Classifications

• • 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
  • C08G77/04—Polysiloxanes
  • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
  • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
• • 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
  • C08G77/04—Polysiloxanes
  • C08G77/06—Preparatory processes
  • C08G77/08—Preparatory processes characterised by the catalysts used
• • 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
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
  • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof

Definitions

• the invention relates to the use of organofunctional carboxy compounds as Silanhydrolysekatalysator and / or silanol condensation catalyst, wherein among carboxy compounds according to the invention an organic acid, preferably an organic carboxylic acid having 4 to 46 carbon atoms, such as fatty acids, or a silicon-containing precursor compound of an organic acid , an ⁇ -carboxy silane ((R 3 - (CO) O) 4-z- ⁇ SiR 2 ⁇ (A) z , ⁇ -Si-oxycarbonyl-R 3 ), or a silicon-free precursor compound of an organic acid.
• Precursor compounds of an organic acid are understood herein to mean esters, lactones, anhydrides, salts of organic cations.
• the invention relates to the use of at least one organofunctional carboxy compound for the surface modification of substrates, the substrates modified therewith and a kit for use in the preparation of the substrates.
• organotin compounds are generally characterized by significant toxicity, for example dibutyltin compounds.
• organotin compounds or aromatic sulfonic acids (Borealis Ambicat®).
• organotin compounds are their significant toxicity, while the sulphonic acids are noticeable by their pungent odor, which continues through all process stages to the end product.
• Typical tin silanol condensation catalysts are dibutyltin dilaurate (dibutyltindilaurate, DBTDL) and dioctyltin dilaurate (diocytyltindilaurate, DOTL), which act as a catalyst via their coordination sphere.
• EP 207 627 discloses further tin containing catalyst systems and co-polymers modified therewith based on the reaction of dibutyltin oxide with ethylene-acrylic acid co-polymers.
• JP 58013613 uses Sn (acetyl) 2 as a catalyst and JP 05162237 teaches the use of tin, zinc or cobalt carboxylates together with bonded hydrocarbon groups as silanol condensation catalysts, such as dioctyltin maleate, monobutyltin oxide, dimethyloxybutyltin or dibutyltin diacetate.
• JP 3656545 uses for networking zinc and aluminum soaps, such as zinc octylate, aluminum laurate.
• JP 1042509 also discloses the use of organic tin compounds for cross-linking silanes, but also alkyl titanate esters based on titanium chelate compounds.
• Polyurethanes are also crosslinked in the presence of metal-containing catalysts JP 2007045980.
• the catalyst system mentioned therein consists of a beta-diketone complex with metals, such as cobalt, a tertiary amine and acids.
• the object of the present invention is to develop new silane hydrolysis and / or silanol condensation catalysts which do not have the stated disadvantages of the known catalysts of the prior art and preferably with organofunctional silanes and / or organofunctional siloxanes, as well as with silane-grafted, silane-co-polymerized polymers, monomers or prepolymers disperse or homogenize.
• the silane hydrolysis catalysts and / or silanol condensation catalysts are preferably liquid, wax-like to solid and / or applied or encapsulated on a carrier material.
• An object of the invention is achieved by the use according to the invention according to the features of claim 1 and 2 as well as by the substrate according to 7 and the kit according to claim 12 and the method according to claim 13 and the composition according to claim 15.
• An object of the invention is also a silane-terminated , in particular metal-free, polyurethane. Preferred embodiments are given in the dependent claims and the description.
• carboxy compounds in particular an organic carboxylic acid having 4 to 46 carbon atoms, such as fatty acids, or a silicon-containing precursor compound of an organic acid, in particular a long-chain carboxylic acid or a corresponding silicon-free precursor compound of an organic acid, such as an organofunctional salt, Anhydride, can be used as Silanhydrolysekatalysator and / or silanol condensation catalyst.
• silicon-containing precursor compounds of an organic acid can be used as silane hydrolysis catalyst and / or silanol condensation catalyst, in particular as catalyst for the hydrolysis of organofunctional silanes, oligomeric organofunctional siloxanes and as catalyst for crosslinking or condensation of silanols, siloxanes or with condensation other functional groups of substrates, for example, with hydroxy-functionalized silicon compounds or hydroxy-functionalized substrates (HO-Si or HO substrate).
• the systems catalyzed with the carboxy compounds according to the invention, in particular with fatty acids and / or silicon precursor compounds of an organic acid, in particular a fatty acid have compared to standard systems with, for example, HCl or acetic acid longer pot life and the shelf life of the systems improved significantly.
• coated fillers according to the invention exhibit faster curing and a shorter after-reaction time than the non-catalyzed systems. Therefore, through the use according to the invention of the carboxy compounds, the throughput in the production of coated substrates, in particular of the fillers, such as the flame retardant fillers, can be increased. This measure makes production significantly more economical.
• the precursor compound is that it be hydrolyzable, especially in the presence of moisture, and thus release the free organic acid, especially under the given process conditions of the particular process.
• the silicon-containing precursor compound of the organic acid is hydrolyzed under heat, better in the molten state in the presence of moisture, and at least partially or completely releases the organic acid.
• At least one organofunctional carboxy compound is used as the silane hydrolysis catalyst and / or silanol condensation catalyst and / or for the surface modification of substrates, in particular substrates with functional groups capable of condensation or reaction, such as HO-functionalized substrates, silicates, passivated metals, oxidic compounds, zeolites , Granite, quartz and other familiar to the expert substrates.
• Carboxylic compounds of an organic acid according to the invention are carboxylic acids having 4 to 46 carbon atoms, such as unsaturated, mono- or polyunsaturated fatty acids, synthetic or natural, which may also be further functionalized, or a silicon-containing precursor compound of an organic acid, such as mono, di, tri or tetra ⁇ -carboxysilane, ie which may release an acid as defined above, or a precursor compound of one organic acid, for example an ester, lactone, anhydride, salt of an organic compound of the acid, such as an organic cation, an ammonium, iminium salt of a corresponding acid, or correspondingly protonated secondary, tertiary amines or N-containing heterocycles which can be found in the Disperse silanes or siloxanes.
• the released acid corresponds to the above definition of a carboxylic acid having 4 to 46 carbon atoms, preferably having 8 to 22 carbon atoms.
• the organofunctional carboxy compound is selected from b.1) a silicon-containing precursor compound of an organic acid of the general formula IVa,
• A is independently of one another in formula IVa and / or IVb a monovalent organofunctional group, and A is the bivalent radical in formula IVb is a divalent organofunctional group,
• R 1 independently corresponds to a carbonyl-R 3 group, wherein R 3 corresponds to a radical having 1 to 45 carbon atoms, in particular a saturated or unsaturated hydrocarbon radical (hydrocarbon radical), which may be unsubstituted or substituted,
• R 2 is independently a hydrocarbon group, and / or
• an organic acid selected from the group iii.a) a carboxylic acid containing 4 to 45 C atoms, iii.b) a saturated and / or unsaturated fatty acid and / or iii.c) a natural or synthetic amino acid and /or
• a silicon-free precursor compound of an organic acid in particular an anhydride, ester, lactone, salt of an organic cation, a natural or synthetic triglyceride and / or phosphoglyceride.
• organofunctionalized silane in particular an alkoxysilane
• at least one organofunctionalized silane in particular an alkoxysilane
• a (b.1) silicon-containing precursor compound of an organic acid is not a terminal carboxy-silane compound and according to the invention is a compound of general formula IVa,
• A is independently of one another in formula IVa and / or IVb a monovalent organofunctional group, and A is the bivalent radical in formula IVb for a divalent organofunctional group,
• a as an organofunctional group preferably independently of one another in formula IVa and / or IVb an alkyl, alkenyl, aryl, epoxy, dihydroxyalkyl, aminoalkyl, polyalkylglykolalkyl-, haloalkyl, mercaptoalkyl-, sulfanalkyl-, ureidoalkyl- and or acryloxyalkyl-functional group, in particular a linear, branched and / or cyclic alkyl radical having 1 to 18 C atoms and / or a linear, branched and / or cyclic alkoxy, alkoxyalkyl, arylalkyl, -, aminoalkyl-, haloalkyl- , Polyether, alkenyl, alkynyl, epoxy, methacryloxyalkyl and / or acryloxyalkyl group having 1 to 18 C atoms and / or an aryl group having 6 to 12 C atoms and / or
• A can also be one:
• A may be as divalent radical an olefin radical in formula IVb, such as the corresponding alkenylenes, for example 2-pentenylene, 1,3-butadienylene, iso-3-butenylene, pentenylene, hexenylene, hexenedienylene, cyclohexenylene, terpenylene, Squalanylene, squalene, polyterpenylene, cis / trans polyisoprenylene, and / or
• an olefin radical in formula IVb such as the corresponding alkenylenes, for example 2-pentenylene, 1,3-butadienylene, iso-3-butenylene, pentenylene, hexenylene, hexenedienylene, cyclohexenylene, terpenylene, Squalanylene, squalene, polyterpenylene, cis / trans polyisoprenylene, and / or
• An A may independently of each other in both IVa and IVb be a monovalent amino-functional radical or a divalent amino-functional radical in IVb, in particular A may correspond to an aminopropyl-functional group of the formula - (CH 2 ) S -NH 2 , - (CH 2 ) S -NHR ', - (CH 2 ) 3 -NH (CH 2 ) 2 -NH 2 and / or - (CH 2 ) 3 -NH (CH 2 ) 2 -NH (CH 2 ) 2 -NH 2 , in which R 'is a linear, branched or cyclic alkyl group having 1 to 18 C atoms or an aryl group having 6 to 12 C atoms, A can correspond to one of the following amino-functional groups of the general formula Va or Vb [(CH 2 ) 1 (NH)] n - (CH 2 ) k - (Va)
• R 10 corresponds to a benzyl, aryl, vinyl, formyl radical and / or a linear, branched and / or cyclic alkyl radical having 1 to 8 C atoms, and / or
• a in IVb may correspond to a bivalent bis-amino-functional group of formula VI,
• A may correspond to an epoxy and / or ether radical, in particular a 3-glycidoxyalkyl, 3-glycidoxypropyl, epoxyalkyl, epoxycycloalkyl, epoxycyclohexyl, polyalkylglycolalkyl radical or a polyalkylglycol-3-propyl radical, or the corresponding ring-opened epoxides present as diols.
• A may be a polymer, in particular a silane-terminated polyurethane prepolymer-NH-CO-nBuN- (CH 2 ) 3-; a polyethylene polymer, a polypropylene polymer, an epoxy or other polymer known to those skilled in the art.
• the radical R 1 in the formula IVa and / or IVb can independently of one another correspond to a carbonyl-R 3 group, where R 3 corresponds to a radical having 1 to 45 carbon atoms, in particular a saturated or unsaturated hydrocarbon radical (hydrocarbon radical) unsubstituted or substituted,
• fatty acids such as caprylic acid, oleic acid, lauric acid, capnic acid, stearic acid, palmitic acid, behenic acid and / or myristic acid are used, a particularly preferred fatty acid being selected from caprylic acid, lauric acid, capnic acid, behenic acid and / or myristic acid.
• R 2 in formula IVa and / or IVb independently of one another is a hydrocarbon group, in particular a substituted or unsubstituted linear, branched and / or cyclic alkyl, alkenyl, alkylaryl, alkenylaryl and / or aryl group having 1 to 24 C atoms, preferably having 1 to 18 carbon atoms. In particular with 1 to 3 C atoms in the case of alkyl groups.
• Particularly suitable alkyl groups are ethyl, n-propyl and / or i-propyl groups.
• Suitable substituted hydrocarbons are in particular halogenated hydrocarbons, such as 3-halopropyl, for example 3-chloropropyl or 3-bromopropyl groups, which are optionally accessible to a nucleophilic substitution or which can be used in PVC.
• halogenated hydrocarbons such as 3-halopropyl, for example 3-chloropropyl or 3-bromopropyl groups, which are optionally accessible to a nucleophilic substitution or which can be used in PVC.
• examples of these are methyl-, dimethyl-, ethyl- or methylethyl-substituted carboxysilanes based on caprylic acid, capric acid, myristic acid, stearic acid, palmitic acid, behenic acid, oleic acid or lauric acid, preferably based on myristic acid.
• Carbonyl-R 3 groups are understood to mean the acid radicals of the organic carboxylic acids, such as R 3 - (CO) -, which are bonded as a carboxyl group corresponding to the formulas to the silicon Si-OR 1 , as stated above.
• Silanhydrolysekatalysatoren and / or silanol condensation catalysts can be used.
• fatty acids are used in the formula IVa and / or IVb with a hydrophobic hydrocarbon radical which is sufficiently hydrophobic or lipophilic or dispersible in an organofunctional silane, organofunctional siloxane or optionally in a mixture of one or both compounds and optionally in the presence of a substrate or are homogenizable with the compounds, and after release do not have an unpleasant odor, and not from the produced substrates or polymers efflorescence.
• a hydrocarbon radical is sufficiently hydrophobic if the acid is dispersible or homogenizable in the silane, the siloxane and / or a mixture, optionally with the substrate and optionally with a polymer or a monomer or prepolymer.
• Preferred acid radicals in the formulas IVa and / or IVb result from the following acids, such as capnic acid, caprylic acid, stearic acid, palmitic acid, oleic acid, lauric acid, myristic acid but also behenic acid can be used, myristic acid is preferred.
• the naturally occurring or synthetic unsaturated fatty acids can be converted to the precursor compounds of the formula IVa and / or IVb. They can fulfill two functions at once, on the one hand they serve as silane hydrolysis catalyst and / or as silanol condensation catalyst and they can participate directly in an optionally desired, in particular ionic, radical polymerization by their unsaturated hydrocarbon radicals.
• Suitable acids from which the precursor compounds of the formula IVa and / or IVb with R 3 -COO or R 1 O can be prepared are glutaric acid, lactic acid (R 1 is (CH 3 ) (HO) CH-), citric acid (R 1 equal to HOOCCH 2 C (COOH) (OH) CH 2 -), vulpinic acid, terephthalic acid, gluconic acid, Adipic acid, wherein all carboxyl groups may be Si-functionalized, benzoic acid (R 1 is phenyl), nicotinic acid (vitamin B3, B5).
• R 1 corresponds to corresponding radicals, such as starting from tryptohan, L-arginine, L-histidine, L-phenyalanine, L-leucine, preference being given to using L-leucine
• corresponding compounds of formula IVa and / or IVb can be used based on residues of these acids as Silanhydrolysekatalysator and / or silanol condensation catalyst.
• the silicon-containing precursor compound of an organic acid is active in particular in hydrolyzed form as silane hydrolysis and / or condensation catalyst via the liberated organic acid and even in hydrolyzed or unhydrolyzed form for the reaction of the organofunctional radical in a position, for example, a secondary amine react with a polyurethane prepolymer, grafted onto a polymer and / or co-polymerized with a prepolymer or base polymer or is suitable for crosslinking, for example as a primer.
• the silanol compound formed during condensation contributes to crosslinking by means of formed Si-O-Si siloxane bridges and / or
• Si-O substrate or carrier material bonds This crosslinking can be carried out with other silanols, siloxanes or, in general, with crosslinking functional groups on substrates, fillers and / or support materials and / or components, in particular inorganic substrates, such as mortars, bricks, concrete, aluminates, silicates, metals, metal alloys and others the skilled worker familiar oxydischen and / or hydroxy groups substrates.
• inorganic substrates such as mortars, bricks, concrete, aluminates, silicates, metals, metal alloys and others the skilled worker familiar oxydischen and / or hydroxy groups substrates.
• Preferred fillers and / or support materials are therefore aluminum hydroxides, magnesium hydroxides, fumed silica, precipitated silica, silicates and further of the following fillers and support materials.
• Very particularly preferred precursor compounds are organofunctional A-silane trimyristates, A-silane tricaprylates, A-silane tricaprinates, A-silane trioleates or A-silane trilaurates, wherein A has the above meaning, vinylsilane trimyristate, vinylsilane trilaurate, vinylsilane tricaprate and corresponding alkylsilane compounds or amino-functional silane compounds of aforementioned acids, and / or silane tetracarboxylates Si (OR 1 ) 4 , such as silane tetramyristate, silane tetralaurate, silanetetracate, or mixtures of these compounds.
• R 2 is independently in IVa and / or IVb a hydrocarbon group, preferably R 2 is methyl, ethyl, iso-propyl and / or n-propyl or an octyl group.
• the amino-functional silane tricarboxylates according to the invention can be prepared by reacting 3-halopropyl silane tricarboxylates with ammonia, ethyleneamine or other primary and / or secondary alkylamines. In this way, both the aniofunctional and diaminofunctional tricarboxysilanes can be prepared.
• Organic acids are understood as meaning carboxylic acids which have no sulphate or sulphonic acid groups; in particular they are organic acids corresponding to R 3 -COOH; the silicon-free precursor compound can also be anhydrides, esters or salts, in particular salts of organic cations, of these organic acids More preferably, they have a long-chain, nonpolar, especially substituted or unsubstituted hydrocarbon radical, wherein the hydrocarbon radical may be saturated or unsaturated, for example, R 3 may have 1 to 45 carbon atoms and optionally have further organic groups, with the exception of sulphonic acid and sulfate groups.
• R 3 is preferably a hydrocarbon radical having 1 to 45 C atoms, in particular having 4 to 45 C atoms, preferably having 8 to 45 C atoms, more preferably having 6 to 22 C atoms, preferably having 8 to 22 C atoms , particularly preferably having 6 to 14 carbon atoms, more preferably having R 3 is 8 to 13 carbon atoms, wherein with R 3 11 to 13 C atoms are particularly preferred, these are, for example, lauric or myristic; or hydrogen (R 3 ) and at least one carboxylic acid group (COOH).
• organic acids are organic aryl sulfonic acids, such as sulfonic acid but also naphthalenedisulfonic acids. Thus, those acids with long chain, hydrophobic hydrocarbon radicals are clearly preferred. These acids can also function as dispersing aids and / or processing aids.
• a general requirement of the silicon-containing precursor compound is that it be hydrolyzable under the process conditions of the processes and thus release the free organic acid.
• the hydrolysis should preferably take place only in the crosslinking step of the processes, for example after application to a substrate, a component or even after shaping, for example when heating, in the presence of moisture or entering a water bath after a shaping process or after shaping Presence of moisture.
• the silicon-free precursor compounds are excluded from those which are hydrolyzed by hydrolysis to an inorganic and an organic acid. In the present case no silanol is detected as the inorganic acid.
• Preferred amino-functional tricarboxysilanes are functionalized with myristic acid, Lauhnsäre, Carpylklare, caphnic acid, oleic acid, stearic acid and / or palmitic acid.
• According to the invention are functionalized with myristic acid and Lauhnklare used ⁇ -carboxysilane.
• b.2 is an organic acid selected from the group iii.a) a carboxylic acid containing 4 to 45 carbon atoms, which definition may comprise further functional groups, iii.b) a saturated and / or unsaturated fatty acid and / or iii.c) a natural or synthetic amino acid, wherein as at least one organic acid, iii.b) a saturated and / or unsaturated fatty acid
• Fatty acid valine acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid,
• Capnic acid lauric acid, undecanoic acid, tridecanoic acid, myristic acid, Pentadecanoic, palmitic, margaric, stearic, nonadecanoic, arachidic, behenic, lignoceric, cerotic, montanic, melicic, valeric, butyric, propionic, acetic, formic, undecylenic, palmitoleic, oleic, elaidic, vaccenic, icosenoic, cetolanic Linoleic acid, alpha-linolenic acid, gamma-linolenic acid, arachidonic acid, timnodonic acid, clupanodonic acid, cervonic acid, lignoceric acid (H 3 C- (CH 2 ) 22 -COOH), cerotic acid, lactic acid, citric acid, benzoic acid, nicotinic acid, arachidonic acid (5,8,11 (, 14
• the acids having longer hydrophobic hydrocarbon radicals starting with valeric acid, preferably capric acid, lauric acid and / or myristic acid, are well suited as silanol condensation catalyst.
• the less hydrophobic acids, such as propionic acid, acetic acid, formic acid are only suitable for the reaction with substrates, organofunctional silanes and / or organofunctional siloxanes.
• the odor-intensive fatty acids, such as butyric acid and caprylic acid due to the pungent odor only expedient or less suitable to be unsuitable for use, to be used as a component in a kit, or a method.
• siloxanes, modified substrates, polymers or polymer compounds used for the production of drinking water pipes, in the food sector or for products in direct contact with food or even by the end user is used directly.
• the manufactured siloxanes or modified substrates also in the field of medical technology, for tubes, ect. should continue to be used.
• Organic acids are understood as meaning carboxylic acids which have no sulfate or sulphonic acid groups; in particular they are organic acids corresponding to R 3 -COOH; the silicon-free precursor compound may also be the anhydrides, esters or salts of these organic acids, particularly preferably they have via a long-chain, nonpolar, in particular substituted or unsubstituted hydrocarbon radical, where the hydrocarbon radical may be saturated or unsaturated, for example where R 3 is 1 to 45 C atoms, in particular 4 to 45 C atoms, preferably 8 to 45 C atoms , in particular having 6 to 22 carbon atoms, preferably having 8 to 22 carbon atoms, more preferably having 6 to 14 carbon atoms, particularly preferably having R 3 is 8 to 13 carbon atoms, where R 3 is 11 to 13 C atoms are particularly preferred, these are, for example, lauric acid or myristic acid; or hydrogen (R 3 ) and at least one carboxylic acid group (COOH). Explicitly excluded from the definition of organic
• acids with long chain, hydrophobic hydrocarbon radicals are clearly preferred. These acids can also function as dispersing aids and / or processing aids.
• unsaturated fatty acids can be used, which can fulfill two functions, on the one hand they serve as silanol condensation catalyst and they can participate directly in the radical polymerization by their unsaturated hydrocarbon radicals.
• Suitable acids are lignoceric acid (H 3 C- (CH 2 ) 22 -COOH), cerotic acid, lactic acid, citric acid, benzoic acid, nicotinic acid (vitamin B3, B5), gluconic acid or mixtures of the acids.
• a silicon-free precursor compound of an organic acid for example an organic anhydride or an ester, in particular the abovementioned acids or else natural or synthetic triglycerides, as occur in fats, oils, in particular neutral fats, and / or phosphoglycerides, such as lecithin, Phosphatidylethynolamine, phosphatidynositol, phosphatidylserine and / or diphosphatidylglycehn, or salts, for example, salts of organofunctional cations such as quaternary ammonium salts with alkyl chains or conventional ionic phase transfer catalysts.
• synthetic triglycerides can also be used.
• a general requirement of the precursor compound (Si-free and / or Si-containing) is that it is hydrolyzable under the respective process conditions and thus releases the free organic acid.
• the hydrolysis should preferably occur only in the crosslinking step of the process, in particular after mixing, application and / or shaping, for example by adding moisture and optionally heat.
• the silicon-free precursor compounds are excluded from those which are hydrolyzed by hydrolysis to an inorganic and an organic acid. In the present case no silanol is detected as the inorganic acid.
• silicon-free precursor compounds are not understood to be acid chlorides or generally not corresponding acid halides of the abovementioned organic acids.
• organic acid peroxides should not be construed as a silicon-free precursor compound.
• the abovementioned carboxy compounds are reacted in the presence of at least one organofunctionalized silane; and / or at least one linear, branched, cyclic and / or space-crosslinking oligomeric organofunctionalized siloxane and / or mixtures thereof and optionally in the presence of the substrate as Silanhydrolysekatalysator and / or silanol condensation catalyst and / or used as a catalyst for or in the surface modification of substrates.
• a surface modification is preferably understood to mean the formation of a covalent bond by a condensation step.
• the surface modification can also be carried out by ionic or free-radical reaction of unsaturated carboxy compounds with the substrate. Bonding via supramolecular interactions, especially hydrogen bonds, is also preferred, especially the carboxy compound or its reaction products.
• the organofunctional silicon compound and, optionally, a reaction product of the organofunctional carboxy compound is bonded to the substrate. This can be done according to the invention covalently but also supramolecularly.
• Organofunctionalized silanes and / or organofunctionalized siloxanes which can be used according to the invention can correspond to a.1) at least one organofunctional silane, in particular an alkoxysilane of the general formula III,
• R 5 is independently methyl, ethyl, n-propyl and / or iso-propyl,
• R 4 is independently a substituted or unsubstituted hydrocarbon group and / or
• a.2 correspond to at least one linear, branched, cyclic and / or spatially crosslinked oligomeric organofunctionalized siloxane, the siloxane with chain-like and / or cyclic structural elements being represented in idealized form by the two general formulas I and II, the crosslinked structural elements becoming room-crosslinked Can lead to siloxane oligomers,
• substituents R of the chain-like, cyclic and / or crosslinked structural elements consist of organic radicals and / or hydroxyl groups
• degree of oligomerization for oligomers of the general formula I m in the range of O ⁇ m ⁇ 50, preferably O ⁇ m ⁇ 30, particularly preferred 0 ⁇ m ⁇ 20 and for oligomers of the general formula Il n is in the range of 2 ⁇ n ⁇ 50, preferably 2 ⁇ n ⁇ 30, and / or a.3) a mixture of at least two of said general formula I, II and / or III correspond and / or
• organofunctional silanes are known in the art and may be prepared according to the disclosure of EP 0 518 057.
• the systems catalyzed with the carboxy compounds according to the invention, in particular with fatty acids and / or silicon, containing precursor compounds of an organic acid, in particular a fatty acid, have a longer pot life compared to standard systems with, for example, HCl or acetic acid as the catalyst. Overall, with these systems, the shelf life can be improved and greater flexibility can be achieved.
• organofunctional silanes in particular an alkoxysilane of the general formula III, preferably correspond to
• tetralkoxysilanes are tetramethoxysilane, tetraethoxysilane or mixtures of the aforementioned alkoxysilanes, for trimethoxy, triethoxy and / or tripropoxysilanes a or b is 0, for diethoxy, dimethoxysilanes b is 1 and a is 1, or b equal to 2, or a is equal to 2;
• R 5 is independently methyl, ethyl, n-propyl and / or iso-propyl,
• R 4 is independently a substituted or unsubstituted hydrocarbon group, preferably methyl, ethyl, propyl, hexyl, octyl.
• - B may preferably be independently of one another a monovalent organofunctional group in formula III, wherein
• B is preferably, independently of one another, in formula III an alkyl, alkenyl, aryl, epoxy, dihydroxyalkyl, aminoalkyl, polyalkylglykolalkyl, haloalkyl, mercaptoalkyl, sulfanalkyl, ureidoalkyl and / or acryloxyalkyl-functional group, in particular a linear, branched and / or cyclic alkyl radical having 1 to 18 C atoms and / or a linear, branched and / or cyclic alkoxy, alkoxyalkyl, arylalkyl, -, aminoalkyl, haloalkyl, polyether, alkenyl-, Alkynyl, epoxy, methacryloxyalkyl and / or acryloxyalkyl group having 1 to 18 carbon atoms and / or an aryl group having 6 to 12 carbon atoms and / or a Ureidoalkyl-, mercap
• C atoms or an aryl group or an aralkyl group, preferably a methyl group or a phenyl group means groups F 'are identical or different and F' is a group from the group -CH 2 -, - (CH 2 ) 2 -, - (CH 2 ) 3 -, -O (O) C (CH 2 ) 3 - or -C (O) O- (CH 2 ) 3 -, r 1 is 1 to 100, in particular 1 or 2, and g 'is 0 or 1;
• B may independently of one another in formula III be a monovalent amino-functional radical, in particular B may correspond to an aminopropyl-functional group of the formula - (CH 2 ) 3 -NH 2 , - (CH 2 ) S -NHR ', - (CH 2 ) 3 -NH (CH 2 ) 2 -NH 2 and / or - (CH 2 ) 3 -NH (CH 2 ) 2 -NH (CH 2 ) 2 -NH 2 , wherein R 'is a linear, branched or cyclic alkyl group with 1 to 18 C atoms or an aryl group having 6 to 12 C atoms,
• B can be a cycloalkylaminoalkyl radical, cyclohexylaminoalkyl radical, such as, for example, cyclohexylaminopropyl sesin,
• B can correspond to one of the following amino-functional groups of the general formula Va * or Vb * [(CH 2 ) i (NH)] n - (CH 2 ) k - (Va * )
• R 10 corresponds to a benzyl, aryl, vinyl, formyl radical and / or a linear, branched and / or cyclic alkyl radical having 1 to 8 C atoms, and / or
• B may correspond to an epoxy and / or ether radical, in particular a 3-glycidoxyalkyl, 3-glycidoxypropyl, epoxyalkyl, epoxycycloalkyl, epoxycyclohexyl, polyalkylglycolalkyl radical or a polyalkylglycol-3-propyl radical, or den corresponding ring-opened epoxides present as diols;
• organofunctional siloxanes can be obtained by processes known to those skilled in the art, for example according to EP 0 518 057 A1 and DE 196 24 032 A1, EP 0 518 057 and US 5282998, respectively.
• Preferred organofunctional silanes of the formula III are: alkylsilanes, such as methylthmethoxysilane, methyltriethoxysilane, ethylthmethoxysilane, ethylthethoxysilane, propylthmethoxysilane, propyltriethoxysilane, n- and i-butyltrimethoxysilane, n- and i-butylthethoxysilane, n- and i-pentylthmethoxysilane, n- and i Pentyltriethoxysilane, n- and i-hexylthmethoxysilane, n- and i-octylthmethoxysilane, n- and i-octyltriethoxysilane, hexadecyltrimethoxysilane, hexadecylthethoxysilane,
• Preferred organofunctional siloxanes in particular oligomeric siloxanes corresponding to the idealized formulas I and II, as in a.2) correspond to a linear, branched, cyclic and / or space-crosslinked oligomeric organofunctionalized siloxane, having chain-like and / or cyclic structural elements which in an idealized form the two general formulas I and II are reproduced, it being possible for the crosslinked structural elements to lead to space-crosslinked siloxane oligomers,
• substituents R of the chain-like, cyclic and / or crosslinked structural elements consist of organic radicals and / or hydroxyl groups, and the degree of oligomerization for oligomers of the general formula I m in the range of 0 ⁇ m ⁇ 50, preferably 0 ⁇ m ⁇ 30, particularly preferred 0 ⁇ m ⁇ 20 and for oligomers of the general formula Il n in the range of 2 ⁇ n ⁇ 50, preferably 2 ⁇ n ⁇ 30, and / or
• substituents R Preferably corresponding to the substituents R predominantly or substantially organic radicals and preferably only partially hydroxy groups. Also useful may be the use of siloxanes in which a plurality of substituents R correspond to hydroxy groups.
• the substituents R of the chain-like, cyclic and / or crosslinked structural elements preferably correspond independently of one another to the following organic radicals - a linear, branched and / or cyclic alkyl radical having 1 to 18 C atoms and / or an organofunctional radical having linear, branched and / or cyclic Alkoxy, alkoxyalkyl, arylalkyl, - aminoalkyl, haloalkyl, polyether, alkenyl, alkynyl, epoxy, methacryloxyalkyl and / or acryloxyalkyl group having 1 to 18 carbon atoms and / or an aryl group with 6 to 12 carbon atoms and / or a ureidoalkyl, mercaptoalkyl, cyanoalkyl and / or Isocyanoalkyl- group having 1 to 18 carbon atoms, particularly preferred are the following organic radicals - linear and / or branched alkoxy groups with 1 to 4
• Preferred oligomer mixtures of the siloxanes of the formulas I and / or II have a quotient of the molar ratio Si / alkoxy moiety> 0.5, particularly preferably> 1.
• an oligomer mixture comprises n-propylethoxysiloxanes, where the oligomer mixture comprises 80 to 100 Wt .-% of n-propylethoxysiloxanes having a Oligomehs michsgrad the oligomers of 2 to 6, wherein in particular for oligomers of the general formula I and / or the formula Il n is 1 to 5 and / or m is 0 to 4.
• the degree of oligomerization of the oligomers having chain-like, cyclic and / or crosslinked structural elements corresponds to the number of Si units per molecule.
• the degree of oligomerization is increased by two Si units compared with the counter m and, in the case of the formula II, by an Si unit.
• the composition of each siloxane oligomer is in consideration of the fact that each oxygen atom of a monomeric siloxane unit can function as a bridging agent between two silicon atoms.
• the number of oxygen atoms available also determines the functionality of each individual siloxane unit;
• the organosiloxane units are therefore mono-, di-, tri- and partially tetrafunctional.
• siloxane oligomers with chain-like, cyclic and / or crosslinked structural elements existing structural units accordingly comprise the monofunctional (R) 3-Si-O- with the notation M, the difunctional -O-Si (R) 2-O- with the notation D, the trifunctional (-O-) sSiR to which the symbol T has been assigned and the tetrafunctional Si (-O-) 4 with the symbol Q.
• the designation of the units is carried out according to their functionality with the symbols M, D, T and Q. Based on the knowledge of which building blocks an oligomer is constructed, conclusions about the structural elements possible.
• a structural element can correspond to a section of a conceivable overall structure of an oligomer or to the idealized overall structure of an oligomer in a mixture.
• an oligomer may be composed of chainlike as well as cyclic and / or simultaneously crosslinked structural elements.
• oligomeric siloxanes can also be composed exclusively of chain-like or cyclic or crosslinked structural elements.
• the oligomeric, organofunctional siloxanes can be modified in the presence of the carboxy compounds, in particular of the formula IVa, IVb and / or the organic carboxylic acids, preferably with R 3 equal to 4 to 22 C atoms, particularly preferably with 8 to 14 C atoms be used by substrates.
• they are outstandingly suitable for water-repellent finishing of smooth, porous and / or particulate substrates, in particular of inorganic substrates, such as structural elements, in particular of concrete and porous mineral facade materials.
• the mixture according to the invention has excellent application properties.
• substrates treated according to the invention generally show no color changes.
• mixtures according to the invention of the oligomeric siloxanes and the carboxy compound are generally evaporation-proof and have excellent storage stability, even for emulsions in water, a 50% aqueous emulsion is usable after a period of one year.
• the present mixture can also advantageously be used together, in particular as a finished composition, with monomeric, organofunctional silanes and / or siloxanes and / or silicic acid esters.
• x for the formula VIII represents the degree of oligomerization.
• the degree of oligomerization reflects the number of Si units per molecule.
• GPC method gel permeation chromatography
• 29Si-NMR method 29Si-NMR method
• the present invention also relates to the use of a mixture according to the invention of siloxane oligomers together with the compounds listed below, preferably as a kit comprising an organofunctional silane and / or an organofunctional siloxane and / or mixtures of these and / or their condensation products, in particular with at least one organofunctional silane from the series alkylsilanes, such as methylthmethoxysilane, methylthethoxysilane, ethylthmethoxysilane, ethylthethoxysilane,
• a mixture according to the invention of oligomeric, organofunctional siloxanes is suitable for use as the oil phase in an aqueous, low-viscosity to highly viscous, pasty emulsion, for example as described in EP 0 538 555 A1.
• siloxane-containing mixture together, for example with emulsifiers, buffers, such as sodium carbonate, thickeners, biocides, in particular fungicides, algicides, in an aqueous emulsion.
• the mixture comprising siloxanes together with at least one water-dissolved silane condensate as described, for example, in DE 15 18 551 A, EP 0 587 667 A, EP 0 716 127 A, EP 0 716 128 A, EP 0 832 911 A, EP 0 846 717 A, EP 0 846 716 A, EP 0 885 895 A, DE 198 23 390 A and DE 199 55 047 A, and / or at least one optionally water-soluble fluoroorganic compound, as described in US Pat. No. 5,112,393, US Pat. No. 3,354,022 or WO 92/06101, and / or a water-emulsified silicone wax.
• the substrates to be modified according to the invention have, preferably at least one HO group, MO group and / or O " group, as a rule they have a multiplicity of corresponding functional groups, and are based on or are an organic material, an inorganic one A material or a composite material, where M corresponds to an organic or inorganic cation, M can be a cation, for example a metal cation or an organic cation,
• a Si substrate such as the formation of an Si-O substrate bond or a Si substrate, is preferred Si-O-Si bond, for example between silanols and / or siloxanes, such as the hydrolyzed organofunctionalized silane (III), the hydrolyzed silicon precursor compound of the formula Iva and / or IVb, a siloxane (formula I and / or II), silicates, Silica or derivatives All suitable substrates for condensation functionalized substrates, in particular in particular the fillers, support materials, additives, pigments or flame retardant compounds mentioned
• Suitable substrates are preferably inorganic compounds which have oxidic and / or hydroxyl groups, such as silicates, carbonates, such as calcium carbonate, gypsum, aluminates, zeolites, metals, metal alloys, oxidized or passivated metals and / or alloys, or organic substrates, such as a polymer matrix a polymer, in particular activated (corona treated) polymers such as PE or PP, or also polymers such as PE; PP, EVA, resin, such as epoxy resin, acylate resin, phenolic resin, polyurethane as a polymer matrix, in each case filled or unfilled, as a compound or in the form of an intermediate, a shaped body, granules, pellets and other familiar to the expert substrates with conventional habit and / or used in conventional particle size.
• oxidic and / or hydroxyl groups such as silicates, carbonates, such as calcium carbonate, gypsum, aluminates, zeoli
• Substrates can be smooth, porous, rough, and / or particulate, all the way to complete works, components, parts of buildings, or buildings.
• the substrates are, for example but not limited to powder, dusts, Sands, fibers, flakes of inorganic or organic substrates such as quartz, silicic acid, flame silicic acid, silica-containing minerals, titanium oxides and other oxygen-containing titanium minerals, alumina and other alumina-containing minerals, aluminum hydroxides such as aluminum trihydroxide, magnesium oxide and magnesium oxide-containing minerals, magnesium hydroxides such as magnesium dihydroxide, calcium carbonate and calcium carbonate-containing minerals Minerals, glass fibers, mineral wool fibers, but also special ceramic powders, such as silicon carbide, silicon nitride, boron carbide, boron nitride, aluminum nitride, tungsten carbide, metal or metal powder, in particular aluminum, magnesium, silicon, copper, iron and metal alloys, carbon blacks.
• a substrate, a component, glass, quartz glass, a flame retardant to which reference is made fully to the disclosure of EPO 970985 and EP 955344 and the disclosure to the content of this application, a filler, carrier material, stabilizer, additive, pigments, additive and / or aids.
• the substrate may also be organic, such as textile, wood, paper, cardboard, leather, silk, wool and natural, organic substrates such as vegetable fibers such as linen, flax, silk, cotton and other organic substrates known in the art.
• inorganic substrates such as granite, mortar, brick, concrete, screed, yton, gypsum, in particular as a structural element in the field of building protection, as well as other known to those skilled organic substrates.
• a component can be part of a building, a trade, a work of art or artificial stones, such as Kunststoffmamor, art granite or the like.
• the support may be porous, particulate, swellable or optionally foamy.
• Polyolefins such as PE, PP, EVA or polymer blends, and inorganic or mineral fillers which may advantageously be reinforcing, stretching and flame-retardant, are suitable as the carrier material.
• the support can also be calcined, precipitated and / or ground.
• the carrier materials and fillers are specified below. For example, even a shy glass be used as a substrate.
• the carrier matehal may include, for example, wollastonite, kaolin, as well as calcined, precipitated or ground variants.
• the following flame retardants are preferably used: ammonium orthophosphates, eg. NH4H2PO4, (NH4) 2HPO4 or mixtures thereof (eg FR CROS TM 282, FABUTIT TM 747S), ammonium diphosphates, e.g. NH4H3P2O7, (NH4) 2H2P2O7, (NH4) 3HP2O7, (NH4) 4P2O7, or mixtures thereof (e.g., FR CROS TM 134), ammonium polyphosphates, particularly, but not exclusively, from J. Am. Chem. Soc. 91, 62 (1969), z.
• ammonium orthophosphates eg. NH4H2PO4, (NH4) 2HPO4 or mixtures thereof (eg FR CROS TM 282, FABUTIT TM 747S)
• ammonium diphosphates e.g. NH4H3P2O7, (NH4) 2H2P
• crystal structure phase 1 e.g., FR CROS TM 480
• crystal structure phase 2 e.g., FR CROS TM 484
• mixtures thereof e.g., FR CROS TM 485
• melamine orthophosphates e.g. C3H6N6.H3PO4, 2C3H6N6.H3PO4, 3C3H6N6.2H3PO4, C3H6N6.H3PO4, melamine diphosphates, e.g. B.
• the filler used is preferably inorganic or mineral materials. You can act in an advantageous manner reinforcing, stretching and flame retardant. They carry at least on their surfaces groups which can react with the alkoxy groups, the hydroxyl groups of the silanols or the unsaturated silane compound or the hydrolyzed compound of the siloxanes of the formula I and / or II. As a result, the silicon atom having the functional group bonded thereto can be chemically fixed on the surface. Such groups on the surface of the filler are especially hydroxyl groups.
• fillers are metal hydroxides with a stoichiometric proportion or, in their different dehydration stages, with a substoichiometric proportion of hydroxyl groups up to oxides with comparatively few remaining, but detectable by DRIFT-IR spectroscopy or NIR spectroscopy hydroxyl groups.
• Particularly preferred fillers used are aluminum trihydroxide (ATH), aluminum oxide hydroxide (AIOOH.aq), magnesium dihydroxide (MDH), brucite, huntite, hydromagnesite, mica and montmorillonite.
• ATH aluminum trihydroxide
• AIOOH.aq aluminum oxide hydroxide
• MDH magnesium dihydroxide
• brucite huntite
• hydromagnesite hydromagnesite
• mica and montmorillonite montmorillonite.
• calcium carbonate talc and glass fibers can be used as a filler calcium carbonate, talc and glass fibers can be used.
• char former such as ammonium polyphosphate, stannates, borates, talc, or such can be used in combination with other fillers.
• Surface-modified fillers according to the invention are preferably aluminum hydroxide, magnesium hydroxide, chalk, dolomite, talc, kaolin, bentonite, montmohllonite, mica, silica and titanium dioxide.
• metal stabilizers, processing aids, inorganic or organic pigments, adhesion promoters may optionally be used as stabilizer and / or as further additives.
• titanium dioxide TiO 2
• talc clay, quartz, kaolin, aluminum hydroxide, magnesium hydroxide, bentonite, montmorillonite, mica (muscovite mica), calcium carbonate (chalk, dolomite), paints, talc, carbon black, SiO 2 , precipitated silica, fumed silica, Aluminum oxides such as alpha and / or gamma-alumina, alumina hydroxides, boehmite, barite, barium sulfate, lime, silicates, aluminates, aluminum silicates and / or ZnO or mixtures thereof.
• the additives such as pigments or additives, are preferably in pulverulent, particulate, porous, swellable or possibly foam-like form.
• the carrier material may be nanoscale.
• Preferred support materials, fillers or additives are aluminum hydroxide, magnesium hydroxide, fumed silica, precipitated silica, wollastonite, calcined variants, chemically and / or physically modified, for example kaolin, modified kaolin, in particular ground, exfoliating materials, such as sheet silicates, preferably special kaolins, a calcium silicate , a wax, such as a polyolefin wax based on low density polyethylene (PE-LD), or a carbon black.
• the support material may encapsulate or physically or chemically bond the silicon-containing precursor compound and / or the organofunctional silane compound. It is advantageous if the loaded or unloaded carrier material is swellable.
• ATH aluminum tri hydroxide, Al (OH) 3
• magnesium hydroxide Mg (OH) 2
• fumed silica which is produced on an industrial scale by continuous hydrolysis of silicon tetrachloride in a blast gas flame.
• the silicon tetrachloride is vaporized and then reacts spontaneously and quantitatively within the flame with the water resulting from the oxyhydrogen gas reaction.
• the fumed silica is an amorphous modification of the silica in the form of a loose, bluish powder.
• the particle size is usually in the range of a few nanometers, the specific surface area is therefore large and is generally from 50 to 600 m 2 / g.
• Precipitated silicas are generally prepared from soda water solutions by neutralization with inorganic acids under controlled conditions. After separation from the liquid phase, washing and drying, the crude product is finely ground, z. B. in steam jet mills.
• Precipitated silica is also a broad amorphous silica which typically has a specific surface area of 50 to 150 m 2 / g. Precipitated silica has a certain porosity, in contrast to fumed silica, for example approx. 10% by volume.
• the uptake of the vinylalkoxysilanes and / or the silicon-containing precursor compound or mixtures thereof can therefore be effected both by adsorption on the surface and by absorption in the pores.
• Calcium silicate is generally produced industrially by fusing quartz or diatomaceous earth together with calcium carbonate or oxide or by precipitating aqueous sodium metasilicate solutions with water-soluble calcium compounds. The carefully dried product is usually porous and can absorb water or oils up to five times the weight.
• a porous polymer selected from the group consisting of polypropylene, polyolefins, low carbon carbon ethylene copolymer, ethylene-vinyl acetate copolymer, high density polyethylene, low density polyethylene or linear polyethylene low density.
• the porous polymer may have a pore volume of 30 to 90% and in particular granulated or can be used in pellet form.
• porous polyolefins such as polyethylene (PE) or polypropylene (PP)
• co-polymers such as ethylene copolymers with low-carbon alkenes, for example propene, butene, hexene, octene, or ethylene vinyl acetate (EVA), which are produced via special polymerization techniques and processes.
• the particle sizes are generally between 3 and ⁇ 1 mm, and the porosity can be over 50% by volume, so that the products suitably, in particular large amounts of carboxy compounds IVa and / or IVb and / or the silanes of the formula III and or the siloxanes of the formula I and / or II or mixtures thereof, without losing their free-flow properties.
• Such loaded carrier materials may comprise the kit according to the invention.
• Suitable waxes are in particular polyolefin waxes based on "low density polyethylene” (PE-LD), preferably branched, with long side chains.
• PE-LD low density polyethylene
• the melting and solidification point is generally between 90 and 120 ° C.
• the waxes can generally be mixed well in a low-viscosity melt with the carboxy compounds and / or organofunctional silanes and / or the organofunctional siloxanes or mixtures thereof.
• the solidified mixture is generally sufficiently hard that it can be granulated.
• the kit according to the invention comprises such a mixture, preferably granulated. Soot in its various forms of trade is suitable for. B. for the production of black cable sheathing.
• organofunctional silanes and / or organofunctional siloxanes and / or carboxy compounds such as organofunctional silane-carboxy silane, such as vinyl silane carboxylate of myristic acid or lauric acid, and carrier material, or else of vinylsilane stearate and carrier material or of a tetracarboxysilane and vinylalkoxysilane with carrier material, the following methods are available, inter alia:
• mineral carriers or porous polymers are generally preheated, eg. B. in a heating cabinet at 60 0 C, and placed in a cylindrical container, which was purged with dry nitrogen and filled.
• a silane and / or siloxane and / or a carboxy compound are then added and the container placed in a rolling device which rotates for about 30 minutes.
• highly viscous or waxy silane, siloxane and / or carboxy compound for example, carboxysilane, a free-flowing, superficially dry granules have formed, which is expediently stored under nitrogen in opaque containers.
• the heated carrier may be placed in a dry nitrogen purged and filled mixer, e.g. As a ploughshare mixer type L ⁇ DIGE or a propeller mixer type HENSCHEL.
• the mixer can now be put into operation and the organofunctional silane and / or the organofunctional siloxane and / or carboxysilane, in particular the formula IVa, or mixtures of these are sprayed after reaching the maximum mixing power through a nozzle. After completion of the addition is generally homogenized for about 30 minutes and then the product, for. B. by means of a dry Nitrogen-powered pneumatic conveying, filled into opaque, nitrogen-filled containers.
• Wax / polyethylene wax in pelleted form with a melting point of 90 to 120 0 C or higher can be melted in portions in a heatable vessel with stirrer, reflux condenser and diesstechnikszugabevorides and kept in the molten state. Dry nitrogen is conveniently passed through the apparatus throughout the manufacturing process.
• the liquid propylcarboxysilanes, vinylcarboxysilanes, propylsiloxanes or mixtures can be added to the melt gradually and mixed with the wax by intensive stirring.
• the melt is then discharged to solidify in molds, and the solidified product is granulated.
• the melt may be dropped onto a chilled forming belt, on which it solidifies in a convenient pastille mold.
• surface-modified flame retardants are prepared. It has surprisingly been found that surface-modified flame retardants are obtainable in a simpler, more economical and at the same time environmentally friendly manner by reacting an organofunctional silane or a mixture of organofunctional silanes or an oligomeric, organofunctional siloxane or a mixture of oligomeric siloxanes or a solvent-based preparation based on monomer organofunctional silanes and / or oligomeric, organofunctional siloxanes or a preparation based on water-soluble organofunctional siloxanes on a powdered flame retardant and keeps the flame retardant during the coating in the presence of an inventively usable for carboxy compound in motion.
• the coating agent is dropped, sprayed or sprayed directly into a fluidized bed of the flame retardant to be treated, wherein the Coating usually reacts with the surface of the flame retardant and thus envelops the particles.
• This condensation water and optionally small amounts of alcohol may be formed by condensation or hydrolysis, which with the process exhaust air in a conventional manner an exhaust air purification, eg. As a condensation or a catalytic or thermal afterburning, are supplied.
• a nearly medium free coating can be carried out particularly advantageously, so that it is possible to dispense substantially with additional solvents on account of the dispersibility or homogeneity of the carboxy compounds.
• Suitable solvents are pentane, ethanol, methanol, xylene, toluene, THF, ethyl acetate.
• Economical and environmentally friendly is the use of a pasty or solid preparation based on organofunctional siloxanes and / or organofunctional silanes.
• small amounts of solvent are used or no solvent is added.
• the present invention therefore relates to a process for modifying the surface of substrates, in particular of inorganic fillers, such as kaolin, TiO 2, and pigments, the process according to the invention is explained in more detail with reference to a flame retardant, without restricting the process to it.
• inorganic fillers such as kaolin, TiO 2, and pigments
• the method of modifying the surface of a substrate with a flame retardant by coating the particles with a silicon-containing coating agent wherein an organofunctional silane or a mixture of organofunctional silanes or an oligomeric organofunctional siloxane or a mixture of at least two of the compounds or a solvent-containing preparation the basis of monomeric organofunctional silanes and / or oligomeric, organofunctional siloxanes or a preparation based on siloxanes on an especially pulverulent, flame retardant is applied and the flame retardant is kept in motion during the coating, in the presence of a carboxy-compound according to the invention, in particular as Silanhydrolyskatalysator and / or as Silanolkondensations- catalyst.
• a carboxy-compound according to the invention in particular as Silanhydrolyskatalysator and / or as Silanolkondensations- catalyst.
• the coating agent is brought in the course of 10 seconds to 2 hours at a temperature of 0 to 200 ° C., preferably in the course of 30 seconds to 10 minutes at a temperature of 20 to 100 ° C., particularly preferably in the course of 1 to 3 Minutes at a temperature of 30 to 80 ° C, on.
• the coating agent-coated substrate in particular the filler or the flame retardant, is treated under heat or under reduced pressure or under reduced pressure with simultaneous exposure to heat.
• such a post-treatment of coated with coating agent substrate in particular the filler or flame retardant at a temperature of 0 to 200 ° C., more preferably at a temperature of 80 to 150 ° C., most preferably at a temperature of 90 to 120 ° C. ,
• the process according to the invention is suitably carried out in flowing air or in flowing inert gas, for example nitrogen, carbon dioxide.
• substrates in particular support materials, fillers or flame retardants, having an average particle size (d 50 value) of from 1 to 100 ⁇ m (microns), particularly preferably from 2 to 25 ⁇ m, very particularly preferably from 5 to 15 ⁇ m one.
• d 50 value average particle size
• such a powdered flame retardant is dry, i. H. pourable
• a solvent-containing preparation which has an alcohol content of less than 0.5% by weight, based on the total preparation, and a pH of from 2 to 6 or 8 to 12.
• organofunctional silanes are preferably used for this purpose, such as aminoalkyl- or epoxyalkyl- or acryloyloxyalkyl- or methacryloxyalkyl- or mercaptoalkyl- or alkenyl- or alkyl-functional alkoxysilanes, where the abovementioned hydrocarbon units suitably contain 1 to 8 C atoms and the alkyl groups are in linear, branched or cyclic form may be present.
• organofunctional alkoxysilanes are: 3-aminopropyltrialkoxysilanes, 3-aminopropylmethyldialkoxysilanes, cyclohexylaminopropyltrimethoxysilane, cyclohexylaminopropyltrithoxysilane, cyclohexylaminopropylmethyldimethoxysilane, cyclohexylaminopropylmethyldiethoxysilane, 3-glycidyloxypropyltrialkoxysilanes, 3-acryloxypropyl trialkoxysilanes, 3-methacryloxypropyltrialkoxysilanes, 3-mercaptopropyltrialkoxysilanes, 3-mercaptopropylmethyldialkoxysilanes, vinyltrialkoxysilanes, vinyltris (2-methoxyethoxy) silane, propylthalkoxysilanes, butyltrialkoxysilane
• oligomeric organofunctional siloxanes it is possible according to the invention to use those which emerge in particular from EP 0 518 057 A1 and DE 196 24 032 A1. Preference is given to using those which have as substituents (i) alkyl and alkoxy groups, in particular linear, branched or cyclic alkyl groups having 1 to 24 carbon atoms and alkoxy groups having 1 to 3 carbon atoms, or (ii) vinyl and Alkoxy groups and optionally alkyl groups, in particular alkoxy groups having 1 to 3 carbon atoms and optionally linear, branched or cyclic alkyl groups having 1 to 24 carbon atoms, said oligomeric organoalkoxysiloxanes preferably having a degree of oligomerization of from 2 to 50, particularly preferably from 3 to 20, exhibit.
• Oligomeric, vinyl-functional methoxysiloxanes for example DYNASYLAN® 6490 or Protecsosil® 166, or oligomeric, propyl-functional methoxysilanes, for example DYNASYLAN TM BSM 166, are particularly preferably used
• a solvent-based preparation based on monomeric organofunctional alkoxysilanes and / or oligomeric organofunctional alkoxysiloxanes, which preferably comprises methanol, ethanol, n-propanol, isopropanol and / or water as solvent.
• solvent-containing preparations may also contain emulsifiers.
• the process according to the invention can be carried out as follows:
• the generally liquid coating agent can be fed directly into a bed of pulverulent flame retardant fluidized by the introduction of a gas, such as e.g. As ammonium polyphosphate, are introduced.
• a gas such as e.g. As ammonium polyphosphate
• the particles of the flame retardant are coated with coating agent, wherein the coating agent reacts with the surface of the flame retardant and hydrolysis alcohol or condensation water can be released.
• the thus treated flame retardant is optionally freed after application of the coating agent in a subsequent mixing of the still adhering hydrolysis or condensation water, z. B. by supplying dry warm air and a reduction of pressure.
• the present method may also include the following procedural practices:
• a suitable aggregate into a fluidized bed.
• a suitable aggregate into a fluidized bed.
• This may be, for example, a more or less fast-running mixer or a similar apparatus, wherein the introduced powdered flame retardant is suitably constantly in motion and there is a continuous contact of the individual particles to one another.
• a heatable unit for example, air, nitrogen or CO2 feed, the gas is optionally preheated.
• the amount of the coating agent to be applied depends generally on the intended use of the flame retardant to be coated and is usually dependent on the size of the specific surface of the flame retardant to be coated and the amount of the flame retardant to be coated, wherein z.
• the ratio may take as a guideline the specific surface area of the flame retardant to the specific mesh area of the coating agent for monomolecular coverage.
• Surface-modified flame retardants according to the invention are not only available in a simpler, more economical and environmentally friendly manner, but also have lower water solubility and advantageous properties in the further processing in polymer compositions compared to untreated or treated with other coating compositions flame retardants such.
• the present invention also relates to surface-modified flame retardants obtainable by the process according to the invention.
• the surface-modified and stabilized flame retardants according to the invention can be incorporated with particularly advantageous action in many combustible polymers, for example in polyolefins, such as polyethylene, polypropylene, polystyrene and its Copolmerisate, such as ABS, SAN, saturated or unsaturated polyesters, polyamides. Resins, for example epoxy resins, phenolic resins, acrylic resin, furan resins, polyurethanes and natural or synthetic rubbers.
• polyolefins such as polyethylene, polypropylene, polystyrene and its Copolmerisate, such as ABS, SAN, saturated or unsaturated polyesters, polyamides.
• Resins for example epoxy resins, phenolic resins, acrylic resin, furan resins, polyurethanes and natural or synthetic rubbers.
• surface-modified flame retardants according to the invention can also be advantageously used for the intumescent coating of combustible materials.
• Flammable natural substances such as wood, chipboard or paper
• the flame retardants obtainable according to the invention in a flame-retardant or flame-resistant manner or be intumescent-coated with a dispersion containing the flame retardants according to the invention.
• Also advantageous is the freedom from halogens of the flame retardants of the invention, which thus meet the increasing demands of the market for the environmental friendliness of the products made therefrom.
• the subject matter of the present invention is also the use of flame retardants according to the invention in polymer compounds and for flammable furnishing of combustible natural products.
• the invention also relates to a modified substrate, wherein the modified substrate, in particular its outer and / or inner surface is modified with at least one organofunctional silicon compound and optionally with at least one reaction product of an organofunctional carboxy compound.
• the preparation of the modified substrate can be carried out analogously to the coating of the above-described flame retardant. According to the method, another substrate is then used instead of the flame retardant.
• the substrate as such, d. H. modified as a bulk, for example, when the substrate is first prepared using the silanes, siloxanes and carboxy compound.
• An example is the production of plaster or plasterboard,
• the substrate with an organofunctional silicon compound of a reaction product of the reaction of at least one organofunctionalized silane, in particular a silanol of the general formula III, preferably an alkoxysilane of the formula III; and / or at least one linear, branched, cyclic and / or space-crosslinked oligomeric organofunctionalized siloxane, in particular the generalized in idealized formulas I and / or II, in the presence of at least one organofunctional carboxy compound selected from the group consisting of a silicon-containing precursor compound of an organic acid, in particular the general formula IVa and / or IVb, an organic Acid, and / or a silicon-free precursor compound of an organic acid.
• organofunctional silicon compound of a reaction product of the reaction of at least one organofunctionalized silane in particular a silanol of the general formula III, preferably an alkoxysilane of the formula III; and / or at least one linear, branched, cyclic and / or space-crosslinked
• the abovementioned silanes, siloxanes, organic acids and / or silicon-containing precursor compounds of an organic acid are preferably used to obtain the substrate modified according to the invention.
• Modified is a functionalized substrate, wherein the functionalization via supramolecular interactions, in particular hydrogen bonds, and according to the invention via covalent Si-O substrate bonds or other covalent bridging between Si and the substrate, in particular the organofunctional silicon compound is covalent and the reaction product the organofunctional carboxy compound covalently and / or supramolecularly bound to the substrate.
• the substrate according to the invention is modified with an organofunctional silicon compound of a reaction product from the reaction a.1) of at least one alkoxysilane of the general formula III
• B is, independently of one another, a monovalent organofunctional group in formula III, where B has the meaning defined above,
• R 5 is independently methyl, ethyl, n-propyl and / or iso-propyl,
• R 4 is independently a substituted or unsubstituted carbon-containing group, in particular a hydrocarbons group and / or a.2) at least one linear, branched, cyclic and / or space-crosslinking oligomeric organofunctionalized siloxane having chain-like and / or cyclic structural elements, wherein the siloxanes are represented in an idealized form by the two general formulas I and II, the crosslinked structural elements can lead to space-crosslinked siloxane Lead oligomers,
• Structural elements consist of organic radicals and / or hydroxyl groups, and the degree of oligomerization of oligomers of the general formula I m in the range of
• 0 ⁇ m ⁇ 50 preferably 0 ⁇ m ⁇ 30, particularly preferably 0 ⁇ m ⁇ 20 and for
• organofunctional carboxy compound selected from the group:
• A is independently of one another in formula IVa and / or IVb a monovalent organofunctional group, and A is the bivalent radical in formula IVb is a divalent organofunctional group,
• R 1 independently corresponds to a carbonyl-R 3 group, wherein R 3 corresponds to a radical having 1 to 45 carbon atoms, in particular a hydrocarbon radical;
• R 2 is independently a hydrocarbon group, wherein z, x, y, u A, R 2 , R 1 have the abovementioned meaning, and / or
• an organic acid selected from the group iii.a) a carboxylic acid containing 4 to 45 C atoms, iii.b) a saturated and / or unsaturated fatty acid and / or iii.c) a natural or synthetic amino acid and /or
• a silicon-free precursor compound of an organic acid such as an anhydride, an ester, lactone, salt of an organic cation, in particular a natural or synthetic triglyceride and / or phosphoglyceride, the acids and or precursor compounds corresponding to the above definition, and / or or
• the substrate according to the invention comprises HO groups, MO groups and / or "O groups, and preferably a plurality of substrate-O-silicon-organofunctional compound, and is an organic material, an inorganic material or a composite material Substrate, as well as the meaning of M are called protrude.
• the invention also provides a silane-terminated, preferably metal-reduced, preferably metal-free, polyurethane as adhesive and sealant, this being based on the reaction of at least one aliphatic primary or secondary aminoalkoxysilane and / or the general formula VIa and / or VIb, in particular the general formula Va
• R 6 represents a linear or branched alkyl group having 1 to 18 carbon atoms
• R 7 is independently a methyl group
• R 8 are independently a methyl, ethyl or propyl group
• v 'is 0 or 1 n 'is 0 or 1
• m' is 0, 1, 2 or 3, in particular m 'is 3, is obtainable with a polyurethane prepolymer or thereafter,
• a hydrolysis and / or condensation in particular the alkoxy groups or optionally also the crosslinking of the polyurethanes, in the presence of the carboxy compound as defined above, in particular as Silanhydrolysekatalysator and / or silanol condensation catalyst and / or takes place as a polyurethane crosslinking catalyst.
• joints serve to compensate for movements between individual components, which are caused, for example, by thermal expansions or settling processes.
• sealants are used to seal the joints, for example according to DIN EN ISO 11600. In addition to the sealing function, the sealants also have to compensate for movements due to elastic deformation.
• the base polymers used to make these sealants are silicones, acrylates, butyl rubbers, polysulfides, polyurethanes and MS polymers. Silane-crosslinking polyurethanes are new to this application.
• the reaction of primary, preferably secondary, aminosilanes with isocyanate-containing polyurethane prepolymers leads to silane-terminated polyurethanes which can be crosslinked by means of moisture.
• the crosslinking of corresponding sealants and adhesives can be accelerated by adding a catalyst.
• the carboxy compounds according to the invention such as the organic acid and / or the silicon-containing precursor compound of an organic acid, in particular of the formulas IVa and / or IVb, are corresponding catalysts which accelerate the crosslinking.
• isocyanate-containing polyurethane prepolymers are generally obtained from polyols, usually composed of ethylene oxide and / or propylene oxide, and aliphatic or aromatic isocyanates. It has been found that the reaction of aliphatic secondary aminosilanes of the general formula (VIa) or (VIb) with isocyanate-containing polyurethane prepolymers in the absence of a metal catalyst, in particular a tin catalyst, leads to colorless and low-viscosity silane-terminated polyurethanes.
• a metal catalyst such as. Dibutyltin dilaurate (DBTL) is not necessary for the present silane termination reaction. This is advantageous since in particular an increased content of tin compounds promotes the thermal cleavage of -NR-CO-NR groups.
• these silane-terminated polyurethanes are reacted with a carboxy compound as catalyst, in particular to form adhesives and sealants.
• the low-viscosity, metal-free silane-terminated polyurethanes can be formulated in a simple and economical manner with other additives, such as fillers, plasticizers, thixotropic agents, stabilizers, pigments, etc., into adhesives and sealants.
• silane-terminated polyurethane sealants and adhesives according to the invention are particularly environmentally friendly, since substantially free of residues of metal catalysts, d. H. metal-free.
• metal-containing crosslinking catalysts in the presence of carboxy compounds.
• the metal-containing crosslinking catalysts such as dibutyltin or other common crosslinking catalysts, are used at only 0.06 wt.% To 0 wt.% Relative to the total amount of the sealant in the presence of carboxy compounds.
• the amount of metal-containing crosslinking catalyst can be reduced to below 0.01 to 0 wt.%, More preferably 0.005 to 0 wt.% Relative to the total sealant in the presence of a carboxy compound, as defined above.
• silane-terminated polyurethanes are also the rapid reaction of the isocyanate groups of the polyurethane prepolymer with a secondary aliphatic aminosilane of the general formula (VIa) or (VIb), preferably with DYNASYLAN® 1189 according to the reaction scheme:
• the present invention thus provides metal-free, in particular tin-free, silane-terminated polyurethanes as adhesives and sealants.
• the present invention further provides a metal-free silane-terminated polyurethane which is obtainable by the reaction of at least one aliphatic secondary aminoalkylalkoxysilane of the general formula V, for example where n 'is 1 in (VIa) R "-NH- (CH 2 ) 3 Si (R 1 ) x (OR 2 ) ( 3-X ) or at least one aliphatic secondary aminoalkylalkoxysilane of the general formula (VIb) with n 'equal to 1 (VIb) R "-NH-CH 2 -CH (R 1 ) -CH 2 -Si (R 1 ) ⁇ (OR 2 ' ) (3-X ), where in the formulas (VIa) and (VIb) R "is a linear, branched or cyclic (eg cyclohexyl) alkyl group having 1 to 18 C atoms , preferably having 1 to 6 C atoms, R 1 is a methyl group and R 2 'is
• n ' may be 0 for a primary amine.
• reaction of an aliphatic secondary aminoalkylalkoxysilane with a polyurethane prepolymer is carried out in the absence of a tin catalyst.
• Dibutyltin dilaurate (DBTL) or another dialkyltin dicarboxylate compound is usually used as the tin catalyst in the prior art.
• the polyurethane prepolymer is usually a reaction product of a diol, for example, so-called polyether polyols, such as a polyethylene oxide or polypropylene oxide having terminal hydroxyl groups and a molecular weight of 200 to 2,000 g / mol, or a polyol, d. H. a polyether polyol or a polyester polyol, or mixtures thereof and at least one diisocyanate. As a rule, an excess of diisocyanate is used so that the polyurethane prepolymers contain terminal isocyanate (NCO) groups.
• the diol / polyol component of the polyurethane prepolymer may have both polyether and polyester structures of widely variable molecular weight.
• As diisocyanates can be suitably both aliphatic, z. B. isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), as well as aromatic compounds, e.g. As toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) use.
• IPDI isophorone diisocyanate
• HDI hexamethylene diisocyanate
• aromatic compounds e.g. As toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) use.
• polyurethane prepolymer based on an aliphatic diisocyanate, preferably isophorone diisocyanate (IPDI) or hexamethylene diisocyanate (HDI).
• IPDI isophorone diisocyanate
• HDI hexamethylene diisocyanate
• MDI diphenylmethane diisocyanate
• the present invention is the process for preparing a tacky and sealant of a metal-free silane-terminated polyurethane, wherein at least one aliphatic primary and / or secondary aminoalkylalkoxysilane of the general formula (VIa), as defined above, or at least one aliphatic primary and / or secondary aminoalkylalkoxysilane of the general formula (VIb), as defined above, with a polyurethane prepolymer, in particular in the absence of a metal catalyst, wherein the polyurethane prepolymer carries at least one terminal isocyanate group, - wherein in a further step, a crosslinking in the presence of the carboxy compound accordingly above definition.
• the present invention furthermore relates to the use of carboxy compounds together with at least one primary and / or secondary aliphatic aminosilane of the general formula (VIa) or (VIb) for the preparation of an inventive, in particular metal-free, preferably tin-free, silane-terminated polyurethane adhesive and Sealant, in particular for adhesive and sealant applications.
• the process is carried out as follows:
• an anhydrous mixture of polyetherdiol and polyethertherol at about 30 to 40 ° C. with a diisocyanate.
• the reaction is carried out under protective gas cover and with the exclusion of water.
• the mixture is allowed to react at about 70 ° C. until a constant isocyanate (NCO) content is reached.
• NCO isocyanate
• the reaction mixture may further contain a diluent, preferably inert, for example, toluene. According to the content of NCO can now add a secondary aminosilane.
• the reaction of the polyurethane prepolymer with the secondary aminosilane is preferably carried out at 25 to 80 ° C, with the secondary aminosilane being added preferably in an excess of 5 to 25 mol%.
• the approach is suitably carried out at a temperature in the range of 60 to 75 ° C, especially at approx. 70 ° C, stirred until no more free NCO is detectable.
• a "water scavenger” for example an organofunctional alkoxysilane, preferably vinyltrimethoxysilane or vinyltriethoxysilane.
• metal catalyst-free, silane-terminated polyurethane which can be used advantageously in the presence of a carboxy compound, in particular an organic acid and / or a silicon-containing precursor compound of an organic acid for adhesive and sealant applications.
• silane-terminated polyurethanes preferably have a viscosity of from 12,000 to 25,000 mPa s, more preferably from 15,000 to 20,000 mPa s (viscosity values at 25 ° C. to DIN 53 015) before crosslinking.
• Silane-terminated polyurethanes can thus advantageously together with carboxy compounds for the preparation of preparations for adhesives and Sealant applications are used.
• the silane-terminated polyurethane may suitably be used as the base material. For this purpose, it is generally before the polyurethane and mix this first with plasticizer. Preference is then given to the incorporation of the filler with subsequent degassing of the mass. Thereafter, desiccants, adhesion promoters and other additives are added as a rule. The mass is usually mixed well and filled for example in cartridges.
• the crosslinking can be carried out in the presence of a carboxy compound.
• Adhesives and sealants based on silane-terminated polyurethanes preferably contain, in addition to the silane-terminated polyurethanes, the following components:
• Fillers and / or pigments plasticizers, dry agents, adhesion promoters, rheological additives, eg. To produce thixotropy, stabilizers and preservatives.
• the present invention is also the use, in particular metal-free, silane-terminated polyurethanes in preparations for adhesive and sealant applications in the presence of carboxy compounds according to the above definition.
• the invention also provides a kit comprising at least one organofunctionalized silane, in particular of the general formula III and corresponding definition above, and / or at least one linear, branched, cyclic and / or room-crosslinked oligomeric, organofunctionalized siloxane and / or mixtures, in particular of the formulas I. and / or II, as defined above, this and / or their condensation products and at least one organofunctional carboxy compound, in particular a silicon-containing precursor compound of an organic acid, in particular of the formula IVa and / or IVb, and / or an organic acid, in particular a saturated and / or unsaturated fatty acid according to the above Versions.
• the silane, the siloxane or mixtures thereof have been formulated together with the carboxysilane or formulated separately.
• the carboxy compound according to the above definition is only active by heat treatment as a catalyst in the presence of moisture.
• kits include a diaminofunctional alkoxysilane, an alkylthyryrinic acid silane and a solvent and / or a secondary aminoalkoxysilane, alkylthyryrinic acid silane.
• kits according to the invention may be a substrate mentioned above, in particular a filler, flame retardant, carrier material, pigment, additive, additive and / or adjuvant.
• the invention also provides a process for the preparation of a composition, in particular a modified substrate or articles, comprising organofunctional silicon compounds and a silane hydrolysis catalyst and / or silanol condensation catalyst and optionally a solvent and optionally water, wherein at least one organofunctional silane according to the above Definition and / or a linear, branched, cyclic and / or space-crosslinked oligomeric, organofunctional siloxane as defined above and / or mixtures thereof and / or their condensation products in the presence of a carboxy compound, in particular b.1) a silicon-containing precursor compound of an organic acid the general formula Iva
• A is independently of one another in formula IVa and / or IVb a monovalent organofunctional group, and A is the bivalent radical in formula IVb is a divalent organofunctional group,
• R 1 independently of one another corresponds to a carbonyl-R 3 group, where R 3 corresponds to a radical having 1 to 45 C atoms,
• R 2 is independently a hydrocarbon group, and / or
• an organic acid selected from the group iii.a) a carboxylic acid containing 4 to 45 C atoms, iii.b) a saturated and / or unsaturated fatty acid and / or iii.c) a natural or synthetic amino acid and /or
• a silicon-free precursor compound of an organic acid in particular an anhydride, an ester, a lactone, a salt of an organic cation, in particular a natural or synthetic triglyceride and / or phosphoglyceride,
• a substrate is present during the hydrolysis and / or condensation.
• the composition comprising optionally the substrate can cure, in particular to an article or a coating or coating.
• the substrate may be, in particular inorganic, such as gypsum, mortar, masonry, concrete, or organic, preferably a filler, flame retardant, carrier material, pigment, additive, additive and / or adjuvant.
• the process is usually carried out at a pH between pH 1 to 12, preferably at pH 2 to 9, preferably at pH 2 to 6 or 7 to 9.
• solvents are pentane, toluene, xylene, alcohols, such as ethanol, propanol, methanol, ethers, such as THF, tert-butyl methyl ether and other solvents known to the person skilled in the art.
• the solvents can be used pure or mixed with water. Alternatively, water or a water / alcohol mixture can be used as the solvent.
• the process is particularly preferably carried out without the separate addition of a solvent. Therefore, the process is particularly environmentally friendly and significantly reduces the amount of solvent. It is particularly preferred if the hydrolysis and / or condensation in the composition takes place at elevated temperature with the surrounding moisture or moisture contained in the composition.
• the hydrolysis and / or condensation is preferably carried out between 20 and 120 ° C. ( 0 C), particularly preferably between 30 and 100 ° C.
• modified substrates Various methods are available for the preparation of modified substrates. These are the so-called pre-treatment method, the in-situ method and the dry-silane method, generally for the production of modified substrates analogous to the above-performed method for coating flame retardant fillers.
• the invention thus also provides a composition, in particular a modified substrate or an article, obtainable by the above process optionally after crosslinking and or curing.
• the invention also provides the silicon-containing precursor compound of an organic acid of the formula IVa and / or IVb as defined above, in particular where a silicon-containing precursor compound of an organic acid is not a terminal carboxy-silane compound. According to the invention, it is a compound of the general formula IVa,
• A is independently of one another in formula IVa and / or IVb a monovalent organofunctional group, and A is the bivalent radical in formula IVb for a divalent organofunctional group,
• a as an organofunctional group preferably independently of one another in formula IVa and / or IVb an alkyl, alkenyl, aryl, epoxy, dihydroxyalkyl, aminoalkyl, polyalkylglykolalkyl-, haloalkyl, mercaptoalkyl-, sulfanalkyl-, ureidoalkyl- and or acryloxyalkyl-functional group, in particular a linear, branched and / or cyclic alkyl radical having 1 to 18 C atoms and / or a linear, branched and / or cyclic alkoxy, alkoxyalkyl, arylalkyl, -, Aminoalkyl, haloalkyl, polyether, alkenyl, alkynyl, epoxy, methacryloxyalkyl and / or acryloxyalkyl group having 1 to 18 carbon atoms and / or an aryl group having 6 to 12 carbon atoms and / or a
• A can also be one:
• A may be as divalent radical an olefin radical in formula IVb, such as the corresponding alkenylenes, for example 2-pentenylene, 1,3-butadienylene, isobutyl, 3-butenylene, pentenylene, hexenylene, hexenedienylene, cyclohexenylene, terpenylene, squalanylene, squalene, polyterpenylene, cis / trans-polyisoprenylene, and / or
• an olefin radical in formula IVb such as the corresponding alkenylenes, for example 2-pentenylene, 1,3-butadienylene, isobutyl, 3-butenylene, pentenylene, hexenylene, hexenedienylene, cyclohexenylene, terpenylene, squalanylene, squalene, polyterpenylene, cis / trans-polyisopre
• an A may independently of each other in both IVa and IVb be a monovalent amino-functional radical or a bivalent amino-functional radical in IVb, in particular A may correspond to an aminopropyl-functional group of the formula - (CH 2 ) S-NH 2 , - (CH 2 ) S-NHR ', - (CH 2 ) 3 -NH (CH 2 ) 2 -NH 2 and / or - (CH 2 ) 3 -NH (CH 2 ) 2 -NH (CH 2 ) 2 -NH 2 , in which R 'is a linear, branched or cyclic alkyl group having 1 to 18 C atoms or an aryl group having 6 to 12 C atoms,
• A can be a cycloalkylaminoalkyl radical, cyclohexylaminoalkyl radical, such as, for example, cyclohexylaminopropyl sesin,
• A can correspond to one of the following amino-functional groups of the general formula Va or Vb
• R 10 corresponds to a benzyl, aryl, vinyl, formyl radical and / or a linear, branched and / or cyclic alkyl radical having 1 to 8 C atoms, and / or
• VIb can correspond to a bivalent bis-amino-functional group of formula VI,
• A may correspond to an epoxy and / or ether radical, in particular a 3-glycidoxyalkyl, 3-glycidoxypropyl, epoxyalkyl, epoxycycloalkyl, epoxycyclohexyl, polyalkylglycolalkyl radical or a polyalkylglycol-3-propyl radical, or the corresponding ring-opened epoxides present as diols.
• A may be a silane-terminated polyurethane prepolymer-NH-CO-nBuN- (CH 2 ) 3.
• the radical R 1 in the formula IVa and / or IVb can independently of one another correspond to a carbonyl-R 3 group, where R 3 corresponds to a radical having 1 to 45 carbon atoms, in particular a saturated or unsaturated hydrocarbon radical (hydrocarbon radical) unsubstituted or substituted,
• R 2 in formula IVa and / or IVb independently of one another is a hydrocarbon group, in particular a substituted or unsubstituted linear, branched and / or cyclic alkyl, alkenyl, alkylaryl, alkenylaryl and / or aryl group having 1 to 24 C atoms, preferably having 1 to 18 carbon atoms. In particular with 1 to 3 C atoms in the case of alkyl groups.
• Particularly suitable alkyl groups are ethyl, n-propyl and / or i-propyl groups.
• Suitable substituted hydrocarbons are in particular halogenated hydrocarbons, such as 3-halopropyl, for example 3-chloropropyl or 3-bromopropyl groups, which are optionally accessible to a nucleophilic substitution or which can be used in PVC.
• x is 0 and z is 1 or 2 or optionally 3
• A is not an alkyl radical and no vinyl radical or k is 1.
• R 3 has preferably 4 to 22 C-atoms, particularly preferably 8 to 14 C-atoms.
• -OR 1 is a myristyl radical
• A is in particular no vinyl and optionally no olefin and / or unsubstituted alkyl radical, preferably x is 0.
• Preferred carboxysilanes have as functional group A aminopropyl, aminoethyl-aminopropyl, aminoethyl -aminoethyl-aminopropyl, N-butyl-aminopropyl, N-ethylaminopropyl, cyclohexylaminopropyl, glycidyloxypropyl, methacryloxypropyl, perfluoroalkyl,
• the preparation of said carboxysilanes is carried out by reacting the substituted with the corresponding organofunctional group A halosilanes optionally in a solvent with the corresponding organic acids, in particular with the corresponding carboxylic acids.
• the invention also provides the use of the modified substrate according to one of claims 1 to 10 or in particular of the polyurethane according to claim 11 for or as adhesives, sealants, polymer compounds, adhesives, adhesives, paints and / or paints.
• the invention also provides the use of carboxy compounds, in particular of the formula IVa and / or IVb and / or an organic acid, together with at least one organofunctionalized silane, in particular the Formula III, and / or at least one linear, branched, cyclic and / or space-crosslinked oligomeric organofunctionalized siloxane, in particular of the formula I and / or II, and / or mixtures thereof as defined above for the treatment, modification, hydrophobization and / or oleophobation of substrates or for finishing substrates with anti-fingerprint and / or anti-graffiti properties, as a primer, as a binder, as building protection.
• organofunctionalized silane in particular the Formula III
• at least one linear, branched, cyclic and / or space-crosslinked oligomeric organofunctionalized siloxane in particular of the formula I and / or II, and / or mixtures thereof as defined above for the treatment, modification, hydrophobization and / or
• Another object of the invention provides for the use of at least one silicon-containing precursor compound of an organic acid in the production of articles, in particular moldings, preferably of cables, hoses or pipes, more preferably of drinking water pipes or hoses in the medical field.
• the present invention relates to the use of a silane and / or siloxane, in particular an oligomeric mixture of n-propylethoxysiloxanes and a carboxy compound according to the invention for the treatment of substrate surfaces, in particular of smooth, porous and / or particulate substrates, particularly preferably water (Hydrophobing), oil (oleophobization), dirt-repellent, biofouling and / or corrosion-preventing equipment of inorganic surfaces.
• the oligomeric mixture can be used for antigraffiti applications or in agents, in particular in compositions for anti-graffiti applications, in particular in compounds with fluoroorganic compounds or fluoro-functional silanes or siloxanes.
• silanes and / or siloxanes and the carboxy compounds according to the invention are suitable for use in the deep impregnation of building materials or structures, especially mineral building materials such as concrete, limestone , Granite, lime, marble, pearlite, Clinker, bricks, porous tiles and tiles, terracotta, natural stone, aerated concrete, fiber cement, prefabricated concrete components, mineral plaster, screed, pottery but also artificial stone, masonry, facades, roofs and buildings, such as bridges, port facilities, residential buildings, industrial buildings and public buildings Buildings such as multi-storey car parks, train stations or schools, but also finished parts such as railway sleepers or L-bricks - to name just a few examples.
• building materials or structures especially mineral building materials such as concrete, limestone , Granite, lime, marble, pearlite, Clinker, bricks, porous tiles and tiles, terracotta, natural stone, aerated concrete, fiber cement, prefabricated concrete components, mineral plaster, screed, pottery but also artificial stone, masonry, facades, roofs
• siloxane oligomers for hydrophobing, oil, dirt and / or color-repellent equipment, biofouling and / or corrosion-preventing or adhesion-promoting equipment and / or Surface modification of textiles, leather, cellulose and starch products, for the coating of glass and mineral fibers, as binders or as an additive to binders, for the surface modification of fillers, for improving the rheological properties of dispersions and emulsions, as adhesion promoters, for example the improvement of the adhesion of organic polymers to inorganic substrates, as release agents, as crosslinkers or as additives for paints and varnishes.
• the resulting mixtures of silanes and / or siloxanes can be used with the carboxy compounds of the invention, for anti-graffiti applications, or in compositions, especially in compositions for anti-graffiti applications, especially in compounds containing fluoroorganic compounds or fluoro-functional silanes or siloxanes
• the present invention relates to the use of a mixture according to the invention of n-propylethoxysiloxanes and carboxy compound for treating smooth, porous and / or particulate substrates, for example powders, dusts, sands, fibers, flakes of inorganic or organic substrates, such as quartz, silicic acid, flame silicic acid, Silica-containing minerals, titanium oxides and other oxygen-containing titanium minerals, alumina and other alumina-containing minerals Minerals, aluminum hydroxides such as aluminum trihydroxide, magnesium oxide and magnesium oxide-containing minerals, magnesium hydroxides such as magnesium dihydroxide, calcium carbonate and calcium carbonate-containing minerals, kaolin, wollastonite, talc, silicates, phyllosilicates and their respective modified vehicles, ie calcined ground kaolin, etc .; Glass fibers, mineral wool fibers, but also special ceramic powders, such as silicon carbide, silicon nitride, boron carbide, boron n
• organofunctional carboxysilanes of the general formula Iva and / or IVb for example, for preparing an organofunctional tricarboxysilane 1 mol of the silane, reacted with 3 mol or an excess of organic mono-carboxylic acid directly or in an inert solvent, in particular elevated temperature, implemented.
• amino-functional silanes it may be preferable to react the reaction with salts of the carboxylic acid, such as magnesium salts, for example of stearic acid, lauric acid or myristic acid, or to carry out a reaction with corresponding esters of the acids with water separation.
• the amino groups are previously blocked with conventional protecting groups.
• Aminocarboxysilanes are preferably prepared by the process described under g).
• an organofunctional tricarboxysilane corresponding to 1 mol of an organofunctional trichlorosilane with 3 mol or an excess of an organic mono-carboxylic acid directly reacted or reacted in an inert solvent.
• the reaction takes place at elevated Temperature, for example up to the boiling point of the solvent or the melting temperature of the organic fatty acid or organic acid.
• tetracarboxysilanes 1 mol of tetrahalosilane, in particular tetrachlorosilane or tetrabromosilane, is reacted with 4 mol or an excess of at least one mono-carboxylic acid, for example a fatty acid or fatty acid mixture.
• the reaction can be carried out directly by melting or in an inert solvent, preferably at elevated temperature.
• alkenyltricarboxysilane 1 mol of an alkenyltrichlorosilane, or generally an alkenyltrihalosilane, is reacted directly with 3 mol or an excess of the organic mono-carboxylic acid or reacted in an inert solvent, in particular at elevated temperature.
• an alkyltricarboxysilane 1 mol of an alkyltrichlorosilane is reacted directly with 3 mol or an excess of an organic monocarboxylic acid or reacted in an inert solvent.
• the reaction preferably takes place at elevated temperature, for example up to the boiling point of the solvent or around the melting point of the organic fatty acid or of the organic acid.
• tetracarboxysilanes 1 mol of tetrahalosilane, in particular tetrachlorosilane or tetrabromosilane, is reacted with 4 mol or an excess of at least one mono-carboxylic acid, for example a fatty acid or fatty acid mixture.
• the reaction can be carried out directly by melting or in an inert solvent, preferably at elevated temperature.
• the halopropyl or haloalkylsilanes for example a chloropropyltricarboxysilane
• the aminocarboxysilane can be reacted in the presence of an aminoalkylsilane or of ammonia getting produced.
• the diaminoalkyls of the carboxy silanes can also be prepared.
• the clear liquid was transferred to a one-necked flask and the toluene was removed by rotary evaporation.
• the oil bath temperature was about 80 0 C set.
• the vacuum was adjusted stepwise to ⁇ 1 mbar.
• the product was a clear liquid.
• the liquid was characterized by NMR ( 1 H, 13 C, 29 Si) as Vinyltricaprylsilan.
• the vacuum was adjusted stepwise to ⁇ 1 mbar.
• the product was an oily yellow liquid with a slightly pungent odor.
• the liquid was essentially characterized by NMR ( 1 H, 13 C, 29 Si) as hexadecyltricarprylsilane.
• the solid was remelted and stirred at an oil bath temperature of about 90 0 C and a vacuum of ⁇ 1 mbar. After about 4.5 hours, no more gas bubbles were detected.
• the solid was characterized by NMR ( 1 H, 13 C, 29 Si) as chloropropyltripalmitylsilane.
• Reaction Dynasylan® VTC with myristic acid 40.5 g of myristic acid and 130 g of toluene are introduced into the reaction flask, mixed and heated to about 60 0 C. 9.5 g of Dynasylan® VTC are added dropwise within 15 minutes by means of a dropping funnel. Upon addition, the temperature in the flask is increased by about 10 0 C. After the addition is stirred for 15 minutes and then the temperature of the oil bath to 150 0 C increased. During the stirring, a gas evolution (HCL gas) is observed. It was stirred until no more gas evolution was observed (Gasabgangshahn) and stirred for 3h.
• HCL gas gas evolution
• Reaction Dynasylan® PTCS with myristic acid 40.5 g of myristic acid and 150 g of toluene are introduced into the reaction flask, mixed and heated to about 60 0 C. By means of a dropping funnel, Dynasylan® PTCS is added dropwise within 15 minutes. When added, the temperature in the flask increases by about 10 ° C. After the addition, the temperature of the oil bath is raised to 150 0 C and stirred for 3 h. During the stirring, a gas evolution, HCL gas, is observed. It was stirred until no more gas evolution was observed at the gas outlet cock.
• the magnesium stearate and toluene were submitted.
• the vinyltrichlorosilane was rapidly added dropwise in two steps with a pipette. It formed a white suspension.
• the suspension was heated to about 100 ° C. with permanent stirring (magnetic stirrer).
• the vapor phase in the flask was analyzed with a pH paper. The vapor phase was very acidic.
• the oil bath was left at 100 0 C and left at this temperature with continuous stirring. Subsequently, the oil bath temperature was raised to 150 ° C.
• the examined vapor phase is still very acidic. The experiment was stopped for about 6 hours.
• the liquid in the flask was filtered by means of a pleated filter and filled into a one-necked flask. The solid on the pleated filter is not water soluble.
• a Vigreux column In addition to the four-necked flask, a Vigreux column, a simple distillation bridge with a downstream water separator was used in this approach. (Magnetic stirrer, oil bath and the N 2 overlay). In order to avoid a vapor in the water separator on the return connection, a small water cooler was installed, which enforced by condensation of the steam at this point only an escape of the vapor through the Vigreux column. First, the myristic (tetradecanoic), then the n-heptane and Finally, the vinyltrimethoxysilane was added. The oil bath was set at 155 ° C.
• the product obtained was mainly characterized by NMR analysis as Vinyltrimyristinat.
• Solvent, acid and water are presented.
• the silanes are mixed and metered into the acid-water solvent mixture with stirring. Within a few minutes, the solution becomes clear and continues for about 30 minutes. touched. This solution can be used for several days. Brushed onto aluminum, flexible, transparent, 0.5 to 15 ⁇ m thick coatings are achieved. Curing is best carried out at elevated temperature (eg 5 min, 200 ° C.).
• the solution becomes clear and continues for about 30 minutes. touched. This solution can be used for several days. Brushed onto aluminum, flexible, transparent, 0.5 to 15 ⁇ m thick coatings are achieved. Curing is best carried out at elevated temperature (e.g., 5 min.
• Solvent, acid and water are presented.
• the silanes are mixed and metered into the acid-water solvent mixture with stirring.
• the solution becomes clear within 24 h and stirring is continued for about 24 h.
• This solution can be used for several months.
• Rigged on aluminum, flexible, transparent, 0.5 to 15 ⁇ m thick coatings with a strong beading effect are achieved compared to applied liquids (contact angle> 90 °).
• the curing is best carried out at elevated temperature (eg 10 min 200 0 C).
• the solution becomes clear and continues for about 30 minutes. touched. This solution can be used for several days. Brushed onto aluminum, flexible, transparent, 0.5 to 15 ⁇ m thick coatings are achieved. Curing is best carried out at elevated temperature (eg 15 min, 200 ° C.).
• the filler is filled in the heated mixing chamber (about 60 ° C) and started the mixing process.
• the measured temperature in the chamber falls first to below 50 0 C.
• the speed is reduced and, where the silane into the mixer (injecting / Spot-on filler). It should be noted that the silane in any case only comes into contact with the filler.
• the speed is then slowly adjusted to approximately 200 rpm and mixed for 20 minutes. After the 20 min, a vacuum is applied (about 400 mbar), wherein before applying the vacuum, the speed is reduced to about 50 U / min and slowly after reaching the desired negative pressure again increased to 200 rev / min. After drying for 60 minutes, the filler is removed from the mixer.
• silanes alkylsilane oligomer Dynasylan® 9896 or alkylsilane Dynasylan® OCTEO with additionally 1% by weight of stearic acid, based on the silane
• the filler is filled in the heated mixing chamber (about 60 0 C) and started the mixing process.
• the temperature measured in the chamber initially drops below 50 ° C.
• the speed is reduced and, where the silane into the mixer (injecting / Spot-on filler). It should be noted that the silane in any case only comes into contact with the filler.
• the speed is then slowly adjusted to approximately 200 rpm and mixed for 15 minutes. After the 15 minutes, a vacuum is applied (about 400 mbar), wherein before applying the vacuum, the speed is reduced to about 50 U / min and slowly after reaching the desired negative pressure again increased to 200 rev / min. After 40 minutes drying time, the filler is removed from the mixer.
• Two beakers are filled with water.
• One spatula tip sample each of the untreated and the treated filler is placed on a respective water surface and the time is stopped until the filler decreases. - sinking test
• Each treated and untreated sample are piled side by side and a drop of water from 1 ml of water placed on the respective heap, It is the time determined until the water droplet is sunken.
• TiO2 (Kronos® 2081) are placed in the stainless steel container of the Primax mixer.
• the silane is added dropwise to the filler in 1 - 2 ml portions. During the dropping, mix the mixer at a slow speed (1 sec.). Between the addition of silane is further mixed at Skt. 1 for about 1 min. After complete addition of the silane, mixing is continued at Skt. 2.5 for 15 minutes.
• the filler is placed on a stainless steel sheet and finally min. Dried at 80 0 C for 3.5 h.
• TiO2 (Kronos® 2081) are placed in the stainless steel container of the Primax mixer.
• the silane containing 1% by weight palmitic acid with respect to the silane is added dropwise to the filler in 1-2 ml portions each. During the dropping, mix the mixer at a slow speed (1 sec.). Between the addition of silane is further mixed at Skt. 1 for about 1 min. After complete addition of the silane, mixing is continued at Skt. 2.5 for 15 minutes.
• the filler is placed on a stainless steel sheet and finally min. Dried at 80 0 C for 2.5 h.
• Efficiency test Stability of the aqueous dispersion
• a curing wedge was filled with the freshly prepared sealant and a button was applied to cardboard. The latter serves to determine the density of the skin.
• the hardening of the sealing compounds is somewhat delayed in the tricarboxysilanes only at the beginning compared to the tin catalyst system. After two days, 4 mm cured in the tricarboxysilane catalysed sealants and 5 mm at
• Formulations 1, 3 and 4 were each added to the gypsum at 2% by weight relative to the total amount, Formulation 2 became 3% by weight and Formulation 5 was 1% by weight based on the total amount of gypsum added.

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• 2008
  • 2008-09-09 DE DE102008041920A patent/DE102008041920A1/de not_active Withdrawn
• 2009
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  • 2009-07-09 WO PCT/EP2009/058723 patent/WO2010028877A1/de active Application Filing
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