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
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
  • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/61—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
  • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
  • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
  • C08G18/765—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group alpha, alpha, alpha', alpha', -tetraalkylxylylene diisocyanate or homologues substituted on the aromatic ring
• • 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
  • C08G2101/00—Manufacture of cellular products
• • 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
  • C08G2110/00—Foam properties
  • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

Definitions

• the invention relates to foamable preparations based on organosilicon compounds, silicone-containing polyurethane foams, in particular molded foams, having low densities and processes for their preparation.
• Polyurethane foams are generally made by reacting a polyisocyanate with compounds containing two or more active hydrogen atoms.
• the active hydrogen-containing compounds are usually polyols, primary and secondary polyamines, and water. Between these reactants, two main reactions take place during the production of a polyurethane foam. These reactions must, in principle, proceed simultaneously and at a competitively balanced rate during the process to obtain a polyurethane foam having desired physical properties.
• the reaction between the isocyanate and the polyol or polyamine commonly referred to as a gel reaction, results in the formation of a high molecular weight polymer. The progress of this reaction increases the viscosity of the mixture and generally contributes to cross-linking formation with polyfunctional polyols.
• the second main reaction takes place between the polyisocyanate and water.
• This reaction contributes to urethane polymer growth and is important for the formation of carbon dioxide gas which promotes foaming.
• this reaction is often referred to as the blowing reaction.
• Both the gel and the blowing reactions take place in foams that are partially or completely driven by carbon dioxide gas. For example, if the carbon dioxide evolution is too fast compared to the gel reaction, the foam tends to collapse. Alternatively, if the gel expansion reaction is too fast compared to the carbon dioxide-generating blowing reaction the foam increase is limited, resulting in a high density foam. Also, poorly aligned cross-linking reactions will adversely affect foam stability.
• the polyols used are generally polypropylene glycols, which can be prepared according to the prior art in a variety of topologies and differ from each other in molecular weight, the degree of branching and the OH number.
• the commercially available polyurethane foams have their inherent flammability as a serious drawback.
• a path to fire-retardant PU flexible foams is taken with silicone flexible silicone foams.
• the readily combustible polyol component used in standard PU foams is replaced by non-combustible OH-terminated siloxanes.
• silicone-polyurethane copolymers i. Of polysiloxanes which also contain polyurethane and / or urea units, it is possible to use such incombustible
• EP 1485419 Bl which describes the preparation of silicone-polyurethane foams starting from alkylamino- or alkylhydroxy-terminated silicone oils and diisocyanates in the so-called “one-shot process.” DE describes further
• silicone PU foams Prepolymers which are prepared on the basis of alkylamino or alkylhydroxy-terminated silicone oils and diisocyanates in a solvent-based process.
• the silicone polyurethane foams described so far have in common that they are based on linear or only very
• NCO-terminated silicone prepolymers must be used when silicone PU foams are to be obtained with low densities.
• prepolymers are associated with an additional synthesis step, and on the other hand, such prepolymers have only a limited storage stability, especially at elevated temperatures.
• the invention relates to foamable compositions containing
• R may be the same or different and is hydrogen or a monovalent, optionally substituted hydrocarbon radical
• R 1 may be the same or different and is a divalent, optionally substituted hydrocarbon radical which may be interrupted by heteroatoms,
• R 2 may be the same or different and is a divalent, optionally substituted hydrocarbon radical which may be interrupted by heteroatoms,
• R 3 may be identical or different and is hydrogen or monovalent, optionally substituted hydrocarbon radical
• X may be the same or different and represents -O-, -S- or -NR 4 -,
• R 4 is hydrogen or monovalent, optionally substituted hydrocarbon radical
• n may be identical or different and an integer greater than or equal to 1, preferably 1 to 1000, particularly preferably 5 to 500, in particular 5 to 50, and
• n is an integer greater than or equal to 1, preferably 1 to 20, particularly preferably 1 to 10, in particular 1 to 5, with the proviso that at least one radical R 3 in formula (I) has the meaning of optionally substituted hydrocarbon radical and at least one hydroxyl group and / or thiol group,
• up to 1%, preferably up to 0.1% of all siloxane units can have branching by way of preparation, such as in RSi0 3/2 or Si0 4/2 units.
• R are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert. Butyl, n-pentyl, iso-pentyl, neo-pentyl, tert.
• hexyl such as the n-hexyl
• heptyl such as the n-heptyl
• octyl such as the n-octyl and iso-octyl, such as
• nonyl radicals such as the n-nonyl radical
• decyl radicals such as the n-decyl radical
• dodecyl radicals such as the n-dodecyl radical
• Alkenyl radicals such as the vinyl and allyl radicals
• Cycloalkyl radicals such as cyclopentyl, cyclohexyl, cycloheptyl radicals and methylcyclohexyl radicals
• Aryl radicals such as the phenyl and the naphthyl radical
• Alkaryl radicals such as o-, m-, p-tolyl radicals, xylyl radicals and ethylphenyl radicals
• Aralkyl radicals such as the benzyl radical, the a- and the ß-phenylethyl radical.
• substituted hydrocarbon radicals R are alkoxyalkyl radicals, such as methoxymethyl and ethoxymethyl radicals, hydroxyalkyl radicals, such as 2-hydroxyethyl radicals, and aminoalkyl radicals, such as dimethylaminoethyl, diethylaminomethyl, 2-aminoethyl and N-methylaminoyethyl radicals.
• Radical R is preferably monovalent, optionally substituted hydrocarbon radicals having 1 to 40 carbon atoms, more preferably hydrocarbon radicals having 1 to 6 carbon atoms, in particular the methyl radical.
• radical R 1 examples are methylene, ethylene, propylene, butylene, pentylene, hexamethylene, Methyloxyethylen-, ie the radical -CH 2 -O-CH 2 CH 2 -, toluene, methylene-bis-phenylene , Phenylene, naphthylene, cyclohexylene and isophorone radicals.
• R 1 is preferably a divalent aliphatic hydrocarbon radical which may be interrupted by heteroatoms, more preferably propylene, methylene and methyl radicals.
• oxyethylene radicals in particular methylene and Methyloxyethyl- enreste, most preferably the methylene radical.
• radical R 2 examples are methylene, ethylene, propylene, butylene, pentylene, hexamethylene, methyloxyethylene, ie the radical -CH 2 -O-CH 2 CH 2 -, toluene, methylene-bis-phenylene , Methylene-bis-cyclohexylene, phenylene, naphthylene, cyclohexylene, 1,3-bis (1-methylethylene) benzene and isophorone radicals.
• R 2 is preferably a divalent, aromatic or aliphatic hydrocarbon radical, particularly preferably toluolylene, methylene-bis-phenylene, methylene-bis-cyclohexylene, phenylene, naphthylene, cyclohexylene, 1, 3 Bis (1-methylethylene) benzene and isophorone radicals, in particular toluene-, phenylene-, 1,3-bis (1-methylethylene) benzene and isophorone radicals, very particularly preferably the toluolylene radical.
• R 3 are the examples given for radical R and optionally substituted hydrocarbon radicals having at least one hydroxyl group and / or thiol group, for example hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl , 1-hydroxybutyl, thiolmethyl, 1-thiolethyl and 1-thiolpropyl radicals.
• R 3 is preferably optionally substituted hydrocarbon radicals having at least one hydroxyl group and / or thiol group, particularly preferably optionally substituted hydrocarbon radicals having at least one hydroxyl group, in particular hydroxyalkyl radicals having 1 to 6 carbon atoms.
• both radicals R 3 preferably carry hydroxyl groups.
• X is -O-
• R 4 are the examples given for radical R.
• Radical R 4 is preferably hydrogen.
• the siloxanes (A) of the formula (I) used according to the invention have a viscosity of preferably 100 to 10,000 mPas, more preferably 500 to 5000 mPas, in each case at 25 ° C. and measured in accordance with AS M D 4283.
• siloxanes (A) used according to the invention are examples of siloxanes (A) used according to the invention.
• siloxanes (A) used according to the invention are preferably:
• siloxanes (A) used according to the invention are:
• At least one radical R 3 in formula (I) has the meaning of optionally substituted hydrocarbon radical and has at least one hydroxyl group and / or thiol group.
• siloxanes ( ⁇ ) used according to the invention can be prepared by methods customary in silicon chemistry.
• siloxanes (A) used according to the invention are preferably prepared by reacting
• Component (i) is preferably siloxanes of the formula
• R, X and n each have one of the meanings given above.
• production-related up to 1%, preferably up to 0.1%, of all units may have branching, such as in RSiO 3/2 or SiO 4/2 units.
• Component (i) is preferably
• siloxanes (i) are commercially available products or can be prepared by methods customary in silicon chemistry.
• the disocyanates (ii) used according to the invention are all known diisocyanates.
• diisocyanates (ii) are diisocyanatodiphenylmethane (MDI), both in the form of crude or industrial MDI and in the form of pure 4,4 "- or 2,4 'isomers or their preparations, tolylene diisocyanate (TDI) in the form of its various Regioisomers, diisocyanato naphthalene (NDI), isophorone diisocyanate (IPDI), 1,3-bis (1-isocyanato-1-methylethyl) benzene (TMXDI), 4,4'-diisocyanatodicyclohexylmethane (H 12 MDI) and hexamethylene diisocyanate (HDI
• diisocyanates (ii) are used in amounts of preferably 0.1 to 30 parts by weight, more preferably 0.1 to 20 parts by weight, in particular 1
• the amines (iii) used according to the invention are preferably those of the formula
• amines (iii) are ethanolamine, N-methylethanolamine, diethanolamine, N-methylpropanolamine, bis (2-hydroxypropyl) amines, N-methyl (thioethanol) amine.
• the amines (iii) are preferably aliphatic amines, more preferably diethanolamine, N-methylethanolamine, bis (2-hydroxypropyl) amines and N-methyl (thioethanol) amine, in particular diethanolamine and bis (2-hydroxypropyl ) amine.
• amines (iii) are used in amounts of preferably 0.1 to 20 parts by weight, more preferably 0.1 to 10 parts by weight. parts, in particular 0.5 to 5 parts by weight, in each case based on 100 parts by weight of siloxane (i) used.
• organic solvents (iv) and catalysts (v) can be used.
• organic solvents (iv) are ethers, in particular aliphatic ethers, such as dimethyl ether, diethyl ether, methyl t-butyl ether, diisopropyl ether, dioxane or tetrahydrofuran, esters, in particular aliphatic esters, such as ethyl acetate or butyl acetate, ketones, especially aliphatic ketones, such as acetone or methyl ethyl ketone, sterically hindered alcohols, especially aliphatic alcohols such as t-butanol, amides such as DMF, aliphatic nitriles such as acetonitrile, aromatic hydrocarbons such as toluene or xylene, aliphatic hydrocarbons such as pentane, cyclopentane, hexane, cyclohexane, heptane, chlorinated hydrocarbons such as methylene chloride or
• organic solvents (iv) are amounts of preferably 1 to 1000 parts by weight, more preferably 10 to 500 parts by weight, in particular 30 to 200 parts by weight, based in each case on 100 parts by weight of siloxane (i). In the reaction according to the invention, preference is given to using no solvents (iv).
• catalysts (v) are tin compounds, such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin bis (dodecylmercaptide), tin (II) - (2-ethylhexanoate) and zinc compounds, such as zinc (II) - ( 2-ethylhexanoate) and bismuth compounds such as bismuth (III) neodecanoate and zirconium compounds such as zirconium tetrakis (2, 2, 6, 6 tetramethylheptane-3,5-dionates) and amines such as 1-diazabicyclo [2,2,2] octane and tetramethylguanidine.
• tin compounds such as dibutyltin dilaurate, dioctyltin dilau
• the catalysts (v) are tin, zirconium or bismuth compounds, with bismuth compounds being particularly preferred.
• catalysts (v) are used, these are amounts of preferably 1 to 1000 ppm by weight, more preferably 10 to 500 ppm by weight, in particular 50 to 150 ppm by weight, in each case based on the total weight of the reaction mixture.
• the components used for the reaction according to the invention may in each case be one type of such a component as well as a mixture of at least two types of a respective component.
• siloxanes (i) are preferably reacted in a first stage with diisocyanates (ii) optionally in the presence of solvent (iv) and optionally in the presence of catalyst (v), and the reaction mixture obtained in a second stage with amines ( iii) implemented.
• the reaction according to the invention is carried out at temperatures of preferably 10 to 100.degree. C., particularly preferably 20 to 80.degree.
• the reaction according to the invention is preferably carried out at the pressure of the surrounding atmosphere, ie 900 to 1100 hPa. she but can also at higher pressures, such as at 1200 to
• the reaction according to the invention is preferably carried out under an inert gas atmosphere, e.g. Nitrogen and argon, performed.
• an inert gas atmosphere e.g. Nitrogen and argon
• the reaction mixture obtained after completion of the reaction can be worked up by any and previously known methods. If a solvent is used in the reaction, it is preferably removed during the work-up, which is particularly preferably carried out by distillation and, within the scope of the technical possibilities, completely.
• the reaction mixture preferably contains no starting materials. If the reaction mixture still contains unreacted educts, these remain preferentially there.
• isocyanates (B) used according to the invention it is possible to use all known diisocyanates or polyisocyanates, for example the diisocyanates listed above under (ii), and polymeric MDI (p-MDI), triphenylmethane triisocyanate or biuret or isocyanurate trimers of the abovementioned isocyanates.
• diisocyanates or polyisocyanates for example the diisocyanates listed above under (ii), and polymeric MDI (p-MDI), triphenylmethane triisocyanate or biuret or isocyanurate trimers of the abovementioned isocyanates.
• Preferred polyisocyanates (B) are those of the general formula used, where
• Q is a b-functional, optionally substituted hydrocarbon radical
• b is an integer of at least 2, preferably from 2 to 10, particularly preferably 2 or 4, in particular 2 to 3, means.
• Q is optionally substituted hydrocarbon radicals having 4 to 30 carbon atoms, more preferably hydrocarbon radicals having 6 to 25 carbon atoms.
• the preparations according to the invention contain polyisocyanates (B) in amounts of preferably 0.1 to 150 parts by weight, more preferably 1 to 100 parts by weight, in particular 10 to 50 parts by weight, based in each case on 100 parts by weight of siloxane (A).
• the preparations of the invention may contain other substances, e.g. Fillers (C), emulsifiers (D), physical blowing agents (E), catalysts (F), chemical blowing agents (G) and additives (H).
• Fillers C
• emulsifiers D
• E physical blowing agents
• F catalysts
• G chemical blowing agents
• H additives
• fillers (C) can be any non-reinforcing fillers, ie fillers with a BET surface area of up to 50 m 2 / g, such as chalk, or reinforcing fillers, ie fillers with a BET surface area of at least 50 m 2 / g, such as carbon black, precipitated silica or fumed silica.
• hydrophobic and hydrophilic fumed silicic acids are a preferred filler.
• a hydrophobic fumed silica whose surface has been modified with trimethylsilyl groups is used.
• the optionally used fillers (C) - in particular pyrogenic silicas - can perform various functions.
• fillers (C) in particular by the use of fumed silica.
• fillers (C) there may be added exfoliation graphite, inorganic silicates such as wollastonite, talc or glass powder, and inorganic phosphates such as calcium hydrogenphosphate or ammonium polyphosphate.
• fillers (C) these are amounts of preferably 0.1 to 30 parts by weight, more preferably 0.1 to 20 parts by weight, in particular 0.1 to 15 parts by weight, based in each case on 100 parts by weight of siloxane (A) .
• the preparations according to the invention preferably contain fillers (C).
• emulsifiers (D) which also serve as foam stabilizers are all commercially available silicone oligomers modified by polyether side chains, which are also used to prepare conventional polyurethane foams. If emulsifiers (D) are used, these are amounts of preferably up to 6% by weight, particularly preferably from 0.3 to 3% by weight, in each case based on the total weight of the foamable preparations.
• the preparations according to the invention preferably contain no emulsifiers (D).
• the preparations according to the invention may also contain compounds (E) which may serve as physical blowing agents.
• component (E) are preferably low molecular weight Hydrocarbons such as propane, butane or cyclopentane, dimethyl ether, fluorinated hydrocarbons such as 1, 1-difluoroethane or 1, 1, 1, 2-tetrafluoroethane or CO2 used.
• the Schaura Struktur preferably takes place by a reaction of the polyisocyanates (B) with the component (G) as a chemical blowing agent.
• the use of physical blowing agents (E) in combination with component (G) as a chemical blowing agent may be advantageous in order to obtain lesser density foams.
• preparations according to the invention comprise constituent (E), these are amounts of preferably 0.1 to 30 parts by weight, more preferably 0.1 to 20 parts by weight, in particular 0.1 to 15 parts by weight, based in each case on 100 parts by weight of siloxane (A) ,
• constituent (E) these are amounts of preferably 0.1 to 30 parts by weight, more preferably 0.1 to 20 parts by weight, in particular 0.1 to 15 parts by weight, based in each case on 100 parts by weight of siloxane (A) .
• the preparations according to the invention preferably contain no physical blowing agent (E).
• the foamable preparations according to the invention may contain catalysts (F) which accelerate foam curing.
• Suitable catalysts (F) include organotin compounds. Examples are dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin bis (dodecylmercaptide) or tin (II) - (2-ethylhexanoate).
• tin-free catalysts (F) such as heavy metal compounds or amines come into question.
• tin-free catalysts include iron (III) acetylacetonate, zinc (II) octoate, zirconium (IV) acetylacetonate, bismuth (III) neodecanoate.
• amines are triethylamine, tributylamine, 1,4-diazabicyclo [2,2,2] octane, N, N-bis (N, N-dimethyl-2-aminoethyl) -methylamine, N, N-dimethylcyclohexylamine, N, -dimethylphenylamine, bis-N, -dimethylaminoethyl ether, N, N-dimethyl-2-aminoethanol, N, N-dimethylaminopyridine, N, N, N, N-tetramethyl-bis (2-aminoethylmethylamine, 1, 5 Diazabicyclo [4.3.0] ⁇ -5-ene, 1,8-diazabicyclo [5. .0] undec-7-ene, N-ethylmorpholine, tetramethylguanidine or ⁇ , ⁇ '-dirnethylaminopyridine.
• the catalysts (F) can be used individually or as a mixture. If appropriate, the catalysts used in the preparation of the siloxanes (A) can simultaneously also serve as catalysts (F) for foam curing.
• catalyst (F) is used, the amounts are preferably from 0.1 to 6.0% by weight, more preferably from 0.1 to 3.0% by weight, in each case based on the total weight of the inventive foamable preparation.
• the preparations according to the invention preferably contain catalysts (F).
• catalysts (G) both water and all compounds having preferably at least one isocyanate-reactive function can serve as chemical blowing agents (G).
• component (G) are aminoalkyl- or hydroxy-functional siloxanes which are different from component (A), monomeric alcohols, monomeric diols, such as glycol, propanediol and butanediol, monomeric oligools, such as pentaerythritol or
• component (G) are preferably hydroxy compounds, with water being particularly preferred.
• component (G) are amounts of preferably 0.1 to 20 parts by weight, more preferably from 0.1 to 15 parts by weight, in particular from 0.1 to 10 parts by weight, based in each case on 100 parts by weight of siloxane.
• the compositions according to the invention contain component (G).
• optional additives (H) are cell regulators, plasticizers, e.g. Silicone oils which are different from component (A), flame retardants, e.g. Melamine or phosphorus-containing compounds, especially phosphates and phosphonates, as well as halogenated polyesters and polyols or chlorinated paraffins.
• flame retardants e.g. Melamine or phosphorus-containing compounds, especially phosphates and phosphonates, as well as halogenated polyesters and polyols or chlorinated paraffins.
• silicone oils (H) are triorganosiloxy-terminated polydiorganosiloxanes, such as trimethylsiloxy-terminated polydimethylsiloxanes, and the siloxanes mentioned above under i).
• the additives (H) are preferably cell regulants and flame retardants, with flame retardants being particularly preferred.
• additives (H) are used, these are amounts of preferably 0.1 to 30 parts by weight, more preferably from 0.1 to 20 parts by weight, in particular from 0.1 to 15 parts by weight, based in each case on 100 parts by weight of siloxane (A) .
• the preparations according to the invention preferably contain no additives (H).
• the compositions according to the invention preferably contain no silicone resins, silicone resins meaning siloxanes in which more than 50% of all siloxane units are known Meaning of T units (-Si0 3/2 ) and Q units (Si0 / 2 ) have.
• the components of the foamable preparation used according to the invention may each be one type of such a component as well as a mixture of at least two types of a particular component.
• the preparations according to the invention are those containing
• preparations according to the invention contain at least one blowing agent selected from components (E) and (G), in particular at least (G).
• the preparations according to the invention preferably contain no further constituents.
• the preparations according to the invention can now be prepared by any desired methods known per se, such as simple mixing of the individual components, it also being possible to prepare premixes of individual constituents.
• 2-component systems are preferably prepared, the two components of the foamable preparation according to the invention containing all constituents in any desired combinations and proportions, with the proviso that one component does not simultaneously contain siloxanes (A) and polyisocyanates (B) or the constituents (B) and (G).
• Another object of the invention is a process for the preparation of the preparations according to the invention, characterized in that 2-component systems are prepared, wherein the two components of the foamable preparation contain all ingredients in any combination and proportions, with the proviso that a component not simultaneously Siloxanes (A) and polyisocyanates (B) or the components (B) and (G) contains.
• the preparation according to invention prefers a mixture containing component (A), if necessary component (C), if necessary component (D), if necessary component (E), if necessary component (F), if necessary component (G) and if necessary component (H ) as component 1 and a component 2 comprising component (B), which are then mixed together to prepare the foam according to the invention.
• the preparations according to the invention are preferably liquid to viscous and have a viscosity of preferably 250 to
• the preparations according to the invention are preferably used for the production of foams, more preferably of hard or
• Flexible foams in particular soft foams.
• Another object of the present invention is a process for the preparation of silicone-containing polyurethane foams, characterized in that siloxanes (A), polyisocyanate (B) and at least one blowing agent are mixed and allowed to react.
• siloxane (A), polyisocyanate (B), catalyst (F) and chemical blowing agent (G) and optionally component (C) are mixed and allowed to react in direct connection thereto.
• the foamable composition is preferably placed in a mold, which is subsequently sealed so that the overpressure created during foaming can escape.
• a mold which is subsequently sealed so that the overpressure created during foaming can escape.
• the mold has a pressure relief valve or small openings, so incompletely closed, for example, over one or more narrow gaps.
• the molds which may be used in the process of the invention may be any of the types of molds heretofore used to make molded foams. Examples of such forms are closable and heatable metal molds which are used to escape the displaced
• the molds used according to the invention are preferably heatable molds of a solid material, such as glass fiber reinforced polyester or epoxy resins and metals, such as steel or aluminum, wherein molds made of steel and aluminum preferably with a primer, preferably once before use, are rendered hydrophobic ,
• primer pastes with which the forms used in the process according to the invention can be rendered hydrophobic are high-melting waxes based on hydrocarbons, as are commercially available, for example, from Chem-Trend GmbH, D-Maisach under the trade name Klüberpur 55-0005 are available. If desired, the molds can be wetted with a release agent for better releasability of the foam bodies produced.
• release agents are high-melting waxes dissolved in hydrocarbons, such as those obtainable, for example, from Chemtrend Kunststoff GmbH, D-Maisach under the trade name Klüberpur 41-0057.
• the molds used are preferably used without release agent.
• the molds used in the process according to the invention are adjusted to temperatures of preferably 0 to 150.degree. C., more preferably 10 to 100.degree. C., in particular 40 to 80.degree.
• the expansion of the foam as it is formed is limited by the mold used, ie the mold is "overpacked.” This overpacking is typically usually between 20% by volume and 100% by volume. Typical filling levels at a target foam density of 50 kg / m 3 are 5% by volume.
• the heat produced in the reaction according to the invention preferably remains in the system and contributes to the formation of foam.
• reaction temperatures up to preferably 50 to 150 ° C are achieved in the foam core.
• the process of the invention is preferably carried out at the pressure of the surrounding atmosphere, that is about 900 to 1100 hPa.
• the demolding time ie the time from filling the mold to removing the molded foam from the mold, is preferably 1 to 20 minutes, more preferably 2 to 15 minutes, in particular 3 to 10 minutes.
• partially closed-cell foams are obtained, which can be converted by the application of an external pressure into completely open-celled foams, such as by the mechanical compression of the foamed bodies by two immediately adjacent free-running rollers, through which Foam body is driven through, wherein it is compressed to preferably over 75%.
• foams which can be prepared by reacting siloxanes (A) with polyisocyanate (B) and at least one blowing agent.
• the foams according to the invention are distinguished by a fine, open-cell foam structure. Its mechanical properties correspond to those of commercially available PU foams.
• the molded foams of the invention have a density of preferably 10 to 500 kg / m 3 , more preferably 15 to 200 kg / m 3 , in particular 20 to 120 kg / m 3 , in each case determined at 25 ° C. and 1013 hPa.
• the foams of the invention have the advantage that they have on the outer sides of compact, defect-free and homogeneous surfaces.
• compositions according to the invention and the process according to the invention for producing foams have the advantage that no release agents are required.
• the foamable preparations according to the invention have the advantage that they can be processed in a very simple manner and with the hitherto known methods from PU technology.
• the preparations according to the invention have the advantage that they can be prepared with commercially readily available educts.
• the preparations according to the invention have the advantage that they can be prepared without the addition of a solvent, whereby no solution during the manufacturing process. incurred remnants and can be saved with the elimination of solvent removal time and cost.
• preparations according to the invention have the advantage that they are easy to process and can be prepared with low viscosity.
• the preparations according to the invention have the advantage that silicone polyurethane foams with low densities can be produced by the one-shot process.
• the foams of the invention have the advantage that they are flexible and extremely flame retardant.
• the foams according to the invention also have the advantage that they have high mechanical strengths, in particular in combination with low foam densities.
• the foams according to the invention can be used wherever polyurethane foams have hitherto been used. In particular, they are suitable for upholstery.
• MDI polymeric MDI with. a functionality of 2.9 (commercially available under the name Suprasec ® 2085 from Huntsman Polyurethanes, D-Deggendorf);
• Toluene diisocyanate mixture of 2,4- and 2,6-toluene diisocyanate in the ratio 80:20 (commercially available under the name
• TMXDI 1,3-bis (1-isocyanato-1-methylethyl) benzene (commercially available from Sigma-Aldrich Chemie GmbH, D-Munich)
• iftminkatalysator diazabicyclooctane (commercially available under the name DABCO ® Crystal Air Products GmbH, D-Hamburg);
• Expanded graphite Exfoliation graphite with a minimum expansion rate of 350 at a starting temperature of 250 ° C. (commercially available under the name ES 350 F5 from Graphit Kropfmühl AG, D-Hauzenberg);
• Wollastonite Surface-modified, acicular wollastonite having an aspect ratio of 6: 1 (commercially available under the name Tremin 939-304 from Quarzwerke GmbH, D-Frechen);
• the mold used in the following examples has dimensions of 40cm x 20cm x 5cm and was hydrophobed once before start-up with 25 g of primer paste with the name "Klüberpur 55-0005" from Chem-Trend Germany GmbH, D-Maisach. Comparative Example 1
• 200.0 g of the hyperbranched organopolysiloxane thus obtained were first emulsified with 500 mg of diazabicyclooctane and 5.1 g of water through a high-speed stirrer to a homogeneous mixture and then 56.7 g of toluene diisocyanate were added to this emulsion and 10 seconds with a long-running stirrer incorporated. From the mixture thus obtained, 200 g was immediately added to a tempered at 70 ° C 4L aluminum mold and the mold for a period of 10 min. was closed except for a 100 ⁇ wide and 40 cm long gap to escape the air to be displaced. After a demolding time of 10 min. a silicone PU foam having a density of 50 kg / m 3 was obtained. Compared to the foam of Comparative Example 1, a significantly more homogenous surface could be seen here, but the foam surface still had an irregular structure.
• 180.0 g of the organopolysiloxane thus obtained were first emulsified with 600 mg of diazabicyclooctane and 6.30 g of water through a high-speed stirrer to a homogeneous mixture and then 65.4 g of toluene diisocyanate were added to this emulsion and incorporated for 10 s with a high-speed stirrer , Of the mixture thus obtained, 200 g of was placed in a tempered to 70 ° C 4L aluminum mold and the mold was sealed for a period of 10 minutes to a 100 ⁇ wide and 40 cm long and 40 cm long gap to escape the air to be displaced. After a demolding time of 10 minutes, a silicone PU foam with a density of 50 kg / m 3 was obtained, which had a homogeneous and defect-free surface.
• 180.0 g of the organopolysiloxane thus obtained were first emulsified with 600 mg of diazabicyclooctane and 7.20 g of water through a schneiHäufenden stirrer to a homogeneous mixture and then 73.2 g of toluene diisocyanate were added to this emulsion and incorporated for 10 s with a high-speed stirrer , Of the mixture thus obtained, 180 g were immediately put into a tempered 4L aluminum mold heated to 70 ° C and the mold for a period of 10 min. was closed to a 100 ⁇ wide and 40 cm long and 40 cm long gap to escape the air to be displaced. After a demolition time of 10 min. was a silicone PU foam with a
• Density of 45 kg / m 3 obtained, which had a homogeneous and defect-free surface.
• 180.0 g of the organopolysiloxane thus obtained were first emulsified with 600 mg of diazabicyclooctane and 7.20 g of water through a high-speed stirrer to give a homogeneous mixture and then 74.6 g of toluene diisocyanate were added to this emulsion and incorporated for 10 s with a high-speed stirrer , 200 g of the mixture thus obtained were immediately poured into a 4L aluminum mold heated to 70 ° C. and the mold was heated for a period of 10 minutes. was closed to a 100 ⁇ wide and 40 cm long and 40 cm long gap to escape the air to be displaced. After a demoulding time of 10 min. was obtained a silicone PU foam with a density of 45 kg / m 3 , which had a homogeneous and defect-free surface.
• 160.0 g of the organopolysiloxane thus obtained were first emulsified with 600 mg of diazabicyclooctane and 6.40 g of water through a schneiHäufenden stirrer to a homogeneous mixture and then 20.0 g of expandable graphite and 66.3 g of toluene diisocyanate were added to this emulsion and incorporated for 10 s with a high-speed stirrer. From the mixture thus obtained, 200 g were immediately placed in a tempered at 70 ° C 4L aluminum mold and the mold for a period of 10 min. was closed to a 100 ⁇ wide and 40 cm long and 40 cm long gap to escape the air to be displaced. After a demolding time of 10 min. a gray silicone PU foam was obtained with a density of 45 kg / m 3 , which had a homogeneous and defect-free surface.
• 160.0 g of the organopolysiloxane thus obtained were first emulsified with 600 mg of diazabicyclooctane and 6.40 g of water through a high-speed stirrer to a homogeneous mixture and then 10.0 g of expandable graphite, 10.0 g of wollastonite and 66.3 g of toluene diisocyanate added to this emulsion and incorporated for 10 s with a high-speed stirrer.
• 200 g were immediately placed in a heated to 70 ° C 4L aluminum mold and the mold for a period of 10 min. was closed except for a 100 ⁇ wide and 40 cm long and 40 cm long gap to escape the air to be displaced. After a demolding time of 10 min. a gray silicone PU foam was obtained with a density of 45 kg / m 3 , which had a homogeneous and defect-free surface.
• 160.0 g of the organopolysiloxane thus obtained were first emulsified with 600 mg of diazabicyclooctane and 6.40 g of water through a high-speed stirrer to a homogeneous mixture and then 10.0 g of expanded graphite, 5.0 g of wollastonite and 5.0 g of calcium hydrogen phosphate and 66.1 g of toluene diisocyanate added to this emulsion and incorporated for 10 s with a fast-running stirrer. From the mixture thus obtained, 200 g was immediately added to a tempered at 70 ° C 4L aluminum mold and the mold for a period of 10 min.

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