WO1994020568A1 - Thermoplastic polyurethane-based foamed materials - Google Patents
Thermoplastic polyurethane-based foamed materials Download PDFInfo
- Publication number
- WO1994020568A1 WO1994020568A1 PCT/EP1994/000606 EP9400606W WO9420568A1 WO 1994020568 A1 WO1994020568 A1 WO 1994020568A1 EP 9400606 W EP9400606 W EP 9400606W WO 9420568 A1 WO9420568 A1 WO 9420568A1
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- WIPO (PCT)
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- foams
- particulate
- blowing agent
- expandable
- thermoplastic polyurethane
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/228—Forming foamed products
- C08J9/232—Forming foamed products by sintering expandable particles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
- C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
Definitions
- the invention relates to foams based on thermoplastic polyurethanes and expandable, particulate, thermoplastic polyurethanes, which are particularly suitable for the production of foam moldings.
- Foams especially also particle foams, have long been known and have been widely described in the literature, e.g. in Ullmann's "Encyclopedia of Technical Chemistry", 4th edition, volume 20, p. 416 ff.
- Polystyrene or polyolefins such as polyethylene and polypropylene, are usually used as base polymers. They are used in many areas. Expanded polystyrene is e.g. used as an insulating material in construction or for the production of packaging, expanded polyolefins can be used, for example, as shock-absorbing foams in motor vehicle construction. Other uses are e.g. in Ullmann, op. cit.
- Varying the base polymers can produce particle foams with very different properties.
- the object of the invention was to produce new foams, in particular particle foams, with good elasticity and temperature behavior.
- thermoplastic polyurethanes TPU
- the invention accordingly relates to foams, in particular particulate foams, based on thermoplastic polyurethanes and expandable, particulate, thermoplastic polyurethanes which are particularly suitable for the production of foam molded articles.
- all customary TPUs can be used, both those based on polyether and those based on polyester.
- the polymer chains can be branched, the branching is preferably carried out by allophanate bridges or the incorporation of polyfunctional alcohols.
- polyhydroxyl compounds preferably essentially linear polyhydroxyl compounds with molecular weights of 500 to 8000, in particular polyalkylene glycol polyadipates with 2 to 6 carbon atoms in the alkylene radical and molecular weights of 500 to 6000 or hydroxyl-containing polytetrahydrofuran with a molecular weight of 500 to 8000 and
- the organic diisocyanates (a) are preferably aliphatic, cycloaliphatic and aromatic diisocyanates.
- aliphatic diisocyanates such as 1,6-hexamethylene-diisocyanate, 1,5-2-methyl-pentamethylene-diisocyanate, 1,4-2-ethyl-butylene-diisocyanate or mixtures of at least two of the aliphatic mentioned Diisocyanates
- cycloaliphatic diisocyanates such as isophorone diisocyanate, 1,4-cyclohexane diisocyanate, l-methyl-2,4- * and -2,6-cyclohexane diisocyanate and the corresponding isomer mixtures
- the organic diisocyanates can optionally be used in minor amounts, e.g. in amounts up to 3 mol%, preferably up to 1 mol%, based on the organic diisocyanate, can be replaced by a trifunctional or higher-functional polyisocyanate, the amount of which must however be limited so that thermoplastically processable polyurethanes can be obtained.
- a larger amount of such more than difunctional isocyanates is expediently compensated for by the use of less than difunctional compounds with reactive hydrogen atoms, so that chemical crosslinking of the polyurethane which is too extensive is avoided.
- Examples of more than difunctional isocyanates are mixtures of diphenylmethane diisocyanates and polyphenylpolymethylene polyisocyanates, so-called raw MDI, as well as liquid 4 modified with isocyanurate, urea, biuret, allophanate, urethane and / or carbodiimide groups 4, 4'- and / or 2,4'-diphenylmethane diisocyanates.
- Suitable monofunctional compounds with a reactive hydrogen atom which can also be used as molecular weight regulators, are e.g. called: monoamines such as Butyl, dibutyl, octyl, stearyl, N-methylstearylamine, pyrrolidone, piperidine and cyclohexylamine, and monoalcohols such as e.g. Butanol, amyl alcohol, 1-ethylhexanol, octanol, dodecanol, cyclohexanol and ethylene glycol monoethyl ether.
- monoamines such as Butyl, dibutyl, octyl, stearyl, N-methylstearylamine, pyrrolidone, piperidine and cyclohexylamine
- monoalcohols such as e.g. Butanol, amyl alcohol, 1-ethylhexanol, octanol,
- Suitable higher molecular weight polyhydroxyl compounds (b) with molecular weights of 500 to 8000 are preferably polyetherols and in particular polyesterols.
- other hydroxyl-containing polymers with ether or ester groups as bridge members are also suitable, for example polyacetals, such as polyoxymethylenes, and especially water-insoluble formal forms, for example polybutanediol formal and polyhexanediol-for al, and polycarbonates, in particular those made from diphenyl carbonate and hexanediol-1, 6, prepared by transesterification.
- the polyhydroxyl compounds must be at least predominantly linear and difunctional in the sense of the isocyanate reaction.
- the polyhydroxyl compounds mentioned can be used as individual components or in the form of mixtures.
- Suitable polyetherols can be prepared by known processes, for example by anionic polymerization with alkali hydroxides, such as sodium or potassium hydroxide or alkali alcoholates, such as sodium methylate, sodium or potassium ethylate or potassium isopropylate, as catalysts and with the addition of at least one starter molecule, preferably 2 to 3 Contains 2 reactive hydrogen atoms bound, or by cationic polymerization with Lewis acids, such as antimony pentachloride, boron fluoride etherate and others or bleaching earth as catalysts from one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical.
- alkali hydroxides such as sodium or potassium hydroxide or alkali alcoholates, such as sodium methylate, sodium or potassium ethylate or potassium isopropylate
- at least one starter molecule preferably 2 to 3 Contains 2 reactive hydrogen atoms bound, or by cationic polymerization with Lewis acids, such as antimony pentachloride, boro
- Suitable alkylene oxides are preferably, for example, tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide and particularly preferably ethylene oxide and 1,2-propylene oxide.
- the alkylene oxides can be used individually, alternately in succession or as mixtures.
- suitable starter molecules are: water, organic dicarboxylic acids such as succinic acid, adipic acid and / or glutaric acid, alkanolamines such as e.g. Ethanolamine, N-alkylalkanolamines, N-alkyldialkanolamines, e.g.
- ether bridges such as e.g. Ethanediol, 1,2-and 1,3-propanediol, 1,4-butanediol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, dipropylene glycol, 2-methylpentanediol, 5 and 2-ethyl -butanediol-1,4.
- Starter molecules can be used individually or as mixtures.
- Polyetherols of 1,2-propylene oxide and ethylene oxide are frequently used in which more than 50%, preferably 60 to 80% of the OH groups are primary hydroxyl groups and in which at least part of the ethylene oxide is arranged as a terminal block.
- Such polyetherols can be obtained, for example, by first polymerizing the 1,2-propylene oxide and then the ethylene oxide onto the starter molecule or first copolymerizing all of the 1,2-propylene oxide in a mixture with part of the ethylene oxide and the rest of the Ethylene oxide then polymerized or gradually polymerized first part of the ethylene oxide, then all 1,2-propylene oxide and then the rest of the ethylene oxide onto the starter molecule.
- hydroxyl-containing polymerization products of tetrahydrofuran are also particularly suitable.
- the essentially linear polyetherols have molecular weights of 500 to 8000, preferably 600 to 6000 and in particular 800 to 3500. They can be used both individually and in the form of mixtures with one another.
- Suitable polyesterols can be prepared, for example, from dicarboxylic acids having 2 to 12, preferably 4 to 6, carbon atoms and polyhydric alcohols.
- suitable dicarboxylic acids are: aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid and sebacic acid and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid.
- the dicarboxylic acids can be used individually or as mixtures, e.g. in the form of a mixture of succinic, glutaric and adipic acids.
- dicarboxylic acid derivatives such as dicarboxylic acid mono- and / or diesters having 1 to 4 carbon atoms in the alcohol radical, dicarboxylic acid anhydrides or dicarboxylic acid dichlorides instead of the dicarboxylic acids.
- polyhydric alcohols are glycols with 2 to 10, preferably 2 to 6 carbon atoms, such as ethylene glycol, diethylene glycol, 1,4-butanediol,
- Pentanediol-1,5, hexanediol-1,6, decanediol-1,10, 2,2-dimethyl-propanediol-1,3, propanediol-1,3 and dipropylene glycol can be used alone or, if appropriate, in mixtures with one another.
- esters of carbonic acid with the diols mentioned in particular those with 4 to 6 carbon atoms, such as 1,4-butanediol and / or 1,6-hexanediol, condensation products of ⁇ -hydroxycarboxylic acids, for example ⁇ -hydroxycaproic acid, and preferably polymerization products of lactones, for example optionally substituted ⁇ -caprolactones.
- polyesterols used are ethanediol polyadipates, 1,4-butanediol polyadipates, ethanediol-1,4-butanediol diol polyadipates, 1,6-hexanediol-neopentylglycol polyadipates, 1,6-hexanediol-1,4-butanediol -polyadipate and polycaprolatone.
- the polyesterols have molecular weights from 500 to 6000, preferably from 800 to 3500.
- Suitable chain extenders (c) with molecular weights of 60 to 400, preferably 60 to 300, are preferably aliphatic diols having 2 to 12 carbon atoms, preferably having 2, 4 or 6 carbon atoms, such as e.g. Ethanediol, hexane-1,6-diol, diethylene glycol, dipropylene glycol and in particular 1,4-butanediol.
- diesters of terephthalic acid with glycols having 2 to 4 carbon atoms such as Terephthalic acid-bis-ethylene glycol or
- hydroquinone e.g. 1,4-Di ( ⁇ -hydroxyethyl) hydroquinone and polytetramethylene glycols with molecular weights from 162 to 378.
- Suitable catalysts which in particular accelerate the reaction between the NCO groups of the diisocyanates (a) and the hydroxyl groups of the structural components (b) and (c), are the conventional tertiary amines known and known in the art, such as e.g. Triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, diazabicyclo (2,2,2) octane and the like, and in particular organic metal compounds such as titanium acid esters, iron compounds, tin compounds, e.g.
- the catalysts are usually used in amounts of 0.001 to 0.1 part by weight per 100 parts by weight of the mixture of polyhydroxyl compounds (b) and diols (c).
- auxiliaries (e) and / or additives (f) can also be incorporated into the structural components.
- auxiliaries (e) and / or additives (f) can also be incorporated into the structural components.
- examples include lubricants, inhibitors, stabilizers against hydrolysis, light, heat or discoloration, flame retardants, dyes, pigments, inorganic and / or organic fillers and nucleating agents.
- the auxiliaries (e) and / or additives (f) can be introduced into the structural components or into the reaction mixture for producing the TPU.
- the auxiliaries (e) and / or additives (f) can also be mixed with the TPU and then melted.
- the last-mentioned method is used in particular for Introducing aluminum oxide, talc and / or silica gel and, if necessary, reinforcing fillers.
- the build-up components (a), (b) and (c) are reacted in the presence of catalysts (d) and optionally auxiliary agents (e) and / or additives (f) in amounts such that the Equivalence ratio of NCO groups of the diisocyanates to the sum of the hydroxyl groups of components b) and (c) is 0.80 to 1.20: 1, preferably 0.95 to 1.1: 1 and in particular approximately 1: 1. 0
- the TPUs which can be used according to the invention can be produced by the extruder or, preferably, belt process, by batchwise or continuous mixing of the components (a) to (d) and, if appropriate, (e) and / or (f), allowing the reaction mixture to react in the extruder or on a carrier tape at temperatures from 60 to 250 ° C., preferably 70 to 150 ° C., and then granulating the TPU obtained. If appropriate, it may be expedient to anneal the TPU obtained at 80 to 120 ° C., preferably 100 to 110 ° C., for a period of 0 to 1 to 24 hours before further processing.
- the foams according to the invention are produced in accordance with the methods known from the prior art and e.g. described in Ullmanns "Encyklopadie der Technische Chemie *, 4th edition, volume 20, 5 p. 416 ff.
- the impregnation or the extrusion process are used in particular.
- a mini granulate with a particle weight of in particular 0.5 to 10 mg 40 is used as the starting product for the impregnation process. This is preferably obtained by processing the TPU in a single- or twin-screw extruder with a downstream granulator.
- the extrusion is usually carried out at temperatures from 180 to 45 250 ° C., preferably 200 to 220 ° C.
- strand, water ring, knife roller or underwater granulators are used as granulators.
- the use of single-screw extruders has proven to be favorable;
- the mini granules obtained in this way have a high crystallite content and can be processed into foams with particularly favorable mechanical properties.
- the mini granulate obtained as described is impregnated with the blowing agent.
- blowing agents known in the prior art can be used as blowing agents.
- Examples include low-boiling halogenated, in particular partially halogenated, hydrocarbons, but preferably aliphatic hydrocarbons with 3 to 5 carbon atoms, such as propane, n-butane, isobutane, n-pentane, isopentane and / or neopentane.
- inorganic blowing agents are also possible. Carbon dioxide and nitrogen are mentioned here as examples.
- blowing agents can be used individually or as a mixture.
- the mini-granulate is impregnated with the blowing agent at elevated pressure of up to 10 MPa, in particular up to 7.5 MPa.
- the temperature during the impregnation is generally 100 to 200 ° C., in particular 120 to 190 ° C., preferably 130 to 175 ° C.
- the mini-granulate it is usually used together with the blowing agent, a suspension stabilizer, e.g. Calcium phosphate, magnesium carbonate or zinc carbonate, and a dispersant, e.g. Sodium dodecylbenzenesulfonate or sodium N-paraffin sulfonates, suspended in water and then transferred to a pressure vessel, which should expediently be equipped with a stirrer.
- a suspension stabilizer e.g. Calcium phosphate, magnesium carbonate or zinc carbonate
- a dispersant e.g. Sodium dodecylbenzenesulfonate or sodium N-paraffin sulfonates
- the proportion of the blowing agent in the water is usually 5 to 50% by weight, based on the polymeric starting material.
- the pressure vessel is relaxed, the granules foaming.
- the foamed granulate particles are cleaned from the additives and dried. The drying is expediently carried out with hot air.
- the TPU particles After impregnation, the TPU particles usually have an average diameter between 1 mm and 20 mm and a bulk density of 30 g / 1 to 400 g / 1, but preferably from 50 g / 1 to 200 g / 1.
- the foamed particles thus obtained can be processed into moldings.
- the particles can be pressurized before the molded part is manufactured.
- inert gas usually nitrogen
- elevated pressure up to a maximum of 1 MPa and elevated temperatures, usually from about 80 ° C.
- the pre-expanded, possibly pressure-loaded TPU particles are placed in a heatable mold and heated to such an extent that the particles are welded together.
- the heating is usually carried out by applying water vapor.
- the molded part can then be removed. After removal from the mold, the molded part should be tempered to constant weight. The tempering should be carried out at temperatures from 20 to 120 ° C.
- the TPU is extruded together with the blowing agent.
- the temperature should be between 180 ° C and 250 ° C.
- blowing agents mentioned here can be the substances mentioned in the description of the impregnation process, but also solid blowing agents which release gas when heated, such as azole carbonamide or p-toluenesulfonic acid hydrazide.
- the TPU foams up and can, for example, be formed into strands and plates.
- TPUs with a high crystallite content lead to foams with better mechanical properties.
- the crystallite content in the TPU used can e.g. can be increased by using single screw extruders when extruding the TPU.
- the foams according to the invention are distinguished by improved mechanical properties compared to known particle foams based on other polymers.
- the elasticity of the foams according to the invention is very high.
- the compressive stress with the same molded part density is significantly lower than the corresponding values of particle foams based on polyolefin.
- the foams according to the invention are also clearly superior to conventional particle foams with other mechanical properties such as abrasion resistance and crack resistance.
- particle foams according to the invention are notable for good low-temperature flexibility and high long-term use temperatures.
- the glass fibers can be added in an amount of 20 to 30% by weight, based on the TPU.
- the glass fibers are expediently added during the melting of the polymer in the extruder.
- the foams according to the invention can be thermoplastic recycled without problems.
- the foamed TPUs are extruded using an extruder with a degassing device, where the extrusion can optionally be preceded by mechanical comminution. Then they can be processed into foams again in the manner described above.
- the foam particles produced according to Example 1 were introduced into a preheated mold under pressure and compression. This was alternately heated with steam from 4.5 to 7 bar.
- the molded part density and the mechanics of the molded parts were determined in accordance with DIN 53 577.
- the compressive stress of the molded parts was determined with two molded parts with different molded part densities.
- the production parameters of the molded parts and the molded part parameters can be found in Table 3.
- the Shore hardness of the PU elastomers was determined in accordance with DIN 53 505.
Abstract
Foamed materials, in particular particulate foamed materials, based on thermoplastic polyurethanes are disclosed, as well as expandable, particulate, thermoplastic polyurethanes suitable in particular for producing shaped foamed material bodies.
Description
SCHAUMSTOFFE AUF BASIS THERMOPLΛSTISCHER POLYURETHANE FOAMS BASED ON THERMOPLASTIC POLYURETHANE
Beschreibungdescription
Die Erfindung betrifft Schaumstoffe auf der Basis von thermo¬ plastischen Polyurethanen sowie expandierbare, partikelförmige, thermoplastische Polyurethane, die insbesondere zur Herstellung von Schaumstoff-Formkörpern geeignet sind.The invention relates to foams based on thermoplastic polyurethanes and expandable, particulate, thermoplastic polyurethanes, which are particularly suitable for the production of foam moldings.
Schaumstoffe, insbesondere auch Partikelschaumstoffe, sind seit langem bekannt und in der Literatur vielfach beschrieben, z.B. in Ullmanns "Encyklopädie der technischen Chemie", 4. Auflage, Band 20, S. 416 ff.Foams, especially also particle foams, have long been known and have been widely described in the literature, e.g. in Ullmann's "Encyclopedia of Technical Chemistry", 4th edition, volume 20, p. 416 ff.
Als Grundpolymere werden üblicherweise Polystyrol oder Polyole- fine, wie Polyethylen und Polypropylen, eingesetzt. Ihr Einsatz erfolgt in vielen Bereichen. So wird expandiertes Polystyrol z.B. als Isolierstoff im Bauwesen oder zur Herstellung von Verpackun¬ gen verwendet, expandierte Polyolefine können beispielsweise als stoßabsorbierende Schaumstoffe im Kraftfahrzeugbau eingesetzt werden. Weitere Einsatzmöglichkeiten werden z.B. in Ullmann, a.a.O., beschrieben.Polystyrene or polyolefins, such as polyethylene and polypropylene, are usually used as base polymers. They are used in many areas. Expanded polystyrene is e.g. used as an insulating material in construction or for the production of packaging, expanded polyolefins can be used, for example, as shock-absorbing foams in motor vehicle construction. Other uses are e.g. in Ullmann, op. cit.
Durch Variationen der Grundpolymeren können Par ikelschaumstoffe mit sehr -unterschiedlichen Eigenschaften erzeugt werden.Varying the base polymers can produce particle foams with very different properties.
Es war jedoch bislang noch nicht möglich, Partikelschaumstoffe bereitzustellen, die eine hohe Elastizität mit einem guten Temperaturverhalten in sich vereinen. Damit sind dem Einsatz der bisher bekannten Produkte Grenzen gesetzt.However, it has not yet been possible to provide particle foams that combine high elasticity with good temperature behavior. This limits the use of the previously known products.
Die Aufgabe der Erfindung bestand darin, neue Schaumstoffe, insbesondere Partikelschaumstoffe, mit gutem Elastizitats- und Temperaturverhalten herzustellen.The object of the invention was to produce new foams, in particular particle foams, with good elasticity and temperature behavior.
Die Aufgabe konnte überraschenderweise gelöst werden durch Schaumstoffe aus thermoplastischen Polyurethanen (TPU) .The task was surprisingly achieved by foams made of thermoplastic polyurethanes (TPU).
Gegenstand der Erfindung sind demzufolge Schaumstoffe, insbeson¬ dere Partikelschaumstoffe, auf Basis von thermoplastischen Poly¬ urethanen sowie expandierbare, partikelförmige, thermoplastische Polyurethane, die insbesondere zur Herstellung von Schaumstoff- Formkörpern geeignet sind.
Erfindungsgemäß können alle gebräuchlichen TPU verwendet werden, sowohl solche auf Polyetherbasis als auch solche auf Polyester¬ basis. Die Polymerketten können verzweigt sein, die Verzweigung erfolgt vorzugsweise durch Allophanatbrücken oder den Einbau von mehrfunktionellen Alkoholen.The invention accordingly relates to foams, in particular particulate foams, based on thermoplastic polyurethanes and expandable, particulate, thermoplastic polyurethanes which are particularly suitable for the production of foam molded articles. According to the invention, all customary TPUs can be used, both those based on polyether and those based on polyester. The polymer chains can be branched, the branching is preferably carried out by allophanate bridges or the incorporation of polyfunctional alcohols.
Die erfindungsgemäß verwendbaren TPU entsprechen dem Stand der Technik und können hergestellt werden durch Umsetzung vonThe TPUs which can be used according to the invention correspond to the prior art and can be produced by reacting
a) organischen und/oder modifizierten organischen Diisocyanaten, mita) organic and / or modified organic diisocyanates, with
b) Polyhydroxylverbindungen, vorzugsweise im wesentlichen linearen Polyhydroxylverbindungen mit Molekulargewichten von 500 bis 8000, insbesondere Polyalkylenglykolpolyadipaten mit 2 bis 6 C-Atomen im Alkylenrest und Molekulargewichten von 500 bis 6000 oder hydroxylgruppenhaltigen Polytetrahydro- furanen mit einem Molekulargewicht von 500 bis 8000 undb) polyhydroxyl compounds, preferably essentially linear polyhydroxyl compounds with molecular weights of 500 to 8000, in particular polyalkylene glycol polyadipates with 2 to 6 carbon atoms in the alkylene radical and molecular weights of 500 to 6000 or hydroxyl-containing polytetrahydrofuran with a molecular weight of 500 to 8000 and
c) Diolen als Kettenverlängerungsmitteln mit Molekulargewichten von 60 bis 400, insbesondere Butandiol-1,4c) Diols as chain extenders with molecular weights of 60 to 400, especially 1,4-butanediol
in Gegenwart vonin the presence of
d) Katalysatoren und gegebenenfallsd) catalysts and optionally
e) Hilfsmitteln und/odere) aids and / or
f) Zusatzstoffenf) additives
bei erhöhten Temperaturen.at elevated temperatures.
Zu den Aufbaukomponenten (a) bis (d) und gegebenenfalls (e) und/oder (f) ist folgendes auszuführen:For the structural components (a) to (d) and optionally (e) and / or (f), the following must be carried out:
a) Als organische Diisocyanate (a) kommen vorzugsweise alipha- tische, cycloaliphatische -und aromatische Diisocyanate in Be¬ tracht. Im einzelnen seien beispielhaft genannt: aliphatische Diisocyanate wie Hexamethylen-diisocyanat-1,6, 2-Methyl- pentamethylen-diisocyanat-1,5, 2-Ethyl-butylen-diisocya- nat-1,4 oder Mischungen aus mindestens zwei der genannten aliphatischen Diisocyanate, cycloaliphatische Diisocyanate wie Isophoron-diisocyanat, 1,4-Cyclohexan-diisocyanat, l-Methyl-2,4- *und -2,6-cyclohexan-diisocyanat sowie die ent- sprechenden Isomerengemische, 4,4'-, 2,4'- und 2,2'-Dicyclo- hexylmethan-diisocyanat sowie die entsprechenden Isomeren¬ gemische und aromatische Diisocyanate, wie 2,4-Toluylen-
diisocyanat, Gemische aus 2,4- und 2, 6-Toluylen-diisocyanat, 4,4'-, 2,4'- und 2,2 '-Diphenylmethan-diisocyanat, Gemische aus 2,4'- und 4,4'-Diphenylmethan-diisocyanat, urethanmodi- fizierte flüssige 4,4'- -und/oder 2,4'-Diphenylmethandiiso- cyanate, 4, 4' -Diisocyanato-diphenylethan-1,2, Gemische aus 4,4'-, 2,4'- und 2,2'-Diisocyanato-diphenylethan-1,2, vor¬ teilhafterweise solche mit einem 4,4'-Diisocyanato-diphenyl- ethan-1,2-Gehalt von mindestens 95 Gew.-%, -und 1,5-Naphthy- len-diisocyanat. Vorzugsweise verwendet werden Diphenyl- methan-diisocyanat-Isomerengemische mit einem 4,4'-Diphenyl- methan-diisocyanatgehalt von größer als 96 Gew.-% und ins¬ besondere im wesentlichen reines 4,4'-Diphenylmethan-diiso¬ cyanat, Hexamethylen-diisocyanat-1, 6, Isophoron-diisocyanat und 4,4'- und/oder 2,4'-Dicyclohexylmethan-diisocyanat.a) The organic diisocyanates (a) are preferably aliphatic, cycloaliphatic and aromatic diisocyanates. The following may be mentioned as examples: aliphatic diisocyanates such as 1,6-hexamethylene-diisocyanate, 1,5-2-methyl-pentamethylene-diisocyanate, 1,4-2-ethyl-butylene-diisocyanate or mixtures of at least two of the aliphatic mentioned Diisocyanates, cycloaliphatic diisocyanates such as isophorone diisocyanate, 1,4-cyclohexane diisocyanate, l-methyl-2,4- * and -2,6-cyclohexane diisocyanate and the corresponding isomer mixtures, 4,4'-, 2, 4'- and 2,2'-dicyclohexylmethane diisocyanate and the corresponding isomer mixtures and aromatic diisocyanates, such as 2,4-tolylene diisocyanate, mixtures of 2,4- and 2,6-tolylene diisocyanate, 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate, mixtures of 2,4'- and 4,4 ' -Diphenylmethane diisocyanate, urethane-modified liquid 4,4'- and / or 2,4'-diphenylmethane diisocyanate, 4, 4 '-Diisocyanato-diphenylethane-1,2, mixtures of 4,4'-, 2, 4'- and 2,2'-diisocyanatodiphenylethane-1,2, advantageously those with a 4,4'-diisocyanatodiphenylethane-1,2 content of at least 95% by weight, and 1 , 5-naphthylene diisocyanate. Diphenylmethane diisocyanate isomer mixtures with a 4,4'-diphenylmethane diisocyanate content of greater than 96% by weight and in particular essentially pure 4,4'-diphenylmethane diisocyanate, hexamethylene, diisocyanate-1, 6, isophorone diisocyanate and 4,4'- and / or 2,4'-dicyclohexylmethane diisocyanate.
Die organischen Diisocyanate können gegebenenfalls in unter¬ geordneten Mengen, z.B. in Mengen bis zu 3 Mol.-%, vorzugs¬ weise bis zu 1 Mol.-%, bezogen auf das organische Diiso¬ cyanat, durch ein tri- oder höherfunktionelles Polyisocyanat ersetzt werden, wobei dessen Menge jedoch so begrenzt werden muß, daß noch thermoplastisch verarbeitbare Polyurethane erhalten werden. Eine größere Menge an derartigen mehr als difunktionellen Isocyanaten wird zweckmäßigerweise durch die Mitverwendung von weniger als difunktionellen Verbindungen mit reaktiven Wasserstoffatomen ausgeglichen, so daß eine zu weit gehende chemische Vernetzung des Polyurethans vermieden wird. Beispiele für mehr als difunktionelle Isocyanate sind Mischungen aus Diphenylmethan-diisocyanaten und Polyphenyl- polymethylen-polyisocyanaten, sog. Roh-MDI, sowie flüssige, mit Isocyanurat-, Harnstoff-, Biuret-, Allophanat-, Urethan- und/oder Carbodiimidgruppen modifizierte 4,4'- und/oder 2,4'-Diphenylmethan-diisocyanate.The organic diisocyanates can optionally be used in minor amounts, e.g. in amounts up to 3 mol%, preferably up to 1 mol%, based on the organic diisocyanate, can be replaced by a trifunctional or higher-functional polyisocyanate, the amount of which must however be limited so that thermoplastically processable polyurethanes can be obtained. A larger amount of such more than difunctional isocyanates is expediently compensated for by the use of less than difunctional compounds with reactive hydrogen atoms, so that chemical crosslinking of the polyurethane which is too extensive is avoided. Examples of more than difunctional isocyanates are mixtures of diphenylmethane diisocyanates and polyphenylpolymethylene polyisocyanates, so-called raw MDI, as well as liquid 4 modified with isocyanurate, urea, biuret, allophanate, urethane and / or carbodiimide groups 4, 4'- and / or 2,4'-diphenylmethane diisocyanates.
Als geeignete monofunktionelle Verbindungen mit reaktivem Wasserstoffatom, die auch als Molekulargewichtsregier ver¬ wendbar sind, seien z.B. genannt: Monoamine wie z.B. Butyl-, Dibutyl-, Octyl-, Stearyl-, N-Methylstearylamin, Pyrrolidon, Piperidin und Cyclohexylamin, und Monoalkohole wie z.B. Butanol, Amylalkohol, 1-Ethylhexanol, Octanol, Dodecanol, Cyclohexanol und Ethylenglykolmonoethylether.Suitable monofunctional compounds with a reactive hydrogen atom, which can also be used as molecular weight regulators, are e.g. called: monoamines such as Butyl, dibutyl, octyl, stearyl, N-methylstearylamine, pyrrolidone, piperidine and cyclohexylamine, and monoalcohols such as e.g. Butanol, amyl alcohol, 1-ethylhexanol, octanol, dodecanol, cyclohexanol and ethylene glycol monoethyl ether.
Als höhermolekulare Polyhydroxylverbindungen (b) mit Mole¬ kulargewichten von 500 bis 8000 eignen sich vorzugsweise Polyetherole und insbesondere Polyesterole. In Betracht kommen jedoch auch andere hydroxylgruppenhaltige Polymere mit Ether- oder Estergruppen als Brückengliedern, beispielsweise Polyacetale, wie Polyoxymethylene, und vor allem wasserunlös-
liehe Formale, z.B. Polybutandiolformal und Polyhexandiol- for al, und Polycarbonate, insbesondere solche aus Diphenyl- carbonat und Hexandiol-1, 6, hergestellt durch Umesterung. Die Polyhydroxylverbindungen müssen zumindest überwiegend linear und im Sinne der Isocyanatreaktion difunktionell aufgebaut sein. Die genannten Polyhydroxylverbindungen können als Ein¬ zelkomponenten oder in Form von Mischungen zur Anwendung 'kommen.Suitable higher molecular weight polyhydroxyl compounds (b) with molecular weights of 500 to 8000 are preferably polyetherols and in particular polyesterols. However, other hydroxyl-containing polymers with ether or ester groups as bridge members are also suitable, for example polyacetals, such as polyoxymethylenes, and especially water-insoluble formal forms, for example polybutanediol formal and polyhexanediol-for al, and polycarbonates, in particular those made from diphenyl carbonate and hexanediol-1, 6, prepared by transesterification. The polyhydroxyl compounds must be at least predominantly linear and difunctional in the sense of the isocyanate reaction. The polyhydroxyl compounds mentioned can be used as individual components or in the form of mixtures.
Geeignete Polyetherole können nach bekannten Verfahren, beispielsweise durch anionische Polymerisation mit Alkali¬ hydroxiden, wie Natrium- oder Kaliumhydroxid oder Alkali- alkoholaten, wie Natriummethylat, Natrium- oder Kaliumethylat oder Kaliumisopropylat als Katalysatoren und unter Zusatz mindestens eines Startermoleküls, das 2 bis 3, vorzugsweise 2 reaktive Wasserstoffatome gebunden enthält, oder durch kationische Polymerisation mit Lewis-Säuren, wie Antimon- pentachlorid, Borfluorid-Etherat u.a. oder Bleicherde als Katalysatoren aus einem oder mehreren Alkylenoxiden mit 2 bis 4 Kohlenstoffatomen im Alkylenrest hergestellt werden.Suitable polyetherols can be prepared by known processes, for example by anionic polymerization with alkali hydroxides, such as sodium or potassium hydroxide or alkali alcoholates, such as sodium methylate, sodium or potassium ethylate or potassium isopropylate, as catalysts and with the addition of at least one starter molecule, preferably 2 to 3 Contains 2 reactive hydrogen atoms bound, or by cationic polymerization with Lewis acids, such as antimony pentachloride, boron fluoride etherate and others or bleaching earth as catalysts from one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical.
Geeignete Alkylenoxide sind bevorzugt beispielsweise Tetra- hydrofuran, 1,3-Propylenoxid, 1,2- bzw. 2,3-Butylenoxid und insbesondere bevorzugt Ethylenoxid und 1,2-Propylenoxid. Die Alkylenoxide können einzeln, alternierend nacheinander oder als Mischungen verwendet werden. Als Startermoleküle kommen beispielsweise in Betracht: Wasser, organische Dicarbon- säuren, wie Bernsteinsäure, Adipinsäure und/oder Glutarsäure, Alkanolamine, wie z.B. Ethanolamin, N-Alkylalkanolamine, N-Alkyl-dialkanolamine, wie z.B. N-Methyl- und N-Ethyl-di- ethanolamin -und vorzugsweise zweiwertige, gegebenenfalls Etherbrücken gebunden enthaltende Alkohole, wie z.B. Ethan- diol, Propandiol-1,2 und -1,3, Butandiol-1,4, Diethylen- glykol, Pentandiol-1, 5, Hexandiol-1,6, Dipropylenglykol, 2-Methylpentandiol-l,5 und 2-Ethyl-butandiol-l,4. DieSuitable alkylene oxides are preferably, for example, tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide and particularly preferably ethylene oxide and 1,2-propylene oxide. The alkylene oxides can be used individually, alternately in succession or as mixtures. Examples of suitable starter molecules are: water, organic dicarboxylic acids such as succinic acid, adipic acid and / or glutaric acid, alkanolamines such as e.g. Ethanolamine, N-alkylalkanolamines, N-alkyldialkanolamines, e.g. N-methyl and N-ethyl-di-ethanolamine and preferably divalent alcohols, optionally containing ether bridges, such as e.g. Ethanediol, 1,2-and 1,3-propanediol, 1,4-butanediol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, dipropylene glycol, 2-methylpentanediol, 5 and 2-ethyl -butanediol-1,4. The
Startermoleküle können einzeln oder als Gemische eingesetzt werden.Starter molecules can be used individually or as mixtures.
Häufig verwendet werden Polyetherole aus 1,2-Propylenoxid und Ethylenoxid, in denen mehr als 50 %, vorzugsweise 60 bis 80 % der OH-Gruppen primäre Hydroxylgruppen sind und bei denen zu¬ mindest ein Teil des Ethylenoxids als endständiger Block an¬ geordnet ist. Derartige Polyetherole können erhalten werden, indem man z.B. an das Startermolekül zunächst das 1,2-Propy- lenoxid und daran anschließend das Ethylenoxid polymerisiert oder zunächst das gesamte 1,2-Propylenoxid im Gemisch mit einem Teil des Ethylenoxids copolymerisiert und den Rest des
Ethylenoxids anschließend anpolymerisiert oder schrittweise zunächst einen Teil des Ethylenoxids, dann das gesamte 1,2-Propylenoxid und dann den Rest des Ethylenoxids an das Startermolekül anpolymerisiert.Polyetherols of 1,2-propylene oxide and ethylene oxide are frequently used in which more than 50%, preferably 60 to 80% of the OH groups are primary hydroxyl groups and in which at least part of the ethylene oxide is arranged as a terminal block. Such polyetherols can be obtained, for example, by first polymerizing the 1,2-propylene oxide and then the ethylene oxide onto the starter molecule or first copolymerizing all of the 1,2-propylene oxide in a mixture with part of the ethylene oxide and the rest of the Ethylene oxide then polymerized or gradually polymerized first part of the ethylene oxide, then all 1,2-propylene oxide and then the rest of the ethylene oxide onto the starter molecule.
Insbesondere geeignet sind ferner die hydroxylgruppenhaltigen Polymerisationsprodukte des Tetrahydrofurans.The hydroxyl-containing polymerization products of tetrahydrofuran are also particularly suitable.
Die im wesentlichen linearen Polyetherole besitzen Molekular- gewichte von 500 bis 8000, vorzugsweise 600 bis 6000 und ins¬ besondere 800 bis 3500. Sie können sowohl einzeln als auch in Form von Mischungen untereinander zur Anwendung kommen.The essentially linear polyetherols have molecular weights of 500 to 8000, preferably 600 to 6000 and in particular 800 to 3500. They can be used both individually and in the form of mixtures with one another.
Geeignete Polyesterole können beispielsweise aus Dicarbon- säuren mit 2 bis 12, vorzugsweise 4 bis 6 Kohlenstoffatomen und mehrwertigen Alkoholen hergestellt werden. Als Dicarbon- säuren kommen beispielsweise in Betracht: aliphatische Dicar- bonsäuren wie Bernsteinsäure, Glutarsäure, Adipinsäure, Kork¬ säure, Azelainsäure und Sebacinsäure und aromatische Dicar- bonsäuren wie Phthalsäure, Isophthalsäure -und Terephthal- säure. Die Dicarbonsäuren können einzeln oder als Gemische, z.B. in Form einer Bernstein-, Glutar- und Adipinsäure- mischung, verwendet werden. Zur Herstellung der Polyesterole kann es gegebenenfalls vorteilhaft sein, anstelle der Dicar- bonsäuren die entsprechenden Dicarbonsäurederivate wie Dicar- bonsäuremono- und/oder -diester mit 1 bis 4 Kohlenstoffatomen im Alkoholrest, Dicarbonsäureanhydride oder Dicarbonsäure- dichloride zu verwenden. Beispiele für mehrwertige Alkohole sind Glykole mit 2 bis 10, vorzugsweise 2 bis 6 Kohlenstoff- atomen wie Ethylenglykol, Diethylenglykol, Butandiol-1,4,Suitable polyesterols can be prepared, for example, from dicarboxylic acids having 2 to 12, preferably 4 to 6, carbon atoms and polyhydric alcohols. Examples of suitable dicarboxylic acids are: aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid and sebacic acid and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid. The dicarboxylic acids can be used individually or as mixtures, e.g. in the form of a mixture of succinic, glutaric and adipic acids. For the preparation of the polyesterols it may be advantageous to use the corresponding dicarboxylic acid derivatives such as dicarboxylic acid mono- and / or diesters having 1 to 4 carbon atoms in the alcohol radical, dicarboxylic acid anhydrides or dicarboxylic acid dichlorides instead of the dicarboxylic acids. Examples of polyhydric alcohols are glycols with 2 to 10, preferably 2 to 6 carbon atoms, such as ethylene glycol, diethylene glycol, 1,4-butanediol,
Pentandiol-1,5, Hexandiol-1,6, Decandiol-1,10, 2,2-Dimethyl- propandiol-1,3, Propandiol-1,3 und Dipropylenglykol. Je nach den gewünschten Eigenschaften können die mehrwertigen Alko¬ hole allein oder gegebenenfalls in Mischungen -untereinander verwendet werden.Pentanediol-1,5, hexanediol-1,6, decanediol-1,10, 2,2-dimethyl-propanediol-1,3, propanediol-1,3 and dipropylene glycol. Depending on the desired properties, the polyhydric alcohols can be used alone or, if appropriate, in mixtures with one another.
Geeignet sind ferner Ester der Kohlensäure mit den genannten Diolen, insbesondere solchen mit 4 bis 6 Kohlenstoffatomen, wie Butandiol-1,4 und/oder Hexandiol-1,6, Kondensations- rodukte von ω-Hydroxycarbonsäuren, beispielsweise ω-Hydroxy capronsäure und vorzugsweise Polymerisationsprodukte von Lactonen, beispielsweise gegebenenfalls substituierten ω-Caprolactonen.
Als Polyesterole vorzugsweise verwendet werden Ethandiol- polyadipate, 1,4-Butandiol-polyadipate, Ethandiol-1,4-butan- diol-polyadipate, 1,6-Hexandiol-neopentylglykol-polyadipate, 1,6-Hexandiol-l,4-butandiol-polyadipate und Polycaprolatone. Die Polyesterole besitzen Molekulargewichte von 500 bis 6000, vorzugsweise von 800 bis 3500.Also suitable are esters of carbonic acid with the diols mentioned, in particular those with 4 to 6 carbon atoms, such as 1,4-butanediol and / or 1,6-hexanediol, condensation products of ω-hydroxycarboxylic acids, for example ω-hydroxycaproic acid, and preferably polymerization products of lactones, for example optionally substituted ω-caprolactones. Preferred polyesterols used are ethanediol polyadipates, 1,4-butanediol polyadipates, ethanediol-1,4-butanediol diol polyadipates, 1,6-hexanediol-neopentylglycol polyadipates, 1,6-hexanediol-1,4-butanediol -polyadipate and polycaprolatone. The polyesterols have molecular weights from 500 to 6000, preferably from 800 to 3500.
c) Als Kettenverlängerungsmittel (c) mit Molekulargewichten von 60 bis 400, vorzugsweise 60 bis 300, kommen vorzugsweise ali phatische Diole mit 2 bis 12 Kohlenstoffatomen, vorzugsweise mit 2, 4 oder 6 Kohlenstoffatomen, wie z.B. Ethandiol, Hexan diol-1,6, Diethylenglykol, Dipropylenglykol und insbesondere Butandiol-1,4 in Betracht. Geeignet sind jedoch auch Diester der Terephthalsäure mit Glykolen mit 2 bis 4 Kohlenstoff- atomen, wie z.B. Terephthalsäure-bis-ethylenglykol oderc) Suitable chain extenders (c) with molecular weights of 60 to 400, preferably 60 to 300, are preferably aliphatic diols having 2 to 12 carbon atoms, preferably having 2, 4 or 6 carbon atoms, such as e.g. Ethanediol, hexane-1,6-diol, diethylene glycol, dipropylene glycol and in particular 1,4-butanediol. However, diesters of terephthalic acid with glycols having 2 to 4 carbon atoms, such as Terephthalic acid-bis-ethylene glycol or
-butandiol-1,4 und Hydroxyalkylenether des Hydrochinons, wie z.B. 1,4-Di (ß-hydroxyethyl)hydrochinon sowie Polytetramethy- lenglykole mit Molekulargewichten von 162 bis 378.-butanediol-1,4 and hydroxyalkylene ethers of hydroquinone, e.g. 1,4-Di (β-hydroxyethyl) hydroquinone and polytetramethylene glycols with molecular weights from 162 to 378.
d) Geeignete Katalysatoren, welche insbesondere die Reaktion zwischen den NCO-Gruppen der Diisocyanate (a) und den Hydroxylgruppen der Aufbaukomponenten (b) und (c) beschleu¬ nigen, sind die nach dem Stand der Technik bekannten und üblichen tertiären Amine, wie z.B. Triethylamin, Dimethyl- cyclohexylamin, N-Methylmorpholin, N,N'-Dimethylpiperazin, Diazabicyclo- (2,2,2) -octan -und ähnliche sowie insbesondere organische Metallverbindungen wie Titansäureester, Eisenver¬ bindungen, Zinnverbindungen, z.B. Zinndiacetat, Zinndioctoat Zinndilaurat oder die Zinndialkylsalze aliphatischer Carbon- säuren wie Dibutylzinndiacetat, Dibutylzinndilaurat oder ähn liche. Die Katalysatoren werden üblicherweise in Mengen von 0,001 bis 0,1 Gew.-Teilen pro 100 Gew.-Teilen der Mischung aus Polyhydroxylverbindungen (b) und Diolen (c) eingesetzt.d) Suitable catalysts, which in particular accelerate the reaction between the NCO groups of the diisocyanates (a) and the hydroxyl groups of the structural components (b) and (c), are the conventional tertiary amines known and known in the art, such as e.g. Triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, diazabicyclo (2,2,2) octane and the like, and in particular organic metal compounds such as titanium acid esters, iron compounds, tin compounds, e.g. Tin diacetate, tin dioctoate tin dilaurate or the tin dialkyl salts of aliphatic carboxylic acids such as dibutyl tin diacetate, dibutyl tin dilaurate or similar. The catalysts are usually used in amounts of 0.001 to 0.1 part by weight per 100 parts by weight of the mixture of polyhydroxyl compounds (b) and diols (c).
Neben Katalysatoren können den Aufbaukomponenten auch Hilfs¬ mittel (e) und/oder Zusatzstoffe (f) einverleibt werden. Genannt seien beispielsweise Gleitmittel, Inhibitoren, Stabilisatoren gegen Hydrolyse, Licht, Hitze oder Verfärbung, Flammschutzmittel, Farbstoffe, Pigmente, anorganische und/oder organische Füllstoff sowie Nukleierungsmittel.In addition to catalysts, auxiliaries (e) and / or additives (f) can also be incorporated into the structural components. Examples include lubricants, inhibitors, stabilizers against hydrolysis, light, heat or discoloration, flame retardants, dyes, pigments, inorganic and / or organic fillers and nucleating agents.
Die Hilfsmittel (e) und/oder Zusatzstoffe (f) können hierzu in die Aufbaukomponenten oder in die Reaktionsmischung zur Her¬ stellung der TPU eingebracht werden. Nach einer anderen Verfah- rensvariante können die Hilfsmittel (e) und/oder Zusatzstoffe (f auch mit dem TPU gemischt und anschließend verschmolzen werden. Die zuletzt genannte Methode findet insbesondere Anwendung zum
Einbringen von Aluminiumoxid, Talkum und/oder Kieselgel sowie gegebenenfalls verstärkend wirkenden Füllstoffen.For this purpose, the auxiliaries (e) and / or additives (f) can be introduced into the structural components or into the reaction mixture for producing the TPU. According to another process variant, the auxiliaries (e) and / or additives (f can also be mixed with the TPU and then melted. The last-mentioned method is used in particular for Introducing aluminum oxide, talc and / or silica gel and, if necessary, reinforcing fillers.
Sofern zu den verwendbaren Hilfsmitteln oder Zusatzstoffen nach- 5 folgend keine näheren Angaben gemacht werden, können diese der Fachliteratur, beispielsweise der Monographie von J.H. Saunders und K.C. Frisch "High Polymers", Band XVI, Polyurethane, Teil 1 und 2 (Verlag Interscience Publishers 1962 bzw. 1964), dem Kunst¬ stoff-Handbuch, Band 7, Polyurethane 1. und 2. Auflage (Carl 0 Hanser Verlag, 1966 bzw. 1983) oder der DE-AS 29 01 774 entnommen werden.If no further details are given below about the auxiliaries or additives that can be used, these can be found in the specialist literature, for example the monograph by J.H. Saunders and K.C. Fresh "High Polymers", volume XVI, polyurethanes, part 1 and 2 (publisher Interscience Publishers 1962 and 1964), the plastics manual, volume 7, polyurethane 1st and 2nd edition (Carl 0 Hanser Verlag, 1966 and 1983) or DE-AS 29 01 774.
Zur Herstellung der TPU werden die Aufbaukomponenten (a) , (b) und (c) in Gegenwart von Katalysatoren (d) und gegebenenfalls Hilfs- 5 mittein (e) und/oder Zusatzstoffen (f) in solchen Mengen zur Reaktion gebracht, daß das ÄquivalenzVerhältnis von NCO-Gruppen der Diisocyanate zur Summe der Hydroxylgruppen der Komponenten b) und (c) 0,80 bis 1,20:1, vorzugsweise 0,95 bis 1,1:1 und ins¬ besondere ungefähr 1:1 beträgt. 0To produce the TPU, the build-up components (a), (b) and (c) are reacted in the presence of catalysts (d) and optionally auxiliary agents (e) and / or additives (f) in amounts such that the Equivalence ratio of NCO groups of the diisocyanates to the sum of the hydroxyl groups of components b) and (c) is 0.80 to 1.20: 1, preferably 0.95 to 1.1: 1 and in particular approximately 1: 1. 0
Die erfindungsgemäß verwendbaren TPU können hergestellt werden nach dem Extruder- oder vorzugsweise Bandverfahren durch batch- weises oder kontinuierliches Mischen der Aufbaukomponenten (a) bis (d) sowie gegebenfalls (e) und/oder (f) , Ausreagierenlassen 5 der Reaktionsmischung im Extruder oder auf einem Trägerband bei Temperaturen von 60 bis 250°C, vorzugsweise 70 bis 150°C, -und an¬ schließendes Granulieren der erhaltenen TPU. Gegebenenfalls kann es zweckmäßig sein, das erhaltene TPU vor der Weiterverarbeitung bei 80 bis 120°C, vorzugsweise 100 bis 110°C über einen Zeitraum 0 von 1 bis 24 Stunden zu tempern.The TPUs which can be used according to the invention can be produced by the extruder or, preferably, belt process, by batchwise or continuous mixing of the components (a) to (d) and, if appropriate, (e) and / or (f), allowing the reaction mixture to react in the extruder or on a carrier tape at temperatures from 60 to 250 ° C., preferably 70 to 150 ° C., and then granulating the TPU obtained. If appropriate, it may be expedient to anneal the TPU obtained at 80 to 120 ° C., preferably 100 to 110 ° C., for a period of 0 to 1 to 24 hours before further processing.
Die Herstellung der erfindungsgemäßen Schaumstoffe erfolgt nach den aus dem Stand der Technik bekannten und z.B. in Ullmanns "Encyklopädie der technischen Chemie*, 4. Auflage, Band 20, 5 S. 416 ff., beschriebenen Verfahren. Insbesondere angewendet werden das Imprägnier- oder das Extrusionsverfahren.The foams according to the invention are produced in accordance with the methods known from the prior art and e.g. described in Ullmanns "Encyklopadie der Technische Chemie *, 4th edition, volume 20, 5 p. 416 ff. The impregnation or the extrusion process are used in particular.
Als Ausgangsprodukt für das Imprägnierverfahren wird ein Mini¬ granulat mit einem Partikelgewicht von insbesondere 0,5 bis 10 mg 40 eingesetzt. Dieses wird vorzugsweise erhalten, indem man das TPU in einem Ein- oder ZweiSchneckenextruder mit einem nachgeschalte¬ ten Granulator verarbeitet.A mini granulate with a particle weight of in particular 0.5 to 10 mg 40 is used as the starting product for the impregnation process. This is preferably obtained by processing the TPU in a single- or twin-screw extruder with a downstream granulator.
Die Extrusion erfolgt üblicherweise bei Temperaturen von 180 bis 45 250°C, vorzugsweise 200 bis 220°C. Als Granulatoren kommen ins¬ besondere Strang-, Wasserring-, Messerwalzen- oder Unterwasser¬ granulatoren zum Einsatz.
Als günstig hat sich der Einsatz von Einschneckenextrudern er¬ wiesen; die hierbei gewonnenen Minigranulate weisen einen hohen Kristallitgehalt auf und können zu Schaumstoffen mit besonders günstigen mechanischen Eigenschaften verarbeitet werden.The extrusion is usually carried out at temperatures from 180 to 45 250 ° C., preferably 200 to 220 ° C. In particular, strand, water ring, knife roller or underwater granulators are used as granulators. The use of single-screw extruders has proven to be favorable; The mini granules obtained in this way have a high crystallite content and can be processed into foams with particularly favorable mechanical properties.
Das wie beschrieben gewonnene Minigranulat wird mit dem Treib¬ mittel imprägniert.The mini granulate obtained as described is impregnated with the blowing agent.
Als Treibmittel können die im Stand der Technik bekannten Treib- mittel eingesetzt werden.The blowing agents known in the prior art can be used as blowing agents.
Beispielhaft seien genannt niedrigsiedende halogenierte, insbe¬ sondere teilhalogenierte Kohlenwasserstoffe, vorzugsweise jedoch aliphatische Kohlenwasserstoffe mit 3 bis 5 Kohlenstoffatomen wie Propan, n-Butan, Isobutan, n-Pentan, Isopentan und/oder Neopentan.Examples include low-boiling halogenated, in particular partially halogenated, hydrocarbons, but preferably aliphatic hydrocarbons with 3 to 5 carbon atoms, such as propane, n-butane, isobutane, n-pentane, isopentane and / or neopentane.
Möglich ist auch der Einsatz von anorganischen Treibmitteln. Hier seien als Beispiel Kohlendioxid und Stickstoff genannt.The use of inorganic blowing agents is also possible. Carbon dioxide and nitrogen are mentioned here as examples.
Die Treibmittel können einzeln oder als Gemisch verwendet werden.The blowing agents can be used individually or as a mixture.
Die Imprägnierung des Minigranulats mit dem Treibmittel erfolgt bei erhöhtem Druck bis 10 MPa, insbesondere bis 7,5 MPa.The mini-granulate is impregnated with the blowing agent at elevated pressure of up to 10 MPa, in particular up to 7.5 MPa.
Die Temperatur bei der Imprägnierung beträgt im allgemeinen 100 bis 200°C, insbesondere 120 bis 190°C, vorzugsweise 130 bis 175°CThe temperature during the impregnation is generally 100 to 200 ° C., in particular 120 to 190 ° C., preferably 130 to 175 ° C.
Temperatur und Druck hängen stark von der Menge des eingesetzten Treibmittels ab.Temperature and pressure strongly depend on the amount of blowing agent used.
Zur Imprägnierung des Minigranulats wird dieses üblicherweise ge meinsam mit dem Treibmittel, einem Suspensionsstabilisator, z.B. Kalziurrphosphat, Magnesiumkarbonat oder Zinkkarbonat, und einem Dispergiermittel, z.B. Natriumdodecylbenzolsulfonat bzw. Natrium N-Paraffinsulfonaten, in Wasser suspendiert und danach in einen Druckbehälter, der zweckmäßigerweise mit einem Rührer ausgerüste sein sollte, überführt.To impregnate the mini-granulate, it is usually used together with the blowing agent, a suspension stabilizer, e.g. Calcium phosphate, magnesium carbonate or zinc carbonate, and a dispersant, e.g. Sodium dodecylbenzenesulfonate or sodium N-paraffin sulfonates, suspended in water and then transferred to a pressure vessel, which should expediently be equipped with a stirrer.
Der Anteil des Treibmittels im Wasser beträgt üblicherweise 5 bi 50 Gew.-%, bezogen auf den polymeren Einsatzstoff. Nach erfolgte Imprägnierung wird der Druckbehälter entspannt, wobei das Granu¬ lat aufschäumt.
Die aufgeschäumten Granulatpartikel werden von den anhaftenden Additiven gereinigt und getrocknet. Die Trocknung erfolgt zweck¬ mäßigerweise mit Heißluft.The proportion of the blowing agent in the water is usually 5 to 50% by weight, based on the polymeric starting material. After the impregnation has taken place, the pressure vessel is relaxed, the granules foaming. The foamed granulate particles are cleaned from the additives and dried. The drying is expediently carried out with hot air.
Die TPU-Partikel haben nach dem Imprägnieren meist einen mittle¬ ren Durchmesser zwischen 1 mm und 20 mm und eine Schüttdichte von 30 g/1 bis 400 g/1, vorzugsweise jedoch von 50 g/1 bis 200 g/1.After impregnation, the TPU particles usually have an average diameter between 1 mm and 20 mm and a bulk density of 30 g / 1 to 400 g / 1, but preferably from 50 g / 1 to 200 g / 1.
Die so erhaltenen aufgeschäumten Partikel können zu Formteilen verarbeitet werden.The foamed particles thus obtained can be processed into moldings.
Wenn nötig, kann vor der Formteilherstellung eine Druckbeladung der Partikel erfolgen.If necessary, the particles can be pressurized before the molded part is manufactured.
Dazu werden sie bei erhöhtem Druck bis maximal 1 MPa und erhöhten Temperaturen, üblicherweise von etwa 80°C, mit einem Inertgas, meist Stickstoff, beaufschlagt und 2 bis 24 h unter diesen Bedin¬ gungen gelagert.For this purpose, they are subjected to an inert gas, usually nitrogen, at elevated pressure up to a maximum of 1 MPa and elevated temperatures, usually from about 80 ° C., and stored under these conditions for 2 to 24 hours.
Zur Formteilherstellung werden die vorgeschäumten, gegebenenfalls druckbeladenen TPU-Partikel in eine beheizbare Form gegeben und so weit erhitzt, daß die Partikel miteinander verschweißt werden. Das Erhitzen erfolgt üblicherweise durch Beaufschlagen mit Was¬ serdampf.For the production of molded parts, the pre-expanded, possibly pressure-loaded TPU particles are placed in a heatable mold and heated to such an extent that the particles are welded together. The heating is usually carried out by applying water vapor.
Danach kann das Formteil entnommen werden. Nach dem Entformen sollte das Formteil bis zur Gewichtskonstanz getempert werden. Die Temperung sollte bei Temperaturen von 20 bis 120°C durchge¬ führt werden.The molded part can then be removed. After removal from the mold, the molded part should be tempered to constant weight. The tempering should be carried out at temperatures from 20 to 120 ° C.
Bei der Herstellung der erfindungsgemäßen Schaumstoffe nach dem Extrusionsverfahren wird das TPU zusammen mit dem Treibmittel extrudiert. Die Temperatur sollte hierbei zwischen 180°C und 250°C liegen.When the foams according to the invention are produced by the extrusion process, the TPU is extruded together with the blowing agent. The temperature should be between 180 ° C and 250 ° C.
Als Treibmittel können hierbei die bei der Beschreibung des Imprägnierverfahrens genannten Stoffe, aber auch feste Treib¬ mittel, die beim Erwärmen Gas abspalten, wie Azolcarbonamid oder p-Toluolsulfonsäurehydrazid, eingesetzt werden.The blowing agents mentioned here can be the substances mentioned in the description of the impregnation process, but also solid blowing agents which release gas when heated, such as azole carbonamide or p-toluenesulfonic acid hydrazide.
Beim Austritt aus dem Extruder schäumt das TPU auf und kann bei¬ spielsweise zu Strängen und Platten geformt werden.As it emerges from the extruder, the TPU foams up and can, for example, be formed into strands and plates.
Es ist auch möglich, das aufgeschäumte TPU zu granulieren und, wie oben beschrieben, zu Formteilen zu verarbeiten.
Zur Herstellung der erfindungsgemaßen Schaumstoffe können prinzi¬ piell alle TPU im gebrauchlichen Hartebereich eingesetzt werden.It is also possible to granulate the foamed TPU and, as described above, to process it into molded parts. To produce the foams according to the invention, it is possible in principle to use all TPUs in the used hard area.
Besonders gute Ergebnisse, insbesondere bezüglich der Elastizi- tatseigenschaften und der Oberflachenstruktur der erfindungsgema¬ ßen Schaumstoffe, werden bei TPU mit einer Härte im Bereich von Shore A85 bis Shore A100 erzielt. Hierbei gibt es keine wesent¬ lichen Unterschiede zwischen Polyether- und Polyester-TPU.Particularly good results, in particular with regard to the elastic properties and the surface structure of the foams according to the invention, are achieved with TPU with a hardness in the range from Shore A85 to Shore A100. There are no significant differences between polyether and polyester TPU.
Weiterhin hat sich überraschenderweise gezeigt, daß TPU mit einem hohen Kristallitanteil zu Schaumstoffen mit besseren mechanischen Eigenschaften führen. Der Kristallitanteil in dem eingesetzten TPU kann z.B. durch Verwendung von Einschneckenextrudern bei der Extrusion des TPU erhöht werden.Furthermore, it has surprisingly been found that TPUs with a high crystallite content lead to foams with better mechanical properties. The crystallite content in the TPU used can e.g. can be increased by using single screw extruders when extruding the TPU.
Die erfindungsgemaßen Schaumstoffe zeichnen sich im Vergleich zu bekannten Partikelschäumen auf Grundlage anderer Polymerer durch verbesserte mechanische Eigenschaften aus.The foams according to the invention are distinguished by improved mechanical properties compared to known particle foams based on other polymers.
So ist die Elastizität der erfindungsgemäßen Schaumstoffe sehr hoch. Beispielsweise liegt die Druckspannung bei gleicher Form¬ teildichte deutlich unter den entsprechenden Werten von Partikel¬ schaumstoffen auf Polyolefinbasis.The elasticity of the foams according to the invention is very high. For example, the compressive stress with the same molded part density is significantly lower than the corresponding values of particle foams based on polyolefin.
Aber auch bei anderen mechanischen Eigenschaften wie Abrieb¬ festigkeit und Rißbeständigkeit sind die erfindungsgemaßen Schaumstoffe herkömmlichen Partikelschäumen deutlich überlegen.However, the foams according to the invention are also clearly superior to conventional particle foams with other mechanical properties such as abrasion resistance and crack resistance.
Außerdem zeichnen sich die erfindungsgemäßen Partikelschaumstoffe durch gute Kälteflexibilitaten und hohe Dauergebrauchstemperatu¬ ren aus.In addition, the particle foams according to the invention are notable for good low-temperature flexibility and high long-term use temperatures.
Durch das Einbringen von Füllstoffen ist es darüber hinaus möglich, die Eigenschaften der erfindungsgemaßen Schaumstoffe gezielt zu verbessern oder zu modifizieren.By introducing fillers, it is also possible to specifically improve or modify the properties of the foams according to the invention.
So ist zur Verbesserung der Festigkeit der Einbau von Glasfasern möglich. Die Glasfasern können in einer Menge von 20 bis 30 Gew.-%, bezogen auf das TPU, zugesetzt werden. Der Zusatz der Glasfasern erfolgt zweckmäßigerweise während des Aufschmelzens des Polymeren im Extruder.This allows the installation of glass fibers to improve the strength. The glass fibers can be added in an amount of 20 to 30% by weight, based on the TPU. The glass fibers are expediently added during the melting of the polymer in the extruder.
Die erfindungsgemäßen Schaumstoffe können problemlos thermo¬ plastisch recycelt werden.
Dazu werden die aufgeschäumten TPU unter Verwendung eines Extru¬ ders mit einer Entgasungsvorrichtung extrudiert, wobei der Extru- sion gegebenenfalls eine mechanische Zerkleinerung vorangehen kann. Danach können sie in der oben beschriebenen Weise wieder zu Schaumstoffen verarbeitet werden.The foams according to the invention can be thermoplastic recycled without problems. For this purpose, the foamed TPUs are extruded using an extruder with a degassing device, where the extrusion can optionally be preceded by mechanical comminution. Then they can be processed into foams again in the manner described above.
Die Erfindung soll an nachfolgenden Beispielen näher erläutert werden:The following examples are intended to illustrate the invention:
Beispiel 1example 1
Herstellung der SchaumpartikelProduction of the foam particles
In einen Autoklaven wurden 100 Teile der in Tabelle 1 angegebenen TPU, die als Granulat mit einem Teilchengewicht von ca. 2 mg vor- lagen, 260 Gewichtsteile Wasser sowie die in der Tabelle angege¬ benen Treibmittel- und Hilfsmittelteile unter Rühren eingetragen, auf die in Tabelle 1 angegebene Temperatur erhitzt und maximal eine Stunde auf dieser Temperatur gehalten. Danach wurde der In¬ halt des Druckgefäßes durch ein Bodenventil ausgetragen und ent- spannt, wobei der Druck im Kessel durch Nachpressen von Stick¬ stoff bzw. des eingesetzten Treibmittels konstant gehalten wurde. Die Schaumpartikel wurden durch Waschen mit Wasser von den an¬ haftenden Hilfsmittelresten befreit und bei 20°C mit Luft getrock¬ net.100 parts of the TPU shown in Table 1, which were in the form of granules with a particle weight of approx. 2 mg, 260 parts by weight of water and the propellant and auxiliary parts indicated in the table were introduced into an autoclave with stirring, to which in Table 1 heated temperature and held at this temperature for a maximum of one hour. The contents of the pressure vessel were then discharged and released through a bottom valve, the pressure in the boiler being kept constant by repressing nitrogen or the blowing agent used. The foam particles were freed from adhering auxiliary residues by washing with water and dried at 20 ° C. with air.
Die Imprägnierbedingungen sowie die eingesetzten Treibmittel und Hilfsstoffe finden sich in Tabelle 2.The impregnation conditions and the blowing agents and auxiliaries used can be found in Table 2.
Beispiel 2 Herstellung der FormteileExample 2 Production of the molded parts
Die gemäß Beispiel 1 hergestellten Schaumpartikel wurden unter Druck und Verdichtung in eine vorgeheizte Form eingefüllt. Diese wurde wechselseitig mit Wasserdampf von 4,5 bis 7 bar beheizt.The foam particles produced according to Example 1 were introduced into a preheated mold under pressure and compression. This was alternately heated with steam from 4.5 to 7 bar.
Anschließend wurde der Druck in der Form abgebaut, diese mit Wasser bzw. Luft gekühlt, geöffnet und das Formteil entnommen.The pressure in the mold was then released, this was cooled with water or air, opened and the molded part was removed.
Nach Lagerung der Formteile bis zur Gewichtskonstanz im Umluft- trockenschrank bei 70°C wurden die Formteildichte und die Mechanik der Formteile nach DIN 53 577 bestimmt.After the molded parts had been stored to constant weight in a forced-air drying cabinet at 70 ° C., the molded part density and the mechanics of the molded parts were determined in accordance with DIN 53 577.
Die Druckspannung der Formteile wurde jeweils mit zwei Formteilen mit unterschiedlicher Formteildichte bestimmt.
Die Herstellungsparameter der Formteile sowie die Formteilkenn¬ werte finden sich in Tabelle 3.The compressive stress of the molded parts was determined with two molded parts with different molded part densities. The production parameters of the molded parts and the molded part parameters can be found in Table 3.
Die Bestimmung der Shore-Härte der PU-Elastomeren erfolgte nach DIN 53 505.
The Shore hardness of the PU elastomers was determined in accordance with DIN 53 505.
Tabelle 1Table 1
TMP - Trimethylolpropan, *) +0,05 Mol TMP
TMP - trimethylolpropane, *) +0.05 mol TMP
Tabelle 2Table 2
Herstellung der SchaumpartikelProduction of the foam particles
TPU-Nr. lt. Treibmittel [Gew-Teile] Tricalcium- Na-dodecyl- Temperatur Zeit Tabelle 1 phosphat benzoylsulfonat Schüttdichte n-Butan co2 [Gew-Teile] [Gew-Teile] [°C] [min] [g/i]TPU no. according to blowing agent [parts by weight] tricalcium sodium dodecyl temperature time Table 1 phosphate benzoyl sulfonate bulk density n-butane co 2 [parts by weight] [parts by weight] [° C] [min] [g / i]
1 20 - 6,8 0,13 152 92 1151 20 - 6.8 0.13 152 92 115
2 20 - 6,8 0,13 152 92 1002 20 - 6.8 0.13 152 92 100
2 - 10 6,8 0,13 152 92 1402 - 10 6.8 0.13 152 92 140
3 20 - 6,8 0,13 150 91 1003 20 - 6.8 0.13 150 91 100
4 20 - 6,8 0,13 149,5 90 954 20 - 6.8 0.13 149.5 90 95
5 20 - 6,8 0,13 159,5 95 905 20 - 6.8 0.13 159.5 95 90
5 - 10 6,8 0,13 158 94 1805 - 10 6.8 0.13 158 94 180
6 20 - 6,8 0,13 161 96 856 20 - 6.8 0.13 161 96 85
7 20 - 6,8 0,13 175 104 1657 20 - 6.8 0.13 175 104 165
8 20 - 6,8 0,13 150 91 1108 20 - 6.8 0.13 150 91 110
9 20 - 6,8 0,13 157 94 959 20 - 6.8 0.13 157 94 95
10 20 - 6,8 0,13 157 94 9510 20 - 6.8 0.13 157 94 95
11 20 - 6,8 0,13 160,5 96 8011 20 - 6.8 0.13 160.5 96 80
12 20 - 6,8 0,13 152 92 8012 20 - 6.8 0.13 152 92 80
13 20 - 6,8 0,13 150 91 8013 20 - 6.8 0.13 150 91 80
14 20 - 6,8 0,13 167 99 5514 20 - 6.8 0.13 167 99 55
15 20 - 6,8 0,13 165 98 100
15 20 - 6.8 0.13 165 98 100
Tabelle 3Table 3
Herstellung der FormteileManufacture of molded parts
Formteilherstellung Formteilkennwer e PU lt. Schütt¬ Verdich¬ Dampfdruck Beda p- Formteil- Wasserge¬ Druckspannung bei Tabelle 1 dichte tungsgrad fungszeit dichte halt*) (Formteildichte)Molding manufacture of molded part characteristics PU according to Schütt¬ compression pressure Beda p- molded part water pressure at table 1 density level time tightness *) (molded part density)
[g/i] [bar] [sec] [g/i] [Gew-%] [N/mm2] ([g/1])[g / i] [bar] [sec] [g / i] [wt%] [N / mm 2 ] ([g / 1])
2 100 2 -3 5 -7 10-30 200-300 1- 9 0,38(250) 0,51(300)2 100 2 -3 5 -7 10-30 200-300 1- 9 0.38 (250) 0.51 (300)
3 100 2,2-3 4,5-7 15-40 220-300 1-103 100 2.2-3 4.5-7 15-40 220-300 1-10
4 95 1,4-3,2 4,5-7 10-40 130-300 1- 9 0,24(150) 0,39(230)4 95 1.4-3.2 4.5-7 10-40 130-300 1- 9 0.24 (150) 0.39 (230)
5 90 2,2-3,3 5 -7 10-35 200-300 1-10 0,41(230) 0,56(300)5 90 2.2-3.3 5 -7 10-35 200-300 1-10 0.41 (230) 0.56 (300)
9 95 2,1-3,2 5 -7 10-40 200-320 1-10 0,40(250) 0,54(300)9 95 2.1-3.2 5 -7 10-40 200-320 1-10 0.40 (250) 0.54 (300)
11 80 2,4-3,5 5 -7 10-40 190-280 1-10 0,44(230) 0,60(280)11 80 2.4-3.5 5 -7 10-40 190-280 1-10 0.44 (230) 0.60 (280)
13 80 2,3-3,5 5 -7 10-40 180-280 1-10 0,38(230) 0,52(280)13 80 2.3-3.5 5 -7 10-40 180-280 1-10 0.38 (230) 0.52 (280)
*) vor der Temperung
*) before tempering
Claims
1. Schaumstoffe auf Basis thermoplastischer Polyurethane.1. Foams based on thermoplastic polyurethanes.
2. Schaumstoffe nach Anspruch 1, dadurch gekennzeichnet, daß die thermoplastischen Polyurethane Polyester-Polyurethane sind.2. Foams according to claim 1, characterized in that the thermoplastic polyurethanes are polyester polyurethanes.
3. Schaumstoffe nach Anspruch 1, dadurch gekennzeichnet, daß die thermoplastischen Polyurethane Polyether-Polyurethane sind.3. Foams according to claim 1, characterized in that the thermoplastic polyurethanes are polyether polyurethanes.
4. Schaumstoffe nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die thermoplastischen Polyurethane eine Shore-Härte von A 85 bis A 100 aufweisen.4. Foams according to one of claims 1 to 3, characterized in that the thermoplastic polyurethanes have a Shore hardness of A 85 to A 100.
5. Schaumstoffe nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Polymerketten über Allophanatbrücken verzweigt sind.5. Foams according to one of claims 1 to 4, characterized in that the polymer chains are branched via allophanate bridges.
6. Schaumstoffe nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Polymerketten über mehrfunktioneile Alkohole verzweigt sind.6. Foams according to one of claims 1 to 4, characterized in that the polymer chains are branched via polyfunctional alcohols.
7. Schaumstoffe nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß sie Füllstoffe enthalten.7. Foams according to one of claims 1 to 6, characterized in that they contain fillers.
8. Schaumstoffe nach Anspruch 7, dadurch gekennzeichnet, daß sie Glasfasern enthalten.8. Foams according to claim 7, characterized in that they contain glass fibers.
9. Expandierbare, partikelförmige, treibmittelhaltige thermo¬ plastische Polyurethane.9. Expandable, particulate, blowing agent-containing thermoplastic polyurethanes.
10. Expandierbare, partikelförmige, treibmittelhaltige thermo¬ plastische Polyurethane nach Anspruch 9, dadurch gekennzeich- net, daß die thermoplastischen Polyurethane Polyester-Poly¬ urethane sind.10. Expandable, particulate, blowing agent-containing thermoplastic polyurethane according to claim 9, characterized in that the thermoplastic polyurethane is polyester-polyurethane.
11. Expandierbare, partikelförmige, treibmittelhaltige thermo¬ plastische Polyurethane nach Anspruch 9, dadurch gekennzeich- net, daß die thermoplastischen Polyurethane Polyether-Poly¬ urethane sind. 11. Expandable, particulate, blowing agent-containing thermoplastic polyurethanes according to claim 9, characterized in that the thermoplastic polyurethanes are polyether-polyurethane.
12. Expandierbare, partikelförmige, treibmittelhaltige thermo¬ plastische Polyurethane nach einem der Ansprüche 9 bis 11, dadurch gekennzeichnet, daß die thermoplastischen Polyure¬ thane eine Shore-Härte von A85 bis A100 aufweisen.12. Expandable, particulate, blowing agent-containing thermoplastic polyurethane according to one of claims 9 to 11, characterized in that the thermoplastic polyurethane have a Shore hardness of A85 to A100.
13. Expandierbare, partikelförmige, treibmittelhaltige thermo¬ plastische Polyurethane nach einem der Ansprüche 9 bis 12, dadurch gekennzeichnet, daß die Polymerketten über Allo¬ phanatbrücken verzweigt sind.13. Expandable, particulate, blowing agent-containing thermoplastic polyurethane according to one of claims 9 to 12, characterized in that the polymer chains are branched via Allo¬ phanate bridges.
14. Expandierbare, partikelförmige, treibmittelhaltige thermo¬ plastische Polyurethane nach einem der Ansprüche 9 bis 12, dadurch gekennzeichnet, daß die Polymerketten über mehr- funktionelle Alkohole verzweigt sind.14. Expandable, particulate, blowing agent-containing thermoplastic polyurethane according to one of claims 9 to 12, characterized in that the polymer chains are branched over polyfunctional alcohols.
15. Expandierbare, partikelförmige, treibmittelhaltige thermo¬ plastische Polyurethane nach einem der Ansprüche 9 bis 14, dadurch gekennzeichnet, daß sie Füllstoffe enthalten.15. Expandable, particulate, blowing agent-containing thermoplastic polyurethane according to one of claims 9 to 14, characterized in that they contain fillers.
16. Expandierbare, partikelförmige, treibmittelhaltige thermo¬ plastische Polyurethane nach Anspruch 15, dadurch gekenn¬ zeichnet, daß sie Glasfasern enthalten. 16. Expandable, particulate, blowing agent-containing thermoplastic polyurethane according to claim 15, characterized gekenn¬ characterized in that they contain glass fibers.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19934307648 DE4307648A1 (en) | 1993-03-11 | 1993-03-11 | Foams based on thermoplastic polyurethanes as well as expandable, particulate, thermoplastic polyurethanes, particularly suitable for the production of foam molded articles |
DEP4307648.3 | 1993-03-11 |
Publications (1)
Publication Number | Publication Date |
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WO1994020568A1 true WO1994020568A1 (en) | 1994-09-15 |
Family
ID=6482472
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/EP1994/000606 WO1994020568A1 (en) | 1993-03-11 | 1994-03-02 | Thermoplastic polyurethane-based foamed materials |
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WO (1) | WO1994020568A1 (en) |
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