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
  • C08G18/28—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
  • C08G18/48—Polyethers
  • C08G18/4804—Two or more polyethers of different physical or chemical nature
  • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three 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
  • C08G18/08—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
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
  • C08G18/12—Prepolymer 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
• • 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
  • C08G18/48—Polyethers
• • 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
  • C08G18/48—Polyethers
  • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene 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
  • C08G18/70—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
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
  • C08G18/7678—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing condensed aromatic rings
• • 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
  • C08G18/83—Chemically modified polymers
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying

Definitions

• the present invention relates to a cellular polyisocyanate polyaddition product having a density according to DIN EN ISO 845 between 200 and 800 kg / m 3 .
• the invention further relates to prepolymer based on the reaction of at least one diisocyanate (a) and at least one polyether alcohol (b), the polyether alcohol (b) containing the following components:
• the present invention relates to processes for the preparation of a cellular polyisocyanate polyaddition product of this prepolymer, as well as this cellular polyisocyanate polyaddition product and its use in the automotive sector.
• microcellular, polyisocyanate polyaddition products usually polyurethanes and / or polyisocyanurates, which may optionally contain urea structures and are obtainable by reacting isocyanates with isocyanate-reactive compounds and processes for their preparation are well known.
• a particular embodiment of these products are cellular, especially microcellular, polyurethane elastomers, which differ from conventional polyurethane foams by their significantly higher density of usually 200 to 800 kg / m 3 , their particular physical properties and the possible applications thereof.
• Such polyurethane elastomers are used, for example, as vibration and shock-absorbing elements, in particular in the automotive industry.
• the suspension elements made of polyurethane elastomers are pushed in automobiles, for example, within the Automatfederbeinkonstrutation consisting of shock absorber, coil spring and the elastomeric spring on the piston rod of the shock absorber.
• Prepolymer prepolymer Products using a prepolymer with a low NCO content are characterized by relatively temperature-stable urea hard phases, especially in the case of high dynamic loading, ie high force and / or high frequency Temperatures of more than 80 0 C show feathers with urea hard phase compared to products with urethane hard phase based on prepolymers with a high NCO content, for example 14-20% (“semi-prepolymer”), a higher dynamic performance
• the formation of urea hard phases in the cellular elastomers usually occurs by the reaction of water with isocyanate.
• the carbamic acid formed decomposes into carbon dioxide and amine, which reacts with urea formation with isocyanate ,
• Polyesterol-containing soft phases lead to the highest dynamic level of properties in the cellular PU urea-hard elastomers. Such products are well known.
• WO 2001018086 A1 describes the use of polyester-polyetherol, obtainable by polycondensation of polyoxytetramethylene glycol having an average molecular weight of 220 to 270 g / mol and adipic acid, for the preparation of cellular polyurethane elastomers having good dynamic properties and high low-temperature flexibility.
• polyester-polyetherol obtainable by polycondensation of polyoxytetramethylene glycol having an average molecular weight of 220 to 270 g / mol and adipic acid
• DE-A 3613964 describes the preparation of products based on pure polyester or polyester-polyetherol soft phases.
• the specimens listed in the comparative example in DE-A 3613964 based on polytetrahydrofuran (M 2000 g / mol) as a soft phase had only a comparatively low bending resistance.
• a disadvantage of the known polyurethane elastomers of the prior art is that they can only be used to a limited extent at temperatures above 120 ° C. If, in addition to the elevated temperature, the polyurethane elastomer is additionally in contact with moisture and / or a high pressure acts on the elastomer, these cellular polyurethane elastomers do not remain in the desired shape.
• Object of the present invention is to provide cellular polyisocyanate polyaddition, preferably cellular polyurethane elastomers, which are dimensionally stable even at high temperatures, preferably in the presence of moisture and / or at high pressures, so that they are in the immediate vicinity of engine, transmission or Exhaust system can be used.
• the polyisocyanate polyaddition products should simultaneously have at least the same advantageous properties with respect to long-lasting elasticity, abrasion resistance, tensile strength, tear resistance and compression set as the elastomers of the prior art
• the polyisocyanate polyaddition products should be inexpensive and have a very good microbial resistance and hydrolysis stability. Furthermore, the cellular polyisocyanate polyaddition products should have a low water absorption and be cold-flexible. It is also an object to provide a prepolymer from which the desired polyisocyanate polyaddition products can be prepared.
• cellular polyisocyanate polyaddition products preferably damping elements, more preferably motor bearings, gearbox bearings and / or exhaust bearings, in particular engine and transmission bearings, with a density according to DIN EN ISO 845 between 200 and 800 kg / m 3 , wherein the cellular Polyisocyanate polyaddition product containing the reaction product of (a) isocyanate with (b) polyether alcohol having a number average molecular weight of 10,000 to 100,000 g / mol.
• the polyether alcohol having a number average molecular weight of 10,000 to 100,000 g / mol in a weight fraction of at least 4 wt .-%, based on the total weight of the cellular polyisocyanate polyaddition product in the cellular polyisocyanate polyaddition product, wherein this weight of the polyether alcohol refers to the weight of the polyether alcohol used for the preparation of the cellular polyisocyanate polyaddition product having a number average molecular weight of 10,000 to 100,000 g / mol.
• the cellular elastomer according to the invention is characterized in that it, by the insectmokularen polyethers, preferably the polyether alcohol (b), which is characterized by a specific, and especially broad molecular weight distribution, a low tendency to creep at high temperatures of up to 150 0 C. has improved low-temperature flexibility, excellent hydrolysis resistance and good mechanical and dynamic properties.
• the (b) is polyether alcohol having a number average molecular weight of 10,000 to 100,000 g / mol of polytetrahydrofuran.
• aliphatic polyether alcohol (b1), (b2) and / or (b3) polytetrahydrofuran are particularly preferred.
• the isocyanate (a) is preferably selected from the group consisting of 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), tolidine diisocyanate (TODI) and mixtures thereof.
• the cellular polyisocyanate polyaddition products according to the invention preferably, the cellular polyurethanes, preferably have a glass transition temperature below -50 0 C, a tensile strength according to DIN EN ISO 1798 of> 2 N / mm, preferably> 4 N / mm 2, an elongation at break according to DIN EN ISO 1798 of> 200%, preferably> 230% and a tear strength according to DIN ISO 34-1 B (b) of> 6 N / mm, preferably> 10 N / mm and particularly preferably a compression set (at 80 0 C) in Based on DIN 53572 of less than 25%.
• the cellular polyisocyanate polyaddition product according to the invention is preferably at storage for 24 h at 150 0 C and a test load of 2 kg / cm 2, a creep of less than 10%, more preferably less than 7%, most preferably less than 5%.
• the water absorption of the cellular polyisocyanate polyaddition products, preferably of the cellular polyurethanes, is preferably less than 50% by weight, preferably less than 30% by weight, more preferably less than 20% by weight, based on the weight of the polyisocyanate polyaddition product, preferably of the polyurethane.
• the present invention further provides a prepolymer comprising at least one diisocyanate (a) and at least one polyether alcohol (b), wherein the at least one polyether alcohol (b) contains the following components:
• the prepolymer of the invention is characterized in that it contains at least one polyether alcohol (b), which is characterized by a specific, and especially broad molecular weight distribution.
• the specific polyether alcohols (b) it is possible to obtain prepolymers from which polyurethane elastomers can be produced which have only a low creep at high temperatures of up to 150 ° C., improved low-temperature flexibility and good mechanical and dynamic properties , Especially when using 1,5-naphthylene diisocyanate (NDI) as the diisocyanate (a), it is possible to obtain prepolymers and, therefrom, polyurethane elastomers which, compared with other cellular and compact polyurethane elastomers, have only a low creep tendency at high temperatures improved low-temperature flexibility and good mechanical and dynamic properties, as well as excellent hydrolysis resistance have.
• the prepolymer of the invention is composed of at least one diisocyanate (a) and at least one polyether alcohol (b).
• the at least one diisocyanate (a) is an aromatic diisocyanate, more preferably the diisocyanate (a) is selected from the group consisting of 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI) , 1, 5-naphthylene diisocyanate (NDI), tolidine diisocyanate (TODI) and mixtures thereof, more preferably 1, 5-naphthylene diisocyanate (NDI), tolidine diisocyanate (TODI) and mixtures thereof, very particularly preferably 1, 5-naphthylene diisocyanate (NDI) ,
• the isocyanates can be used in the form of the pure compound, in mixtures and /
• the diisocyanates used according to the invention can be prepared by processes known to those skilled in the art or are available, at least in part, commercially.
• the prepolymer according to the invention is composed of at least one polyether alcohol (b) which contains the following components:
• the prepolymer of the invention contains at least 12% by weight, more preferably at least 12.5% by weight, most preferably from 12.5 to 25% by weight of component (b1), at least 35% by weight, particularly preferably at least 35.5 wt .-%, most preferably 35.5 to 55 wt .-% component (b2) and at least 4 wt .-%, particularly preferably 5 to 8 wt .-% component (b3), wherein the weights in each case are based on the total weight of the polyether alcohols, preferably component (b).
• the polyether alcohol mixture according to the invention may contain corresponding polymeric compound with number average molecular weight of 1000 to 2000 g / mol, preferably in an amount of 15 to 35 wt .-%.
• the individual mentioned molecular weight fractions Ones preferably complement each other to 100 wt .-%, ie in a preferred embodiment, in addition to polyether alcohols having different number average molecular weights, no further compounds in component (b) before.
• the polyether alcohol (b) used according to the invention has the abovementioned very specific distribution of different number-average molecular weights; in particular, this distribution is very broad, ie polyether alcohols having a low number average molecular weight and also polyether alcohols having very high number average molecular weights are present.
• this broad molecular weight distribution leads to the advantages of the prepolymers according to the invention. For example, in the product prepared from the prepolymer polyisocyanate polyaddition no disturbing soft phase crystallization above -40 0 C occurs due to the broad molecular weight distribution of the polyether alcohol, which is otherwise typical of polyether alcohols having such high molecular weights.
• the number-average molecular weight of the polyether alcohols used according to the invention can be determined by methods known to those skilled in the art, for example by gel permeation chromatography (GPC). In this process, a separation of a mixture of polyether alcohols having different molecular weights takes place owing to their different residence times on a stationary phase. By determining the residence times of the individual fractions and then comparing these values with values which have been determined for a known standard, the number average molecular weights can be determined.
• GPC gel permeation chromatography
• polyether alcohols (b) it is possible to use compounds which are synthesized from the customary and generally known structural units, for example polyether alcohols based on ethylene oxide and / or propylene oxide prepared by alkoxylation of customary starter substances.
• the functionality of the polyether alcohols (b) can be between 1.7 and 2.3, preferably the average functionality of the mixture of the polyether alcohols is between 1.8 and 2.2, more preferably between 1.9 and 2.1.
• the aliphatic polyether alcohol (b1), (b2) and / or (b3) is polytetrahydrofuran (PTHF).
• PTHF polytetrahydrofuran
• Polytetrahydrofurans are polyols which are prepared, for example, by cationic polymerization from tetrahydrofuran. Processes for the preparation of polytetrahydrofurans are known to the person skilled in the art. Corresponding polytetrahydrofurans are also commercially available in part.
• the prepolymer of the invention may more preferably contain allophanate groups. These allophanates can be built up in the preparation of prepolymer by reaction temperatures above 100 0 C, preferably 120 to 150 0 C.
• the Pre- Polymer preparation can thus preferably be carried out in such a way that NDI flakes are added to the polyether alcohols (b) heated to 140 ° C.
• the prepolymer according to the invention is particularly preferably composed of a diisocyanate (a) selected from the group consisting of 1,5-naphthylene diisocyanate (NDI), tolidine diisocyanate (TODI) and mixtures thereof, in particular 1,5-naphthylene diisocyanate (NDI) and polytetrahydrofuran Polyether alcohol (b), the polytetrahydrofuran containing the following components:
• polytetrahydrofurans having a number average molecular weight of 1000 to 2000 g / mol may be present, and the amounts of all polytetrahydrofurans present add up to 100 wt .-%.
• the prepolymer according to the invention preferably has a low NCO content.
• the prepolymer according to the invention has an NCO content of at most 10%, particularly preferably 2 to 8%, very particularly preferably 4 to 7%.
• Methods for determining the NCO content of the prepolymer are known to the person skilled in the art, for example wet-chemical methods.
• the prepolymer is dissolved in a suitable solvent and mixed with excess amine.
• the amine which has not reacted with the isocyanate is then back titrated with HCl.
• the amount of isocyanate is calculated from the difference between the amounts of amine used and the amount of back titrated amine.
• the prepolymer according to the invention generally has a viscosity of 1000 to 5000 mPas at 80 0 C, preferably 2000 to 4000 mPas at 80 0 C, in each case depending on the NCO content of the prepolymer on.
• the stated viscosity is preferably determined using a rotational viscometer.
• step (B) reacting the prepolymer obtained in step (A) in a form having at least one crosslinking component containing water (e) to obtain the cellular polyisocyanate polyaddition product,
• polyether alcohol (b) used in step (A) contains the following components:
• (b1) preferably aliphatic polyether alcohols having a number-average molecular weight of from 300 to 1000 g / mol,
• (b2) preferably aliphatic polyether alcohols having a number average molecular weight of 2,000 to 10,000 g / mol and
• (b3) preferably aliphatic polyether alcohols having a number average molecular weight of 10,000 to 100,000 g / mol.
• the process according to the invention is preferably carried out by preparing a prepolymer having an isocyanate group in a two-stage process in step (A) by reacting (a) with (b) and containing this prepolymer in step (B) in a form having a crosslinking component sulfated fatty acid esters (d) and water (s) is reacted, wherein polysiloxanes (c) and optionally catalysts (f), blowing agents (g) and / or additives (h) may be contained in the prepolymer and / or the crosslinking component.
• the crosslinker component may contain as (h) carbodiimide.
• the crosslinker component thus preferably contains, in addition to the water (e), sulfated fatty acid esters (d), preferably between 0.005 to 1% by weight of sulfated fatty acid esters, based on the weight of the cellular polyisocyanate polyaddition products, preferably of the cellular polyurethanes, and catalysts (f ) and optionally polysiloxanes (c), blowing agents (g) and / or auxiliaries (h).
• the amounts with respect to the fatty acid esters are based on the weight of the sulfated fatty acid esters without water.
• the catalysts used may preferably contain tin compounds in the crosslinker component, particularly preferably tin (IV) compounds, more preferably di-n-octyltin (IV) bis (2-ethylhexyl thioglycolate) and / or n-octyltin - (IV) tris (2-ethylhexyl thioglycolate).
• tin (IV) compounds more preferably di-n-octyltin (IV) bis (2-ethylhexyl thioglycolate) and / or n-octyltin - (IV) tris (2-ethylhexyl thioglycolate).
• the crosslinker component contains, in addition to the tin compounds, amine catalysts, in particular tertiary amines, particularly preferably bis (dimethylaminoethyl) ether, 1,4-diazabicyclo [2,2,2] octane, N, N, N ', N ", N" -pentamethyldiethylenediamine, N-methylimidazole, N-propylimidazole and / or N- (2-dimethylaminoethyl) -N'-piperazine.
• amine catalysts in particular tertiary amines, particularly preferably bis (dimethylaminoethyl) ether, 1,4-diazabicyclo [2,2,2] octane, N, N, N ', N ", N" -pentamethyldiethylenediamine, N-methylimidazole, N-propylimidazole and / or N- (2-dimethyl
• Polysiloxanes which can be used are generally known compounds, for example polymethylsiloxanes, polydimethylsiloxanes and / or polyoxyalkylene-silicone copolymers.
• compounds of the following general structural formula are suitable:
• R alkyl, -O-alkyl, -S-alkyl, -NH-alkyl having 1 to 20 carbon atoms in the alkyl radical.
• the polysiloxanes have a viscosity at 25 0 C from 20 to 2000 mPas.
• sulfated fatty acid esters commonly known sulfated solid acid esters, which are also commercially available, can be used.
• Sulfated castor oil is preferably used as the sulfated fatty acid ester.
• the amount of sulfated fatty acid esters is preferably not beyond the preferred ranges, since in particular a significantly improved, ie lower water absorption of the shaped body is not achieved with a larger amount of this emulsifier. Should be due to the use of other compounds in the crosslinking component, which is described below, for example, hydrolysis, z. As carbodiimides, further amounts of emulsifiers may be required for a sufficient homogenization of this crosslinking component, as well as the well-known amount of sulfated fatty acid esters or as a complete replacement of the sulfated fatty acid esters, for example, further well-known emulsifiers can be used, for.
• alkoxylates of fatty acids preferably polyethylene glycol esters, polypropylene glycol esters, polyethylene glycol propylene glycol, ethoxylates and / or propoxylates of linoleic acid, linolenic acid, oleic acid, arachidonic acid, particularly preferably oleic.
• the sulfated fatty acid esters can preferably be used as aqueous solutions, for example as 50% strength by weight aqueous solutions.
• the preparation of cellular polyisocyanate polyaddition products according to the invention is preferably carried out in a mold at a surface temperature of the mold inner wall of 60 to 90 0 C.
• surface temperature of the inner wall of the mold is to be understood as meaning the temperature which the surface of the inner wall of the mold, ie the surface of the mold, which is usually in contact with the reaction system during the production of the molded parts, during the production of the molded parts, at least for a short time , preferably at least 10 minutes.
• the present invention also relates to the use of the cellular polyisocyanate polyaddition products according to the invention, for example as moldings, as damping elements in vehicle construction, for example in the automotive industry, e.g. as auxiliary springs, bump stops, wishbone bearings, rear axle parking, stabilizer bearings, longitudinal strut bearings, strut support bearings, shock absorber bearings, bearings for wishbones, preferably in the vicinity of hot devices of an automobile or two-wheeler, for example in the vicinity of the exhaust, the engine, the Transmission, and / or as a spare wheel located on the rim, which causes, for example in a puncture, that the vehicle moves on the cellular polyisocyanate polyaddition product and remains controllable.
• the use of the cellular polyisocyanate polyaddition products according to the invention as damping and bearing elements for increased operating temperatures in the automotive industry is preferred, particularly preferred is the use as engine, transmission or exhaust system bearings, especially engine and transmission bearings.
• the shaped bodies according to the invention i. the cellular polyisocyanate polyaddition products, preferably the microcellular polyurethane elastomers, therefore not only have excellent mechanical and dynamic properties, in particular the stability to hydrolysis, the microbial resistance and the low temperature flexibility could be significantly improved according to the invention as desired. In particular, this combination of particularly advantageous properties is not known from the prior art.
• the production of the moldings is advantageously carried out at an NCO / OH ratio of 0.85 to 1.20, wherein the heated starting components are mixed and brought in an amount corresponding to the desired molding density in a heated, preferably tightly closing mold.
• the amount of the introduced into the mold reaction mixture is usually measured so that the resulting moldings have the density already shown.
• the cellular polyisocyanate Polyaddition products preferably have a density according to DIN EN ISO 845 of 200 to 800 kg / m 3 , more preferably 300 to 600 kg / m 3 .
• the starting components are usually introduced at a temperature of 15 to 120 0 C, preferably from 20 to 100 0 C, in the mold.
• the degrees of compaction for the production of the shaped bodies are between 1, 1 and 8, preferably between 2 and 6.
• the cellular polyisocyanate polyaddition products according to the invention are advantageously prepared by the one-shot process using the low-pressure technique or, in particular, the reaction injection molding technique (RIM) in open or preferably closed molding tools.
• the reaction is carried out in particular under compression in a closed mold.
• the reaction injection molding technique is described for example by H. Piechota and H. Rschreib in "Integral Foams", Carl Hanser Verlag, Kunststoff, Vienna 1975; DJ. Prepelka and J.L. Wharton in Journal of Cellular Plastics, March-April 1975, pages 87-98 and U. Knipp in Journal of Cellular Plastics, March-April 1973, pages 76-84.
• the outlet components can be supplied individually and mixed intensively in the mixing chamber. It has proven to be advantageous to work according to the two-component method.
• an NCO-group-containing prepolymer is first prepared in a two-stage process.
• the preparation according to the invention of the shaped bodies preferably takes place in a two-stage process by preparing an isocyanate group-containing prepolymer in the first stage by reacting (a) with (b) and containing this prepolymer in the second stage in a form containing a crosslinking component (i.e. ) and (e), wherein (c) and optionally (f), (g) and / or (h) are contained in the prepolymer and / or the crosslinking component.
• a crosslinking component i.e.
• e crosslinking component
• Component (c) can be added to the prepolymer before, during and / or after its preparation and / or the crosslinker components in the two-stage process.
• the auxiliaries and / or additives (h) may preferably be contained in the crosslinker component.
• the demolding times are up to 60 minutes depending on the size and geometry of the molded part 1.
• the mold parts may preferably be annealed for a period of 1 to 48 hours at temperatures of usually from 70 to 140 0 C.
• the starting components comprising in the reaction mixture according to the invention the following can be carried out:
• the prepolymer according to the invention is preferably used in the process.
• polyether alcohols (b) used are the already described mixtures having a broad molecular weight distribution. These may optionally be used together with generally known polyhydroxyl compounds which do not fall under the definition of component (b) according to the invention, for example polyesterpolyalcohols and / or hydroxyl-containing polycarbonates, preferably those having a functionality of from 2 to 3 and preferably a molecular weight of from 60 to 7000, particularly preferably from 500 to 6000, in particular from 1000 to 6000. Particular preference is given to using exclusively the polyetherols according to the invention as component (b).
• low molecular weight chain extenders (b4) having a molecular weight of less than 500, preferably 60 to 499, which do not fall under the definition of component (b) according to the invention, for example, selected from the group of difunctional alcohols, di-functional polyoxyalkylene polyols.
• alkanediols having 2 to 12, preferably 2, 4 or 6 carbon atoms for example ethane, 1,3-propane, 1,5-pentane, 1,6-hexane, 1, 7-heptane, 1, 8-octane, 1, 9-nonane, 1, 10-decanediol and preferably 1, 4-butanediol, dialkylene glycols having 4 to 8 carbon atoms, such as diethylene glycol and dipropylene glycol and / or difunctional polyoxyalkylene polyols.
• alkyl-substituted aromatics see polyamines with molecular weights preferably from 122 to 400, in particular primary aromatic diamines which have at least one alkyl substituent in the ortho position to the amino groups, which reduces the reactivity of the amino group by steric hindrance, which are liquid at room temperature and with the higher molecular ,
• Preferably at least difunctional compounds (b) under the processing conditions are at least partially, but preferably completely miscible.
• the amounts of water which can be suitably used are 0.01 to 5 wt .-%, preferably 0.3 to 3.0 wt .-%, based on the weight of component (b).
• the water can be used completely or partially in the form of the aqueous solutions of the sulfated fatty acid ester.
• catalysts (f) can be added to the reaction batch in the reaction of a prepolymer with a crosslinker component.
• the catalysts (f) can be added individually as well as in admixture with each other.
• the preferred catalysts have already been shown.
• organometallic compounds such as tin (II) salts of organic carboxylic acids, e.g. Tin (II) dioctoate, tin (II) dilaurate, dibutyltin diacetate and dibutyltin dilaurate, and tertiary amines such as tetramethylethylenediamine, N-
• Methylmorpholine diethylbenzylamine, triethylamine, dimethylcyclohexylamine, diazabicyclooctane, N, N'-dimethylpiperazine, N-methyl, N '- (4-N-dimethylamino) -butylpiperazine, N, N, N ', N ", N" -pentamethyldiethylenediamine or the like.
• amidines such as, for example, 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine
• tris (dialkylaminoalkyl) -s-hexahydrotriazines in particular tris (N, N-dimethylaminopropyl) -s- hexahydrotriazine
• tetraalkylammonium hydroxides such as, for example, tetramethylammonium hydroxide
• alkali metal hydroxides such as, for example, sodium hydroxide
• alkali metal alkoxides for example sodium methylate and potassium isopropylate
• alkali metal salts of long-chain fatty acids having 10 to 20 carbon atoms and optionally pendant OH groups.
• the catalysts (f) are used in amounts of from 0.0001 to 0.5% by weight, based on the prepolymer.
• conventional foaming agents (g) can be used in polyurethane production.
• Suitable examples are low-boiling liquids which evaporate under the influence of the exothermic polyaddition reaction.
• Suitable liquids are those which are inert to the organic polyisocyanate and have boiling points below 100 ° C.
• halogenated preferably fluorinated hydrocarbons, such as methylene chloride and dichloromonofluoromethane, per- or partially fluorinated hydrocarbons, such as trifluoromethane, difluoromethane, difluoroethane, tetrafluoroethane and heptafluoropropane, hydrocarbons, such as n- and iso-butane , n- and iso-pentane and the technical mixtures of these hydrocarbons, propane, propylene, hexane, heptane, cyclobutane, cyclopentane and cyclohexane, dialkyl ethers, such as dimethyl ether, diethyl ether and furan, carboxylic acid esters, such as methyl and ethyl , Ketones, such as acetone, and / or fluorinated and / or perfluorinated, tert
• the most suitable amount of low-boiling liquid for preparing such cell-containing elastic molded body bound from urea groups containing elastomers depends on the density that you want to achieve, as well as the amount of preferably used with water. In general, amounts of from 1 to 15% by weight, preferably from 2 to 11% by weight, based on the weight of component (b), give satisfactory results. Particularly preferably, only water (e) is used as blowing agent.
• Auxiliaries and additives (h) can be used in the production of the molded parts according to the invention. These include, for example, well-known surfactants, hydrolysis, fillers, antioxidants, cell regulators, flame retardants and dyes. Suitable surface-active substances are compounds which serve to assist the homogenization of the starting materials and, if appropriate, are also suitable for regulating the cell structure.
• the emulsifiers according to the invention are additional compounds with emulsifying action, such as the salts of fatty acids with amines, for example, oleic diethylamine, diethanolamine stearate, diethanolamine ricinoleic acid, salts of sulfonic acids, for example alkali metal or ammonium salts of dodecylbenzene- or dinaphthylmethanedisulfonic acid.
• foam stabilizers come into question, such as.
• Example ethoxylated alkylphenols, ethoxylated fatty alcohols, paraffin oils, castor oil or ricinoleic acid esters, Vietnamese red oil and peanut oil and cell regulators, such as paraffins and fatty alcohols.
• the surface-active substances are usually used in amounts of 0.01 to 5 parts by weight based on 100 parts by weight of components (b).
• compounds (c) and (d) do not fall under the auxiliaries and additives (h).
• the present invention also relates to a cellular polyisocyanate polyaddition product, preferably a polyurethane elastomer, which can be prepared by the process according to the invention.
• FIG. 1 shows a molded part according to the invention, produced from the polyurethane elastomer according to the invention.
• PTHF polytetrahydrofuran
• Example 1 (according to the invention):
• reaction temperature was held for complete reaction for at least 15 minutes at above 140 0 C and then cooled. This resulted in an almost colorless liquid with an NCO content of 5.6%.
• Example 4 (according to the invention):
• % of a polyether polyol based on glycerin, propylene oxide and ethylene oxide having an average molecular weight of 5270 and an average functionalities did of 2.5 and 2 ppm of citric acid were in a tinplate pail under a nitrogen atmosphere at 140 0 C. and with stirring, with 24 , 7 wt .-% of naphthylene-1, 5-diisocyanate (NDI). The reaction temperature was held for complete reaction for 25 min at above 140 0 C and then cooled. This resulted in an almost colorless liquid with an NCO content of 6.09%.
• the foams according to the invention combine improved high-temperature resistance with very good resistance to hydrolysis, which enables a long material use even under harsh environmental conditions.
• the new material does not lose its characteristic good dynamic properties.
• the dynamic material properties are determined on the spring element shown in FIG.
• the spring elements according to the invention from Examples 1, 2, 4 and 6 undergo the dynamic test and give low and thus advantageous set amounts.
• the following table summarizes the material properties of the cellular elastomers according to the invention (Examples 1 to 6).
• the static-mechanical properties were determined from the blocks, the dynamic-mechanical properties of the spring elements (see Fig. 1).
• Test conditions The test specimen was loaded with constant 0.2kg / cm 2 and heated to 300 0 C.
• the values given in Table 3 are the temperatures at which the samples sink below their initial height, that is, the temperatures at which the materials are no longer mechanically stable.

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• 2009
  • 2009-07-14 WO PCT/EP2009/058941 patent/WO2010010002A1/de not_active Ceased
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