• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 优先权
    • 专利摘要:
    The present invention relates to a process for the production of polyurethane ureas from a prepolymer which contains isocyanate groups and a mixture of hardeners containing amino groups, in the presence of water, and optionally in the presence of solvents, characterized in that the mixture of hardeners comprises compounds corresponding to the following general formulae:
    公开号:SU741799A3
    申请号:SU772512751
    申请日:1977-08-18
    公开日:1980-06-15
    发明作者:Кениг Эберхард；Педайн Йозеф；Арнольд Вебер Карл；Хайек Манфред
    申请人:Байер Аг (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD FOR OBTAINING POLYURETHANEAN CAPS
    one
    The invention relates to a process for the preparation of polyurethaneureas, which can be used for varnishing, coating and laminating flat-shaped products, as well as for producing films.5
    A known method for the preparation of half-chain ureas by reacting a prepolymer with terminal N4i; 0-groups with an amine-type hardener in {water and solvent solvent {1). | Q
    Aliphatic and cycloaliphatic polyamines are used as hardeners of amnn type.
    However, it is not possible to use such polyureas for coatings | g due to the high reactivity of the polyols.
    There is a known method of obtaining {(b polyurethane ureas, involving the use of blocked diamines 21 as the hardener of the action type). This significantly reduces their reactivity.
    So, for example, instead of free diamine 1, the product of their interaction with aldehye
    Dami with the subsequent removal of the reaction water.
    The closest in technical essence is a method of producing polyurethane urea by converting an NCO-terminated prepolymer with an amine-type hardener in the presence of water and solvent 3. An amine-type hardener is used. ketimine compounds resulting from the reaction of diamines with ketones and the release of water by molecular sieves.
    Coatings and varnishes with good properties can be obtained from blocked diamines of this type. True, this method is technically still not entirely satisfactory because of the following considerations.
    In order to obtain polymeric polycrystalline ureas from & 1 saldamine and bischethimine, a diaclint must first be formed again. For this purpose, water is needed, which is absorbed by the foam from the environment, for example, under wet air. The properties of such varnishes and coatings largely depend on the moisture content of the air. Since the content of moisture in the air can be very changeable, it is often difficult to obtain reproducible results. In addition, moisture affects the film: only to the top, with the result that only the upper layer cures quickly, while the lower layers under certain conditions. the circumstances harden only after several days, which in the case of thicker films leads to the fact that the polyurethane urea itself, is uneven, and the material reaches its final strength only after the expiration of odolzhitelnogo time. For this reason, it is also not possible to produce polyurethane urea coatings by the reactive method when using this type of bisketamines as a hardener and prepolymerization products containing isocyanate groups on modern coating machines. After mixing and spraying of both reactive components onto the substrate, the coating passes through a drying channel, in the shell of which it should be cured, and the material should be able to pack. However, for a short time in the car (not more than 6 minutes), the applied coating does not cure under normal conditions of the method. The aim of the invention is to increase the cure rate. This goal is achieved by using as a hardener a mixture comprising the compounds AHjN-R-NHj, BHjN-R-NRj, CRiN-R-NR, where R is a bivalent aliphatic, cycloalphthic or arylaliphatic residue with 2-18 C atoms which may contain the group —O— or A where X: H, CH 3, C 2 H 5 -, C 3 H 7 -, C 4 H 9, the residue after removal of oxygen from the ketone or aldehyde containing 2-8 C atoms, in the following ratio: 1:10 - 1: 5, 1: 1.5 - 1.5: 1, 1: 1.4 - 1:10. For the synthesis of the isocyanate-containing prepolymers used according to the invention, polynzdata can be used, which have an average MCO-function of at least 1.8. Tammy similar poliizotsian are aliphatic, aromatic and geterotsshsli RP G polyisocyanates tilendiizotsianat e.g., 1,4-tetrametilen1; iizodianat, 1,6-geksametilendiizo1shanat, 1,12-dodekandiizoiianat, cyclobutane-1,3-diisocyanate, 1,3-diisocyanate niklogensan , cyclogenesan-1,4-diisocyanate, as well as any mixtures of these isomers, 1-isocyanato3, 3,5-trimethyl-5-isostoyanatomethylcyclohexane, 2,4-hexahydrotoluenyl diisoislate, 2,6-hexahydrotoluyl diisocyanate, as well as any mixtures of these dimensions, hexahydro-1,3-and / or-1,4-phenylenediisopanate, perhydro-2,4 - and / or-4,4-diphenylmethanediene diisodianate, 1,3-phenyl diene diisosulfate, 1,4-phenyl diene diisocyanate, 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, as well as any mixtures of these isomers, diphenylmethane-2,4-diisocyanate and / or difeshmektay - 4,4-diisocyanate, naphthylene -1,5-diisodianate, triphenylmethane-1,4-4-triisocyanate, polyphenylpolymethylenepolyisocyanates, which are obtained, for example, by condensation of aniline with formaldehyde, followed by phosgenation of the resulting product, m- and p- isocyanatophenylsulfonyl isocyanates, perchlorinated aryl polyistamines, containing ui carbodiimide group of polyisocyanates, diisocyanates containing allophane; groups of polyisocyanates, polyisocyanates, polyisocyanates, polyisocyanates, polyisocyanates, polyisocyanates, polyisocyanates, polyisocyanates, polyisocyanates - products of interaction of ordered isocyanates with acetals and polymeric polyisocyanates containing acid residues t fatty. Distillation residues containing isocyanate groups and pacTBOpeniaie, and in some cases in one or more of the above polyisocyanates, can also be used in industrial isomeric isocyanates. In addition, any mixtures of the above polyisocyanates can be used t1. Preferred in accordance with the invention are 1-iscyanato-3,5,5-trimethyl-5-isocyanatomethylcyclohexane, perhydro-4,4-diphenylmethane diisocyanate, and isomeric toluene diisocyanates. Polyhydroxy compounds, which contain 2–8 hydroxyl groups and have a weight of 800–10,000, preferably 1,000–6,000, are used as the reaction of the 1X comonomers for these polyisocyanates when preparing prepolymerization products containing isocyanate groups. As an example, polyesters containing at least 2-8, preferably 2-4 hydroxyl groups, may be mentioned (polyethers, polythioethers, polyacetals, polycarbonates and polyether amides, which are known for producing homogenous polyurethanes and polyurethane foams. Containing hydroxyl The groups of complex polyesters are, for example, the products of the interaction of polyatomic, mainly dihydric alcohols and in some cases trihydric alcohols with polybasic, mainly biaxial carboxylic acids. Instead of free polycarboxylic acids, appropriate polycarboxylic acid anhydrides or the corresponding polycarboxylic esters and lower alcohols, or mixtures thereof, can be used to make polyesters. Polycarboxylic acids can have aliphatic cycloaliphatic aromatic and / or heterocyclic aromatic acid and / or heterocyclic acid. may contain halogen atom as a substituent, and / or may be unsaturated. As examples of such compounds may include: succinic, adipic, suberic, azelaic, sebacic, phthalic, isophthalic and trimellitic acid, phthalic anhydride hexahydrophthalic, tetrachlorophthalic, endomethylene glutaric acid, maleic acid and its anhydride, fumaric acid, such dimeric and trimeric fatty acid a series, like oleic acid, in some cases dimethyl and bisglygly acid esters of terephthalic acid are used in a mixture with monomeric acids of fatty acids. As polyhydric alcohols, for example, ethylene glycol, propnylene glycol-1, 2 and propylene glycol-13, butylene glycol 1,4 and butylene glycol-23, hexanediol-1,6-octanediol-1, 8, neopentyl glycol, cyclohexanedimethanol (1,4- 2-methyl-1,3-propanediol, glycerol, trimethylolpropane, hexa triol-1,2,6, butan-triol-1,2,4, trimethylol ethane, pentaerythritol, quinite, manshgg and sorbitol, methnoglucoside, further diethyl1, triethylene -, tetraethylene. polyethylene, diproshlen-, polypropylene, dibutyl and polybutylene glycols. The esters may contain carboxyl groups at the ends of the molecules. Polyesters from lactones, nagfimer, X-caprolactone, or hydroxycarboxylic acids, such as CO-hydroxycaproic acid, can also be used. The polyethers used according to the invention, containing less than two psdroxenol groups, typically 2-8, are polyester ethers of known type, which can be obtained, and 1fnmer by polymerization of epoxy compounds such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, oxide styrene or zpichlorohydrin, for example, in the presence of boron trifluoride, or by addition of these epoxy compounds, in some. cases taken in a mixture or sequentially one after another,. to such a component with reactive hydrogen atoms, such as water, alcohols, ammonia or amines, for example ethylene glycol propylene glycol- (13) or ligand glycol-1, 2, trimethylol propane, 4,4-dioxydiphenyl propane, aniline, ethanolamine or ethylene diamine. According to the invention, sucrose esters can also be used. Frequently preferred are also simple supers, which have primarily primary hydroxyl groups (up to 90% by weight, based on all the hydroxyl groups present in the polyether). . Polyether-modified polyethers, which are formed, for example, as a result of styrene and acrylonitrile polymerization in the presence of polyethers, as well as polybutadienes containing hydroxyl groups, can also be used. Of the polythioethers, the condensation products of thiodiglycol with itself and / or with other glycols, dicarboxylic acids, formaldehydes, aminocarboxylic acids or amino alcohols are of particular interest. Depending on the component used, mixed polythioethers, complex polythioethers or complex thioamido esters are obtained. For example, compounds that obtain glycols such as distilyn glycol, triethylene glycol, 4,4-doxyethoxydiphyl dimethyl methane, hexanediol, and formaldehyde can be used as polyacetals. Polyacetals suitable for use in the invention can also be obtained by re-polymerizing cyclic acetals. Lime-type polycarbonates can be used as hydroxyl-containing ipynnbi polycarbonates, which are obtained by reacting such diols as propanediol1, 3, butchal-1,4 and / or hexanediol-1,6, diethylene glycol, triethylene glycol, or tetraethylene glycol, with diaryl carbonates, for example, a diphenylcarbo atom, or a fobgen. Polnamidoesters and polyamides include, for example, predominantly linear condensation products obtained from polybasic saturated and unsaturated carboxylic acids or anhydrides of these acids and polyatomic saturated and unsaturated amino alcohols, diamines, polyamines, and mixtures thereof. Already urethane or urea groups containing polyhydroxyl compounds can also be used, as well as modified natural polyalcohols such as castor oil, carbohydrate 1 or starch. In addition, according to the invention, the products of the addition of alkylene oxides to phenol-formaldehyde resins or to urea-formaldehyde resins can be applied. It is also possible to use mixtures of these compounds containing at least two hydrogen atoms reactive with respect to the isocyanates and having a molecular weight of 400-10000, for example a mixture of polyethers and polyesters. According to the invention, polyhydroxyl compounds can also be used, in which high molecular weight polyacetate or polycondensates are contained in finely dispersed or dissolved form. Modified polyhydroxyl compounds of this type are obtained when a polyaddition reaction (for example, an interaction between a polyisocyanate and a compound containing functional amino groups) is reacted according to ionsensacin (for example, between formaldehyde and phenol and / amine) directly in situ in the compound containing hydroxyl groups. It is also possible to mix the finished aqueous polymer dispersion with the polyhydroxyl compound and immediately after that remove the water from the mixture. In the case of the use of a modified 1Ulhydroxyl compound of the specified type as a starting component, when polyaddition of polyisochdaanate is carried out, polyurethane synthetic materials with significantly better mechanical properties are formed in many cases. In the preparation of prepolymerization products containing isocyanate groups, in some cases low molecular weight polysites with a molecular weight less than OO can also be used, which are known as chain extension agents. Preferred among them are ethandol, butanediol-1,4 and trimetnlolgfolan. In addition, propandiol-1,3 and cropacdiol -1D butanediol-13 can be used, for example. butanediol-1,4 and butandiol-2, 3, pentadiol-1,5, hexanediol-1,6, bisoxyethylhydrohynon, glycerin and methyloxyethylamine. Prepolymerization products containing isocyanate pears are obtained by known methods by introducing high molecular weight polyhydroxyl compounds and in some cases of chain extenders in reaction with excess cyanate. At. In this respect, the ratio of copious and isocular pearls to common pears is chosen in the range of 1.2–6.0, preferably in the range of 1.6–3.0. Using the invention in accordance with the invention, a mixture of j cords of desulfurization on potumines, which contain at least two amino groups bound to an aliphatic residue. Such amiami are, for example, ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylamine -aminoethyl) amine and methylbis- (3-amno1fogosh) amnn. According to the invention, cycloaliphatic diamines are preferred, for example, the compounds nNgng NgN- / -eHg D y-NHj enz. , -. .. . . .A / izN j -dHzNHj Hg-C1Hg Particularly preferably, the compound of the formula L “In the process according to the invention |“ of the method, not pure amines are used, but the mixture is quiet with the corresponding aldimines, ketimine and water. These mixtures are obtained from the diamine and ketosis aldehyde taken in excess, and as a result of heating, respectively, bisketimine or bisaldashia are obtained, which can be allotted
    JB pure form. Water and, in some cases, the free diamine are added to the biskemine present or bisaldimine, and the amount of water required by the invention is greater than the amount required for the complete hydrolytic cleavage of the existing ketimyl or aldmining groups. By further heating, the desired degree of hydrolysis can be achieved. Within the specified limits, the amount of water can vary. so that the reactivity of the curing mixture under the specified curing conditions can be brought into full compliance with the reactivity of the prepolymerization product containing isocyanate groups. According to the invention, by the time of curing, the mixture of hardeners should be in the specified ratio free diamine, diamine blocked by one ketone or aldehyde molecule, and diamine blocked by both amino groups. It was completely unexpected that in spite of the excessive amount of water, most of the amino groups remain blocked at room temperature and only a relatively small amount is in the form of free diamine. The composition of the mixture of hardeners can be determined by various analytical methods (for example, using gas chromatography).
    However, curing mixtures used according to the invention can also be obtained without the isolation of bisketimine or bisaldamin in pure form. For example, the diamine is heated with a ketone and / or aldehyde to the boiling point of the reaction mixture and the water that is not separated in the free state is refluxed. As a result, a mixture of diamine, partially blocked diamine and bisketimine or bisaldimine is obtained, which, due to the low water content, is not yet suitable for use in the process. Only after adding an additional amount of water, a suitable curing mixture is obtained,
    whose quantitative ratio of the components corresponds to the specified grades.
    The aldeshes and ketones used according to the invention are compounds containing 2-8 carbon atoms, preferably 3-6. As an example, acetic acid, propionic acid, butyric and isobutyraldehyde, acetone, methylstilketone, methylisobutylketone, diisopropylketone, cyclopentanone and cyclohexanone can be mentioned.
    According to the invention, the process is advantageously carried out using a small amount of solvent.
    The amount of solvent in the reaction mixture is less than 40-50% by weight. The solvent is most often used in a curing mixture, in order to simplify the dosage. As a solvent, for hardened hydrocarbons, such as toluene, xylene or chlorobenzene, and esters such as, for example, for the product of forpolnmerization containing isocyanate groups and for the curing mixture. ethyl glycol acetate and ethyl acetate; ketones such as acetone, methyl ethyl ketone, metschzobugilketone and shpsloheksanon. Conventional solvents can also be used, for example dimethylformamide.
    However, according to the invention is most preferable; use non-toxic low polarity solvents. Alcohols such as isopropyl, isobutyl, ethyl or monoethyl ether of ethylene glycol can also be used as a solvent for the curing mixture. The reaction of the prepolymerized product containing isocyanate groups with a curing mixture is usually carried out at a temperature of 10-100 ° C, preferably at 50-80 ° C, subject to the ratio of isocyanate and hydroxyushin groups of 0.9-1.2 , preferably 0.95-1.1, and particularly preferably 1.0-1.05. The reaction temperature can reach up to 200 ° C, preferably up to 150 ° C, in the case where a foam coating is to be obtained. In this case, substances which, when heated, release gaseous products are preferably used as the blowing agent. As an example of such agents, azodicarboamide (especially in the presence of salts of metal salts) diphenysulfone-3 3 -sulfonic hydrazide, 5-morpholylthiotriazole or dinitrile azoisobutyric acid can be mentioned.
    According to the invention, the method is mainly used for applying reactive coatings or varnishes. The advantage of the described method, as compared with the known method, is primarily that a fully cured coating or varnish film, whose properties of storage are no longer changing, is formed within a short period of time. In addition, in order to speed up or slow down the curing reaction, there is no need for a 1-name catalyst, which can adversely affect the properties of the cover. Regulation of the reactivity of the invention is realized simply by introducing an additional amount of water.
    According to the invention, in some cases, known agents and additives may be used, as well as thickeners and additives.
    The written method can be applied to obtain coatings on textiles, leather, foamed and compact synthetic materials, as well as for lacquering paper, wood and metals, and the work can be carried out both directly and in reverse with a separating strip. or matrices as an intermediate carrier. a) Preparation of the forpolmerization product containing isocyanate groups Product A. 444 g of 1-isosananato-3-isocyanatomethyl1-3, 5,5-trimethyl1 daclohexane (isophorone diisocyanate) are placed in the reactor. While stirring at room temperature, 9 g of butavdiol-1,4, 9 g of trimethylolpropane and 1600 g of a hydroxyl group containing a polyether derived from adipic acid, ethylene glycol, diethylene glycol and butanediol-1.4, having a hydroxyl number of 56 and a mole of is added, are sequentially added. weight. 2000. The reaction mixture is heated and held for approximately 1 hour (to a constant amount of isocyanate groups) at. After cooling the reaction mixture to 65 ° C, 412 g of methylzinyl ketone and 206 g of toluene were added, which corresponds to a 77% solution. The solution of the prepolymerization product has a viscosity at a temperature of 20 ° C of 1000 cm, and the content of isocyanate groups is 2.95%. From this value, a CO-equivalent weight is calculated, which is 1425 g. Product B. 348 g of 2,4-diisocyanato toluene is placed in the reactor. At room temperature and transportation, 1700 g of hydroxyl groups of polyester derived from adipic acid, neopentyl glycol and hexanediol-1,6 and having a hydroxyl number of 66 and mol are added to it. weight. 1700. The reaction mixture is heated for 1 hour at 60 ° C. After that, the temperature of the reaction mixture is raised to 80 ° C and allowed to proceed to the reaction until a constant number of isocyanate groups is established. Immediately thereafter, 520 g of toluene is added to the reaction mixture, resulting in an 80% ISTATR. The solution of the product of fppolymerization has a 1FI 25 ° C viscosity of 2500 cm, the content of isocyanate groups is 3.26%. {Uncovered NCO-equivalent 1290. Prepolymer product C. Instead of the complex polyester based on alitschic acid used for the pre-polymerization product A, prepared with prepolymer C pala ate in papusarbsiat on the basis of heck and ndvol-1.6 in butastole-1,4 with gyroxp h h s 56 and mol. weighing 2000. Otherwise, the recipe of the method of operation corresponds to the prepolymerization described for the product A. 77% solution of the prepolymerization product in methyl ethyl ketone at 25 ° C had a viscosity of 1500 cm, and the content of isocyanate groups was 2.9%. Calculated from this value is the CO-equivalent of 1450. Forpo, a gamut product. In a reactor at room temperature, 444 g of isophorone diisocyanate is displaced from 2000 g of a hydroxyl rpynin.i-containing polystyrene derived from propanediol 1.2 to propylene oxide and having a hydrockle number of 26 mol. weight 2000. The reaction is carried out at 110-120 ° C until a constant number of isocyanate groups is established. The cooled prepolymerization product has a viscosity of 7000 cP at 20 ° С and a hydroxyl content of 3.4%. Calculated from this value is the NCO equivalent of 1230. c) Creeps 1е1he curing mixes The cure mixes used in the process of the invention of this method are referred to as curing agents for brevity. Hardening 1. A mixture consisting of 170 g of ZuZ, 5-trimetsh-1-5-aminomethyl diclohekshgamin (IPDA), 13 g of water and 417 g of methyl ethyl ketone is heated for 2 hours at boiling temperature of the reaction mixture under reflux. After cooling, the mixture is obtained as a hardener. Out of 170 g (1 mol) of applied IPDA, the mixture is A) 12.9 mol% as free IPDA, B) 41.6 mol% as (iH2 - N-i, Hjti-KjHj C) 45.5 mol.% In the form of bismethylethyl ketoneketimine IPDA. (The composition was calculated according to gas chromatographic analysis of the mixture). In addition, 37.88 g of water is additionally contained in the mixture. (Theoretically, the amount of water needed for hydrolytic cleavage of ketimine groups to amino groups is 24.88 g). The molar ratio of the individual components of the hardener has the following meanings: A + C + C HgO2,1 H2-equivalent hardening mixture 300 g Hardener 2 (for comparison). By analogy with the hardener I, a curing mixture of 170 g of PDA and 430 g of methyl ethyl ketone is obtained without an additional amount of water. According to the gas chromatographic analysis of the final curing mixture, it was established that the molar amount of the individual components of the hardener (cf. hardener 1) refers to the molar amount of water, as A + B + C 1.0 NgOU85 N H2 -equivalent weight of the hardening mixture 300 g. 3. A mixture of 170 g of 3,3,5-trimethyl-5-aminomethylcyclohexylamine (IPDA) and 300 g of mepshizobutyl ketone (MIBK) is heated at the boiling point, water is distilled off until 36 g of water is distilled off. The remaining mass is freed on a rotary evaporator from excess methyl isobutyl ketone. In the form of a residue, 334 g of IPDA bismethyl isophenyl ketimine, which is a 1H4 colorless liquid with a boiling point of 160 ° C at 0.2 mm Hg, are obtained. Art. A mixture of 334 g of bismethyl isobutyl ketimine IPDA, 72 g of water (this is 36 g more than is necessary for complete hydrolysis of bischethimine) and 94 g of isopropyl alcohol are kept for 24 hours at room temperature. The resulting curing mixture, consisting of free, monoblocked, and also released IPDA and iodine, with respect to the prepolymerisadium product containing isocyanate groups, has an activity corresponding to curing mixture 1. NH2-equivalent weight of curing mixture 250 g. Hardeners 4-7. The hardening mixtures described below and corresponding to the invention contain, by analogy with hardeners 1 and 3, different amounts of water, depending on the type of polymine and blocking agent used. Curing the mixture, as in the case of hardener, obtained from the components listed in the table.
    144.5 g IPDA
    420.8 g methyl methyl ketone
    350 g methyl methyl ketone
    144 g of isobutyl aldehyde, 296 g of methyl ethyl ketone
    C) Preparation of polyurethane urea
    The curing mixtures 1 and 3 - 7, corresponding to the invention, have such reactivity with respect to the prepolymerization product containing isocyanate groups, which, with the required viability, is 300 g.
    21.6 g
    300 g
    12 g
    300 g
    24 g
    on an average of 2-5 minutes, they lead, under ambient room conditions, to the desired curing time, averaging 4-8 minutes.
    In this case, the viability time is understood to mean the time after which 1574 in an XX mixture becomes such (approximately 150,000 centipoise) that the mixture is not sprayed at 25 ° C with conventional spraying methods. Example 1. A skin sample is coated with a pistol syringe to interleave two components. The pistol syringe contains a warmed collection for the prepolymerization product, a collection for the hardener, a device for dosing the hardener and a prepolymerization product for mixing and spraying the components in the spray gun, the device is equipped with concentric nozzles, a device for feeding the prepolymerization product, a device for feeding a hardener and a device in for compressed air. Prepolymer product A is placed in a heated collector, and the product is heated to lower viscosity. The curing mixture 1 together with 10% by weight of pigment is introduced into a collection intended for them. By adding pigment, the NHj-equivalent of the curing mixture is increased to 330 g. By separate hoses with built-in metering devices, the prepolymerization product and the hardener are fed to the x-gun according to their equivalent weights. The amounts of components fed can be varied; for example, 480 g of prepolymer product A and 111 g of hardener 1 (including pigment addition) are fed in 1 minute. At the gun exit, both components are mixed due to the air vortex created by compressed air (working pressure 4.5 kg / cm). For unloading the pistol is moved to a width of 100 cm in a circle back and forth 28 times in 1 minute. Under the gun at a speed of 1.6 m / min, a matrix covered with silicone rubber, on which there is an imprint of natural skin, is moved. The mass applied to the matrix spreads in the form of a film and, after about 1 minute from the moment of application, begins to solidify. The cured mass is applied and pressed onto a sample of skin on which it is desired to apply a coating. The coated sample is passed through a drying channel heated to 80 ° C. Approximately 6 minutes after spraying is applied by spraying, the coated material is removed from the matrix. The layer of popiuretan urea has a thickness of 0.22-0.25 mm. A sample of coated leather has a front surface similar to that of natural leather, and after drying for a short time, the resulting material can be processed on shoe machines. The clinging between the coating and the leather sample is different. The material is ten and dry to the touch. The coated skin is flexometrically maintained: - in a dry state with more than 200,000 continuous bends without damage; in the wet state with more than: 100,000 longitudinal bends without damage; - at a temperature of -25 ° C with more than 10,000 longitudinal bends without disintegration. Ironing at a temperature of 150 ° C occurs almost without damage to the surface of the material obtained. The polyurethane urea elastomer has the following mechanical properties: Strength at tensile strength180 kg / cm Tensile strength 30 kg / cm Elongation at break.800% Example 2. (for comparison). Prepolymer product A and hardener 2 ,. which did not contain additional quantities of water, is processed according to example 1. The system has two serious drawbacks. 1. A mixture of hardener and prepolymerization product does not cure quickly enough by spraying onto the matrix. By the time the skin is applied, the mass is still so fluid that it can penetrate into the substrate. As a consequence, not all the fibrous surface of the skin is wrung in mass, but in patches. 2. At the end of the machine, after 6 minutes from the moment of spraying, the coat is not yet cured, so the skin sticks to the matrix and cannot be removed without damage. Example 3. The prepolymer product A and the hardener 1 are mixed at a cooling temperature in the ratio of equivalent weights. Weight viability 3 min. Using the device, the film is stretched and a film 0.5 mm thick is produced on a silicone paper substrate. After 7 minutes, the film is already completely cured and can be easily separated from the substrate. Example 4 (for comparison). The prepolymer product A and the hardener 3 are mixed at room temperature in a ratio of their equivalent weights. Now the mass has a longer viability (V 11 min). However, a 0.5 mm thick film, which is prepared in Example 3, is cured on the surface only after 25 minutes. The film remains soft under the hardened surface for a long time. This example also shows that a hardener 3 is not sufficiently effective for this purpose.
    权利要求:
    Claims (1)
    [1]
    Claim
    A method of producing polyurethane ureas by reacting a prepolymer with terminal NCO groups with a hardener, an amine type in the presence of water and a solvent, characterized in that, in order to increase the curing rate, a mixture comprising
    A B C
    R
    H 2 NR-NH 2 HjN-R-NRj and RjN-R-NRj / are a divalent aliphatic, cycloaliphatic or aripaliphatic residue with 2-18 C atoms, which can contain the group -0- or X, where X: H, CH r , C 2 H 5 -, C 3 H 7 -, C 4 H, -,
    Rj is the residue after removal of oxygen from a ketone or aldehyde containing 2-8 atoms where
    C, in the following ratio; A B ~ +
    IN
    C ~~ A + _
    Water = 1: 1.5 - 1.5: 1
    B + C = 1: 1.4 - 1:10
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    同族专利:
    公开号 | 公开日
    IT1079426B|1985-05-13|
    PL104428B1|1979-08-31|
    JPS6227092B2|1987-06-12|
    CA1114989A|1981-12-22|
    DD133805A5|1979-01-24|
    JPS5324396A|1978-03-07|
    FR2362171A1|1978-03-17|
    SE7709278L|1978-02-19|
    RO72918A|1981-11-04|
    AU514144B2|1981-01-29|
    YU39816B|1985-04-30|
    CS196218B2|1980-03-31|
    ATA591577A|1980-01-15|
    FR2362171B1|1983-11-18|
    BE857854A|1978-02-17|
    YU198277A|1982-05-31|
    DE2637115A1|1978-02-23|
    BR7705457A|1978-05-02|
    DE2637115B2|1979-11-22|
    GB1545005A|1979-04-25|
    NL7709107A|1978-02-21|
    ES461680A1|1978-12-01|
    HU178432B|1982-05-28|
    NL182812C|1988-05-16|
    NL182812B|1987-12-16|
    DE2637115C3|1980-10-09|
    US4108842A|1978-08-22|
    AT358283B|1980-08-25|
    AU2792677A|1979-02-22|
    PL200320A1|1978-04-24|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE2637115A|DE2637115C3|1976-08-18|1976-08-18|Process for the production of polyurethane ureas|
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