EP2547710A2 - Mousse de polyuréthane siliconée - Google Patents

Mousse de polyuréthane siliconée

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Publication number
EP2547710A2
EP2547710A2 EP11708444A EP11708444A EP2547710A2 EP 2547710 A2 EP2547710 A2 EP 2547710A2 EP 11708444 A EP11708444 A EP 11708444A EP 11708444 A EP11708444 A EP 11708444A EP 2547710 A2 EP2547710 A2 EP 2547710A2
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EP
European Patent Office
Prior art keywords
optionally substituted
radical
hydrocarbon radical
different
radicals
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP11708444A
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German (de)
English (en)
Inventor
Jens Cremer
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Wacker Chemie AG
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Wacker Chemie AG
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Publication date
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Publication of EP2547710A2 publication Critical patent/EP2547710A2/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • C08G18/08—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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C08G18/3275—Hydroxyamines containing two hydroxy 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
    • C08G18/70—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
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
    • 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
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers

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 generally 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 the silicone-polyurethane soft foams.
  • the good combustible polyol component used in standard PU foams is replaced by non-combustible OH-terminated siloxanes.
  • silicone-polyurethane copolymers, ie of polysiloxanes, which also contain polyurethane and / or urea units it is possible to develop such incombustible foams, which have new and tailored to the particular application combinations of properties.
  • 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 102006013416 A1 also describes the production of silicone PU foams from prepolymers based on Alkylamino- or alkylhydroxy-terminated silicone oils and diisocyanates are prepared in a solvent-based process.
  • the silicone polyurethane foams described so far have in common that they are based on linear or only very
  • Hyperbranched polymers tough len to dendritic macromolecules and have a stronger branching than conventional branched polymers, which have mainly primary or secondary branches on a linear main chain. So far, divergent synthetic methods have been used for the synthesis of hyperbranched polymers, with a monomer that has exactly two different types of functional groups, but which do not react with each other, the total functionality of the monomers being greater than two. Examples of suitable monomers are those which have a functional group A and two functional groups B, ie an AB 2 monomer. In principle, all monomers AB X with x> 1 can be used.
  • AB x monomers in a monomolecular polymerization is only possible if the A and B groups react with one another only when it is desired in the polymer synthesis, ie after addition of a catalyst or by increasing the temperature.
  • the synthesis of hyperbranched polymers can also be carried out with two different monomer types, each having only one kind of functional groups, but in different numbers, such as A 3 and B 2 building blocks.
  • a reaction of these two types of A 3 and B 2 can then be used to obtain in situ A 2 B and AB 2 monomer blocks (di-molecular polymerization: in general with A x and B y , where x> 1 and y> 2 ).
  • Such methods are well known and described, for example, in US-B 6,534,600.
  • the invention provides foamable compositions containing siloxanes (A) of the formula
  • V is a p-valent hydrocarbon radical which may contain heteroatoms means
  • R may be identical or different and is a monovalent, optionally substituted hydrocarbon radical
  • R 1 may be identical or different and represents -O-, -S- or -NR 3 -,
  • R 2 may be the same or different and represents hydrogen atom and monovalent, optionally substituted hydrocarbon radicals
  • R 3 is hydrogen or monovalent, optionally substituted hydrocarbon radical
  • R 4 may be the same or different and is a divalent, optionally substituted hydrocarbon radical which may be interrupted by heteroatoms,
  • R 5 may be the same or different and is hydrogen or an optionally substituted hydrocarbon radical
  • a is an integer greater than or equal to 1, preferably 1 to 1000, particularly preferably 5 to 500, in particular 10 to 100,
  • p is an integer greater than or equal to 2, preferably 2 to 20, particularly preferably 3 or 4,
  • n is an integer greater than or equal to 1, preferably 1 to 19, particularly preferably 1 to 3,
  • n is an integer greater than or equal to 1, preferably 1 to 19, particularly preferably 1 to 3,
  • R examples of 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. -Pentyl radical, hexyl radicals, such as the n-hexyl radical, heptyl radicals, such as the n-heptyl radical, octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as
  • 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 o- and the ß-phenylethyl radical.
  • substituted hydrocarbon radicals R are alkoxyalkylene radicals, such as methoxymethylene and ethoxymethylene radicals, hydroxyalkylene radicals, such as 2-hydroxyethylene radicals, and aminoalkyl radicals, such as dimethylaminomethylene, diethylaminomethylene, 2-aminoethylene and N-methylaminoyethylene 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.
  • R 3 are hydrogen atom and the examples given for radical R.
  • the radical R 3 is preferably hydrogen.
  • R 1 is preferably -O-.
  • radicals R 2 are hydrogen atom and the examples mentioned for radical R.
  • Radicals R 2 are preferably hydrocarbon radicals having 1 to 6 carbon atoms, more preferably the methyl radical.
  • radical R 4 examples are methylene, ethylene, propylene, butylene, pentylene, hexamethylene, methyloxyethylene, ie the radical -CH 2 -O-CH 2 CH 2 -, Toluolylen-, methylene-bis phenylene, phenylene, naphthylene, cyclohexylene and isophorone radicals.
  • R 4 is preferably divalent aliphatic hydrocarbon radicals which are interrupted by heteroatoms can, particularly preferably propylene, methylene and methyl oxyethylenreste, in particular len to methylene and Methyloxyethy-, most preferably the methyl radical.
  • R 5 are the examples given for R.
  • R 5 is preferably hydrogen and optionally hydrocarbon radicals which are substituted by hydroxyl groups, more preferably hydrocarbon radicals which are optionally substituted by hydroxyl groups, in particular alkyl radicals having 1 to 6 carbon atoms and hydroxyalkyl radicals having 1 to 6 carbon atoms.
  • radical V examples are any hitherto known polyvalent, aliphatic or aromatic hydrocarbon radicals which may have heteroatoms, such as 1, 3, 4 -benzene radicals, 1,3,5-cyanurate radicals, ⁇ , ⁇ , ⁇ '-biuret radicals, 4 , 4 ', 4 "-triphenylmethane radicals and poly ((4-phenyl) -co-formaldehyde) radicals.
  • the radicals V are preferably polyvalent radicals having 1 to 50 carbon atoms, particularly preferably having 6 to 30 carbon atoms.
  • V is preferably a polyvalent, aromatic, optionally heteroatom-containing hydrocarbon radical, particularly preferably polyvalent, aromatic, optionally nitrogen, oxygen and phosphorus containing hydrocarbon radicals, in particular polyvalent aromatic, optionally nitrogen and oxygen-containing hydrocarbon radicals having 6 to 30 carbon atoms ,
  • the sum m + n is preferably equal to p. 3
  • 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 5,000 mPas, in each case at 25 ° C. and measured in accordance with ASTM D 4283.
  • siloxanes (A) used according to the invention are preferably hyperbranched.
  • Examples of siloxanes (A) used according to the invention are
  • siloxanes ( ⁇ ) used according to the invention are preferably:
  • siloxanes (A) used according to the invention are:
  • siloxanes (A) used according to the invention can be prepared by methods customary in silicon chemistry.
  • siloxanes (A) used according to the invention are preferably preparable by reaction of
  • Component (i) is preferably siloxanes of the formula
  • component (i) are HIGH 2 - [SiMe 2 O] 2 -ioo-SiMe 2 CH 2 OH,
  • Component (i) is preferably
  • the siloxanes (i) are commercially available products or can be prepared by methods commonly used in silicon chemistry.
  • the polyisocyanates (ii) used according to the invention are all known di- or polyisocyanates.
  • Preferred polyisocyanates (ii) are those of the general formula
  • V and p each have one of the meanings mentioned above.
  • polyisocyanates (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 use. 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) or also of hexamethylene diisocyanate (HDI), as well as polymeric MDI (p-MDI), triphenylmethane triisocyanate or biuret or isocyanurate trimers of the above-mentioned isocyanates.
  • MDI diisocyanatodiphenylmethane
  • NDI diisocyanato naphthalene
  • IPDI iso
  • Polyisocyanates (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 to 10 parts by weight, based in each case on 100 parts by weight of siloxane (i).
  • the amines (iii) used according to the invention are preferably those of the formula
  • R 5 has one of the abovementioned meanings and preferably has at most one radical R 5 the meaning of hydrogen atom, as well as aliphatic cyclic amines and aromatic cyclic amines which contain additional functional groups such as thiol, hydroxyl or may have further amino groups.
  • amines (iii) are dimethylamine, diethylamine, butylamine, dibutylamine, diisopropylamine, pentylamine, cyclohexylamine, N-methylcyclohexylamine, aniline, morpholine, pyrrolidine, piperidine, imidazole, piperazine, ethylenediamine, ⁇ , ⁇ '- Dimethyl ethylenediamine, ethanolamine, N-methylethanolamine, diethanolamine, propanolamine, alaniol, N-methyl (thioethanol) amine.
  • the amines (iii) are preferably aliphatic amines, more preferably pyrrolidine, diethanolamine, ethane nolamin and N-methylethanolamine, in particular to diethanolamine, ethanolamine and N-methylethanolamine.
  • amines (iii) are used in amounts of preferably 0.1 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, in particular 0.5 to 5 parts by weight, based in each case on 100 parts by weight of siloxane (i).
  • 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 preferably aliphatic ethers, aliphatic ketones or aliphatic nitriles, with aliphatic ketones being particularly preferred. If organic solvents (iv) are used, they 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, in each case based on 100 parts by weight Siloxane (i). In the reaction according to the invention, preference is given to using solvent (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-diazabicy - clo [2,2,2] octane and tetramethylguanidine.
  • tin compounds such as dibutyltin dilaurate, dioctyltin dil
  • the catalysts (v) are preferably 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. In the reaction according to the invention, preference is given to using catalysts (v).
  • the components used for the reaction may in each case be a type of such a component as well as a mixture of at least two types of a particular component.
  • siloxanes (i) are preferably reacted in a first stage with polyisocyanates (ii) optionally in the presence of solvent (iv) and optionally in the presence of catalyst (v), and the resulting reaction mixture in a second stage with amines (iii) implemented.
  • the reaction is carried out at temperatures of preferably 20 to 100 ° C, particularly preferably 30 to 80 ° C.
  • the reaction is preferably carried out at the pressure of the surrounding atmosphere, ie 900 to 1100 hPa. However, it can also be carried out at higher pressures, such as at 1200 to 10,000 hPa.
  • the reaction is preferably carried out under an inert gas atmosphere, such as nitrogen and argon.
  • the reaction mixture obtained after completion of the reaction can be worked up by any desired methods known hitherto.
  • the optionally used organic solvent is preferably removed, 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 preferably remain there.
  • isocyanates (B) used according to the invention it is possible to use all known di- or polyisocyanates, for example the isocyanates listed above under (ii).
  • Preferred polyisocyanates (B) are those of the general formula
  • Q is a b-functional, optionally substituted hydrocarbon radical and 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 isocyanates (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 according to the invention contain organopolysiloxane resins (C) in amounts of preferably 0.1 to 15 parts by weight, more preferably 0.2 to 10 parts by weight, in particular 0.5 to 5 parts by weight, based in each case on 100 parts by weight of siloxane (A).
  • organopolysiloxane resins (C) are preferably those comprising units of the formula R 6 c X d SiO (4-cd) / 2 (VI) wherein
  • R 6 may be identical or different and is hydrogen or a monovalent, optionally substituted, SiC-bonded hydrocarbon radical,
  • X may be identical or different and is halogen, the radical R 7 is 0- or the radical R 7 is 2 N-, R 7 may be the same or different and is hydrogen or a monovalent, optionally substituted hydrocarbon radical,
  • c 0, 1, 2 or 3
  • d 0, 1, 2 or 3
  • radicals R 6 and R 7 are each independently hydrogen atom and the examples given above for R.
  • Radical R 6 is preferably optionally substituted, SiC-bonded hydrocarbon radicals, more preferably hydrocarbon radicals having 1 to 12 carbon atoms, in particular the methyl radical and the phenyl radical, very particularly preferably the methyl radical.
  • radicals X are chlorine atom, bromine atom and iodine atom, hydroxyl radical, alkoxy radicals, H 2 N-, (CH 3 ) 2 N-, CH 3 NH-, (CH 3 CH 2 ) 2 N- and the CH 3 CH 2 NH- Rest.
  • radical X is radicals of the formula R 7 O-.
  • Radical R 7 is preferably hydrogen and monovalent hydrocarbon radicals, particularly preferably hydrogen and hydrocarbon radicals having 1 to 12 carbon atoms, in particular hydrogen, methyl and ethyl.
  • the value of c is 3 or 0.
  • Silicone resins are well known and may contain different siloxane units, such as the so-called - M units
  • a silicon network which consists almost exclusively of Q units, is already close to a pure Si0 2 - or the quartz crystal.
  • the majority of silicone resins are synthesized from D and T units (DT resin) and M and Q units (MQ resin), and other combinations such as MDT, MTQ or pure T resins are also industrially produced ,
  • the component (C) used according to the invention is particularly preferably organopolysiloxane resins of units of the formula (VI) in which less than 25%, preferably less than 10%, more preferably less than 5% of the units in the resin the sum c + d is equal to 2.
  • component (C) to Organopoly- siloxane comprising units of the formula (VI), the 6 SIOI 3/2 (M) consists essentially of R - and consist Si0 4/2 (Q) units, with R s equal to the above meaning; in these MQ resins, the molar ratio of M to Q units is preferably in the range of 0.5 to 2.0, more preferably in the range of 0.6 to 1.0.
  • These silicone resins may also contain up to 10% by weight of free hydroxy or alkoxy groups.
  • the organopolysiloxane resins (C) used according to the invention preferably have a viscosity of more than 1000 mPas at 25 ° C. or are solids.
  • the weight-average molecular weight (based on a polystyrene standard) of these resins determined by gel permeation chromatography is preferably 200 to 200,000 g / mol, more preferably 1,000 to 10,000 g / mol.
  • organopolysiloxane resins (C) used according to the invention is generally known. They are mostly through hydrolytic condensation prepared from various Silanprekusoren, this initially easy to access
  • MQ resins which are usually obtained starting from tetraethoxysilane (Q unit) and trimethylethoxysilane (M unit) by means of hydrochloric acid hydrolysis.
  • Q unit tetraethoxysilane
  • M unit trimethylethoxysilane
  • the chemical structure of the silicone resins can be considered as a three-dimensional network of polysilicic acid units terminated with trimethylsilyl groups.
  • a few ethoxy and hydroxy functions may still be present.
  • the average molecular weight can be adjusted exactly by the ratio of M to Q units.
  • Organopolysiloxane resins are preferably colorless, pulverulent solids which are very readily soluble in nonpolar solvents such as toluene but also in silicones.
  • Suitable solvents for this purpose are e.g. liquid silicone resins of units of the formula (VI), silicone oils and liquid siloxanes of the formulas (I) and (II).
  • the preparations according to the invention may contain further substances, for example fillers (D), emulsifiers (E), physical blowing agents (F), catalysts (G), chemical blowing agents (H) and additives (I). If fillers (D) are used, it can be all non-reinforcing fillers, ie fillers with a
  • hydrophobic as well as hydrophilic fumed silicic acids are a preferred filler.
  • a hydrophobic fumed silica is used whose surface has been modified with trimethylsilyl groups.
  • the fillers (D) used - in particular pyrogenic silicas - can perform various functions. So they can be used to adjust the viscosity of the foamable mixture.
  • the mechanical properties of the resulting foams can also be determined by the use of fillers (D), in particular by the use of pyrogenic silicic acid.
  • fillers (D) in particular by the use of pyrogenic silicic acid.
  • fluring graphite as filler (D).
  • the preparations according to the invention contain fillers (D), 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 (D).
  • emulsifiers (E) are added to the foamable preparations.
  • suitable emulsifiers (E) which also serve as foam stabilizers, for example, all commercially available by Polyetherlitketten modified silicone oligomers are used, which are also used for the production of conventional polyurethane foams.
  • emulsifiers (E) are used, they are amounts of preferably up to 6 wt .-%, particularly preferably from 0.3 to 3 wt .-%, each based on the total weight of the foamable preparations.
  • the preparations according to the invention preferably contain no emulsifiers (E).
  • the preparations according to the invention can also contain compounds (F) which can serve as physical blowing agents.
  • component (F) 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 -Tetrafluorethan or C0 2 are used.
  • Foaming is preferably carried out by a reaction of the polyisocyanates (B) with the component (H) as a chemical blowing agent.
  • the use of physical blowing agents (F) in combination with component (H) as chemical blowing agent may be advantageous in order to obtain foams of lower density.
  • preparations according to the invention comprise constituent (F), 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, in each case based on 100 parts by weight of siloxane ( ⁇ ).
  • the preparations according to the invention preferably contain no physical blowing agent (F).
  • the foamable preparations according to the invention may contain catalysts (G) which accelerate foam curing. Suitable catalysts (G) include organotin compounds.
  • Examples are dibutyltin dilaurate, di- tyltin dilaurate, dibutyltin diacetate, dibutyltin dioctoate, di-butyltin bis (dodecylmercaptide) or tin (II) - (2-ethylhexanoate).
  • tin-free catalysts such as heavy metal compounds or amines come into question.
  • examples of 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, N-dimethylphenylamine, bis-N, N-dimethylaminoethyl ether, N, N-dimethyl-2-aminoethanol, N, -dimethylaminopyridine, ⁇ , ⁇ , ⁇ , ⁇ -tetramethyl-bis (2-aminoethylmethylamine, 1, 5-diazabicyclo [4.3.0] ⁇ -5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, N-ethylmorpholine, tetra methylguanidine or ⁇ , ⁇ '-dirnethylaminopyridine.
  • the catalysts (G) 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 (G) for foam curing.
  • catalyst (G) are amounts of preferably 0.1 to 6.0 wt .-%, particularly preferably from 0.1 to 3.0 wt .-%, each based on the total weight of the foamable invention Preparation.
  • the preparations according to the invention preferably contain catalysts (G).
  • both water and all compounds having preferably at least one isocyanate-reactive function can serve as chemical blowing agents (H).
  • component (H) 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 trihydroxymethylethane, oligomeric or polymeric alcohols having one, two or more hydroxyl groups, such as ethylene or propylene glycols, water, monomeric amines having one, two or more amine functions, such as ethylenediamine and hexamethylenediamine, as well as oligomeric or polymeric amines having one, two or more amine functions.
  • monomeric alcohols monomeric diols, such as glycol, propanediol and butanediol
  • monomeric oligools such as pentaerythritol or trihydroxymethylethane
  • component (H) are preferably hydroxy compounds, with water being particularly preferred.
  • component (H) is used, these 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 ( A).
  • the compositions of the invention contain component (H).
  • optional additives (I) are cell regulators, plasticizers, e.g. Silicone oils other than 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.
  • silicone oils (I) are triorganosiloxy-terminated polydiorganosiloxanes, such as trimethylsiloxy-terminated polydimethylsiloxanes, and the siloxanes mentioned above under i).
  • the additives (I) are cell regulants and flame retardants, with flame retardants being particularly preferred. If additives (I) are used, these are amounts of preferably 0.1 to 30 parts by weight, more preferably of 0.1 to 20 parts by weight, in particular of 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 (I).
  • 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 comprise at least one blowing agent selected from components (F) and (H), in particular at least (H).
  • the preparations according to the invention preferably contain no further constituents.
  • the preparations according to the invention can now be prepared by any desired and known processes, such as simple mixing of the individual components, it also being possible to prepare premixes of individual constituents.
  • a mixture comprising constituent (A) and (C), optionally constituent (D), optionally constituent (E), optionally constituent (F), optionally constituent (G), optionally constituent (H) and optionally component (I) 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
  • a further subject of the present invention is a process for producing silicone-containing polyurethane foams, characterized in that siloxanes (A), polyisocyanate (B), organopolysiloxane resin (C) and at least one blowing agent are mixed and allowed to react.
  • siloxane ( ⁇ ), polyisocyanate (B), organopolysiloxane resins (C), catalyst (G) and chemical blowing agent (H) and optionally component (D) are mixed and allowed to react in direct connection.
  • the foamable composition is preferably added to a mold, which is subsequently sealed in such a way that the overpressure arising during foam formation can escape.
  • the mold has an overpressure valve or small openings, that is to say incompletely closed, for example, via 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 provided for the escape of the displaced air during the foaming process with a pressure relief valve.
  • 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 molds used in the process according to the invention can be rendered hydrophobic are high-melting waxes based on hydrocarbons, such as, for example, commercially available 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.
  • foams 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), organopolysiloxane resin (C) and at least one blowing agent.
  • the foams according to the invention are distinguished by a fine, open-celled 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.
  • 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 density can be produced by the one-shot method.
  • 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 having a functionality of 2.9 (commercially available under the designation 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
  • Desmodur T80 bex Bayer MaterialScience AG, D-Leverkusen);
  • Amine catalyst Diazabicyclooctane (commercially available under
  • Silicone resin 1 Powdered silicone resin consisting of M and Q units and having an M / Q ratio of 2: 3 (commercially available under Belsil ® TMS 803 from Wacker Chemie AG, D-Burghausen)
  • Silicone resin 2 Powdered silicone resin consisting of M and Q units and having an M / Q ratio of 3: 4, which has nyl phenomenon 4% Vi (commercially available under Belsil ® TMS 804, Wacker Chemie AG, D-Burghausen) ;
  • the shape used in the following examples has dimensions of 40cm x 20cm x 5cm and was used once prior to commissioning
  • 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 for 10 s with a high-speed 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. except for a 100 ⁇ m wide and 40 cm long gap for the escape of the urgent air was sealed. 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.
  • 200.0 g of the hyperbranched organopolysiloxane thus obtained were first emulsified with 500 mg of diazabicyclooctane, 5.1 g of water and additionally 3.0 g of silicone resin 1 through a high-speed stirrer to a homogeneous mixture and then 56.7 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 was immediately added to 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. was obtained a silicone PU foam with a density of 50 kg / m 3 , which had a homogeneous and defect-free surface.
  • Example 2 200.00 g of a linear organopolysiloxane of the formula HO-CH 2 -
  • 200.0 g of the hyperbranched organopolysiloxane thus obtained were first emulsified with 500 mg of diazabicyclooctane, 5.1 g of water and additionally 5.0 g of silicone resin 1 through a high-speed stirrer to give a homogeneous mixture, and then 56.7 g of toluene diisocyanate was added to this emulsion and incorporated for 10 s with a high-speed 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. was closed up to a 100 ⁇ wide and 40 cm long gap to escape the air to be displaced. After a demolding time of 10 min. was obtained a silicone PU foam with a density of 50 kg / m 3 , which had a homogeneous and defect-free surface.
  • 200.0 g of the hyperbranched organopolysiloxane thus obtained were first emulsified with 500 mg of diazabicyclooctane, 6.0 g of water and additionally 3.0 g of silicone resin 1 through a high-speed stirrer to a homogeneous mixture and then 64.2 g of toluene diisocyanate were added to this emulsion and incorporated for 10 s with a long-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. except for a 100 ⁇ wide and 40 cm 3
  • 200.0 g of the hyperbranched organopolysiloxane thus obtained were first emulsified with 500 mg of diazabicyclooctane, 5.2 g of water and additionally 3.0 g of silicone resin 1 through a high-speed stirrer to give a homogeneous mixture, and then 60.0 g of toluene diisocyanate was added to this emulsion and incorporated for 10 s with a high-speed 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. 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. was obtained a silicone PU foam with a density of 50 kg / m 3 , which had a homogeneous and defect-free surface.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Medicinal Preparation (AREA)

Abstract

L'invention concerne des préparations transformables en mousse contenant des siloxanes (A) de formule V- (NHC(O)R1R2)p-m-n(NHC(O)R1R4 [SiR2O] a-SiR2R4R1H) m (NHC (O) NR5 2) n (I), des polyisocyanates (B) et des résines d'organopolysiloxane (C), les groupes et indices de ladite formule V étant tels que définis dans la revendication 1. L'invention concerne également des mousses de polyuréthane siliconées, notamment des mousses moulées, de faibles densités et leurs procédés de production.
EP11708444A 2010-03-15 2011-03-04 Mousse de polyuréthane siliconée Withdrawn EP2547710A2 (fr)

Applications Claiming Priority (2)

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DE102010002880A DE102010002880A1 (de) 2010-03-15 2010-03-15 Siliconhaltiger Polyurethanschaum
PCT/EP2011/053253 WO2011113708A2 (fr) 2010-03-15 2011-03-04 Mousse de polyuréthane siliconée

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EP (1) EP2547710A2 (fr)
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DE102010003477A1 (de) * 2010-03-30 2011-10-06 Wacker Chemie Ag Siliconhaltiger Polyisocyanuratschaum
DE102010062482A1 (de) * 2010-12-06 2012-06-06 Wacker Chemie Ag Siliconhaltiger Polyurethanschaum
DE102012200790A1 (de) * 2012-01-20 2013-07-25 Wacker Chemie Ag Silanvernetzende schäumbare Mischungen
DE102013211349A1 (de) 2013-06-18 2014-12-18 Evonik Industries Ag Isocyanat-Siloxanpolyether-Zusammensetzung
CN113101418B (zh) * 2020-01-09 2022-07-19 北京化工大学 一种乳房假体外壳材料、制备方法及应用
CN111660471B (zh) * 2020-05-25 2024-06-21 余姚市远东化工有限公司 耐久型有机硅脱模剂及其制备方法

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KR20120104620A (ko) 2012-09-21
CN102892804A (zh) 2013-01-23
US20130005847A1 (en) 2013-01-03
DE102010002880A1 (de) 2011-09-15
WO2011113708A8 (fr) 2012-08-30
WO2011113708A3 (fr) 2012-11-08

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