sind z.B in den Patentschriften US-PS 3 402 192, US-PS 3 701 815, US-PS 3 189 662, DT-OS 2 445 220 und DT-OS 2 543 966 beschrieben. Diese Produkte werden im allgemeinen über Mehrstufen verfahren hergestellt.The inorganic and organic modifiers already mentioned give the resulting organopolysiloxane compositions different properties. Organopolysiloxanes modified with organic materials, mostly polymers, include e.g. Block copolymers in which organopolysiloxane blocks are chemically linked to organic polymer blocks (e.g. polyethers, polycarbonates, polycarbodiimides, polyurethanes). Such products are described, for example, in U.S. Patents 3,402,192, U.S. Patent 3,701,815, U.S. Patent 3,189,662, DT-OS 2,445,220 and DT-OS 2,543,966. These products are generally manufactured using multi-stage processes.

Es sind ausserdem modifizierte Organopolysiloxanmassen bekannt geworden, die durch radikalische Polymerisation ungesättigter organischer Monomerer in Organopolysiloxanen oder durch Mischen entsprechender Bestandteile entstehen. Dabei bilden sich zum Teil nur mit organischen Polymerpartikeln (z.B. Polyolefin, Polystyrol) gefüllte Massen, zum Teil auch Produkte, in denen das organische Polymer teilweise durch Pfropfung mit dem Siloxan verbunden ist. Derartige Massen und Verfahren zu ihrer Herstellung werden beispielsweise in den Patentschriften US-PS 2 965 593 und US-PS 3 627 836 beschrieben.Modified organopolysiloxane compositions have also become known, which are formed by radical polymerization of unsaturated organic monomers in organopolysiloxanes or by mixing corresponding constituents. In some cases, masses filled only with organic polymer particles (e.g. polyolefin, polystyrene) are formed, in some cases also products in which the organic polymer is partially grafted to the siloxane. Such compositions and processes for their preparation are described, for example, in the patents US Pat. No. 2,965,593 and US Pat. No. 3,627,836.

Die Eigenschaften dieser zuletzt genannten Produkte sind für eine Reihe von Anwendungen jedoch noch unbefriedigend. Die zur Füllung oder Pfropfung bekannt gewordenen Polymere entstehen aus einem oder mehreren ungesättigten Monomeren, die polymerisierbar sind wie z.B. Äthylen, Vinylchlorid oder 1,3 Butadien.However, the properties of these last-mentioned products are still unsatisfactory for a number of applications. The polymers which have become known for filling or grafting result from one or more unsaturated monomers which are polymerizable, e.g. Ethylene, vinyl chloride or 1,3 butadiene.

Diese organischen Polymere haben in der Regel eine geringe Temperaturbeständigkeit. Sie übertragen diese ungünstige Eigenschaft auf die daraus entstehenden gehärteten Organopolysiloxan- massen. Sie besitzen ausserdem ungünstige Elastomereigenschaften wie z.B. hohe Druckverformungsreste. Weiterhin verschlechtern sich die mechanischen Eigenschaften bei erhöhter Temperatur eheblich (z.B. Zugfestigkeit). Die Dauerwärmebeständigkeit, durch die sich die Organopolysiloxane sonst auszeichnen, geht hierbei verloren.These organic polymers usually have a low temperature resistance. They transfer this unfavorable property to the resulting hardened organopolysiloxane masses. They also have unfavorable elastomer properties such as high compression set. Furthermore, the mechanical properties deteriorate significantly at elevated temperatures (e.g. tensile strength). The permanent heat resistance, which otherwise distinguishes the organopolysiloxanes, is lost.

Es war daher die Aufgabe der vorliegenden Erfindung, verbeserte Organopolysiloxanmassen zu schaffen, die auch aus wirtschaftlichen und technischen Gründen die Bedingung erfüllen, dass sie ohne grossen technisch-apparativen Aufwand und ohne lange Reaktionsdauer hergestellt werden können und dass die hergestellten Massen ohne Anwendung von Lösungsmitteln fließfähig und ausreichend lagerstabil sind. Die Massen sollen nach erfolgter Vulkanisation klebfrei aushärten und sich gegenüber anderen organisch modifizierten Organopolysiloxanmassen durch verbesserte mechanische Eigenschaften bei erhöhter Temperatur auszeichnen.It was therefore the object of the present invention to provide improved organopolysiloxane compositions which, for economic and technical reasons, also meet the condition that they can be prepared without great technical outlay and without a long reaction time, and that the compositions prepared are flowable without the use of solvents and are sufficiently stable in storage. After vulcanization, the compositions should cure without tack and should be distinguished from other organically modified organopolysiloxane compositions by improved mechanical properties at elevated temperature.

Gegenstand der vorliegenden Erfindung sind mit Polyurethan modifizierte α,ω-Dihydroxypolysiloxane, welche dadurch gekennzeichnet sind, daß das α,ω-Dihydroxypolysiloxan und das Polyurethan als unterscheidbare Phasen vorliegen. Das Polyurethan wird dabei in an sich bekannter Weise durch Polyaddition von Di- oder Polyisocyanaten der allgemeinen Formel

Figure imgb0001
wobei R' für einen gegebenenfalls substituierten Alkylen- oder Arylenrest mit vorzugsweise bis zu 24 C-Atomen steht, an Diole oder Polyole oder Hydroxylgruppen aufweisende Polymere in a,(0-Dihydroxypolysiloxan erzeugt.The present invention relates to α, ω-dihydroxypolysiloxanes modified with polyurethane, which are characterized in that the α, ω-dihydroxypolysiloxane and the polyurethane are present as distinguishable phases. The polyurethane is made in a manner known per se by polyaddition of di- or polyisocyanates of the general formula
Figure imgb0001
 where R 'represents an optionally substituted alkylene or arylene radical, preferably having up to 24 carbon atoms, on polymers containing diols or polyols or hydroxyl groups in a, (0-dihydroxypolysiloxane.

Die verbesserten Organopolysiloxanmassen gemäß der vorliegenden Erfindung sind somit als mit Polyurethan gefüllte Organopolysiloxan-Mischungen anzusehen, die aus folgenden zwei Phasen zusammengesetzt sind: (i) einer zusammenhängenden Phase einer Organopolysiloxan-Flüssigkeit und (ii) einer nicht zusammenhängenden Phase aus feinverteilten Teilchen eines Polyurethan-Polymers, das durch Polyaddition des entsprechenden Monomeren oder Monomerengemisches in Gegenwart des α,ω-Dihydroxypolysiloxans und eines die Polyurethanbildung beschleunigenden Katalysators erhalten wurde. Die Mischungen enthalten im allgemeinen etwa 3-95 Gew.-% Polyurethan - bezogen auf die Gesamtmischung. Bevorzugt sind etwa 40-80 Gew.-%, besonders bevorzugt 45-55 Gew.-%.The improved organopolysiloxane compositions according to the present invention are thus to be regarded as polyurethane-filled organopolysiloxane mixtures which are composed of the following two phases: (i) a continuous phase of an organopolysiloxane liquid and (ii) a non-continuous phase composed of finely divided particles of a polyurethane Polymer obtained by polyaddition of the corresponding monomer or monomer mixture in the presence of the α, ω-dihydroxypolysiloxane and a catalyst which accelerates the formation of polyurethane. The mixtures generally contain about 3-95% by weight of polyurethane, based on the total mixture. About 40-80% by weight is preferred, particularly preferably 45-55% by weight.

Die mit Polyurethan gefüllten Organopolysiloxan-Massen der vorliegenden Erfindung werden hergestellt durch intensives Vermischen der Organopolysiloxan-Flüssigkeit mit einem Di- oder Polyol oder Gemischen daraus und nachfolgende Zugabe eines Diisocyanats zu dieser Mischung.The polyurethane-filled organopolysiloxane compositions of the present invention are prepared by intensely mixing the organopolysiloxane liquid with a di- or polyol or mixtures thereof and then adding a diisocyanate to this mixture.

Die für den erfindungsgemässen Gebrauch bevorzugten Organopolysiloxan-Flüssigkeiten sind durch die folgende Formel gekennzeichnet:

Figure imgb0002
R steht für einen gegebenenfalls substituierten Alkyl-, Alkenyl-, Aryl- oder Halogenalkylrest mit bis zu 10 C-Atomen, R, für Wasserstoff, einen gegebenenefalls substituierten Alkyl-, Alkenyl-, Aryl- oder Halogenalkylrest mit bis zu 10 C-Atomen; X ist der Hydroxylrest; n = 2 bis 1000, m = 1-50.The organopolysiloxane liquids preferred for the use according to the invention are characterized by the following formula:
Figure imgb0002
 R represents an optionally substituted alkyl, alkenyl, aryl or haloalkyl radical having up to 10 C atoms, R, represents hydrogen, an optionally substituted alkyl, alkenyl, aryl or haloalkyl radical having up to 10 C atoms; X is the hydroxyl radical; n = 2 to 1000, m = 1-50.

Es können Gemische aus verschiedenen Polysiloxanen ebenfalls verwendet werden. Ferner sind für die erfindungsgemässe Verwendung Siliconharze, wie sie beispielsweise durch Cohydrolyse von Methyltrichlorsilan und Dimethyldichlorsilan erhältlich sind, alleine oder in Mischung mit den erwähnten Organopolysiloxanen geeignet.Mixtures of different polysiloxanes can also be used. Also suitable for the use according to the invention are silicone resins, such as are obtainable, for example, by cohydrolysis of methyltrichlorosilane and dimethyldichlorosilane, alone or in a mixture with the organopolysiloxanes mentioned.

Als erfindungsgemäß einzusetzende Ausgangskomponenten kommen aliphatische, cycloaliphatische, araliphatische, aromatische und heterocyclische Polyisocyanate in Betracht, wie sie z.B. von W. Siefgen in Justus Liebigs Annalen der Chemie, 562, Seiten 75 bis 136, beschrieben werden, beispielsweise Äthylen-diisocyanat, 1,4-Tetramethylendiisocyanat, 1,6-Hexamethylendiisocyanat, 1,12-Dodecandiisocyanat, Cyclobutan-1,3-diisocyanat, Cyclohexan-1,3- und -1,4-diisocyanat sowie beliebige Gemische dieser Isomeren, 1-lsocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexan (DAS 1 202 785), 2,4- und 2,6-Hexahydrotoluylendiisocyanat sowie beliebige Gemische dieser Isomeren, Hexahydro-1,3- und/oder -1,4-phenylen-diisocyanat, Perhydro-2,4'- und/oder -4,4'-diphenylmethan-diisocyanat, 1,3-und 1,4-Phenylendiisocyanat, 2,4- und 2,6-Toluylendiisocyanat sowie beliebige Gemische dieser Isomeren, Diphenylmethan-2,4'- und/oder -4,4'-diisocyanat, Naphthylen-1,5-diisocyanat, Triphenylmethan-4,4',4"-triisocyanat, Polyphenyl-polymethylen-polyisocyanate, wie sie durch Anilin-Formaldehyd-Kondensation und anschließende Phosgenierung erhalten und z.B. in den britischen Patentschriften 874 430 und 848 671 beschrieben werden, perchlorierte Arylpolyisocyanate, wie sie z.B. in der deutschen Auslegeschrift 1 157 601 beschrieben werden, Carbodiimidgruppen aufweisende Polyisocyanate, wie sie in der deutschen Patentschrift 1 092 007 beschrieben werden, Dilsocyanate, wie sie in der amerikanischen Patentschrift 3 492 330 beschrieben werden, Allophanatgruppen aufweisende Polyisocyanate, wie sie z.B. in der britischen Patentschrift 994 890, der belgischen Patentschrift 761 626 und der veröffentlichten holländischen Patentanmeldung 7 102 524 beschrieben werden, Isocyanuratgruppen aufweisende Polyisocyanate, wie sie z.B. in den deutschen Patentschriften 1 022 789, 1 222 067 und 1 027 394 sowie in den deutschen Offenlegungsschriften 1 929 034 und 2 004 048 beschrieben werden, Urethangruppen aufweisende Polyisocyanate, wie sie z.B. in der belgischen Patentschrift 752 261 oder in der amerikanischen Patentschrift 3 394 164 beschrieben werden, acylierte Harnstoffgruppen aufweisende Polyisocyanate gemäß der deutschen Patentschrift 1 230 778, Biuretgruppen aufweisende Polyisocyanate, wie sie z.B. in der deutschen Patentschrift 1 101 394, in der britischen Patentschrift 889 050 und in der französischen Patentschrift 7 017 514 beschrieben werden, durch Telomerisationsreaktionen hergestellte Polyisocyanate, wie sie z.B. in der belgischen Patentschrift 723 640 beschrieben werden, Estergruppen aufweisende Polyisocyanate, wie sie z.B. in den britischen Patentschriften 965 474 und 1 072 956, in der amerikanischen Patentschrift 3 567 763 und in der deutschen Patentschrift 1 231 688 genannt werden, Umsetzungsprodukte der obengenannten lsocyanate mit Acetalen gemäß der deutschen Patentschrift 1 072 385.Suitable starting components according to the invention are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, as are described, for example, by W. Siefgen in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, for example ethylene diisocyanate, 1,4 Tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,3, 5-trimethyl-5-isocyanatomethyl-cyclohexane (DAS 1 202 785), 2,4- and 2,6-hexahydrotoluylene diisocyanate and any mixtures of these isomers, hexahydro-1,3- and / or -1,4-phenylene diisocyanate, Perhydro-2,4'- and / or -4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers, diphenylmethane-2 , 4'- and / or -4,4'-diisocyanate, naphthylene-1,5-diisocyanate, triphenylmethane-4,4 ', 4 "-triisocyanate, Pol yphenyl-polymethylene polyisocyanates, as obtained by aniline-formaldehyde condensation and subsequent phosgenation and described, for example, in British Patents 874 430 and 848 671, perchlorinated aryl polyisocyanates, as described, for example, in German Patent Application 1 157 601, which contain carbodiimide groups polyisocyanates, such as are described in German Patent 1,092,007, Di l socyanate, as described in United States Patent specification 3,492,330, polyisocyanates containing allophanate groups as described for example in British Patent 994,890, Belgian Patent 761,626 and The published Dutch patent application 7 102 524 describes polyisocyanates containing isocyanurate groups, such as are described, for example, in German patents 1 022 789, 1 222 067 and 1 027 394 and in German patent applications 1 929 034 and 2 004 048, polyisocyanates containing urethane groups , how they are described, for example, in Belgian patent specification 752 261 or in American patent specification 3 394 164, polyisocyanates containing acylated urea groups according to German patent specification 1 230 778, polyisocyanates containing biuret groups, as described, for example, in German patent specification 1 101 394 in the British patent specification 889 050 and described in French Patent 7 017 514, polyisocyanates prepared by telomerization reactions, such as are described, for example, in Belgian Patent 723 640, polyisocyanates containing ester groups, as described, for example, in British Patents 965 474 and 1 072 956, in which American Patent 3,567,763 and in German Patent 1,231,688, reaction products of the above-mentioned isocyanates with acetals according to German Patent 1,072,385.

Es ist auch möglich, die bei der technischen Isocyanatherstellung anfallenden Isocyanatgruppen aufweisenden Destillationsrückstände, gegebenenfalls gelöst in einem oder mehreren der vorgenannten Polyisocyanate, einzusetzen. Ferner ist es möglich, beliebige Mischungen der vorgenannten Polyisocyanate zu verwenden.It is also possible to use the distillation residues containing isocyanate groups obtained in the technical production of isocyanates, optionally dissolved in one or more of the aforementioned polyisocyanates. It is also possible to use any mixtures of the aforementioned polyisocyanates.

Bevorzugt werden in der Regel die technisch leicht zugänglichen Polyisocyanate, z.B. das 2,4- und 2,6-Toluylendiisocyanat sowie beliebige Gemische dieser Isomeren ("TDI"), Polyphenyl-polymethylen-polyisocyanate, wie sie durch Anilin-Formaldehyd-Kondensation und anschließende Phosgenierung hergestellt werden ("rohes MDI") und Carbodiimidgruppen, Urethangruppen, Allophanatgruppen, Isocyanuratgruppen, Harnstoffgruppen oder Biuretgruppen aufweisenden Polyisocyanate ("modifizierte Polyisocyanate").The technically easily accessible polyisocyanates, e.g. 2,4- and 2,6-tolylene diisocyanate as well as any mixtures of these isomers ("TDI"), polyphenyl-polymethylene polyisocyanates, such as those produced by aniline-formaldehyde condensation and subsequent phosgenation ("crude MDI") and carbodiimide groups, Polyisocyanates containing urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups ("modified polyisocyanates").

Beispiele für diese besonders bevorzugten Polyisocyanate sind durch partielle Carbodiimidisierung verflüssigtes 4,4'-Diphenylmethan-diisocyanat wie es beispielsweise gemäß DT-PS 1 568 501 durch Erhitzen in Gegenwart von 2,5 Mol-% an Harnstoff auf 225°C während 1-2 Stunden erhältlich ist oder durch Umsetzung von 1 Mol 4,4'-Diphenylmethan-diisocyanat mit ca. 0,1 - 0,3 Mol Di- oder Polypropylenglykol eines maximalen Molekulargewichts von 700 erhältliches "verflüssigtes" 4,4'-Diphenylmethan-diisocyanat.Examples of these particularly preferred polyisocyanates are 4,4'-diphenylmethane diisocyanate liquefied by partial carbodiimidization, as described, for example, in DT-PS 1 568 501 by heating in the presence of 2.5 mol% of urea at 225 ° C. for 1-2 Hours is available or by reacting 1 mol of 4,4'-diphenylmethane diisocyanate with about 0.1-0.3 mol of di- or polypropylene glycol with a maximum molecular weight of 700 obtainable "liquefied" 4,4'-diphenylmethane diisocyanate.

Erfindungsgemäß einzusetzende Ausgangskomponenten sind ferner gegebenenfalls Verbindungen mit mindestens zwei gegenüber Isocyanaten reaktionsfähigen Wasserstoffatomen von einem Molekulargewicht in der Regel von 62 - 10,000. Hierunter versteht man neben Aminogruppen, Thiolgruppen oder Carboxylgruppen aufweisenden Verbindungen vorzugsweise Polyhydroxylverbindungen, insbesondere zwei bis acht Hydroxylgruppen aufweisende Verbindungen, speziell selche vom Molekulargewicht 200 bis 10,000, vorzugsweise 1000 bis 6000, z.B. mindestens zwei, in der Regel 2. bis 8, vorzugsweise aber 2 bis 4, Hydroxylgruppen aufweisende Polyester, Polyäther, Polythioäther, Polyacetale, Polycarbonate, Polyesteramide, wie sie für die Herstellung von homogenen und von zellförmigen Polyurethanen an sich bekannt sind. Die genannten höhermolekularen Polyhydroxylverbindungen werden beim erfindungsgemäßen Verfahren oft vorteilhaft im Gemisch mit bis zu 95, vorzugsweise bis zu 50 Gewichtsprozent bezogen auf Gesamtmenge an Polyhydroxylverbindungen an niedermolekularen Polyolen des Molekulargewichtsbereichs 62-200 eingesetzt. Derartige niedermolekulare Polyole sind z.B. Athylenglykol, 1,2-Propandiol, 1,3-Propandiol, 1,2-Butandiol, 1,4-Butandiol, 1,6-Hexandiol, 1,10-Decandioi, Diäthylenglykol, Triäthylenglykol, Tetraäthylenglykol, Dipropylenglykol, Tripropylenglykol, Glycerin, Trimethylolpropan u.dgl.Starting components to be used according to the invention are furthermore optionally connected solutions with at least two isocyanate-reactive hydrogen atoms with a molecular weight of generally from 62 to 10,000. In addition to amino groups, thiol groups or carboxyl group-containing compounds, these are preferably polyhydroxyl compounds, in particular two to eight compounds containing hydroxyl groups, especially those with a molecular weight of 200 to 10,000, preferably 1000 to 6000, for example at least two, usually 2nd to 8, but preferably 2nd to 4, hydroxyl-containing polyesters, polyethers, polythioethers, polyacetals, polycarbonates, polyesteramides, as are known per se for the production of homogeneous and cellular polyurethanes. The higher molecular weight polyhydroxyl compounds mentioned are often advantageously used in the process according to the invention in a mixture with up to 95, preferably up to 50 percent by weight, based on the total amount of polyhydroxyl compounds, of low molecular weight polyols of the molecular weight range 62-200. Such low molecular weight polyols are, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol , Tripropylene glycol, glycerin, trimethylolpropane and the like.

Die in Frage kommenden Hydroxylgruppen aufweisenden Polyester sind z.B. Umsetzungsprodukte von mehrwertigen, vorzugsweise zweiwertigen und gegebenenfalls zusätzlich dreiwertigen Alkoholen mit mehrwertigen, vorzugsweise zweiwertigen, Carbonsäuren. Anstelle der freien Polycarbonsäuren können auch die entsprechenden Polycarbonsäureanhydride oder entsprechende Polycarbonsäureester von niedrigen Alkoholen oder deren Gemische zur Herstellung der Polyester verwendet werden. Die Polycarbonsäuren können aliphatischer, cycloaliphatischer, aromatischer und/ oder heterocyclischer Natur sein und gegebenenfalls, z.B. durch Halogenatome, substituiert und/oder ungesättigt sein. Als Beispiele hierfür seien genannt: Bernsteinsäure, Adipinsäure, Korksäure, Azelainsäure, Sebacinsäure, Phthalsäure, Isophthalsäure, Trimellitsäure, Phthalsäureanhydrid, Tetrahydrophthalsäureanhydrid, Hexahydrophthalsäureanhydrid, Tetrachlorphthalsäureanhydrid, Endomethylentetrahydrophthalsäureanhydrid, Glutarsäureanhydrid, Maleinsäure, Maleinsäureanhydrid, Fumarsäure, dimere und trimere Fettsäuren wie Ölsäure, gegebenenfalls in Mischung mit monomeren Fettsäuren, Terephthalsäuredimethylester, Terephthalsäure-bis-glykolester. Als mehrwertige Alkohole kommen z.B. Äthylenglykol, Propylenglykol-(1,2) und -(1,3), Butylenglykol-(1,4) und -(2,3), Hexandiol-(1,6), Octan-diol-(1,8), Neopentylglykol, Cyclohexandimethanol (1,4-Bis-hydroxymethylcyclohexan), 2-Methyl-1,3-propandiol, Glycerin, Trimethylolpropan, Hexantriol-(1,2,6), Butantriol-( 1 ,2,4), Trimethyloläthan, Pentaerythrit, Chinit, Mannit und Sorbit, Methylglykosid, ferner Diäthylenglykol, Triäthylenglykol, Tetraäthylenglykol, Polyäthylenglykols, Dipropylenglykol, Polypropylenglykole, Dibutylenglykol und Polybutylenglykole in Frage. Die Polyester können anteilig endständige Carboxylgruppen aufweisen. Auch Polyester aus Lactonen, z.B. E-Caprolacton oder Hydroxycarbonsäuren, z.B. w-Hydroxycapronsäure, sind einsetzbar.The polyesters containing hydroxyl groups are, for example, reaction products of polyhydric, preferably dihydric and optionally additionally trihydric alcohols with polyhydric, preferably dihydric, carboxylic acids. Instead of the free polycarboxylic acids, the corresponding polycarboxylic anhydrides or corresponding polycarboxylic esters of lower alcohols or mixtures thereof can also be used to produce the polyesters. The polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and optionally substituted, for example by halogen atoms, and / or unsaturated. mentioned as examples: succinic acid, adipic acid, azelaic acid, phthalic acid, trimellitic anhydride, phthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic endomethylenetetrahydrophthalic, glutaric anhydride, maleic anhydride, fumaric acid, dimeric and trimeric fatty acids such as oleic acid, optionally mixed with monomeric fatty acids, terephthalic acid dimethyl ester, terephthalic acid bis-glycol ester. Polyhydric alcohols include, for example, ethylene glycol, propylene glycol (1,2) and - (1,3), butylene glycol (1,4) and - (2,3), hexanediol (1,6), octane diol ( 1.8), neopentyl glycol, cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane), 2-methyl-1,3-propanediol, glycerin, trimethylolpropane, hexanetriol- (1,2,6), butanetriol- (1,2,4 ), Trimethylolethane, pentaerythritol, quinite, mannitol and sorbitol, methylglycoside, also diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycols, dibutylene glycol and polybutylene glycol in question. The polyesters may have a proportion of terminal carboxyl groups. Polyesters of lactones, for example E- caprolactone or hydroxycarboxylic acids, for example w-hydroxycaproic acid, can also be used.

Auch die erfindungsgemäß in Frage kommenden, mindestens zwei, in der Regel zwei bis acht, vorzugsweise zwei bis drei, Hydroxylgruppen aufweisenden Polyäther sind solche der an sich bekannten Art und werden z.B. durch Polymerisation von Epoxiden wie Äthylenoxid, Propylenoxid, Butylenoxid, Tetrahydrofuran, Syroloxid oder Epichlorhydrin mit sich selbst, z.B. in Gegenwart von BF3, oder durch Anlagerung dieser Epoxide, gegebenenfalls im Gemisch oder nacheinander, an Startkomponenten mit reaktionsfähigen Wasserstoffatomen wie Alkohole oder Amine, z.B. Wasser, Äthylenglykol, Propylenglykol-(1,3) oder -(1,2), Trimethylolpropan, 4,4'-Dihydroxydiphenylpropan, Anilin, Ammoniak, Athanolamin, Äthylendiamin hergestellt. Auch Sucrosepolyäther, wie sie z.B. in den deutschen Auslegeschriften 1 176 358 und 1 064 938 beschrieben werden, kommen erfindungsgemäß in Frage. Vielfach sind solche Polyäther bevorzugt, die überwiegend (bis zu 90 Gew.-% bezogen auf alle vorhandenen OH-Gruppen im Polyäther) primäre OH-Gruppen aufweisen. Auch durch Vinylpolymerisate modifizierte Polyäther, wie sie z.B. durch Polymerisation von Styrol, Acrylnitril in Gegenwart von Polyäthern entstehen (amerikanische Patentschriften 3.383.351, 3.304.273, 3.523.093, 3.110.695, deutsche Patentschrift 1.152.536), sind ebenfalls geeignet, ebenso OH-Gruppen aufweisende Polybutadiene.The at least two, generally two to eight, preferably two to three, hydroxyl groups-containing polyethers which are suitable according to the invention are also of the type known per se and are obtained, for example, by polymerizing epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, syrene oxide or Epichlorohydrin with itself, e.g. in the presence of BF 3 , or by the addition of these epoxides, optionally in a mixture or in succession, to starting components with reactive hydrogen atoms such as alcohols or amines, e.g. water, ethylene glycol, propylene glycol (1,3) or - (1 , 2), trimethylolpropane, 4,4'-dihydroxydiphenylpropane, aniline, ammonia, ethanolamine, ethylenediamine. Sucrose polyethers, such as are described, for example, in German publications 1 176 358 and 1 064 938, are also suitable according to the invention. In many cases, those polyethers are preferred which predominantly (up to 90% by weight, based on all OH groups present in the polyether) have primary OH groups. Polyethers modified by vinyl polymers, such as those produced by polymerizing styrene or acrylonitrile in the presence of polyethers (American patents 3,383,351, 3,304,273, 3,523,093, 3,110,695, German patent 1,152,536) are also suitable. also polybutadienes containing OH groups.

Unter den Polythioäthern seien insbesondere die Kondensationsprodukte von Thiodiglykol mit sich selbst und/oder mit anderen Glykolen, Dicarbonsäuren, Formaldehyd, Aminocarbonsäuren oder Aminoalkoholen angeführt. Je nach den Co-Komponenten handelt es sich bei den Produkten um Polythiomischäther, Polythioätherester, Polythioätheresteramide.Among the polythioethers, the condensation products of thiodiglycol with themselves and / or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino alcohols should be mentioned in particular. Depending on the co-components, the products are polythio ether, polythio ether ester, polythio ether ester amide.

Als Polyacetale kommen z.B. die aus Glykolen, wie Diäthylenglykol, Triäthylenglykol, 4,4'-Dioxäthoxy-diphenyldimethylmethan, Hexandiol und Formaldehyd herstellbaren Verbindungen in Frage. Auch durch Polymerisation cyclischer Acetale lassen sich erfindungsgemäß geeignete Polyacetale herstellen.As polyacetals e.g. the compounds which can be prepared from glycols, such as diethylene glycol, triethylene glycol, 4,4'-dioxethoxy-diphenyldimethylmethane, hexanediol and formaldehyde. Polyacetals suitable according to the invention can also be prepared by polymerizing cyclic acetals.

Als Hydroxylgruppen aufweisende Polycarbonate kommen solche der an sich bekannten Art in Betracht, die z.B. durch Umsetzung von Diolen wie Propandiol-(1,3), Butandiol-(1,4) und/oder Hexandiol-(1,6), Diäthylenglykol, Triäthylenglykol, Tetraäthylenglykol mit Diarylcarbonaten, z.B. Diphenylcarbonat oder Phosgen, hergestellt werden können.Suitable polycarbonates containing hydroxyl groups are those of the type known per se, which e.g. by reacting diols such as propanediol (1,3), butanediol (1,4) and / or hexanediol (1,6), diethylene glycol, triethylene glycol, tetraethylene glycol with diaryl carbonates, e.g. Diphenyl carbonate or phosgene can be produced.

Zu den Polyesteramiden und Polyamiden zählen z.B. die aus mehrwertigen gesättigten und ungesättigten Carbonsäuren bzw. deren Anhydriden und mehrwertigen gesättigten und ungesättigten Aminoalkoholen, Diaminen, Polyaminen und ihre Mischungen gewonnenen, vorwiegend linearen Kondensate.The polyester amides and polyamides include e.g. the predominantly linear condensates obtained from polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyvalent saturated and unsaturated amino alcohols, diamines, polyamines and their mixtures.

Auch bereits Urethan- oder Harnstoffgruppen enthaltende Polyhydroxylverbindungen sowie gegebenenfalls modifizierte natürliche Polyole, wie Rizinusöl, Kohlenhydrate, Stärke, sind verwendbar. Auch Anlagerungsprodukte von Alkylenoxiden an Phenol-Formaldehyd-Harze oder auch an Harnstoff-Formaldehyd-harze sind erfindungsgemäß einsetzbar.Polyhydroxyl compounds which already contain urethane or urea groups and optionally modified natural polyols, such as castor oil, carbohydrates, starch, can also be used. Addition products of alkylene oxides on phenol-formaldehyde resins or also on urea-formaldehyde resins can also be used according to the invention.

Vertreter dieser erfindungsgemäß zu verwenden Verbindungen sind z.B. in High Polymers, Vol. XVI, "Polyurethanes, Chemistry and Technology," verfaßt von Saunders-Frisch, Interscience Publishers, New York, London, Band I, 1962, Seiten 32-42 und Seiten 44-54 und Band II, 1964, Seiten 5-6 und 198-199, sowie im Kunststoff-Handbuch, Band VII, Vieweg-Höchtlen, Carl-Hanser-Verlag, München, 1966, z.B. auf den Seiten 45 bis 71, beschrieben.Representatives of these compounds to be used according to the invention are e.g. in High Polymers, Vol. XVI, "Polyurethanes, Chemistry and Technology," written by Saunders-Frisch, Interscience Publishers, New York, London, Volume I, 1962, pages 32-42 and pages 44-54 and Volume II, 1964, Pages 5-6 and 198-199, as well as in the plastic manual, volume VII, Vieweg-Höchtlen, Carl-Hanser-Verlag, Munich, 1966, e.g. on pages 45 to 71.

Beim erfindungsgemäßen Verfahren kommen die Reaktionspartner in Mengenverhältnissen zum Einsatz, welche einer NCO-Kennzahl von 70-160 entspricht. (Die NCO-Kennzahl 100 bedeutet das Vorliegen von äquivalenten Mengen an Isocyanatgruppen und mit diesen Isocyanatgruppen in Reaktion tretenden aktiven Wasserstoffatomen im Reaktionsgemisch).In the process according to the invention, the reactants are used in proportions which correspond to an NCO index of 70-160. (The NCO index 100 means the presence of equivalent amounts of isocyanate groups and active hydrogen atoms which react with these isocyanate groups in the reaction mixture).

Erfindungsgemäß werden ferner oft Katalysatoren mitverwendet. Als mitzuverwendende Katalysatoren kommen solche der an sich bekannten Art infrage, z.B. tertiäre Amine, wie Triäthylamin, Tributylamin, N-Methyl-morpholin, N-Äthyl-morpholin, N-Cocomorpholin, N,N,N',N'-Tetramethyl- äthylendiamin, 1,4-Diaza-bicyclo-(2,2,2)-octan, N-Methyl-N'-dimethylaminoäthyl-piperazin, N,N-Dimethylbenzylamin, Bis-(N,N-diathylaminoäthyl)-adipat, N,N-Diäthylbenzylamin, Pentamethyldiäthylentriamin, N,N-Dimethylcyclohexylamin, N,N,N',N'-Tetramethyl-1,3-butandiamin, N,N-Dimethyl- ß-phenyläthylamin, 1,2-Dimethylimidazol, 2-Methylimidazol.According to the invention, catalysts are often also used. Suitable catalysts to be used are those of the type known per se, e.g. tertiary amines, such as triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N-cocomorpholine, N, N, N ', N'-tetramethyl-ethylenediamine, 1,4-diaza-bicyclo- (2.2 , 2) octane, N-methyl-N'-dimethylaminoethyl-piperazine, N, N-dimethylbenzylamine, bis (N, N-diathylaminoethyl) adipate, N, N-diethylbenzylamine, pentamethyldiethylenetriamine, N, N-dimethylcyclohexylamine, N , N, N ', N'-tetramethyl-1,3-butanediamine, N, N-dimethyl-ß-phenylethylamine, 1,2-dimethylimidazole, 2-methylimidazole.

Gegenüber Isocyanatgruppen aktive Wasserstoffatome aufweisende tertiäre Amine sind z.B. Triäthanolamin, Triisopropanolamin, N-Methyl-diäthanolamin, N-Äthyl-diäthanolamin, N,N-Dimethyl- äthanolamin, sowie deren Umsetzungsprodukte mit Alkylenoxiden, wie Propylenoxid und/oder Athylenoxid.Tertiary amines which have hydrogen atoms active against isocyanate groups are e.g. Triethanolamine, triisopropanolamine, N-methyl-diethanolamine, N-ethyl-diethanolamine, N, N-dimethyl-ethanolamine, and their reaction products with alkylene oxides, such as propylene oxide and / or ethylene oxide.

Als Katalysatoren kommen ferner Silaamine mit Kohlenstoff-Silizium-Bindungen, wie sie z.B in der deutschen Patentschrift 1 229 290 beschrieben sind, in Frage, z.B. 2,2,4-Trimethyl-2- silamorpholin, 1,3-Diäthylaminomethyl-tetramethyl-disiloxan..Silaamines with carbon-silicon bonds, as described, for example, in German Patent 1,229,290, may also be used as catalysts, e.g. 2,2,4-trimethyl-2-silamorpholine, 1,3-diethylaminomethyl-tetramethyl-disiloxane ..

Als Katalysatoren kommen auch stickstoffhaltige Basen wie Tetraalkylammoniumhydroxide, ferner Alkalihydroxide wie Natriumhydroxid, Alkaliphenolate wie Natriumphenolat oder Alkalialkoholate wie Natriummethylat in Betracht. Auch Hexahydrotriazine können als Katalysatoren eingesetzt werden.Suitable catalysts are also nitrogen-containing bases such as tetraalkylammonium hydroxides, alkali metal hydroxides such as sodium hydroxide, alkali phenolates such as sodium phenolate or alkali metal alcoholates such as sodium methylate. Hexahydrotriazines can also be used as catalysts.

Erfindungsgemäß können auch organische Metallverbindungen, insbesondere organische Zinnverbindungen, als Katalysatoren verwendet werden.According to the invention, organic metal compounds, in particular organic tin compounds, can also be used as catalysts.

Als organische Zinnverbindungen kommen vorzugsweise Zinn(II)-salze von Carbonsäuren wie Zinn(II)-acetat, Zinn(II)-octoat, Zinn(ll)-äthylhexoat und Zinn(II)-laurat und die Dialkylzinnsalze von Car- bonsäuren, wie z.B. Dibutyl-zinndiacetat, Dibutylzinn-dilaurat, Dibutylzinn maleat oder Dioctylzinndiacetat in Betracht.Preferred organotin compounds, tin (II) are salts of carboxylic acids such as tin (II) acetate, tin (II) octoate, tin (ll) ethyl hexoate and tin (II) laurate, and the dialkyltin salts of carboxylic acids b on , such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate or dioctyltin diacetate.

Weitere Vertreter von erfindungsgemäß zu verwendenden Katalysatoren sowie Einzelheiten über die Wirkungsweise der Katalysatoren sind in Kunststoff-Handbuch, Band VII, herausgegeben von Vieweg und Höchtlen, Carl-Hanser-Verlag, München 1966, z.B. auf den Seiten 96 bis 102 beschrieben.Further representatives of catalysts to be used according to the invention and details of the mode of action of the catalysts are in Kunststoff-Handbuch, Volume VII, edited by Vieweg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, e.g. described on pages 96 to 102.

Die Katalysatoren werden in der Regel in einer Menge zwischen etwa 0,001 und 10 Gew.-%, bezogen auf die Menge an Verbindungen mit mindestens zwei gegenüber Isocyanaten reaktionsfähigen Wasserstoffatomen von einem Molekulargewicht von 62 bis 10,000, eingesetzt.The catalysts are generally used in an amount between about 0.001 and 10% by weight, based on the amount of compounds having at least two isocyanate-reactive hydrogen atoms with a molecular weight of 62 to 10,000.

Erfindungsgemäß können auch oberflächenaktive Zusatzstoffe (Emulgatoren und Schaumstabilisatoren) mitverwendet werden. Als Emulgatoren kommen z.B. die Natriumsalze von Ricinusölsulfonaten oder auch von Fettsäuren oder Salze von Fettsäuren mit Aminen wie ölsaures Diäthylamin oder stearinsaures Diäthanolamin infrage. Auch Alkali- oder Ammoniumsalze von Sulfonsäuren wie etwa von Dodecylbenzolsulfonsäure oder Dinaphenylmethandisulfonsäure oder auch von Fettsäuren wie Ricinolsäure oder von polymeren Fettsäuren können als oberflächenaktive Zusatzstoffe mitverwendet werden.According to the invention, surface-active additives (emulsifiers and foam stabilizers) can also be used. The emulsifiers are e.g. the sodium salts of castor oil sulfonates or also of fatty acids or salts of fatty acids with amines such as oleic acid diethylamine or stearic acid diethanolamine. Alkali or ammonium salts of sulfonic acids such as dodecylbenzenesulfonic acid or dinaphenylmethane disulfonic acid or also of fatty acids such as ricinoleic acid or of polymeric fatty acids can also be used as surface-active additives.

Weitere Beispiele von gegebenenfalls erfindungsgemäß mitzuverwendenen oberflächenaktiven Zusatzstoffen und Schaumstabilisatoren sowie Zellreglern, Reaktionsverzögerern, Stabilisatoren, flammhemmenden Substanzen, Weichmachern, Farbstoffen und Füllstoffen sowie fungistatisch und, bakteriostatisch wirksamen Substanzen sowie Einzelheiten über Verwendungs- und Wirkungsweise dieser Zusatzmittel sind im Kunststoff-Handbuch, Band VI, herausgegeben von Vieweg und Höchtlen, Carl-Hanser-Verlag, München 1966, z.B. auf den Seiten 103 bis 113 beschrieben.Further examples of surface-active additives and foam stabilizers to be used according to the invention, as well as cell regulators, reaction retarders, stabilizers, flame-retardant substances, plasticizers, dyes and fillers, as well as fungistatic and, bacteriostatically active substances and details on the use and action of these additives are in the Plastics Manual, Volume VI, edited by Vieweg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, e.g. described on pages 103 to 113.

Überraschenderweise sind die erfindungsgemässen Mischungen stabil. Sie eignen sich zur Herstellung von zu Elastomeren härtbaren Formmassen.Surprisingly, the mixtures according to the invention are stable. They are suitable for the production of molding compositions curable to elastomers.

Im allgemeinen hat die Hauptmenge der festen Teilchen (mehr als 80%) des Homo- oder Copolymers einen mittleren Durchmesser von etwa 0,3 bis 10 Mikron, wobei einige der Teilchen einen Durchmesser von weniger als 0,3 Mikron haben.Generally, the majority of the solid particles (greater than 80%) of the homo- or copolymer have an average diameter of about 0.3 to 10 microns, with some of the particles being less than 0.3 microns in diameter.

Die erfindungsgemässen Polyurethan-modifizierten Polysiloxan-Flüssigkeiten werden mit Vorteil so hergestellt, dass man bei Raumtemperatur oder erhöhter Temperatur (bis ca. 150°C) ein α,ω-Dihydroxypolysiloxan mit einem Diol, Polyol oder Polyätherol mischt, den Katalysator zugibt, und die entsprechende Menge Isocyanat oder Isocyanatgemisch innerhalb eines vorgegebenen Zeitraums gleichmässig und stetig zudosiert. Die Zugabe des Isocyanats oder der Isocyanatmischung erfolgt vorzugsweise bei Temperaturen von 60 bis 120°C.The polyurethane-modified polysiloxane liquids according to the invention are advantageously prepared in such a way that an α, ω-dihydroxypolysiloxane is mixed with a diol, polyol or polyetherol at room temperature or elevated temperature (up to approx. 150 ° C.), the catalyst is added, and the appropriate amount of isocyanate or isocyanate mixture within a predetermined period dosed evenly and continuously. The isocyanate or the isocyanate mixture is preferably added at temperatures from 60 to 120.degree.

Die Geschwindigkeit der Isocyanatzugabe (etwa 1-8 Stunden - je nach Ansatzgröße) wird im allgemeinen so gesteuert, daß die freiwerdende Reaktionswärme abgeführt werden kann und die gewünschte Reaktionstemperatur konstant gehalten wird.The rate of isocyanate addition (about 1-8 hours - depending on the batch size) is generally controlled so that the heat of reaction released can be removed and the desired reaction temperature is kept constant.

Während des Herstellvorgangs steigt die Viskosität der Mischung beträchtlich an. Das Ausmaß des Viskositätsanstiegs ist abhängig von der Anfangsviskosität der verwendeten Siloxankomponente, vom Füllgrad durch das erzeugte Polyurethan und Verteilungsgrad der diskontinuierlichen PhaseThe viscosity of the mixture increases considerably during the manufacturing process. The extent of the viscosity increase depends on the initial viscosity of the siloxane component used, the degree of filling by the polyurethane produced and the degree of distribution of the discontinuous phase

Die Feinteiligkeit der in der Organosiloxanphase verteilten Polyurethanphase hängt von der Rührgeschwindigkeit und der Bauart des verwendeten Rührers, der Reaktionstemperatur und der Viskosität der Organosiloxanphase ab.The fine particle size of the polyurethane phase distributed in the organosiloxane phase depends on the stirring speed and the type of stirrer used, the reaction temperature and the viscosity of the organosiloxane phase.

Die erhaltenen Polyurethan-modifizierten Polysiloxane stellen weiße, meist nicht-transparente, fließfähige und vernetzbare Massen mit mittlerer bis hoher Viskosität dar, die mit vielen der üblichen Katalysatoren, die für die Silanol-kondensation geeignet sind, gehärtet werden können.The polyurethane-modified polysiloxanes obtained are white, mostly non-transparent, flowable and crosslinkable compositions with medium to high viscosity, which can be cured with many of the customary catalysts which are suitable for silanol condensation.

Als Vernetzungsmittel eignen sich solche Substanzen, die herkömmlicherweise zur Herstellung von Ein- oder Zweikomponentensystemen eingesetzt werden. Als solche kommen beispielsweise Alkoxysiliziumverbindungen, Tetraalkoxysilane, Alkylpolysilikate und Acyloxysiliziumverbindungen in Frage.Suitable crosslinking agents are substances which are conventionally used for the production of one- or two-component systems. As such, for example, alkoxysilicon compounds, tetraalkoxysilanes, alkyl polysilicates and acyloxysilicon compounds come into question.

Die Herstellung von Ein- oder Zweikomponentenmassen auf Basis von Polyurethan-Polysiloxan-Mischpolymeren erfolgt durch Vermischen der Polyurethan-Siloxan-Masse mit der Vernetzerkomponente und gegebenenfalls den Füllstoffen und/oder Weichmachern in einem handelsüblichen Mischer oder Kneter. Als Füllstoffe können beispielsweise Quarzmehl, Kreide oder Diatomeenerde oder pyrogen in der Gasphase erzeugtes Si02 oder andere fein verteilte Metalloxide wie z.B. Ti02, Fe203, dienen.One- or two-component compositions based on polyurethane-polysiloxane copolymers are prepared by mixing the polyurethane-siloxane composition with the crosslinking component and, if appropriate, the fillers and / or plasticizers in a commercially available mixer or kneader. For example, quartz powder, chalk or diatomaceous earth or pyrogenic Si0 2 or other finely divided metal oxides such as TiO 2 , Fe 2 O 3 can serve as fillers.

Wie erwähnt, können gegebenenfalls Weichmacher zugesetzt werden. Als solche werden flüssige inerte Polydiorganosiloxane eingesetzt, z.B. a,w-Trimethyl-siloxyendgestoppte Polydimethylsiloxane.As mentioned, plasticizers can optionally be added. As such, liquid inert polydiorganosiloxanes are used, e.g. a, w-trimethyl siloxy end-stopped polydimethyl siloxanes.

Das zur Vulkanisation der Mischpolymeren erforderliche Wasser kann durch Luftfeuchtigkeit oder durch direktes Einmischen den härtbaren Mischpolymerzusammensetzungen beigefügt werden.The water required to vulcanize the copolymers can be added to the curable copolymer compositions by atmospheric moisture or by direct mixing.

Polyuretan-modifizierte Organopolysiloxan-Massen sind, wie erwähnt, sowohl in Substanz für sich verwendbar, als auch als Zusatzkomponente in anderen Polymermassen.As mentioned, polyurethane-modified organopolysiloxane compositions can be used both in substance per se and as an additional component in other polymer compositions.

Sie zeichnen sich aus durch verbesserte Eigenschaften in bezug auf Temperaturbeständigkeit, Zugfestigkeit bei erhöhter Temperatur, niedrigere Druckverformungsreste und gute Haftung (der gehärteten Produkte) auf Glas, Beton, Stein und Metallen.They are characterized by improved properties with regard to temperature resistance, tensile strength at elevated temperatures, lower compression set and good adhesion (of the hardened products) to glass, concrete, stone and metals.

Nachfolgend wird die Erfindung anhand von Beispielen näher erläutert. Die nachfolgend angegebenen Prozentangaben bedeuten, wenn nicht ausdrücklich anders vermerkt. Gewichtsprozente.The invention is explained in more detail below with the aid of examples. The percentages given below mean, unless expressly stated otherwise. Percentages by weight.

Beispiel 1example 1

Dieses Beispiel beschreibt die Herstellung einer Dispersion aus 50% Polyurethan auf Basis von Toluylendiisocyanat und Dipropylenglykol im Molverhältnis 1:1 und 50% α.ω~ Dihydroxypolydimethylsiloxan.This example describes the preparation of a dispersion of 50% polyurethane based on tolylene diisocyanate and dipropylene glycol in a molar ratio of 1: 1 and 50% α.ω ~ dihydroxypolydimethylsiloxane.

Man erwärmt eine Mischung aus 620 g Polydimethylsiloxan mit endständigen Hydroxylgruppen und einer Viskosität von 18000 mPa.s (20°C) und 270 g Dipropylenglykol (Isomerengemisch) auf 80°C und dosiert innerhalb einer Stunde eine Mischung aus 349,5 g Toluylendiisocyanat (Isomerengemenge aus 80% 2,4- und 20% 2,6-Toluylendiisocyanat) und 1,8 g Triäthylamin gleichmässig unter Rühren hinzu. Die Reaktionstemperatur wird während der Zugabedauer zwischen 80 und 90°C gehalten. Nach beendeter Zugabe wird eine weitere Stunde nachgerührt und anschliessend abgekühlt. Man erhält eine weiße, hochviskose Masse (Eta = 2. 106 mPa.s), deren weitere Verarbeitung in Beispiel 6 näher beschrieben ist.A mixture of 620 g of polydimethylsiloxane with terminal hydroxyl groups and a viscosity of 18000 mPa.s (20 ° C.) and 270 g of dipropylene glycol (isomer mixture) is heated to 80 ° C. and a mixture of 349.5 g of tolylene diisocyanate (isomer mixture from 80% 2,4- and 20% 2,6-tolylene diisocyanate) and 1.8 g triethylamine evenly with stirring. The reaction temperature is maintained between 80 and 90 ° C during the addition period. After the addition has ended, the mixture is stirred for a further hour and then cooled. A white, highly viscous mass (Eta = 2. 10 6 mPa.s) is obtained, the further processing of which is described in Example 6.

Zur Herstellung einer kalt härtenden Folie werden 50 g dieser Masse mit 2,5 g Äthyltriacetoxysilan und 0.4 g Dibutylzinndilaurat gehärtet. Man erhält ein elastisches Produkt mit einer Shore-A-Härte von 32.To produce a cold-curing film, 50 g of this mass are cured with 2.5 g of ethyl triacetoxysilane and 0.4 g of dibutyltin dilaurate. An elastic product with a Shore A hardness of 32 is obtained.

Beispiel 2Example 2

Eine Mischung aus 1500 g Polydimethylsiloxan des Beispiels 1 und 804 g Dipropylenglykol wird auf 80°C erhitzt und eine Mischung aus 696 g Toluylendiisocyanat des Beispiels 1 und 3,5 g Triäthylamin innerhalb einer Stunde bei 80°C unter Rühren zugegeben. Das Molverhältnis aus Isocyanaten des Toluylendiisocyanats und Hydroxylgruppen des Dipropylenglykols beträgt 1:2.A mixture of 1500 g of polydimethylsiloxane from Example 1 and 804 g of dipropylene glycol is heated to 80 ° C. and a mixture of 696 g of tolylene diisocyanate from Example 1 and 3.5 g of triethylamine is added at 80 ° C. in the course of one hour with stirring. The molar ratio of isocyanates of tolylene diisocyanate and hydroxyl groups of dipropylene glycol is 1: 2.

Nach beendeter Zugabe wird 1 Stunde bei 80°C gerührt und anschliessend abgekühlt.When the addition is complete, the mixture is stirred at 80 ° C. for 1 hour and then cooled.

Das erhaltene gelblich-weiße Produkt hat eine Viskosität von 217 000 mPa.s (20°C).The yellowish-white product obtained has a viscosity of 217,000 mPa.s (20 ° C).

Eine aus dieser Masse gemäss Beispiel 1 hergestellte und ausgehärtete Folie hat eine Shore-A-Härte von 43.A film produced and cured from this composition in accordance with Example 1 has a Shore A hardness of 43.

Beispiel 3Example 3

Eine Mischung aus 1500 g Polymethylsiloxan des Beispiels 1 und 909,5 g Dipropylenglykol wird auf 80°C erhitzt und eine Mischung aus 800,6 g Toluylendiisocyanat des Beispiels 1 und 2,9 g Triäthylamin innerhalb einer Stunde bei 80°C unter Rühren zugegeben. Das Molverhältnis aus Isocyanatgruppen des Toluylendiisocyanats und Hydroxylgruppen des Dipropylenglykols beträgt 1:2.A mixture of 1500 g of polymethylsiloxane from Example 1 and 909.5 g of dipropylene glycol is heated to 80 ° C. and a mixture of 800.6 g of tolylene diisocyanate from Example 1 and 2.9 g of tri thylamine added within one hour at 80 ° C with stirring. The molar ratio of isocyanate groups of tolylene diisocyanate and hydroxyl groups of dipropylene glycol is 1: 2.

Nach beendeter Zugabe wird 1 Stunde bei 80°C gerührt und anschliessend abgekühlt.When the addition is complete, the mixture is stirred at 80 ° C. for 1 hour and then cooled.

Das erhaltene weisse Produkt hat eine Viskosität 230 000 mPa.s (20°C).The white product obtained has a viscosity of 230,000 mPa.s (20 ° C).

Eine aus dieser Masse gemäss Beispiel 1 hergestellte und ausgehärtete Folie hat eine Shore-A-Härte von 11.A film produced and cured from this composition in accordance with Example 1 has a Shore A hardness of 11.

Beispiel 4Example 4

Verwendet man analog zu Beispiel 3 anstelle eines Polydimethylsiloxans der Viskosität 18 000 mPa.s (20°C) ein solches mit einer Viskosität von 10000 mPa.s (20°C) so hat die resultierende Polyurethan-modifizierte Masse eine Viskosität von 85 000 mPa.s (20°C). Eine hieraus gemäss Beispiel 1 hergestellte Folie besitzt eine Shore-A-Härte von 13.If, analogously to Example 3, instead of a polydimethylsiloxane with a viscosity of 18,000 mPa.s (20 ° C.), one with a viscosity of 10,000 mPa.s (20 ° C.) is used, the resulting polyurethane-modified composition has a viscosity of 85,000 mPa .s (20 ° C). A film produced from this in accordance with Example 1 has a Shore A hardness of 13.

Beispiel 5Example 5

368,5 g Dipropylenglykol werden in 600 ml trockenem Toluol gelöst und bei 80°C innerhalb einer Stunde unter Rühren mit einer Mischung aus 239,2 g Toluylendiisocyanat des Beispiels 1 und 2,8 g Triäthylamin versetzt. Nach beendeter Zugabe wird das Lösungsmittel destilliert. Man erhält eine gelbliche, zähe Masse, deren weitere Verarbeitung in Beispiel 6 näher beschrieben ist.368.5 g of dipropylene glycol are dissolved in 600 ml of dry toluene, and a mixture of 239.2 g of tolylene diisocyanate from Example 1 and 2.8 g of triethylamine is added at 80 ° C. with stirring within one hour. When the addition is complete, the solvent is distilled. A yellowish, viscous mass is obtained, the further processing of which is described in Example 6.

Beispiel 6Example 6

Eine Mischung aus 1200 g des Produkts aus Beispiel 1, 600 g des Produkts aus Beispiel 4 und 600 g Polydimethylsiloxan des Beispiels 1 werden 2 Stunden bei 70°C gemischt.A mixture of 1200 g of the product from Example 1, 600 g of the product from Example 4 and 600 g of polydimethylsiloxane from Example 1 are mixed at 70 ° C. for 2 hours.

Die daraus erhaltene weisse, fließfähige Mass hat eine Viskosität von 300 000 mPa.s. Die Große der dispergierten Teilchen wurde zu etwa 1 bis 2,5 Mikron ermittelt.The white, flowable mass obtained from it has a viscosity of 300,000 mPa.s. The size of the dispersed particles was found to be about 1 to 2.5 microns.

Die Zusammensetzung einer kalt härtenden Masse sowie die Eigenschaften des gehärteten Produkts werden in Beispiel 10, Tabelle 1 (Einkomponentensystem) und Tabelle 2 (Zweikomponentensystem) angegeben.The composition of a cold-curing composition and the properties of the cured product are given in Example 10, Table 1 (one-component system) and Table 2 (two-component system).

Beispiel 7Example 7

Eine Lösung von 402 g Trimethylolpropan und 576 g Polydimethylsiloxan des Beispiels 1 in 1150 g trockenem Toluol wird aus 80°C erwärmt und eine Mischung aus 174 g Toluylendiisocyanat des Beispiels 1 und 5 g Triäthylemin bei 80 bis 100°C innerhalb von 2 Stunden unter Rühren zugegeben. Nach Abdestillieren des Lösungsmittels erhält man eine weisse Masse, die in Beispiel 8 weiter verwendet wird.A solution of 402 g of trimethylolpropane and 576 g of polydimethylsiloxane from Example 1 in 1150 g of dry toluene is heated from 80 ° C. and a mixture of 174 g of tolylene diisocyanate from Example 1 and 5 g of triethylemine at 80 to 100 ° C. within 2 hours with stirring admitted. After the solvent has been distilled off, a white mass is obtained which is used further in Example 8.

Beispiel 8Example 8

Eine Mischung aus 50% des Produktes aus Beispiel 1 und 50% des Produktes aus Beispiel 7 ergibt eine weisse, fließfähige Dispersion mit einer Viskosität von 300 000 mPa.s. (20°C). Die mittlere Teilchengrösse der dispergierten Polyurethanpartikel wurde zu 1 bis 2 ,um gefunden.A mixture of 50% of the product from Example 1 and 50% of the product from Example 7 gives a white, flowable dispersion with a viscosity of 300,000 mPa.s. (20 ° C). The average particle size of the dispersed polyurethane particles was found to be 1 to 2 μm.

Die Zusammensetzung einer kalt härtenden Masse sowie die Eigenschaften des gehärteten Produkts sind in Beispiel 9, Tabelle 1 (Einkomponentensystem) und Tabelle 2 (Zweikomponentensystem), gegeben.The composition of a cold-curing composition and the properties of the cured product are given in Example 9, Table 1 (one-component system) and Table 2 (two-component system).

Beispiel 9Example 9

Dieses Beispiel gibt eine Übersicht über die Zusammensetzung einiger kalt härtender Massen und Eigenschaften daraus hergestellter gehärteter Produkte.

Figure imgb0003
Figure imgb0004
Figure imgb0005
 This example provides an overview of the composition of some cold-curing compositions and properties of the hardened products made from them.
Figure imgb0003
Figure imgb0004
Figure imgb0005

Beispiel 10Example 10

Eine Lösung von 35,7 g Dipropylenglykol, 8,9 g Trimethylolpropan und 76,5 g Polymethylsiloxan des Beispiels 1 in 150 g trockenem Toluol wird auf 100°C erwärmt und innerhalb einer Stunde eine Mischung von 0,4 g Triäthylamin und 31,9 g Toluylendiisocyanat zugegeben. Man rührt eine weitere Stunde bei 100°C nach und destilliert anschliessend das Lösungsmittel ab. Der Rückstand hat eine Viskosität von 72 000 mPa.s (20°C) Eine daraus nach Beispiel 1 hergestellte gehärtete Folie hat die Shore-A-Härte 16.A solution of 35.7 g of dipropylene glycol, 8.9 g of trimethylolpropane and 76.5 g of polymethylsiloxane from Example 1 in 150 g of dry toluene is heated to 100 ° C. and a mixture of 0.4 g of triethylamine and 31.9 within one hour g of tolylene diisocyanate added. The mixture is stirred for a further hour at 100 ° C. and then the solvent is distilled off. The residue has a viscosity of 72,000 mPa.s (20 ° C.) A hardened film produced therefrom according to Example 1 has a Shore A hardness of 16.

Beispiel 11 1Example 11 1

Zu einer auf 80°C erwärmten Mischung aus 100 g Polydimethylsiloxan des Beispiels 1,40 g Dipropylenglykol und 2,1 g Glycerin wird eine Mischung von 57,9 g Toluylendiisocyanat des Beispiels 1 und 0,3 g Triäthylamin unter Rühren innerhalb von 0,5 Stunden zugegeben. Nach beendeter Zugabe wird 2 Stunden bei 80°C nachgerührt. Man erhält eine schwach gelbliche, vernetzbare Masse mit einer Viskosität von 220 000 mPa.s (20°C). Eine daraus nach Beispiel 1 hergestellte gehärtete Folie hat die Shore-A-Härte 25.A mixture of 57.9 g of tolylene diisocyanate of Example 1 and 0.3 g of triethylamine is added to a mixture of 100 g of polydimethylsiloxane from Example 1.40 g of dipropylene glycol and 2.1 g of glycerol with stirring within 0.5 Hours added. After the addition has ended, the mixture is stirred at 80 ° C. for 2 hours. A slightly yellowish, crosslinkable mass with a viscosity of 220,000 mPa.s (20 ° C.) is obtained. A hardened film produced therefrom according to Example 1 has the Shore A hardness 25.

Beispiel 12Example 12

Der Versuch des Beispiels 3 wird mit der Abweichung durchgeführt, dass anstelle von Dipropylenglykol Buten-(2)-diol(1,4) verwendet wird.The experiment in Example 3 is carried out with the difference that butene (2) diol (1,4) is used instead of dipropylene glycol.

Man erhält ein hellbraunes, homogenes und vernetzbares Produkt mit einer Viskosität von 145000 mPa.s.A light brown, homogeneous and crosslinkable product with a viscosity of 145000 mPa.s.

Eine daraus nach Beispiel 1 hergestellte gehärtete Folie hat die Shore-A-Härte 17.A hardened film produced therefrom according to Example 1 has the Shore A hardness 17.

Beispiel 13Example 13

Der Versuch des Beispiels 3 wird mit der Abweichung durchgeführt, dass anstelle von Dipropylenglykol Butandiol-1,4) verwendet wird.The experiment in Example 3 is carried out with the difference that butanediol-1,4) is used instead of dipropylene glycol.

Man erhält ein weisses vernetzbares Produkt mit einer Viskosität von 143 000 mPa.sA white crosslinkable product with a viscosity of 143,000 mPa.s is obtained

Eine daraus nach Beispiel 1 hergestellte gehärtete Folie hat die Shore-A-Härte 13.A hardened film produced therefrom according to Example 1 has the Shore A hardness 13.

Beispiel 14.Example 14.

Der Versuch des Beispiels 3 wird mit der Abweichung durchgeführt, dass anstelle von Dipropylenglykol Propandiol-(1,3) verwendet wird.The experiment in Example 3 is carried out with the difference that propanediol- (1,3) is used instead of dipropylene glycol.

Man erhält eine weisse vernetzbare Masse mit einer Viskosität von 182 000 mPa.s.A white crosslinkable mass is obtained with a viscosity of 182,000 mPa.s.

Eine daraus nach Beispiel 1 hergestellte gehärtete Folie hat die Shore-A-Härte 13.A hardened film produced therefrom according to Example 1 has the Shore A hardness 13.

Beispiel 15Example 15

Dieses Beispiel illustriert die Herstellung einer Dispersion aus 50% Polyurethan auf Basis von Toluylendiisocyanat und einem Polyester im Molverhältnis 1:0,9 und 50% eines α,ω-Dihydroxypolydimethylsiloxans.This example illustrates the preparation of a dispersion of 50% polyurethane based on tolylene diisocyanate and a polyester in a molar ratio of 1: 0.9 and 50% of an α, ω-dihydroxypolydimethylsiloxane.

Eine Lösung von 100 g linearem Polyester auf Basis von Adipinsäure und Äthylenglykol mit einem Hydroxygruppengehalt von 1,65% und 107,5 g Polydimethylsiloxan des Beispiels 1 in 200 g Toluol wird auf 80°C erwärmt und hierzu innerhalb eines Stunde eine Mischung von 7,6 g Toluylendiisocyanat des Beispiels 1 und 0,5 g Triäthylamin zugegeben. Nachdem während einer Stunde bei 80°C nachgerührt wurde, erhält man nach Abdestillieren des Lösungsmittels ein weisses, vernetzbares Produkt.A solution of 100 g of linear polyester based on adipic acid and ethylene glycol with a hydroxyl group content of 1.65% and 107.5 g of polydimethylsiloxane from Example 1 in 200 g of toluene is heated to 80 ° C. and a mixture of 7. 6 g of tolylene diisocyanate from Example 1 and 0.5 g of triethylamine were added. After stirring for one hour at 80 ° C., a white, crosslinkable product is obtained after distilling off the solvent.

Beispiel 16Example 16

Eine Mischung aus 1500 g Polydimethylsiloxan des Beispiels 1,909,5 g Dipropylenglykol und 1,5 g Äthylendiaminomethyldimethyläthoxysilan wird auf 80°C erwärmt und 1 Stunde gerührt. Nun werden innerhalb einer Stunde bei 80°C 800,6 g Toluylendiisocyanat des Beispiels 1 zugegeben und 2 Stunden bei gleicher Temperatur nachgerührt. Man erhält eine weisse Masse mit einer Viskosität von 230000 mPa.s (2µ°C).A mixture of 1500 g of polydimethylsiloxane from Example 1.909.5 g of dipropylene glycol and 1.5 g of ethylenediaminomethyldimethylethoxysilane is heated to 80 ° C. and stirred for 1 hour. 800.6 g of tolylene diisocyanate from Example 1 are then added at 80 ° C. in the course of one hour and the mixture is stirred at the same temperature for 2 hours. A white mass with a viscosity of 230,000 mPa.s (2µ ° C) is obtained.

Eine daraus nach Beispiel 1 hergestellte gehärtete Folie hat die Shore-A-Härte 16.A hardened film produced therefrom according to Example 1 has a Shore A hardness of 16.

Beispiel 17Example 17

Der Versuch des Beispiels 3 wird mit der Abweichung durchgeführt, dass man als Katalysator anstelle des Triäthylamins 0,06 ml Dibutylzinndilaurat einsetzt.The experiment in Example 3 is carried out with the difference that 0.06 ml of dibutyltin dilaurate is used as the catalyst instead of the triethylamine.

Man erhält ein weisses Produkt mit einer Viskosität von 185000 mPa.s.A white product with a viscosity of 185,000 mPa.s.

Eine daraus nach Beispiel 1 hergestellte gehärtete Folie hat die Shore-A-Härte 15.A hardened film produced therefrom according to Example 1 has the Shore A hardness 15.

Claims (3)

1. α,ω-Dihydroxypolysiloxanes modified with polyurethane, characterised in that the α,ω-dihydroxypolysiloxane and the polyurethane are present as discernible phases.
2. Method of manufacturing α,ω-dihydroxypolysiloxanes modified with polyurethane, characterised in that the polyurethane is produced by a polyaddition reaction of di- or poly-isocyanates of the general formula
Figure imgb0008
wherein
R' represents an alkylene or arylene radical with preferably up to 24 C atoms which is optionally also substituted by NCO groups, with diols, polyols or polymers containing hydroxyl groups, in α,ω-dihydroxypolysiloxane.
3. Use of the α,ω-dihydroxypolysiloxanes modified with polyurethane for producing one- or two- component systems which cure under the effect of moisture.
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