WO1994010219A1 - Verfahren zur herstellung von stabilisierten aromatischen diaminen und ihre verwendung zur herstellung von wärmestandfesten polyurethanharnstoff-elastomeren - Google Patents
Verfahren zur herstellung von stabilisierten aromatischen diaminen und ihre verwendung zur herstellung von wärmestandfesten polyurethanharnstoff-elastomeren Download PDFInfo
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- WO1994010219A1 WO1994010219A1 PCT/EP1993/002898 EP9302898W WO9410219A1 WO 1994010219 A1 WO1994010219 A1 WO 1994010219A1 EP 9302898 W EP9302898 W EP 9302898W WO 9410219 A1 WO9410219 A1 WO 9410219A1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
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- 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
- C08G18/089—Reaction retarding agents
-
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
- C09K3/1021—Polyurethanes or derivatives thereof
Definitions
- the present invention relates to a technically simplified process for the production of polyurethane urea elastomers, in which aromatic diamines stabilized in the solid phase and reacted with organic and / or inorganic acid chlorides are reacted with isocyanate prepolymers.
- Another way of controlling the reaction rate between polyisocyanates and aromatic diamines is to carry out the reaction in an organic solvent.
- Methods of this type are described, for example, in US Pat. No. 3,926,922 and Japanese Laid-Open Publication 9195/70.
- the disadvantage of using organic solvents is obvious: on the one hand the risk of fire and explosion is increased and on the other hand a technically complex recovery of the solvent is required for economic and ecological reasons.
- Aromatic diamines with a higher melting point which are of particular technical interest in general, are either used in dissolved form in accordance with the prior art, which is associated with the disadvantages just described, or else are reacted in the melt with polyisocyanates.
- the processing of aromatic diamines in the melt is described, for example, in the above-mentioned US Pat. No. 3,926,922 or in DE-A 1 122 699.
- DE-A 1 122 699 relates to a process for the production of polyurethane elastomers by crosslinking liquid isocyanate prepolymers by reaction with mixtures of primary diamines and compounds having several hydroxyl groups with shaping, in which a dispersion of a powdery crystalline diamine in a liquid polyester, polyether or in castor oil having several hydroxyl groups is introduced into the prepolymer at a temperature below the melting point of the diamine and the composition is cured in the mixture at temperatures above the melting point of the diamine in a manner known per se.
- the actual "amine crosslinking" also takes place in this process in the liquid, homogeneous phase.
- US Pat. No. 3,105,062 describes a process for the production of polyurethane ureas, in which
- High molecular weight pre-adducts containing isocyanate groups are reacted with preferably aromatic diamines in the heterogeneous phase. These reaction mixtures are solidified at a temperature at which the "two-phase system” changes into a “one-phase system”. This temperature is usually 100 to 170 ° C.
- DE-A 26 35 400 describes a further process for the production of polyurethane urea elastomers, in which aromatic diamines react as chain extenders in a one- or multi-step process.
- This process is characterized in that the aromatic diamines are present in solid form in the reaction mixtures and have a melting point above 130 ° C.
- the heat consolidation of these batches takes place in a temperature range from 80 to 120 ° C. and thus below the melting point of the aromatic diamine. Due to the selection of the corresponding diamines as chain extenders, there is no preliminary preliminary reaction with the NCO-containing pre-adduct (NCO prepolymer), which leads to a thickening of the batches.
- NCO prepolymer NCO-containing pre-adduct
- the finished PUR plastics should generally have good mechanical properties and in many cases also heat stability adapted to the intended use. According to the state of the art, this thermal stability of PUR elastomers is strongly dependent on the type of chain extender. Are used for the production of elastomers such. B. glycolic chain extender, this results in PUR bodies with lower thermal stability than when using compounds containing amino groups. Of course, within the respective type of chain extender (HO or N ⁇ group-containing connections) there are also clear differences in terms of the heat level. In DE-A 26 35 400 numerous diamines with different constitution were specified as suitable chain extenders for the production of polyurethane urea elastomers. 2,2'-Diaminodiphenylurea is mentioned as the only representative of a diaminodiphenylurea.
- test example is missing.
- DE-A 3 732 728 describes a process for the preparation of polyurethane urea elastomers in which diaminodiphenyl ureas of the general formula are present in finely divided form
- the heterogeneous reaction batches can be solidified at a relatively low temperature in an economically interesting reaction time.
- the chain extenders according to the invention are added to the NCO pre-adducts in dissolved form, they behave like conventional aromatic diamines. After a few seconds, the reaction mixture is crosslinked and the tortured secondary product can no longer be processed.
- polyhydroxyl compounds with a molecular weight of 400 to 10,000 are described. These also include the polyester and polycarbonate polyols which are particularly suitable for cast elastomers with the highest mechanical properties, as described in DE-A 3 732 728 on page 5, lines 51 et seq.
- the reaction components are reacted in accordance with the known single-step process, the prepolymer process or the semi-prepolymer process, mechanical devices often being used, for example those described in US Pat. No. 2,764,565.
- the implementation of the method according to DE-A 3 732 728 is described in detail there on page 8, lines 17 ff.
- the processing temperature depends on the one hand on the nature of the NCO pre-adduct and on the other hand must not be in too high a range, since pre-reactions cannot then be ruled out. This becomes particularly critical when highly reactive, at room temperature solid or highly viscous NCO preliminary products are to be processed using the casting technique. It is then forced to raise the processing temperature to such an extent that the reaction mixture can be degassed and poured properly. In general, the temperatures are up to 130 ° C. In the case of the in DE-A
- 3,732,728 prepolymers based on polyester polyol used in Examples 1 and 7 are generally a temperature of at least 80 ° C. Under these conditions, there is a need for long-term systems with a processing time of at least several
- the aim of the present invention was therefore to find a process for the production of polyurethane ureas in which the processing time of the reaction batches, consisting of the combination of highly reactive and
- Prepolymers based on polyester and / or polycarbonate polyols and the stabilized ureas mentioned above are lengthened at the respective reaction temperature so that perfect degassing and
- the diaminodiphenylureas suitable according to the invention are prepared by methods known per se. So z. B. nitroanilines with phosgene or diphenylcar- bonat converted into the corresponding dinitrodiphenylureas and then converted into the desired diaminodiphenylureas by reduction. Another generally applicable method is the reaction of aminoacetanilides with phosgene or diphenyl carbonate with subsequent alkaline saponification of the acetamide group to give the desired product.
- a particularly simple and therefore preferred method for producing the ureas according to the invention is the reaction of aromatic m-diamines with urea, as described in US Pat. No. 1,617,847 (in an inert solvent or in the melt) or US Pat 25 03 797 (in sulfuric acid or neutral aqueous solution) is described.
- a simple process with which diaminodiphenylureas can be prepared in high yield and with very low proportions of higher-core ureas is the reaction of aromatic m-diamines with urea in chlorobenzene described in EP-A 374 653 while maintaining certain concentration ratios.
- the solid diaminodiphenylureas are generally first finely ground, which, for. B. can be done in a ball mill, they have an average grain size of 1 to 50 ⁇ m, preferably 3 to 10 ⁇ m.
- Examples of preferred diamines for the preparation of the ureas according to the invention are, for example, m-phenyldiamine, 2,4-diaminotoluene, 2,6-diaminotoluene, l-methyl-3,5-diethyl-2,6-diaminobenzene and 1,3,5-triethyl -2,4-diaminobenzene.
- the examples of preferred diamines for the preparation of the ureas according to the invention are e.g. B.
- diamino powders obtained can be mixed directly with the NCO pre-adduct or they can preferably be applied as a suspension with little high molecular weight polyol on which the NCO pre-adduct is based.
- polyhydroxyl compounds suitable for the processes according to the invention for the preparation of the NCO groups containing pre-adducts have a molecular weight of about 400 to 10,000, preferably 600 to 6,000. These are at least two, preferably 2 to 4,
- Polyesters and polycarbonates containing hydroxyl groups as are known per se for the production of homogeneous and cellular polyurethanes.
- the hydroxyl-containing polyesters are z.
- B Reaction products of polyhydric, preferably dihydric and optionally additionally trihydric alcohols with polyhydric, preferably dihydric, carboxylic acids.
- polyhydric preferably dihydric and optionally additionally trihydric alcohols
- polyhydric preferably dihydric, carboxylic acids.
- the corresponding polycarboxylic anhydrides or corresponding polycarbonate esters of lower alcohols or mixtures thereof can also be used to produce the polyesters.
- the polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and optionally, for. B. by halogen atoms, substituted and / or unsaturated.
- Examples include: succinic acid, adipic acid, cork acid, azelaic acid, sebacic acid, phthalic acid, Isophthalic acid, trimelitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylene tetrahydrophthalic anhydride, glutaric anhydride, malic acid, fatty acids, fatty acids, fatty acid, fumaric acid, fatty acid, fumaric acid, fatty acid, fatty acid, fumaric acid, fatty acid, fumaric acid, fatty acid -bi ⁇ -glycol ester.
- polyhydric alcohols such as polyhydric alcohols such.
- B ethylene glycol, propylene glycol- (1, 2) and - (1,3), butylene glycol- (1, 4) and - (2,3), hexanediol- (1,6), octanediol- (1, 8th ), Neopentyl glycol, cyclohexanedimethanol (1, 4-bis-hydroxymethylcyclohexane), 2-methyl-l, 3-propanediol, glycerin, trimethylolpropane, hexanetriol- (1, 2.6), butanetriol- (1, 2,4), trimethylolethane, pentaerythritol, quinite, mannitol and sorbitol, methylglycoside, also diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycols, dibutylene glycol and poly
- Suitable polycarbonates having hydroxyl groups are those of the type known per se, which, for. B. by reacting diols such as propanediol (1, 3), butanediol (1, 4) and / or hexanediol (1,), diethylene glycol, triethylene glycol or tetraethylene glycol with diaryl carbonates, eg. B. diphenyl carbonate, or with Pho ⁇ gen can be produced.
- diols such as propanediol (1, 3), butanediol (1, 4) and / or hexanediol (1,)
- diethylene glycol triethylene glycol or tetraethylene glycol
- diaryl carbonates eg. B. diphenyl carbonate, or with Pho ⁇ gen
- Representatives of these compounds to be used according to the invention are e.g. B. in High Polymers, Vol.
- aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates such as, for. B. by W. Siefken in Justus Liebig's Annalen der Chemie, 562, pages 75 to 136, are described, for example ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,2- Dodecanediocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and 1,4-diisocyanate and any mixtures of these isomers, l-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (DAS 1 202 785), 2,4- and 2,6-hexahydrotoluenediocyanate as well as any mixtures of these isomers, hexahydro-1
- ester groups-containing polyisocyanates such as z. B. in GB-A 965 474 and 1 072 956, in US-A 3 567 763 and in DE-A 1 231 688, and reaction products of the above-mentioned isocyanates with acetals according to DE-A 1 072 385. It is also possible to use the distillation residues containing isocyanate groups obtained in the technical production of isocyanates, optionally dissolved in one or more of the aforementioned polyisocyanates. It is also possible to use any mixtures of these polyisocyanates.
- polyisocyanates for. B. 2,4- and, 6-tolylene diisocyanate and any mixtures of these isomers (“TDI”), polyphenyl-polymethylene-polyisocyanates, such as those produced by anion-formaldehyde condensation and subsequent phosgenation (“crude MDI”) and carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups-containing polyisocyanates (“modified polyisocyanates”).
- TDI 2,4- and, 6-tolylene diisocyanate and any mixtures of these isomers
- CADI polyphenyl-polymethylene-polyisocyanates
- modified polyisocyanates modified polyisocyanates
- polyisocyanates or the isocyanate prepolymers produced from the polyisocyanates mentioned and the above-mentioned higher and / or lower molecular polyols are said to be present in liquid form in the reaction with the powdered or suspended aromatic diamine.
- polyurethane foams are to be produced by the process according to the invention, then water and / or volatile organic substances are also used as blowing agents.
- organic blowing agents such.
- the propellant effect can also be achieved by adding compounds which decompose at higher temperatures with the elimination of gases, for example nitrogen, e.g. B. azo compound fertilizers such as azoisobutyronitri1 can be achieved. Further examples of propellants as well as details on the use of propellants can be found in the plastic handbook, volume VII, published by Vieweg and Höchtlen, Carl-Hanser-Verlag, Kunststoff 1966, e.g. B. on pages 108 and 109, 453 and 455 and 507 to 510.
- catalysts can often also be used. Suitable catalysts to be used are those of the type known per se, for. B. tertiary amines such as triethylamine, tributylamine, N-methyl-morpholine, N-ethyl-morpholine, N, N, N ', N' -tetramethyl-ethylenediamine, 1, 4-diaza-bicyclo- (2,2,2) octane, N-methyl-N'-dimethylaminoethyl-iperazine, N, N-dimethylbenzylamine, Bi ⁇ - (N, N-diethylaminoethyl) adipate, N, N-diethylbenzylamine, pentamethyldiethylenetriamine, N , N-dimethylcyclohexylamine, N, N, N ', N * -tetramethyl-1, 3-butanediamine, N, N-dimethyl-ß-phenyle
- Tertiary amines which have active hydrogen atoms with respect to isocyanate groups are e.g. B. triethanolamine, tri- isopropanolamine, N-methyl-diethanolamine, N-ethyl-diethanolamine, N, N-dimethylethanolamine and their reaction products with alkylene oxides such as propylene oxide and / or ethylene oxide.
- Silaamines with carbon-silicon bonds such as z. B. are described in DE-A 1 229 290, in question, for. B. 2,2,4-trimethyl-2- ⁇ ilamorpholine and 1, 3-diethylaminomethyl-tetramethyl-di ⁇ iloxane.
- Bases which contain nitrogen such as tetraalkylammonium hydroxides, alkali metal hydroxides such as sodium hydroxide, alkali metal phenolates such as sodium phenolate or alkali metal alcoholates such as sodium methylate are also suitable as catalysts. Hexahydrotriazines can also be used as catalysts.
- organic metal compounds in particular organic tin compounds, can also be used as catalysts.
- Al ⁇ organic tin compounds are preferably tin (II) salts of carboxylic acids such as tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate and tin (II) lactate and the dialkyltin salts of carboxylic acids, such as e.g. B. dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate or dioctyltin diacetate.
- carboxylic acids such as tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate and tin (II) lactate and the dialkyltin salts of carboxylic acids, such as e.g. B. dibutyltin diacetate, dibutyltin dilaurate, dibutyltin male
- catalysts to be used according to the invention and details of the mode of action of the catalysts are in the plastics manual, volume VII, published by Vieweg and Höchtlen, Carl-Hanser-Verlag, Kunststoff 1966, e.g. B. be ⁇ described on pages 96 to 102.
- the catalysts are generally used in an amount between about 0.001 and 10% by weight, based on the amount of polyhydroxyl compounds with a molecular weight of 400 to 10,000.
- surface-active additives emulsifiers and foam stabilizers
- emulsifiers such.
- Alkali or ammonium salts of sulfonic acids such as, for example, dodecylbenzenesulfonic acid or dinaphthylmethanedisulfonic acid or else of fatty acids such as ricinoleic acid or of polymeric fatty acids can also be used as surface-active additives.
- Water-soluble polyether siloxanes are particularly suitable as foam stabilizers. These compounds are generally constructed in such a way that a copolymer of ethylene oxide and propylene oxide with a polydimethyl-Rilfixanriüil. vi.r_.i_nd._n i ⁇ t. Such foam stabilizers are e.g. B. described in US-A-2,764,565.
- cell regulators of the type known per se such as paraffins or fatty alcohols or dimethyl polyolsilanes, as well as pigments or dyes and flame retardants of the type known per se, eg. B. trischloroethyl phosphate or ammonium phosphate and polyphosphate, further stabilizers against aging and weathering, plasticizers and fungistatic and bacteriostatic substances, fillers such as barium sulfate, diatomaceous earth, carbon black or sludge chalk are also used.
- surface-active additives and foam stabilizers to be used according to the invention, as well as cell regulators, reaction retarders, stabilizers, flame-retardant substances, plasticizers, dyes and fillers, as well as fungi-static and bacteriostatic substances, and the details of these additives Volume VI, edited by Vieweg and Höchtlen, Carl-Hanser-Verlag, Kunststoff 1966, z. B. described on pages 103 to 113.
- N can be.
- compounds according to the invention are acetic acid chloride, oleic acid chloride, stearic acid chloride, phthalic acid chloride, terephthalic acid chloride, tolylene-2,4-biscarbamoyl chloride.
- Inorganic acid chloride derived from oxygen acids, such as sulfuric acid or phosphoric acid, can also be used. Examples of this are thionyl chloride or phosphorus pentachloride.
- Hydrochloric acid when added to the NCO prepolymer by immediate in situ reaction with free isocyanate carbamic acid chlorides, which are listed under the aforementioned org. Acid chlorides are classified.
- reaction components are reacted according to the prepolymer process known per se or the semiprepolymer process, machine equipment often being used, eg. B. such which are described in US-A 2,764,565. Details about processing devices that are also suitable according to the invention are described in the plastics manual, volume VI, published by Vieweg and Höchtlen, Carl-Hanser-Verlag, Kunststoff 1966, e.g. B. described on pages 121 to 205.
- the amounts of reaction components in the process according to the invention are generally chosen so that the molar ratio of polyisocyanates to chain extender plus compound with reactive OH groups - depending on the processing method used - generally between 0.7 and 1, 5 lies, preferably between 0.90 and 1.15.
- the percentage of NCO in the prepolymer, if the prepolymer stage is used, can be 1.8 to 6% by weight.
- the molar ratio of reactive hydrogen of the chain extender to reactive OH groups can vary within wide limits, preferably it should be between 0.4 and 1.5, resulting in soft to hard types of polyurethane.
- other diamines or diols can also be used in part as chain extenders, e.g. B. ⁇ cheche as they were mentioned above in the preparation of the polyhydroxy compounds.
- the mole fraction of the ⁇ min according to the invention in the chain extender should be between 1 and 0.5, preferably between 1 and 0.8.
- the method according to the invention is carried out using simple working techniques.
- the polyol component having at least two hydroxyl groups 400 to 10,000 are reacted in a manner known per se with an excess of diisocyanate to form the pre-adduct containing NCO groups.
- the course of the reaction can be checked by NCO titration.
- the stabilizer is added.
- the temperature when the stabilizer is added depends on the solubility of the stabilizer in the NCO pre-adduct.
- the easiest way to add the stabilizer is at the respective processing temperature of the casting batches. The temperature is in most cases around 80 ° C. Of course, the processing temperature must not be too high, since a pre-reaction after adding the chain extender cannot be ruled out.
- the diaminodiphenylurea is introduced in the form of a solid powder (particle size " 5 to 50 ⁇ ) using a suitable stirrer and the resulting suspension is mixed thoroughly.
- the processing time (pot life) of these systems depends on the type of diaminodiphenylurea, the NCO-
- the amount of stabilizer is measured in such a way that perfect degassing and pouring is possible under the respective processing conditions.
- the upper limit of the stabilizer concentration is about 5,000 to 10,000 ppm, based on the prepolymer used. The easiest way to estimate the optimal amount of stabilizer for the respective system and the respective processing conditions is to carry out a preliminary test using a series of concentrations.
- the solid diamine powder first with the high-molecular liquid polyols on which the NCO pre-adduct is based.
- This batch can then be degassed, if necessary at elevated temperature.
- the stabilizer can be added both, as already described on the NCO pre-adduct side, and also into the polyol / diamine suspension.
- the pourable suspension or paste obtained in this way can then be added to the NCO pre-adduct. This method offers the advantage of being easy to carry out.
- the solidification temperature of the reactive systems according to the invention is in a range from 100 to 180 ° C.
- the hardening time decreases with increasing hardening temperature.
- the baking time can be from less than 1 minute to several hours. Sometimes it is advantageous to anneal the plastics at 100 ° C for a while after demolding to ensure complete hardening.
- Elastomers produced according to the invention are used in many ways, e.g. B. for mechanically stressed Shaped bodies such as tires, rollers, V-belts or seals which are subjected to high thermal or chemical stresses for hot water pipes or engines or for the production of foils, textile coatings and polyurethane powders.
- the chain extension can also be carried out in the presence of the blowing agents and additives described above, preferably in closed forms, foams having a cellular core and a compact surface being formed.
- the elastic and semi-elastic foams obtainable by the process according to the invention are used, for example, as cushioning materials, mattresses, packaging material and, because of their flame resistance, also in those areas where these properties are particularly important, such as, for example, B. in automobile and aircraft construction and in general transportation.
- the foams can either be produced by the molded foaming process or can be obtained from block-foamed material by assembly.
- Prepolymer B By reacting adipic acid with ethylene glycol and 1,4-butanediol, linear polyester produced with 2,4-diisocyanatotoluene in a molar ratio of 1: 2 at 60 to 80 ° C. in a conventional process technology also contains a pre-adduct containing NCO groups an NCO content of 3.3 to 3.5% by weight.
- prepolymer A 100 g are produced at 70 to 80 ° C. with 26.32 g of 3,3 * -diamino-4,4'-dimethyl-diphenylurea (according to EP 0 374 653 from 2,4-diaminotoluylene and urea, NH - Number 390 mg KOH / g) intimately mixed. At this temperature, a considerable increase in viscosity occurs in the shortest possible time ( ⁇ 60 seconds), so that the batch can neither be degassed nor poured.
- Example 2 according to the invention
- prepolymer B 400 g are heated to 70 to 80 ° C. After 0.4 g (1,000 ppm) of terephthalic acid dichloride has been added, stirring is continued for 30 minutes. 45.1 g of 3, 3 '-diamino-4,' -dimethyl-diphenylurea (according to EP 0 374 653 from 2,4-diaminotoluylene and urea, NH number 390 mg KOH / g) are then intensively mixed with the Prepolymer mixed. The suspension is thoroughly degassed using a water jet vacuum.
- the processing time of the reactive system thus obtained is at least 6.5 hours at 80 ° C. During this time there is no pre-reaction which leads to a considerable increase in the viscosity of the batch.
- the liquid reactive system is poured into a preheated mold provided with a release agent, which is then heated at 140 to 150 ° C.
- the mixture is solidified and the molding can be removed from the mold. It is advantageously post-annealed at 150 ° C. for a further 4 hours.
- prepolymer B 400 g are heated to 70 to 80 ° C. After adding 0.2 g (500 ppm) of terephthalic acid dichloride, stirring is continued for 30 minutes. Then 45.1 g of 3,3'-diamino-4,4'-dimethyl-diphenylurea (according to EP 0 374 653 made from 2,4-diaminotoluylene and urea, NH number 390 mg KOH / g) are intensively mixed with mixed the prepolymer. The suspension is thoroughly degassed using a water jet vacuum.
- the processing time of the reactive system thus obtained is at least 6.5 hours at 80 ° C. Within this time there is no pre-reaction, which leads to a considerable increase in the viscosity of the batch.
- the liquid reactive system is poured into a preheated mold with a release agent, which is then heated at 140 to 150 ° C.
- prepolymer B 400 g are heated to 70 to 80 ° C. After adding 0.08 g (200 ppm) of terephthalic acid dichloride, stirring is continued for 30 minutes. 45.1 g of 3,3'-diamino-4,4'-dimethyl-diphenylurea (according to EP 0 374 653 made from 2,4-diaminotoluylene and urea, NH number 390 mg KOH / g) are then intensively added mixed the prepolymer. After 10 minutes, the batch is thickened by pre-reaction to such an extent that degassing and casting into a high-quality molded part is not possible.
- prepolymer A 200 g are heated to 70 to 80 ° C. After adding 0.25 g (1,250 ppm) of oleic acid chloride, stirring is continued for 30 minutes. Subsequently, 26.3 g of 3,3'-diamino-4,4'-dimethyl-diphenylharnetoff (according to EP 0 374 653 made from 2,4-diaminotoluylene and urea, NH number 390 mg KOH / g) are intensively prepared mixed with the prepolymer. The suspension is thoroughly degassed using a water jet vacuum.
- the processing time of the reactive system thus obtained is at least 5 hours at 80 ° C. Within this time there is no pre-reaction, which leads to a considerable increase in the viscosity of the batch.
- the liquid reactive system is poured into a preheated mold with a release agent, which is then heated at 140 to 150 ° C.
- the mixture solidifies and the molding can be removed from the mold. It is advantageously post-annealed at 150 ° C. for a further 4 hours.
- prepolymer A 300 g are heated to 70 to 80 ° C. After adding 0.25 g (833 ppm) of sebacic acid dichloride, the mixture is stirred for 30 minutes. Then 39.5 g of 3,3'-diamino-4,4'-dimethyl-diphenylurea (prepared according to EP 0 374 653 from 2,4-diaminotoluylene and urea, NH number 390 mg KOH / g) are intensively mixed with mixed with the prepolymer. The suspension is thoroughly degassed by means of a water jet vacuum.
- the processing time of the reactive system obtained in this way is at least 4 hours at 80 ° C. During this time there is no pre-reaction which leads to a considerable increase in the viscosity of the approach.
- the liquid reactive system is poured into a preheated mold provided with a release agent, which is then heated at 140 to 150 ° C.
- the ⁇ satze ⁇ solidifies and the molding can be removed from the mold. It is advantageously post-perted for a further 4 hours at 150 ° C.
- prepolymer A 200 g are heated to 70 to 80 ° C. After adding 0.25 g (1,250 ppm) of stearic acid chloride, stirring is continued for 30 minutes. Subsequently, 26.3 g of 3,3'-diamino-4,4'-dimethyl-diphenylurea (according to EP 0 374 653 made from 2,4-diaminotoluene and urea, NH number 390 mg KOH / g) are intensively mixed with mixed with the prepolymer. The suspension is thoroughly degassed using a water jet vacuum.
- the processing time of the reactive system thus obtained is at least 5 hours at 80 ° C. Within this time there is no pre-reaction, which leads to a considerable increase in the viscosity of the batch.
- the liquid reactive system is poured into a preheated mold provided with a release agent, which is then heated at 140 to 150 ° C.
- the mixture is solidified and the molding can be removed from the mold. It is advantageously post-annealed at 150 ° C. for a further 4 hours.
- the liquid reactive system is poured into a preheated mold provided with a release agent, which is then heated at 140 to 150 ° C.
- the mixture solidifies and the molding can be removed from the mold. It is advantageously post-annealed at 150 ° C. for a further 4 hours.
- prepolymer A 200 g are heated to 70 to 80 ° C. After adding 0.5 g (2,500 ppm) of S0C1 2 , stirring is continued for 30 minutes. Then 26.3 g of 3,3 'diamino 4,4'-dimethyl-diphenylurea (prepared according to EP 0 374 653 from 2,4-diaminotoluylene and urea, NH number 390 mg KOH / g) mixed intensively with the prepolymer. The suspension is thoroughly degassed by means of a water jet vacuum.
- the processing time of the reactive system obtained in this way is at least 6 hours at 80 ° C. During this time there is no pre-reaction which leads to a considerable increase in the viscosity of the batch.
- the liquid reactive system is poured into a preheated mold provided with a release agent, which is then heated at 140 to 150 ° C.
- the mixture solidifies and the molding can be removed from the mold. It is advantageously post-annealed at 150 ° C. for a further 4 hours.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP93923507A EP0666879A1 (de) | 1992-11-02 | 1993-10-20 | Verfahren zur herstellung von stabilisierten aromatischen diaminen und ihre verwendung zur herstellung von wärmestandfesten polyurethanharnstoff-elastomeren |
JP6510639A JPH08502538A (ja) | 1992-11-02 | 1993-10-20 | 安定化された芳香族ジアミンの製造方法、および耐熱性ポリウレタン/尿素エラストマーの製造におけるその使用 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19924236939 DE4236939A1 (de) | 1992-11-02 | 1992-11-02 | Verfahren zur Herstellung von stabilisierten aromatischen Diaminen und ihre Verwendung zur Herstellung von wärmestandfesten Polyurethanharnstoff-Elastomeren |
DEP4236939.8 | 1992-11-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994010219A1 true WO1994010219A1 (de) | 1994-05-11 |
Family
ID=6471894
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1993/002898 WO1994010219A1 (de) | 1992-11-02 | 1993-10-20 | Verfahren zur herstellung von stabilisierten aromatischen diaminen und ihre verwendung zur herstellung von wärmestandfesten polyurethanharnstoff-elastomeren |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0666879A1 (de) |
JP (1) | JPH08502538A (de) |
CA (1) | CA2146670A1 (de) |
DE (1) | DE4236939A1 (de) |
WO (1) | WO1994010219A1 (de) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1050275A (de) * | 1963-03-05 | |||
EP0186618A2 (de) * | 1984-12-14 | 1986-07-02 | Hüttenes-Albertus Chemische-Werke GmbH | Unter Polyurethanbildung kalthärtendes Formstoff-Bindemittelsystem |
EP0309866A2 (de) * | 1987-09-29 | 1989-04-05 | Bayer Ag | Verfahren zur Herstellung von kalthärtenden Polyurethanharnstoff-Elastomeren |
EP0309865A2 (de) * | 1987-09-29 | 1989-04-05 | Bayer Ag | Verfahren zur Herstellung von wärmestandfesten Polyurethanharnstoff-Elastomeren |
EP0341516A1 (de) * | 1988-05-11 | 1989-11-15 | Bayer Ag | Stabilisierte Polyisocyanate |
JPH0459882A (ja) * | 1990-06-29 | 1992-02-26 | Sanyo Chem Ind Ltd | ゴム粉の接着剤 |
-
1992
- 1992-11-02 DE DE19924236939 patent/DE4236939A1/de not_active Withdrawn
-
1993
- 1993-10-20 CA CA 2146670 patent/CA2146670A1/en not_active Abandoned
- 1993-10-20 WO PCT/EP1993/002898 patent/WO1994010219A1/de not_active Application Discontinuation
- 1993-10-20 JP JP6510639A patent/JPH08502538A/ja active Pending
- 1993-10-20 EP EP93923507A patent/EP0666879A1/de not_active Withdrawn
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1050275A (de) * | 1963-03-05 | |||
EP0186618A2 (de) * | 1984-12-14 | 1986-07-02 | Hüttenes-Albertus Chemische-Werke GmbH | Unter Polyurethanbildung kalthärtendes Formstoff-Bindemittelsystem |
EP0309866A2 (de) * | 1987-09-29 | 1989-04-05 | Bayer Ag | Verfahren zur Herstellung von kalthärtenden Polyurethanharnstoff-Elastomeren |
EP0309865A2 (de) * | 1987-09-29 | 1989-04-05 | Bayer Ag | Verfahren zur Herstellung von wärmestandfesten Polyurethanharnstoff-Elastomeren |
EP0341516A1 (de) * | 1988-05-11 | 1989-11-15 | Bayer Ag | Stabilisierte Polyisocyanate |
JPH0459882A (ja) * | 1990-06-29 | 1992-02-26 | Sanyo Chem Ind Ltd | ゴム粉の接着剤 |
Non-Patent Citations (1)
Title |
---|
CHEMICAL ABSTRACTS, vol. 117, no. 2, 27 July 1992, Columbus, Ohio, US; abstract no. 28482S, SHIMADA ET AL: "ADHESIVES FOR RUBBER POWDERS" * |
Also Published As
Publication number | Publication date |
---|---|
JPH08502538A (ja) | 1996-03-19 |
EP0666879A1 (de) | 1995-08-16 |
CA2146670A1 (en) | 1994-05-11 |
DE4236939A1 (de) | 1994-05-05 |
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