WO2001005883A1 - Elastomeres de polyurethanne, compacts et/ou cellulaires, presentant des charges nanometriques - Google Patents

Elastomeres de polyurethanne, compacts et/ou cellulaires, presentant des charges nanometriques Download PDF

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WO2001005883A1
WO2001005883A1 PCT/EP2000/006523 EP0006523W WO0105883A1 WO 2001005883 A1 WO2001005883 A1 WO 2001005883A1 EP 0006523 W EP0006523 W EP 0006523W WO 0105883 A1 WO0105883 A1 WO 0105883A1
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weight
parts
molecular weight
acid
nanoscale
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PCT/EP2000/006523
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German (de)
English (en)
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Michael Schneider
Joachim Wagner
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Bayer Aktiengesellschaft
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Priority to AU66908/00A priority Critical patent/AU6690800A/en
Publication of WO2001005883A1 publication Critical patent/WO2001005883A1/fr

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633Compounds of group C08G18/42
    • C08G18/6662Compounds of group C08G18/42 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7678Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing condensed aromatic rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066Use of inorganic compounding ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • C08K3/36Silica
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00Foam properties
    • C08G2110/0041Foam properties having specified density
    • C08G2110/0066≥ 150kg/m3
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00Foam properties
    • C08G2110/0083Foam properties prepared using water as the sole blowing agent
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives

Definitions

  • the invention relates to compact and / or cellular polyurethane elastomers (PUR elastomers) with nanoscale fillers and processes for their production.
  • PUR elastomers polyurethane elastomers
  • the invention relates to compact and / or cellular polyurethane elastomers which contain 0.01 to 20% by weight, preferably 0.2 to 10% by weight, of nanoscale SiO 2 .
  • the invention further relates to a method for producing such elastomers by reaction
  • nanoscale filler used is nanoscale SiO 2 or a filler which is present as nanoscale SiO in the resulting PUR elastomer by using a suitable process.
  • the PUR elastomers are preferably produced by the prepolymer process, with a polyaddition adduct containing isocyanate groups advantageously being produced in the first step from the higher molecular weight polyhydroxy compound (b) and at least one di- or polyisocyanate (a).
  • massive PUR elastomers made from prepolymers containing such isocyanate groups can be reacted with low molecular weight chain extenders and / or crosslinking agents (d) and / or higher molecular weight ones
  • Polyhydroxyl compounds (b) can be produced. If water or mixtures of water and optionally low molecular weight chain extenders and / or crosslinking agents (d) and / or higher molecular weight polyhydroxyl compounds (b) are used in the second step, microcellular PUR elastomers can be produced in this way.
  • low-boiling liquids which evaporate under the influence of the exothermic polyaddition reaction and advantageously have a boiling point under atmospheric pressure in the range from -40 to 120 ° C., preferably from 10 to 90 ° C., or Gases can be used as physical blowing agents or chemical blowing agents.
  • Dispersions of the nanoscale filler (c) in protic or aprotic solvents such as, for. B. water, methanol, ethanol, z ' so-propanol, ethanediol, 1,4-butanediol, 1,6-hexanediol, THF, diethyl ether, pentane, cyclopentane, hexane, heptane, toluene, acetone, 2-butanone or dilute acids such as hydrochloric acid, sulfuric acid, acetic acid or phosphoric acid used and added to the higher molecular weight polyhydroxyl compound (b) and / or optionally to the low molecular weight chain extender and / or crosslinking agent (d).
  • the solvent of the dispersion can then optionally be removed, for example distilled off.
  • nanoscale filler (c) in solvents which are inert towards NCO groups, e.g. Acetone, tetrahydrofuran, 1,4-dioxane, hydrocarbons such as e.g. Pentane, hexane, heptane, cyclohexane, toluene used, these can also be added to the polyisocyanate (a) and / or optionally the prepolymer containing isocyanate groups.
  • NCO groups e.g. Acetone, tetrahydrofuran, 1,4-dioxane, hydrocarbons such as e.g. Pentane, hexane, heptane, cyclohexane, toluene used, these can also be added to the polyisocyanate (a) and / or optionally the prepolymer containing isocyanate groups.
  • the nanoscale filler can also be used as a powder, in which the primary particles of the filler can also be agglomerated, in the di- and / or polyisocyanate (a) and / or in the higher molecular weight polyhydroxyl compound (b) and / or optionally in the low molecular chain extension and / or crosslinking agent (d) can be introduced.
  • the shear forces that occur during the incorporation of the powder detach the primary particles from the nanoparticles present in the powder in agglomerated form, so that they are largely dispersed in the system component.
  • dispersing aids can also be used, e.g. in the article by P. Walstra: "Formation of Emulsions" in
  • Suitable starting components a) for the process according to the invention are aliphatic, cycloaliphatic, aromatic and heterocyclic polyisocyanates, such as those e.g. by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, for example those of the formula
  • Diphenylmethane-2,4'- and / or -4,4'-diisocyanate (MDI) or naphthylene-1,5-diisocyanate (NDI) are suitable.
  • triphenylmethane-4,4 ', 4 "-triisocyanate polyphenyl-polymethylene-polyisocyanates, such as those obtained from
  • ester-containing polyisocyanates as described in GB-PS 965,474 and 1,072,956, in US-PSt 3 567 763 and mentioned in DE-PS 12 31 688, reaction products of the above-mentioned isocyanates with acetals according to DE-PS 1 072 385 and polyisocyanates containing polymeric fatty acid esters according to US-PS 3 455 883.
  • distillation residues obtained in industrial isocyanate production and containing isocyanate groups optionally dissolved in one or more of the aforementioned polyisocyanates. It is also possible to use any mixtures of the aforementioned polyisocyanates.
  • polyisocyanates e.g. 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers
  • TDI 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers
  • CADI polyphenyl-polymethylene polyisocyanates, such as those produced by aniline-formaldehyde condensation and subsequent phosgenation, are (“crude MDI”), 4 , 4'- and / or 2,4'-diphenylmethane diisocyanate and carbodiimide groups,
  • Modified polyisocyanates containing urethane groups, aophanate groups, isocyanurate groups, urea groups or biuret groups, in particular those modified polyisocyanates derived from 2,4- and / or 2,6-tolylene diisocyanate or from 4,4'- and / or 2nd Derive 4'-diphenylmethane diisocyanate. Naphthylene-1,5-diisocyanate and mixtures of the polyisocyanates mentioned are also very suitable.
  • prepolymers containing isocyanate groups are particularly preferably used in the process according to the invention, which are prepared by reacting a partial amount or the total amount of at least one higher molecular weight
  • the prepolymers containing isocyanate groups are prepared by reacting exclusively higher molecular weight polyhydroxyl compounds (b) with the polyisocyanates (a), preferably 4,4'-MDI, 2,4-TDI and / or 1,5- NDI.
  • Difunctional polyhydroxyl compounds with a number average molecular weight of 500 to 6,000, preferably 800 to 3,500 and in particular 1,000 to 3,300, which are selected from the group of polyester polyols, hydroxyl-containing polycarbonates and polyoxyalkylene polyols, are particularly suitable for this purpose.
  • the prepolymers containing isocyanate groups can be prepared in the presence of catalysts. However, it is also possible to prepare the prepolymers containing isocyanate groups in the absence of catalysts and to incorporate these into the reaction mixture for producing the PUR elastomers.
  • Suitable higher molecular weight polyhydroxyl compounds b) are those having at least two H atoms reactive toward isocyanate groups; be preferred
  • Such polyether polyols can be prepared by known processes, for example by anionic polymerization of alkylene oxides in the presence of alkali metal hydroxides or alkali metal alcoholates as catalysts and with the addition of at least one starter molecule which contains 2 to 3 reactive hydrogen atoms, or by cationic polymerization of alkylene oxides in the presence of Lewis acids such as Antimony pentachloride or boron fluoride etherate.
  • Suitable alkylene oxides contain 2 to 4 carbon atoms in the alkylene radical.
  • Examples are tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide, preferably ethylene oxide and / or 1,2-propylene oxide are used.
  • the alkylene oxides can be used individually, alternately in succession or as mixtures. Come as a starter molecule
  • Water or dihydric and trihydric alcohols such as ethylene glycol, propanediol-1,2 and 1,3, diethylene glycol, dipropylene glycol, glycerol, trimethylotpropane etc.
  • the polyether polyols preferably polyoxypropylene-polyoxyethylene polyols, have a functionality from 2 to 3 and number average molecular weights from 500 to 8,000, preferably 800 to 3,500.
  • Suitable polyester polyols can be prepared, for example, from organic dicarboxylic acids with 2 to 12 carbon atoms, preferably aliphatic dicarboxylic acids with 4 to 6 carbon atoms and polyhydric alcohols, preferably diols, with 2 to 12 carbon atoms, preferably 2 carbon atoms.
  • dicarboxylic acids examples include: succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid and terephthalic acid.
  • the dicarboxylic acids can be used both individually and in a mixture with one another. Instead of the free dicarboxylic acids, the corresponding dicarboxylic acid derivatives, such as. B. dicarboxylic acid mono and / or diesters of alcohols having 1 to 4 carbon atoms or dicarboxylic acid anhydrides.
  • Dicarboxylic acid mixtures of succinic, glutaric and adipic acid are preferably used in proportions of, for example, 20 to 35/35 to 50/20 to 32 parts by weight, and in particular adipic acid. Examples of two- and multi-valued
  • Alcohols are ethanediol, diethylene glycol, 1,2- or 1,3-propanediol, dipropylene glycol, methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol 1,6-hexanediol, neopentylglycol, 1.10 -Decanediol, glycerin, trimethylolpropane and pentaerythritol.
  • 1,2-ethanediol diethylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerol, trimethylolpropane or mixtures of at least two of the diols mentioned, in particular mixtures of ethanediol, 1,4-butanediol and 1,6-hexanediol, glycerin and / or trimethylolpropane.
  • insert gases such as e.g. Nitrogen, carbon monoxide, helium, argon and also in the melt at temperatures from 150 to 300 ° C., preferably 180 to 230 ° C., if appropriate under reduced pressure, up to the desired acid number, which is advantageously less than 10, preferably less than 1 , be polycondensed.
  • the esterification mixture is polycondensed at the above-mentioned temperatures up to an acid number of 80 to 30, preferably 40 to 30, under normal pressure and then under a pressure of less than 500 mbar, preferably 10 to 150 mbar.
  • suitable esterification catalysts are iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and tin catalysts in the form of metals, metal oxides or metal salts.
  • the polycondensation can also be carried out in the liquid phase in the presence of diluents and / or entraining agents, e.g. Benzene, toluene, xylene or chlorobenzene, for azeotropic distillation of the water of condensation.
  • the organic polycarboxylic acids and / or their derivatives are polycondensed with polyhydric alcohols advantageously in a molar ratio of 1: 1 to 1.8, preferably 1: 1.05 to 1.2.
  • the polyester polyols obtained preferably have a functionality of 2 to 3, in particular 2 to 2.6 and a number average molecular weight of 400 to 6,000, preferably 800 to 3,500.
  • Suitable polyester polyols also include hydroxyl-containing polycarbonates.
  • Suitable polycarbonates containing hydroxyl groups are those of the type known per se which, for example, react with diols, such as 1,2-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, trioxyethylene glycol and / or tetraoxyethylene glycol
  • diols such as 1,2-propanediol, 1,4-butanediol, 1,6-hexanediol
  • diethylene glycol trioxyethylene glycol and / or tetraoxyethylene glycol
  • Diaryl carbonates for example diphenyl carbonate, or phosgene can be produced.
  • the amount of the nanoscale filler is chosen so that the polyurethane elastomer according to the invention contains 0.01 to 20% by weight, preferably 0.2 to 10% by weight, of nanoscale SiO 2 .
  • the filler is preferably used in the process according to the invention as a dispersion, water or protic or aprotic organic solvents preferably being chosen as the dispersion medium, particularly preferably alcohols, in particular isopropanol. Mixtures of different solvents can of course also be used.
  • the solids content of the dispersions is preferably from 5 to 50% by weight, particularly preferably 15-40% by weight, the solid in the dispersion preferably being completely dispersed and not aggregated.
  • Dispersions which have a pH of 6 to 10, particularly preferably 7 to 9, are preferably used. It has been found that acidic dispersions are more difficult to process than neutral or slightly alkaline dispersions. The stability of the dispersion is ensured by the uniform charging of the surface of the dispersed particles.
  • Such dispersions of nanoparticles can be produced by methods known to those skilled in the art. For example, such
  • Aqueous suspensions of SiO 2 nanoparticles can be produced, for example, from silica using the sol-gel process.
  • the charge on the surface of the suspended particles can be adjusted by the pH of the solvent, for example anionic surfaces can be adjusted by a sufficiently alkaline medium.
  • Cationic top Areas can be obtained from this, for example, by pH drop, ie the introduction of the suspension in acetic acid, hydrochloric acid, sulfuric acid or the like acidic solutions.
  • low molecular weight functional chain extenders and / or low molecular weight preferably trifunctional or tetrafunctional crosslinking agents or mixtures of chain extenders and crosslinking agents can be used.
  • Such chain extenders and crosslinking agents d) are used to modify the mechanical properties, in particular the hardness of the PUR elastomers.
  • Suitable chain extenders such as alkane diols, dialkylene glycols and polyalkylene polyols and crosslinking agents, e.g. Trihydric or tetravalent alcohols and oligomeric polyalkylene polyols with a functionality of 3 to 4, usually have molecular weights ⁇ 800, preferably from 18 to 400 and in particular from 60 to 300.
  • Alkane diols with 2 to 12, preferably, are preferably used as chain extenders 2, 3, 4 or 6 carbon atoms, e.g.
  • Dialkylene glycols with 4 to 8 carbon atoms e.g. Diethylene glycol and dipropylene glycol as well as polyoxyalkylene glycols.
  • Branched-chain and / or unsaturated alkanediols with usually no more than 12 carbon atoms such as e.g. 1,2-propanediol, 2-methyl-l, 2-propanediol, 2,2-dimethyl-l, 3-propanediol, 2-butyl-2-ethyl-l, 3-propanediol, 2-butene-l, 4- diol and 2-butyne-1,4-diol,
  • terephthalic acid with glycols having 2 to 4 carbon atoms such as, for example, terephthalic acid-bis-ethylene glycol or terephthalic acid-bis-1,4-butanediol, hydroxyalkylene ether of hydroquinone or resorcinol, for example 1,4-di- ( ⁇ -hydroxyethyl) - hydroquinone or 1,3- ( ⁇ -hydroxyethyl) resorcinol, alkanolamines with 2 to 12 carbon atoms such as ethanolamine, 2-aminopropanol and 3-amino-2,2-dimethylpropanol, N-alkyldialkanolamines, for example N-methyl and N-ethyl-diethanolamine, (cyclo) aliphatic diamines with 2 to 15 carbon atoms, such as 1,2-ethylenediamine, 1,3-propylenediamine, 1, 4-butylenediamine and 1,6-hexamethylened
  • Chloro-4,4'-diamino-diphenylmethane 3,3'-dichloro-4,4'-diaminodiphenylmethane
  • MOCA 3,5-diamino-4-chlorobenzoic acid ester
  • DETDA diethyltoluenediamine
  • 2,4- and 2,6-toluenediamine 3,5-diamino-4-chlorobenzoic acid ester
  • chain extenders and crosslinking agents d) are polyether polyols, preferably those with an average functionality of 2 to 8, a hydroxyl number from 200 to 1 240.
  • These polyether polyols which have proven themselves as chain extenders and crosslinking agents d), are e.g. Polyoxyethylene polyols started with 1,2-propanediol, water, trimethylolpropane with a hydroxyl number from 630 to 970 and / or with glycerol or trimethylolpropane or one
  • Glycerol / trimethylolpropane mixture started polyoxypropylene polyols with a hydroxyl number of 210 to 930.
  • polyether polyols are polyoxypropylene polyols with an average functionality of 4 to 8, preferably 4 to 6 and a hydroxyl number of 230 to 500, preferably from 250 to 380, which are obtained under Use of sucrose or sorbitol or mixtures of sucrose and sorbitol as starter molecules, water, propylene glycol, glycerol or mixtures of at least two of the co-starters mentioned additionally being able to be used as co-starters.
  • polyoxypropylene and / or polyoxyethylene polyols with a hydroxyl number of 450 to 750 which can be obtained by reacting pentaerythritol or a mixture of
  • Pentaerythritol and glycerol and / or trimethylolpropane advantageously in a molar ratio of pentaerythritol to glycerol and / or trimethylolpropane of 1: 1, with 1,2-propylene oxide or ethylene oxide.
  • Trifunctional and tetrafunctional alcohols such as glycerol, trimethylolpropane, pentaerythritol and trihydroxycyclohexane and tetrahydroxyalkylenediamines, for example tetra- (2-hydroxyethyl) ethylenediamine or tetra- (2-hydroxypropyl) ethylenediamine, are also very suitable as crosslinking agents.
  • the compounds of component d) can be used in the form of mixtures or individually. Mixtures of chain extenders and crosslinking agents can also be used.
  • the structural components b) and d) can be varied in relatively wide quantitative ratios of the hardness of the PUR elastomers.
  • the required amounts of the structural components b) and d) can be determined experimentally in a simple manner. 0.5 to are advantageously used
  • tertiary amines such as triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N, N, N ', N'-tetramethylethylene diamine, pentamethyl-diethylene triamine and higher homologs (DE-OS 26 24 527 and 26 24 528), 1,4-diaza-bicyclo (2,2,2) octane, N-methyl-N'-dimethylaminoethyl-piperazine, bis- (dimethylaminoalkyl) piperazines (DE-OS 26 36 787), N, N-dimethylbenzylamine, N, N-dimethylcyclohexylamine, N, N-diethylbenzylamine, bis- (N, N-diethylaminoethyl) adipate, N, N , N ', N'
  • Tertiary amines which have hydrogen atoms active against isocyanate groups as a catalyst are e.g. Triethanolamine, triisopropanolamine, N-methyl-diethanolamine, N-ethyl-diethanolamine, N, N-dimethylethanolamine, their reaction products with alkylene oxides such as propylene oxide and / or ethylene oxide and secondary tertiary amines according to DE-OS 27 32 292 Silaamines with carbon-silicon bonds, as described in US Pat. No.
  • 3,620,984 can also be used as catalysts, for example 2,2,4-trimethyl-2-silamorpholine and 1,3-diethylaminomethyl-tetramethyl-disiloxane.
  • nitrogen-containing bases such as tetraalkylammonium hydroxides, furthermore alkali hydroxides such as sodium hydroxide, alkali phenolates such as sodium phenolate or alkali alcoholates such as
  • Hexahydrotriazines can also be used as catalysts (DE-OS 17 69 043).
  • the reaction between NCO groups and Zerewitinoff-active hydrogen atoms is also greatly accelerated by lactams and azalactams, an association being initially formed between the lactam and the compound with acidic hydrogen.
  • Such associates and their catalytic action are described in DE-OS 20 62 286, 20 62 289, 21 17 576, 21 29 198, 23 30 175 and 23 30 211.
  • organic metal compounds in particular organic tin compounds, can also be used as catalysts.
  • sulfur-containing compounds such as di-n-octyl-tin mercaptide (US Pat. No.
  • organic tin compounds which are preferably tin (II) salts of carboxylic acids such as tin (II) acetate and tin (II) octoate , Tin (II) ethylhexoate and tin (II) laurate and tin (IV) compounds, for example dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate or dioctyltin diacetate.
  • tin (II) salts of carboxylic acids such as tin (II) acetate and tin (II) octoate , Tin (II) ethylhexoate and tin (II) laurate and tin (IV) compounds, for example dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate,
  • the catalysts or catalyst combinations are generally used in an amount between about 0.001 and 10% by weight, in particular 0.01 to 1% by weight, based on the total amount of compounds having at least two hydrogen atoms which are reactive toward isocyanates.
  • compact PUR elastomers e.g. PUR cast elastomers are manufactured.
  • blowing agent f For the production of cellular, preferably microcellular PUR elastomers, water is used as blowing agent f), which in situ with the organic polyisocyanates a) or with prepolymers having isocyanate groups to form
  • the build-up components b) and d) or the dispersions containing the inorganic nanoscale fillers may be water-based and / or because of their composition, in some cases it is not necessary to add water separately to the build-up components b), d) or the reaction mixture. However, if water has to be added to the polyurethane formulation in order to set the desired density, this is usually in
  • Substances which evaporate under the influence of the exothermic polyaddition reaction and which advantageously have a boiling point under normal pressure in the range from -40 to 120 ° C., preferably from 10 to 90 ° C., are used as physical blowing agents.
  • organic blowing agents come e.g. Acetone, ethyl acetate, halogen-substituted alkanes such as methylene chloride, chloroform, ethylidene chloride,
  • a blowing effect can also be achieved by adding compounds which are released at temperatures above room temperature with the elimination of gases, for example nitrogen and / or
  • Carbon dioxide decompose like azo compounds e.g. Azodicarbonamide or azoisobutyronitrile, or salts such as ammonium bicarbonate, ammonium carbamate or ammonium salts of organic carboxylic acids, e.g. the monoammonium salts of malonic acid, boric acid, formic acid or acetic acid.
  • azo compounds e.g. Azodicarbonamide or azoisobutyronitrile
  • salts such as ammonium bicarbonate, ammonium carbamate or ammonium salts of organic carboxylic acids, e.g. the monoammonium salts of malonic acid, boric acid, formic acid or acetic acid.
  • Liquid or gas mixtures or as gas-liquid mixtures can depend on the density that you want to achieve and the amount of water used. The required amounts can easily be determined experimentally. Satisfactory results usually provide amounts of solids of 0.5 to 35 parts by weight, preferably 2 to 15 parts by weight, liquid amounts of
  • the gas loading with, for example, air, carbon dioxide, nitrogen and / or helium can be carried out both via the higher molecular weight polyhydroxyl compound b), via the low molecular chain extender and / or crosslinking agent d) and also via the polyisocyanates a) or via a) and b) and if necessary, d).
  • Additives g) can optionally be incorporated into the reaction mixture for producing the compact and / or cellular PUR elastomers.
  • examples include surface-active additives such as emulsifiers, foam stabilizers, cell regulators, flame retardants, nucleating agents, oxidation retarders, stabilizers, lubricants and mold release agents, dyes, dispersants and pigments.
  • the emulsifiers are e.g. the sodium salts of castor oil sulfonates or salts of fatty acids with amines such as oleic acid diethylamine or stearic acid diethanolamine in question. Also alkali or ammonium salts of
  • Sulphonic acids such as dodecylbenzenesulphonic acid or dinaphthylmethane disulphonic acid or fatty acids such as ricinoleic acid or polymeric fatty acids can also be used as surface-active additives.
  • Foam stabilizers in particular are polyether siloxanes, especially water-soluble representatives. These compounds are generally constructed in such a way that a copolymer of ethylene oxide and propylene oxide is linked to a polydimethylsiloxane radical. Such foam stabilizers are e.g. in U.S. Patents 2,834,748, 2,917,480 and 3,629,308.
  • polysiloxane-polyoxyalkylene copolymers branched via AUophanate groups in accordance with DE-OS 25 58 523.
  • Other organospolysiloxanes, oxyethylated alkylphenols, oxyethylated fatty alcohols, paraffin oils, castor oil or ricinoleic acid esters, turkish red oil and peanut oil and cell regulators such as paraffin oil are also suitable , Fatty alcohols and dimethylpolysiloxanes.
  • Oligomeric polyacrylates with polyoxyalkylene and fluoroalkane radicals are also suitable as side groups for improving the emulsifying effect, the dispersion of the filler, the cell structure and / or for stabilizing them.
  • the surface-active substances are usually used in amounts of 0.01 to 5 Parts by weight, based on 100 parts by weight of the higher molecular weight polyhydroxyl compounds b) applied.
  • Reaction retarders for example acidic substances such as hydrochloric acid, or organic acids and acid halides, cell regulators known per se such as paraffins or fatty alcohols or dimethylpolysiloxanes as well as pigments or dyes and flame retardants known per se, for example tris-chloroethyl phosphate, tricresyl phosphate or ammonium phosphate and -polyphosphate, also stabilizers against aging and weather influences, plasticizers and fungistatic and bacteriostatic substances.
  • the PUR elastomers according to the invention can be produced in several variants.
  • mixtures of higher molecular weight polyhydroxyl compound b), optionally low molecular weight chain extender and / or crosslinking agent d) and optionally chemical blowing agents, preferably water can be reacted with organic polyisocyanates a).
  • prepolymers containing isocyanate groups from a), b) and c) are reacted with chain extenders and or crosslinking agents d), or with mixtures of subsets of b) and d), or mixtures of d) and Water, or preferably with mixtures of subsets of b), d) and water.
  • the components are reacted in amounts such that the equivalence ratio of the NCO groups of the polyisocyanates a) to the sum of the isocyanate group-reactive hydrogens of components b), c), d) and such as any chemical blowing agent used is 0.8: 1 to 1.2: 1, preferably 0.95: 1 to 1.15: 1 and in particular 1.00: 1 to 1.10: 1.
  • Solvent or in a mixture of protic and or aprotic solvents of the higher molecular weight polyhydroxyl compound b) and / or optionally the low molecular weight chain extender and / or crosslinking agent d) is added and the solvent of component c) is optionally distilled off.
  • Suitable solvents are e.g.
  • dispersions of nanoscale filler c) in solvents which are inert to NCO groups such as acetone, tetrahydrofuran or hydrocarbons, e.g. Pentane, hexane, heptane, cyclohexane, toluene, the polyisocyanate a) or an isocyanate group-containing prepolymer.
  • the filler can also be in the form of a powder, in which the primary particles of the filler can also be agglomerated, in the di- and / or polyisocyanate a) and / or in the higher molecular weight polyhydroxyl compound b) and / or optionally in the low molecular chain extender and / or Crosslinking agents d) are introduced.
  • Powder in agglomerated form the nanoparticles present the primary particles so that they are dispersed in the system component.
  • dispersion technology care must be taken that fillers in which there are strong interactions between the primary particles are redispersed at high shear rates; apparatus suitable for this are known to the person skilled in the art (G.W. Becker,
  • PUR elastomers is generally 0.1 to 20% by weight, preferably 0.2 to 10% by weight, particularly preferably 0.3-10% by weight.
  • the PUR elastomers according to the invention can be prepared by the processes described in the literature, e.g. the one-shot or the prepolymer process, with the aid of mixing devices known in principle to the person skilled in the art. They are preferably produced by the prepolymer process.
  • the starting components are mixed homogeneously in the absence of blowing agents f), usually at a temperature of 80 to 160 ° C., preferably 110 to 150 ° C., and the reaction mixture is introduced into an open, optionally tempered mold and allowed to harden.
  • the structural components are mixed in the same way in the presence of blowing agents f), preferably water, and poured into the mold, which may be tempered. After filling, the mold is closed and the reaction mixture is left under compression, e.g.
  • Foam with a degree of compaction from 1.1 to 8, preferably from 1.2 to 6 and in particular 2 to 4 to form shaped articles.
  • the demolding times include depending on the temperature and geometry of the mold and the reactivity of the reaction mixture and are usually
  • compact PUR elastomers according to the invention have a density of 1.1 to 1.8 g / cm 3 (for comparison: corresponding filler-free products have a density of 1.0 to 1.4 g / cm 3 , preferably 1.1 up to 1.25 g / cm).
  • Cellular PUR elastomers according to the invention have densities of 0.2 to 1.8 g / cm, preferably 0.35 to 1 g / cm.
  • the PUR elastomers according to the invention show increased heat resistance under dynamic stress and can therefore be used up to a higher temperature range. At higher temperatures (> 80 ° C) they show a lower loss factor (tan ⁇ ) compared to the elastomer not filled with nanoscale fillers. The crystallization in the soft segment and in the hard segment of the elastomers according to the invention is increased by the nanoscale filler.
  • the PUR elastomers according to the invention are used for the production of moldings, preferably for mechanical engineering and the transport sector.
  • the cellular PUR elastomers are particularly suitable for the manufacture of damping and spring elements, for example for means of transport, preferably motor vehicles, buffers and cover layers.
  • the compact PUR elastomers are suitable, for example, for use in tires, rolls and rollers, as roller coatings or for the production of belts.
  • the nanoscale filler was in the form of a 30.2% by weight SiO 2 with an average particle size of approx. 9 nm and a specific surface area of 300 m 2 / g in dispersion containing isopropanol with a pH of 8- 9 used (Organosol ® 300, Bayer AG).
  • the crosslinker component consisted of 80.74% by weight of a poly (ethanediol-1,4-butanediol adipate) (molar ratio of ethanediol: 1,4-butanediol: adipic acid 1: 1: 2), 8.68% by weight of water , 8.68% by weight sodium salt of sulfated castor oil
  • reaction mixture was then poured into a closable, metallic molding tool heated to 90 ° C., the molding tool was sealed and the reaction mixture was allowed to harden. After 25 minutes, the microcellular molded body was removed from the mold and heat-treated at 110 ° C. for 16 hours for thermal post-curing.
  • the crosslinker component consisted of 84.74% by weight of a poly (ethanediol adipate), 15.26% by weight of 1,4-butanediol and 100 ppm of dibutyltin dilaurate.
  • the crosslinker component consisted of 1,4-butanediol.
  • the solid molded body was demolded for minutes and annealed at 110 ° C for 16 hours for thermal post-curing.
  • the crosslinker component consisted of 80.74% by weight of a poly (ethanediol-1,4-butanediol adipate) (molar ratio of ethanediol: 1,4-butanediol: adipic acid 1: 1: 2), 8.68% by weight of water, 8 , 68% by weight sodium salt of sulfated castor oil (manufacturer: Rheinchemie), 1.74% by weight of a mixture of ethoxylated oleic and ricinoleic acid with an average of 9 oxyethyl units and the monoethanolamine salt of n-alkylbenzenesulfonic acid with C 9 to cis Alkyl residues (manufacturer: Rheinchemie) and 1.27% by weight dimethylcyclohexylamine.
  • a poly ethanediol-1,4-butanediol adipate
  • Example 1 a) Preparation of a prepolymer containing isocyanate groups and containing SiO 2 nanoparticles and based on 1,5-NDI
  • the crosslinker component consisted of 80.74% by weight of a poly (ethanediol-1,4-butanediol adipate) (molar ratio of ethanediol: 1,4-butanediol: adipic acid 1: 1: 2), 8.68
  • % By weight of water, 8.68% by weight of sodium salt of sulfated castor oil (manufacturer: Rheinchemie), 1.74% by weight of a mixture of ethoxylated oleic and ricinoleic acids with an average of 9 oxyethyl units and the monoethanolamine salt of n-alkylbenzenesulfonic acid C ⁇ > - C ⁇ to 5 alkyl groups (manufactured by Rhein Chemie) and 1.27 wt .-% of dimethylcyclohexylamine.
  • the mold was closed and the reaction mixture was allowed to harden. After 25 minutes, the microcellular molded body was removed from the mold and annealed at 110 ° C. for 16 hours for thermal post-curing.
  • Example 2 a) Preparation of a prepolymer containing 4,4'-MDI and containing isocyanate groups and containing SiO 2 nanoparticles
  • 1,000 parts by weight (0.5 mol) of a poly (ethanediol adipate) with a number average molecular weight of 2,000 (calculated from the experimentally determined hydroxyl number) were 30.2% by weight with 195.1 parts by weight Dispersion of SiO 2 (average particle diameter approx. 9 nm) in iso-propanol is added with vigorous stirring and the iso-propanol is distilled off in vacuo at 80 ° C. The mixture was then heated to 50 ° C. and 149.9 parts by weight (0.86 mol) of 4,4′-MDI were added at this temperature, with vigorous stirring, and the mixture was reacted.
  • the mold was closed and the reaction mixture was allowed to harden. After 25 minutes, the massive molded body was removed from the mold and annealed at 120 ° C. for 16 hours for thermal post-curing.
  • the massive molded body was demolded for minutes and annealed at 120 ° C for 16 hours for thermal post-curing.
  • the crosslinker component consisted of 80.74% by weight of a poly (ethanediol-1,4-butanediol adipate) (molar ratio of ethanediol: 1,4-butanediol: adipic acid 1: 1: 2), 8.68% by weight of water, 8 , 68% by weight sodium salt of sulfated castor oil (manufacturer: Rheinchemie), 1.74% by weight of a mixture of ethoxylated oleic and ricinoleic acid with an average of 9 oxyethyl units and the monoethanolamine salt of n-alkylbenzenesulfonic acid with C 9 - to C, 5 Alkyl residues (manufacturer: Rheinchemie) and 1.27% by weight dimethylcyclohexylamine.
  • a poly ethanediol-1,4-butanediol adipate
  • the crosslinker component consisted of 80.74% by weight of a poly (ethanediol-1,4-butanediol adipate) (molar ratio of ethanediol: 1,4-butanediol: adipic acid 1: 1: 2), 8.68% by weight of water, 8 , 68% by weight sodium salt of sulfated castor oil (manufacturer: Rheinchemie), 1.74% by weight of a mixture of ethoxylated oleic and ricinoleic acid with an average of 9 oxyethyl units and the monoethanolamine salt of n-alkylbenzenesulfonic acid with Cg to cis alkyl residues ( Manufacturer: Rheinchemie) and 1.27% by weight dimethylcyclohexylamine.
  • a poly ethanediol-1,4-butanediol adipate
  • the mechanical properties of the elastomers produced in the examples are summarized in the table below.
  • the compression set was measured based on DIN 53 572; Tensile strength and elongation at break were in
  • Tab. 1 Static and dynamic properties of the solid and cellular PUR elastomers according to comparative examples u
  • the nanoscale filler is not aggregated and completely dispersed in the polymer material.

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Abstract

La présente invention concerne des élastomères de polyuréthanne (élastomères PUR), compacts et/ou cellulaires, présentant des charges nanométriques, ainsi qu'un procédé pour les produire.
PCT/EP2000/006523 1999-07-20 2000-07-10 Elastomeres de polyurethanne, compacts et/ou cellulaires, presentant des charges nanometriques WO2001005883A1 (fr)

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DE19933819A DE19933819A1 (de) 1999-07-20 1999-07-20 Kompakte und/oder zellige Polyurethanelastomere mit nanoskaligen Füllstoffen
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KR100458984B1 (ko) * 2001-08-24 2004-12-03 (주)나눅스 수분산 폴리우레탄-콜로이달 실리카 나노 복합재료 및그의 제조방법
WO2005090429A1 (fr) 2004-03-16 2005-09-29 Albany International Corp. Courroies revetues de polyurethane et recouvrements de rouleau comprenant des nanocharges
EP1683831A1 (fr) 2005-01-24 2006-07-26 Goldschmidt GmbH Nanoparticules destinées à la préparation de mousses de polyuréthane
DE102004004237C5 (de) * 2004-01-27 2009-11-12 Woco Industrietechnik Gmbh Verfahren zur Herstellung von mikroporösen Kunststoffprodukten und die nach diesem Verfahren erhältlichen Formteile, Profile und Granulate
US7736468B2 (en) * 2004-03-16 2010-06-15 Albany International Corp. Belts and roll coverings having a nanocomposite coating
WO2010103072A1 (fr) 2009-03-13 2010-09-16 Basf Se Procédé de fabrication de dispersions contenant de la silice, contenant des polyéthérols ou des polyétheramines
US20110159281A1 (en) * 2009-12-29 2011-06-30 3M Innovative Properties Company Polyurethane nanocomposites
US8088880B2 (en) 2006-11-17 2012-01-03 Bayer Materialscience Ag Nanoparticle-modified polyisocyanates
US8119716B2 (en) 2005-06-04 2012-02-21 Solvay Infra Bad Hoenningen Gmbh Method of generating a dispersion of deagglomerated barium sulphate in plastics or plastics precursors
WO2012069264A1 (fr) * 2010-11-24 2012-05-31 Evonik Degussa Gmbh Procédé de préparation de polyuréthane thermoplastique
CN104140666A (zh) * 2014-07-30 2014-11-12 东莞市吉鑫高分子科技有限公司 用于球膜的高耐磨透明热塑性聚氨酯弹性体及其制备方法
CN104177817A (zh) * 2014-07-30 2014-12-03 东莞市雄林新材料科技股份有限公司 一种高耐磨透明tpu球膜及其制备方法
DE102013022173A1 (de) * 2013-12-23 2015-06-25 Gt Elektrotechnische Produkte Gmbh Polyurethan-Elastomere auf der Basis von Polyetheralkoholgemischen und trimerisierten Diisocyanaten
US9403932B2 (en) 2008-10-15 2016-08-02 Basf Se Process for producing silica-comprising polyol dispersions and their use for producing polyurethane materials

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WO2003016370A1 (fr) * 2001-08-10 2003-02-27 Chemiewerk Bad Köstritz GmbH Procede de production de nanocomposites a base d'acide silique/de polyurethane
DE10231001A1 (de) 2002-07-09 2004-02-12 Volkswagen Ag Aus Kunststoff bestehendes Werkzeug
SE529440C2 (sv) * 2005-06-01 2007-08-14 Small Particles Technology Gbg Dispergerbart pulver av kiselsyra
DE102005042826B4 (de) * 2005-09-09 2021-07-01 Volkswagen Ag Lagerelement
DE102005051914B4 (de) * 2005-10-29 2008-02-21 Ab Skf Käfig für ein Wälzlager
FR2938548B1 (fr) * 2008-11-19 2012-08-10 Seppic Sa Utilisation de nanocharges pour la preparation d'elastomeres polyurethanes
CN107266716A (zh) * 2016-04-08 2017-10-20 中国石油天然气股份有限公司 纳米白炭黑的改性方法

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WO1998051736A1 (fr) * 1997-05-12 1998-11-19 Bayer Aktiengesellschaft Procede de production de mousses de polyurethane et/ou de polyisocyanurate rigides a alveoles ouvertes

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Publication number Priority date Publication date Assignee Title
KR100458984B1 (ko) * 2001-08-24 2004-12-03 (주)나눅스 수분산 폴리우레탄-콜로이달 실리카 나노 복합재료 및그의 제조방법
DE102004004237C5 (de) * 2004-01-27 2009-11-12 Woco Industrietechnik Gmbh Verfahren zur Herstellung von mikroporösen Kunststoffprodukten und die nach diesem Verfahren erhältlichen Formteile, Profile und Granulate
WO2005090429A1 (fr) 2004-03-16 2005-09-29 Albany International Corp. Courroies revetues de polyurethane et recouvrements de rouleau comprenant des nanocharges
JP2007530800A (ja) * 2004-03-16 2007-11-01 アルバニー インターナショナル コーポレイション ナノフィラーを有する、ポリウレタンでコートされたベルト及びロールカバー
US7413633B2 (en) 2004-03-16 2008-08-19 Albany International Corp. Belts and roll coverings having a nanocomposite coating
US7736468B2 (en) * 2004-03-16 2010-06-15 Albany International Corp. Belts and roll coverings having a nanocomposite coating
CN1934151B (zh) * 2004-03-16 2013-01-30 阿尔巴尼国际公司 含有纳米填料的聚氨酯涂覆带和辊面包覆层
JP4909884B2 (ja) * 2004-03-16 2012-04-04 アルバニー インターナショナル コーポレイション ナノフィラーを有する、ポリウレタンでコートされたベルト及びロールカバー
EP1683831A1 (fr) 2005-01-24 2006-07-26 Goldschmidt GmbH Nanoparticules destinées à la préparation de mousses de polyuréthane
US8119716B2 (en) 2005-06-04 2012-02-21 Solvay Infra Bad Hoenningen Gmbh Method of generating a dispersion of deagglomerated barium sulphate in plastics or plastics precursors
US8088880B2 (en) 2006-11-17 2012-01-03 Bayer Materialscience Ag Nanoparticle-modified polyisocyanates
US9403932B2 (en) 2008-10-15 2016-08-02 Basf Se Process for producing silica-comprising polyol dispersions and their use for producing polyurethane materials
WO2010103072A1 (fr) 2009-03-13 2010-09-16 Basf Se Procédé de fabrication de dispersions contenant de la silice, contenant des polyéthérols ou des polyétheramines
US8901186B2 (en) 2009-03-13 2014-12-02 Basf Se Process for producing silica-comprising dispersions comprising polyetherols or polyether amines
US20110159281A1 (en) * 2009-12-29 2011-06-30 3M Innovative Properties Company Polyurethane nanocomposites
US9540479B2 (en) * 2009-12-29 2017-01-10 3M Innovative Properties Company Polyurethane nanocomposites
WO2012069264A1 (fr) * 2010-11-24 2012-05-31 Evonik Degussa Gmbh Procédé de préparation de polyuréthane thermoplastique
DE102013022173A1 (de) * 2013-12-23 2015-06-25 Gt Elektrotechnische Produkte Gmbh Polyurethan-Elastomere auf der Basis von Polyetheralkoholgemischen und trimerisierten Diisocyanaten
DE102013022173B4 (de) 2013-12-23 2017-03-30 Gt Elektrotechnische Produkte Gmbh Polyurethan-Elastomere auf der Basis von Polyetheralkoholgemischen und trimerisierten Diisocyanaten
CN104140666A (zh) * 2014-07-30 2014-11-12 东莞市吉鑫高分子科技有限公司 用于球膜的高耐磨透明热塑性聚氨酯弹性体及其制备方法
CN104177817A (zh) * 2014-07-30 2014-12-03 东莞市雄林新材料科技股份有限公司 一种高耐磨透明tpu球膜及其制备方法

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