Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • 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
  • 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
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/708—Isocyanates or isothiocyanates containing non-reactive high-molecular-weight compounds
• • 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
  • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
  • C08G18/725—Combination of polyisocyanates of C08G18/78 with other polyisocyanates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2110/00—Foam properties
  • C08G2110/0008—Foam properties flexible
• • 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
  • C08G2110/0041—Foam properties having specified density
  • C08G2110/005—< 50kg/m3
• • 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
  • C08G2410/00—Soles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/04—Homopolymers or copolymers of styrene
  • C08L25/08—Copolymers of styrene
  • C08L25/12—Copolymers of styrene with unsaturated nitriles

Definitions

• the invention relates to polymer-modified polyisocyanates and to those produced therefrom
• polymer modifiers for example styrene polymers
• polymer-filled polyether polyols as also mentioned in DE-A 40 32 148
• special polymer-filled polymer polyester polyols as described for example in EP-A 0250351.
• the disadvantage of this is that it is not possible to use commercially available polymers, since these are compatible with the
• Polyols are incompatible and / or sediment.
• polyol dispersions can only be stabilized using special techniques; e.g. by using macromers that contain double bonds and by in situ polymerization of styrene and acrylonitrile monomers in polyether polyols, as described in EP-A 780 410 and EP-A 731 118.
• organic fillers for example polyureas or polyhydrazocarbonamides into polyols
• diisocyanatotoluene 80:20 mixture of the 2,4- and 2,6-isomers
• these processes lead to cloudy, milky dispersions.
• These polyols containing organic fillers can then optionally be reacted with a polyisocyanate to form an NCO prepolymer or else directly to the finished polyurethane.
• ABS styrene-acrylonitrile-butadiene polymers
• the disadvantage here is that the transparency of the polyisocyanate is lost and, for example, it is not possible to distinguish optically between crystallized isocyanate and dispersed filler.
• a disadvantage of the known processes for the production of polyurethanes modified with polymers is that the polymers are either in the polyol dispersions sediment and thereby the polyol dispersions are difficult to process or must be stabilized by additional use of macromers.
• this object was achieved with certain polymer modifiers which are added to the polyisocyanate component and are present in solution therein.
• This transparent solution of the polymer-modified polyisocyanate component can be used to produce elastic polyurethanes with high hardness, which also show a significantly improved green strength when processed into molded parts (e.g. shoe soles), which in turn leads to improved demolding behavior and thus shorter cycle times.
• the invention thus relates to polymer-modified transparent polyisocyanates (PMP) which essentially consist of the following components
• AI polyisocyanate components with an NCO content of 15 to
• NCO content 12 to 45 wt .-%
• polyether polyols with OH numbers from 10 to 149 and functionalities from 2 to 8
• polyester polyols with OH numbers from 20 to 280 and
• thermoplastic vinyl polymers with a number average molecular weight of 15 to 90 kg / mol (measured by high pressure exclusion chromatography (HPSEC))
• the polymer modifier B) is evenly distributed in the polyurethane product which was produced on the basis of the corresponding modified polyisocyanate.
• the polymer-modified polyisocyanates (PMP) can preferably be prepared in the following ways:
• Components (C) and optionally (D) to form prepolymers 3. Dissolving the polymer modifier (B) in the isocyanate (AI) and (A2) and simultaneous reaction with the components (C) and optionally (D),
• Polyols cannot be used directly with their total amount.
• the remaining quantities, here in particular partial quantities of the isocyanate component (A) can also be added later to complete the process.
• the prepolymers are generally produced between RT and 120 ° C., preferably between 60-90 ° C. If aliphatic or cycloaliphatic isocyanates are used or used for the preparation of the prepolymers, the preferred temperature range is between 70 and 110 ° C. The use of other additives and / or additives such as catalysts, viscosity regulators etc. is also possible.
• the invention further relates to polymer-modified polyurethanes which are essentially obtainable from:
• the PMP according to the invention essentially consisting of components (A) and (B) and, if appropriate, further additives and / or additives,
• Functionality from 1.8 to 3.5 from the group consisting of poly polyols, polyether polyamines, polyester polyols, polyether ester polyols, polycarbonate diols and polycaprolactones,
• the polyurethanes according to the invention can be prepared by the processes described in the literature, e.g. the one-shot, the semi-prepolymer or the prepolymer process can be produced with the aid of mixing devices known in principle to the person skilled in the art. They are preferably produced by the prepolymer process.
• an isocyanate component (A) and the polymer modifier (B) dissolved therein, optionally component (D), is used to produce an isocyanate group-containing polyaddition adduct (PMP).
• massive PUR elastomers can be produced from such prepolymers containing isocyanate groups by reaction with polyol components (C) and optionally low molecular weight chain extenders and / or crosslinkers (D).
• Catalysts (E) and additives and / or additives (F) can optionally be used both in the isocyanate component (PMP) and in components (C) and (D).
• microcellular PUR elastomers can be produced.
• the components are reacted in amounts such that the equivalence ratio of the NCO
• the starting components are usually mixed homogeneously at a temperature of 20 to 80 ° C., preferably 25 to 60 ° C., the reaction mixture is introduced into an open, optionally tempered mold and then is cured.
• the structural components are mixed in the same way in the presence of blowing agents, preferably water, and introduced into the mold, which may have been tempered. After filling, the mold is closed and the reaction mixture is left under compression, e.g. with a degree of compaction (ratio of
• Foam body density to free foam density from 1.05 to 8, preferably from 1.1 to 6 and in particular 1.2 to 4 to form molded bodies. As soon as the molded bodies have sufficient strength, they are removed from the mold.
• the demolding times depend, inter alia, on the temperature and the geometry of the molding tool and the reactivity of the reaction mixture and are usually 1 to 10 minutes.
• compact PUR elastomers according to the invention have a density of 0.8 to 1.4 g / cm 3 , preferably 0.9 to 1.25 g / cm 3 .
• Cellular PUR elastomers according to the invention have densities of 0.1 to 1.4 g / cm 3 , preferably 0.15 to 0.8 g / cm 3 .
• the polyurethanes according to the invention are particularly valuable materials for molded plastics which, despite the reduced density of molded parts, are distinguished by a constant or increased hardness in comparison to commonly used materials.
• the materials according to the invention are used, for example, in the manufacture of shoe components or shoe soles in a single or multi-layer structure.
• Suitable starting components A) for the process according to the invention are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, as described, for example, by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136.
• those of the formula Q (NCO) n) in which n 2-4, preferably 2, and Q are an aliphatic hydrocarbon radical having 2-18, preferably 6-10, carbon atoms, a cycloaliphatic hydrocarbon radical having 4-15 are suitable , preferably 5-10 C atoms, an aromatic hydrocarbon radical having 6-15, preferably 6-13 C atoms, or an aralipliatic hydrocarbon radical having 8-15, preferably 8-13 C atoms.
• ethylene diisocyanate 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 1,12-dodecane diisocyanate, cyclobutane-1, 3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate and any mixtures of these isomers, l-isocyanato-3,3,5-tri-methyl-5-isocyanatomethyl-cyclohexane, 2,4- and 2,6- hexahydrotoluenediisocyanate as well as any mixtures of these isomers, hexa- hydro-1,3- and -1,4-phenylene diisocyanate, perhydro-2,4'- and -4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 1,4-durol diisocyanate (DDI)
• TKI Toluene diisocyanate
• MDI diphenylmethane-2,4'- and / or -4,4'-diisocyanate
• NDI naphthylene-1,5-diisocyanate
• triphenylmethane-4,4 ', 4 "-triisocyanate polyphenyl-polymethylene-polyisocyanates, as obtained by aniline-formaldehyde condensation and subsequent phosgenation, and for example in GB-PS 874 430 and GB-PS 848 671.
• m- and p-isocyanatophenylsulfonyl isocyanates according to US Pat. No. 3,454,606, perchlorinated aryl polyisocyanates as described in US Pat. No. 3,277,138, polyisocyanates containing carbodiimide groups as described in US Pat. No.
• distillation residues obtained in the industrial production of isocyanates and having 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 for example 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers (TDI), 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate are preferably used and polyphenyl-polymefhylene-polyisocyanates, such as those produced by aniline-formaldehyde condensation and subsequent phosgenation (crude MDI), and carbodiimide groups, uretonimine groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups, modified polyisocyanates (modified polyisocyanates) in particular those modified polyisocyanates which are derived from 2,4- and / or 2,6-tolylene diisocyanate or from 4,4'- and / or 2,4'-diphenylmethan
• modified polyisocyanates A2) and prepolymers A3) containing isocyanate groups which are prepared by reacting a polyol component C) and / or chain extender and / or crosslinker D) with at least one aromatic diisocyanate from the group TDI, MDI, TODI, NDI, DDI, preferably with 4,4'-MDI and / or 2,4-TDI and / or 1,5-NDI.
• the resulting prepolymer A3) containing isocyanate groups preferably has an NCO content of 8 to 45% by weight, preferably 10 to 25% by weight.
• the polymer modifier B) is dissolved in the reaction mixture during the production process of the PMP, as already explained in more detail above.
• the components AI), A2), B), C) and D) can be used to prepare the polymer-modified prepolymers (PMP) containing isocyanate groups.
• prepolymers containing isocyanate groups (PMP) are prepared from components AI), A2), B) and C).
• the prepolymers containing isocyanate groups can be prepared in the presence of catalysts.
• Polymer modifiers B) which are suitable according to the invention are resinous, thermoplastic vinyl polymers, in particular those composed of one or more vinyl aromatic monomers from the group styrene, ⁇ -methylsyrrole or a core-substituted styrene with ethylenically unsaturated vinyl nonomers from the group acrylonitrile, methacrylonitrile, esters of acrylic acid or methacrylic acid, maleic anhydride and N-substituted maleimide, and optionally an additional diene.
• Preferred vinyl polymers are those composed of styrene / acrylonitrile mixtures, ⁇ -memylstyrene / acrylonitrile mixtures, styrene / ⁇ -mernylstyrene / acrylonitrile mixtures,
• Particularly preferred vinyl polymers are those composed of styrene / acrylonitrile mixtures, .alpha.-MemylstyroyAcrylmtrilgeimschen and styrene / methyl methacrylate mixtures with preferably 67 to 84% by weight of vinyl aromatic.
• the vinyl polymers according to the invention preferably have number-average molar masses between 15,000 g / mol and 90,000 g / mol, measured by means of GPC in dichloromethane at 25 ° C., and intrinsic viscosities [ ⁇ ] between 20 and 100 ml / g, measured in dimethylformamide at 25 ° C. ,
• Such vinyl polymers are widely known. These polymers can be prepared by radical bulk, solution, suspension or emulsion polymerization, if appropriate with the addition of suitable polymerization initiation. goals. Preferred production processes for the vinyl polymers according to the invention are solution and suspension polymerization.
• the vinyl polymers are often also used in the presence of up to 15% of additional diene compounds, e.g. Butadiene, isoprene and ethylene / propylene / -
• Polyester polyols can be used as the polyol component C).
• Suitable polyester polyols can, 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 to 6 carbon atoms.
• suitable dicarboxylic acids are: succinic acid, malonic 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.
• dicarboxylic acid derivatives such as, for example, mono- and / or diesters of dicarboxylic acids 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 65/20 to 60 parts by weight, and in particular adipic acid.
• dihydric and polyhydric alcohols examples include ethanediol, diethylene glycol, 1,2- or 1,3-propanediol, dipropylene glycol, 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 called diols, in particular mixtures of ethanediol, 1,4-butanediol and 1,6-hexanediol, glycerol and / or trimethylolpropane.
• organic e.g. aromatic and preferably aliphatic polycarboxylic acids and / or derivatives and polyhydric alcohols without a catalyst or in the presence of esterification catalysts, advantageously in an atmosphere of inert gases, such as e.g. Nitrogen, carbon monoxide, carbon dioxide, helium, argon, in solution and also in the melt
• 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.
• Esterification catalysts include, for example, iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and tin catalysts in the form of metals, metal oxides or
• 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 azeotr ⁇ pen distillation of the water of condensation.
• diluents and / or entraining agents e.g. Benzene, toluene, xylene or chlorobenzene
• 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 polyol polyols obtained preferably have a functionality of 1 to 3, in particular 1.8 to 2.4 and a number average molecular weight of 400 to
• Suitable polyesters polyols also include polycarbonates containing hydroxyl groups.
• Suitable polycarbonates containing hydroxyl groups are those of the type known per se, which can be obtained, for example, by reacting diols, such as 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol,
• Diethylene glycol, trioxyethylene glycol and / or tetraoxyethylene glycol with dialkyl carbonates, diaryl carbonates, e.g. Diphenyl carbonate or phosgene can be produced.
• difunctional polyesters polyols with a number-average molecular weight of 500 to 6000, preferably 800 to 3500 and in particular 1000 to 3300.
• Polyethene polyols can be prepared by known processes, for example by anionic polymerization of alkylene oxides in the presence of alkali hydroxides or alkali 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
• Lewis acids such as antimony pentachloride or boron fluoride etherate. It is also possible to use the double metal cyanide process described in the examples and teachings of US Pat. No. 5,470,813 and US Pat. No. 5,482,908.
• Suitable alkylene oxides contain 2 to 4 carbon atoms in the alkylene radical.
• Examples are tetrahydrofuran, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide; ethylene oxide and / or 1,2-propylene oxide are preferably used.
• the alkylene oxides can be used individually, alternately in succession or as mixtures. Mixtures of 1,2-propylene oxide and ethylene oxide are preferably used, the ethylene oxide. is used in amounts of 10 to 50% as an ethylene oxide end block ("EO-cap”), so that the resulting polyols over 70% have primary OH end groups.
• EO-cap ethylene oxide end block
• Suitable starter molecules are water or dihydric and trihydric alcohols, such as ethylene glycol, 1,2-propanediol and 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-ethanediol, glycerol, trimethylolpropane etc.
• Suitable polyethene polyols preferably polyoxy - Propylene-polyoxyethylene-polyols, have a functionality of 2 to 4 and number average molecular weights of 500 to 8000, preferably 1500 to 8000.
• polyethene polyols are polymer-modified polyethene polyols, preferably graft polyethene polyols, in particular those based on styrene and / or acrylonitrile, which can be obtained by in situ polymerization of acylonitrile, styrene or, preferably, mixtures of styrene and acrylonitrile, e.g. in a weight ratio of 90:10 to 10:90.
• polymer-modified polyethene polyols preferably graft polyethene polyols, in particular those based on styrene and / or acrylonitrile, which can be obtained by in situ polymerization of acylonitrile, styrene or, preferably, mixtures of styrene and acrylonitrile, e.g. in a weight ratio of 90:10 to 10:90.
• polyether polyols preferably 70:30 to 30:70
• polyethene polyol dispersions which are used as the disperse phase, usually in an amount of 1 to 50% by weight, preferably 2 to 25% by weight, included: e.g. inorganic fillers, polyureas, polyhydrazides, tertiary amino groups containing bound polyurethanes and / or melamine.
• amino polyethers known per se from polyurethane chemistry as described in the examples and teachings of EP-A 0 219 035 and EP-A 0 335 274, can also be used.
• polyether esters are obtained by propoxylation or ethoxylation of polyol polyols, preferably with a functionality of 1 to 3, in particular 1.8 to 2.4 and a number average molecular weight of 400 to 8,000, preferably 800 to 6,000.
• polyether esters which are obtained by esterifying polyethers, prepared by the process described above, with organic dicarboxylic acids and two or more highly functional alcohols, also mentioned above.
• These polyether esters have preferably a functionality of 1 to 3, in particular 1.8 to 2.4 and a number average molecular weight of 400 to 8000, preferably 800 to 6000.
• low-molecular-weight difunctional chain extenders, trifunctional or tetrafunctional crosslinkers or mixtures of chain extenders and crosslinkers can additionally be used as component D).
• Such chain extenders and crosslinkers D) are used to modify the mechanical properties, in particular also the hardness of the polyurethanes.
• 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.
• Alkanediols with 2 to 12, preferably, are preferably used as chain extenders 2, 4 or 6 carbon atoms, e.g.
• Carbon atoms such as 1,2-propanediol, 2-methyl-l, 3-propanediol, 2,2-dimethyl-l, 3-propanediol, 2-butyl-2-ethyl-l, 3-propanediol, 2-butene l, 4-diol and 2-butyn-l, 4-diol, diesters of terephthalic acid with glycols having 2 to 4 carbon atoms, such as terephthalic acid-bis-ethylene glycol or terephthalic acid-bis-1,4-butanediol, hydroxyalkylene ether of hydroquinone or resorcinol , for example 1,4-di- (ß-hychoxye yl) hydroquinone or l, 3- (ß-hydroxyethyl) resorcinol, alkanolamines with 2 to 12 carbon atoms such as emanolamine, 2-aminopropanol and 3-amino
• the compounds of component D) can be used in the form of mixtures or individually. Mixtures of chain extender and crosslinker can also be used.
• the hardness of the polyurethanes is determined by the combination of components A) and B) with components C) and D), as well as by the variation of
• Components C) and D) are set in relatively wide quantitative ratios, the hardness increasing with increasing content of components A), B) and D) in the reaction mixture.
• Amounts of components A) to D) can be determined experimentally in a simple manner. 0.2 to 50 parts by weight, preferably 0.5 to 30 parts by weight, of the polymer modifier B), based on 100 parts by weight of component A), are advantageously used. 1 to 50 parts by weight, preferably 3 to 20 parts by weight of the chain extender and / or are also advantageously used
• Crosslinker D based on 100 parts by weight of component C).
• Amine catalysts familiar to the person skilled in the art can be used as component E), for example tertiary amines such as triethylamine, tributylamine, N-methyl-mo ⁇ holin, N-ethyl-mo ⁇ holin, N, N, N ', N'-tetiamemyl-e ylendia-min, Pentamethyl-diethylene triamine and higher homologs (DE-OS 26 24 527 and 2624 528), 1,4-diaza bicyclo [2,2,2] octane, N-methyl-N'-dimethylaminoethyl-piperazine, bis (dimethylaminoalkyl) piperazine, N, N-dimethylbenzylamine, N, N-dimethylcyclohexylamine, N, N-diethylbenzylamine , Bis (N, N-diethylaminoethyl) adipate, N, N, N
• Amidines bis (dialkylamino) alkyl ethers and amide groups (preferably form amide groups) having tertiary amines according to DE-OS 25 23 633 and 27 32 292.
• Mannich bases known per se from secondary amines, such as dimethylamine, and aldehydes also come as catalysts , preferably formaldehyde, or ketones such as acetone, methyl ethyl ketone or cyclohexanone and phenols, such as
• 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
• Silica with carbon-silicon bonds as described in U.S. Patent No. 3,620,984 may also be used as catalysts, e.g. 2,2,4-trimethyl-2-silamophyll and 1,3-diethylaminomethyl-tetramethyl-disiloxane.
• Nitrogen-containing bases such as tetraalkylammonium hydroxides and hexahydrotriazines are also suitable. The reaction between NCO
• organic metal compounds in particular organic tin compounds
• organic tin compounds can also be used as additional catalysts.
• the organic tin compounds which are preferably tin (II) salts of carboxylic acids such as tin (II) acetate, tin (TI) octoate, tin (H) ethylhexoate and Tin (II) laurate and tin (IV) compounds, for example dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate or dioctyltin diacetate.
• the catalysts or catalyst combinations are generally used in an amount between about 0.001 and 10% by weight, in
• compact PUR elastomers e.g. PUR cast elastomers are manufactured.
• water vi is preferably used as the blowing agent, which reacts in situ with the organic polyisocyanates or with prepolymers containing isocyanate groups to form carbon dioxide and amino groups, which in turn react with other isocyanate groups to form urea groups and act as a chain extender.
• water has to be added to the polyurethane formulation in order to set the desired density, this is usually used in amounts of from 0.001 to 5.0% by weight, preferably from 0.01 to 3.0% by weight and in particular from 0. 05 to 1.5 wt .-%, based on the weight of the structural components A), B), C), D) and optionally E) used.
• blowing agents can also be gases or highly volatile inorganic or organic substances and their mixtures which evaporate under the influence of the exothermic polyaddition reaction and advantageously have a boiling point under normal pressure in the range from -40 to 120 ° C, preferably from -27 ° to 90 ° C, are used as physical blowing agents.
• suitable organic blowing agents are acetone, ethyl acetate, halogen-substituted alkanes or perhalogenated alkanes such as R134a, R141b, R365mfc, R245fa, R227ea, butane, pentane, cyclopentane, hexane, cyclohexane, heptane or diethyl ether, and inorganic blowing agents, for example air, CO 2 or N 2 O, in question.
• halogen-substituted alkanes or perhalogenated alkanes such as R134a, R141b, R365mfc, R245fa, R227ea, butane, pentane, cyclopentane, hexane, cyclohexane, heptane or diethyl ether
• inorganic blowing agents for example air, CO 2 or N 2 O, in question.
• a propelling effect can also be achieved by adding Compounds which decompose at temperatures above room temperature with the elimination of gases, for example nitrogen and / or carbon dioxide, such as azo compounds, for example azodicarbonamide or azoisobutyronitrile, or salts such as ammonium bicarbonate, ammonium carbamate or ammonium salts of organic carboxylic acids, for example the monoammonium salts of malonic acid, boric acid Formic acid or acetic acid.
• gases for example nitrogen and / or carbon dioxide
• azo compounds for example azodicarbonamide or azoisobutyronitrile
• salts such as ammonium bicarbonate, ammonium carbamate or ammonium salts of organic carboxylic acids, for example the monoammonium salts of malonic acid, boric acid Formic acid or acetic acid.
• blowing agents and details on the use of blowing agents are in R. Vieweg, A. Höchtlen (ed.): "Kunststoff
• the appropriate amount of solid blowing agents, low-boiling liquids or gases to be used, each individually or in the form of mixtures, for. B. can be used as liquid or gas mixtures or as gas-liquid mixtures depends on the desired density 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% by weight, preferably 2 to 15% by weight, liquid amounts of 0.1 to 30% by weight, preferably 0.2 to 10% by weight and / or gas quantities of 0.01 to 80% by weight, preferably 0.2 to 50% by weight, in each case based on the weight of the structural components A), B), C), D) and, if appropriate, E).
• the gas loading with e.g. Air, carbon dioxide, nitrogen and / or helium can take place both via component C), optionally in combination with component D) and / or E) and F), and also via the polymer-modified polyisocyanate (PMP).
• Further additives F can optionally be incorporated into the reaction mixture for producing the compact and cellular PUR elastomers.
• 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.
• emulsifiers are 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.
• Alkali or ammonium salts of sulfonic acids such as dodecylbenzenesulfonic acid or dinaphthylmethane disulfonic acid or of fatty acids such as ricinoleic acid or of polymeric fatty acids can also be used as surface-active additives.
• Polyether siloxanes especially water-soluble representatives, are particularly suitable as foam stabilizers. These compounds are generally constructed in such a way that a copolymer of ethylene oxide and propylene oxide is linked to a polydimethylsiloxane radical. Foam stabilizers of this type are described, for example, in US Pat. Nos. 2,834,748, 2,917,480 and 3,629,308.
• polysiloxane-polyoxyalkylene copolymers which are branched via allophanate groups in accordance with DE
• OS 25 58 523 Other organopolysiloxanes, oxyethylated alkylphenols, oxyethylated fatty alcohols, paraffin oils, castor oil or ricinoleic acid esters, Turkish red oil, peanut oil and cell regulators such as paraffins, fatty alcohols and poly-dimethyl siloxanes are also suitable. 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 from 0.01 to 5 parts by weight, based on 100 parts by weight of the higher molecular weight polyhydroxyl compounds c) and d).
• Reaction retarders furthermore pigments or dyes and known flame retardants and antistatic agents, furthermore stabilizers against aging and weathering effects, plasticizers, viscosity regulators and fungistatic and bacteriostatic substances can also be added.
• the components are reacted in amounts such that the equivalence ratio of the NCO groups of the polyisocyanates (PMP) to the sum of the isocyanate group-reactive hydrogens of components C), D), E) and F) and any used chemical blowing agent is 0.8: 1 to 1.2: 1, preferably 0.9: 1 to 1.15: 1 and in particular 0.95: 1 to 1.05: 1.
• PMP polyisocyanates
• the polyurethanes according to the invention can be prepared by the methods described in the literature, e.g. the one-shot, the semi-prepolymer or the prepolymer
• Processes are produced 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, usually at a temperature of 20 to 80 ° C., preferably 25 to 60 ° C., the reaction mixture is introduced into an open, optionally tempered mold and cured calmly.
• the structural components are mixed in the same way in the presence of blowing agents, preferably water, and introduced into the mold, which may have been tempered.
• the mold After filling, the mold is closed and the reaction mixture is left under compression, for example with a degree of compression (ratio of molded body density to free foam density) from 1.05 to 8, preferably from 1.1 to 6 and in particular from 1.2 to 4, for formation foaming from molded articles.
• a degree of compression ratio of molded body density to free foam density
• the demolding times depend, inter alia, on the temperature and the geometry of the mold and the reactivity of the reaction mixture and are usually 1 to 10 minutes.
• compact PUR elastomers according to the invention have a density of 0.8 to 1.4 g / cm 3 , preferably 0.9 to 1.25 g / cm 3 .
• Cellular PUR elastomers according to the invention have densities of 0.1 to 1.4 g / cm 3 , preferably 0.15 to 0.8 g / cm 3 .
• Such polyurethanes represent particularly valuable raw materials for molded plastics, which are distinguished by a constant or increased hardness in comparison to commonly used raw materials, despite the reduced molded part density. Such raw materials are also used in the production of shoe components or shoe soles in a single or multi-layer structure.
• the production of the polyuran test specimens was carried out in such a way that the A component containing isocyanate groups was at 45 ° C. in a low-pressure processing machine, e.g. a PSA 95 from Klöckner DESMA Schuhmaschinen GmbH, mixed with the B component at 45 ° C, metered the mixture into an aluminum mold (size 200 * 200 * 10 mm) heated to 50 ° C, the mold closed and after 3 minutes the elastomer removed.
• a low-pressure processing machine e.g. a PSA 95 from Klöckner DESMA Schuhmaschinen GmbH
• the hardness of the elastomer sheets produced in this way was measured after storage for 24 hours using a Shore A hardness measuring device in accordance with DIN 53 505.
• Polymer-modified polyisocyanates and polymer-modified isocyanate-containing prepolymers were used in the examples given.
• a powder, styrene / acrylonitrile polymer (styrene / acrylonitrile copolymer) with an acrylonitrile content of 28.0% and a number-average molecular weight Mn of 39,000 g / mol was used as the vinyl polymer:
• PMP1 Polymer modified polyisocyanate
• Product is a clear liquid.
• NCO content 20.7% viscosity at 20 ° C. approx. 1000 mPa-s
• the prepolymer (PMP4) is made with a mixture (Gl) consisting of
• the mixing ratio of components (Gl) to (PMP4) is 100: 74 parts by weight, the resulting molded part density 480 kg / m 3 .
• the test specimens, which can be demolded after just 3.5 minutes of mold life, have a positive kink test (++) and a Sh A hardness of 57.
• the prepolymer (MP5) is also processed with the mixture (Gl) as described in Example 1.
• the mixing ratio of components (Gl) to (MP5) is 100:72 parts by weight, the resulting molded part density 480 kg / m 3 .
• Example 3
• the prepolymer (PMP4) is made with a mixture (G2) consisting of
• the mixing ratio of components (G2) to (PMP4) is 100:92 parts by weight, the resulting molded part density is 500 kg / m 3 .
• the test specimens removed from the mold after 4 minutes have a Sh A hardness of 74 in addition to a positive kink test (++).
• the prepolymer (MP5) is also processed with the mixture (G2) as described in Example 3.
• the mixing ratio of components (G2) to (MP5) is 100: 91 parts by weight, the resulting molded part density is 500 kg / m 3 .
• the prepolymer (PMP4) is made with a mixture (G3) consisting of
• the mixing ratio of components (G3) to (PMP4) is 100: 67 parts by weight, the resulting molded part density is 500 kg / m 3 .
• the test specimens have a Sh A hardness of 41.
• the prepolymer (MP5) is also processed with the mixture (G3) as described in Example 5.
• the mixing ratio of components (G3) to (MP5) is 100: 68 parts by weight, the resulting molded part density is 500 kg / m 3 .
• the test specimens have a Sh A hardness of 36.
• the prepolymer (PMP2) is made with a mixture (G4) consisting of
• the mixing ratio of components (C4) to (PMP2) is 100: 52 parts by weight, the resulting molded part density is 400 kg / m 3 .
• Test specimens have a Sh A hardness of 34.
• the prepolymer (MP3) is also processed with the mixture (G4) as described in Example 7.
• the mixing ratio of components (G4) to (MP3) is 100: 48 parts by weight, the resulting molded part density is 400 kg / m 3 .
• the test specimens have a Sh A hardness of 31.

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