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    • 专利摘要:
    1477623 Inorganic-organic plastics BAYER AG 16 March 1976 [20 March 1975] 10459/76 Heading C3R Inorganic-organic plastics are prepared by reacting, in the absence of a water binding inorganic filler, an aqueous silicate solution with an organic polyisocyanate which is free from hydrophilic groups and which has a viscosity of at least 400 cP at 25‹ C. and an average functionality greater than 2 the polyisocyanate either being liquid or being used in the form of a solution or dispersion. Particularly suitable polyisocyanates are polyphenyl-polymethylene-polyioscyanates of the type obtained by condensing aniline with formaldehyde, followed by phosgenation. Other suitable polyisocyanates are solutions of residual isocyanates in monomeric polyisocyanates, polyisocyanates containing carbodiimide, allophanate, isocyanurate, urea or biuret groups and polyisocyanates in the form of semi-prepolymers or prepolymers. The aqueous silicate solution is that of sodium and/or potassium silicate in water. Foams may be produced from the reaction mixture, suitably by the addition of a blowing agent. Catalysts, foam stabilizers, emulsifying agents, fillers and flame-proofing agents may also be included in the reaction mixture.
    公开号:SU850009A3
    申请号:SU762335244
    申请日:1976-03-19
    公开日:1981-07-23
    发明作者:Маркуш Петер；Дитерих Дитер；Дитрих Манфред
    申请人:Байер Аг (Фирма)；
    IPC主号:
    专利说明:

    one
    The invention contributes to the production of foam and can be used in various areas of industry in the manufacture of insulation coatings, building elements, multilayer materials, etc.
    Methods are known for the preparation of foams used in the manufacture of construction scaffolds (coatings, multilayer materials, based on an aqueous solution of alkali silicate and a low molecular weight polyisocyanate of the general formula
    OCN-R-NCO
    where R is alkylene, aralkylene or arylene radical.
    Other polyisocyanates, polyisothiocyanates and their derivatives can be used in the same way. Fatty acid diisocyanates of the general formula are also suitable.
    NCO
    (CH
    CH, j, ((CH2) NCO, where X + y is generally 6-22 and Z is 0-2, for example; isocyanatostearyl isocyanate. Of the indicated
    p, diphenylmethane diisocyanate compounds are most suitable for their practical use. Toluene diisocyanate, e.g. 2,4- and 2,6-isomers, are also readily prepared and suitable for use f 1.
    According to the invention, solutions of sodium silicate are respectfully used as solutions of alkali silicates. The following indications are given on the proportion of isocyanate to alkaline silicate used.
    15
    The relative amounts of alkaline silicate and isocyanate can be changed. As a result, as stated earlier, products with different physical properties and
    20 probably with a deviating chemical structure.
    It is advisable and desirable to use an excess of silicate, i.e. more than stoichiometrically equivalent amount.
    However, coarse emulsions form a mixture of an aqueous solution of sodium silicate and a low-viscosity polyisocyanate used, resulting in the introduction of emulsifying additives and foam stabilizers into the system.
    The resulting foam is brittle and fragile, has cracks and shells in the structure.
    The closest to the proposed invention to the technical essence and the achieved result is a method for producing foams, it is intended to use polyisocyanates with ionic groups as the isocyanate component, which provide the best emulsifiability between the organic and inorganic phases G23.
    However, at the same time, the reactivity and sensitivity in relation to moisture in the air is increased.
    The purpose of the invention is to obtain a foam material with improved mechanical properties.
    The goal is achieved by using an aniline-formaldehyde condensate phosgenating product with an viscosity of 400-10000 cps, preferably 50010000 cps, and an average functionality equal to more than 2, as the isocyanate component and the weight ratio of the isocyanate component to the aqueous solution of silicate Composed from 70:30 to 20:80.
    The prepolymers suitable for the implementation of the proposed method are obtained by reacting an excess of the product of the phosgenation of aniline-formaldehyde condensate with various compounds containing an active hydrogen atom that satisfy the criteria according to the invention with respect to viscosity and functionality.
    Under aqueous solutions of silicates, the use of solutions of sodium silicate and / or potassium in water is suggested. Raw technical solutions can also be used, which additionally contain calcium silicate, magnesium silicate, borates and aluminates. The molar ratio tO / j (Me metal) is not critical and can vary within wide limits; preferably it is 4-0.2, in particular 1.5-0.3.
    Neutral sodium silicate can be used, from which 25-35% by weight solutions are prepared. Preferably, 32-54 wt.% PacTBOi silicates are used, which, only with sufficient alkalinity, must have a viscosity of less than 500 poise for processing. Amlyunium silicate solutions, for example, guanidine silicate solutions can also be used, although they are less preferred. It may be true or colloidal solutions.
    The choice of concentration depends primarily on the desired desired product. Compact or closed cellular materials are preferably prepared using concentrated solutions of silicates, which, if necessary, are obtained by adding low viscosity alkali metal hydroxide. Thus prepare 40-70 wt.% - and other solutions. On the other hand, for the preparation of open cellular light foams, solutions of silicates with a content of 20-40% are preferred.
    Also, when using highly dispersed fillers in large quantities, solutions of silicates with 20-44% content are preferred.
    The mixture of necessary components is not stable. The viability, during which the mixtures are processed, depends primarily on the reactivity, on the total amount of liberated silicate solution, and on the concentration of the silicate solution. It ranges from 0.2 s to approximately 15 hours.
    Viability from 1 s to 20 min is preferred.
    From this it follows that mixing is carried out immediately prior to molding.
    The preparation of an isocyanate component based foam and a silicic acid gel can be carried out according to known techniques, for example, polyurethanes foaming, and the reaction should take place in the absence of a water-binding inorganic filler. Since, as a result, the viability of the cell is only lower and the reaction often proceeds spontaneously already at -20 ° C, the possibility of periodic production is limited. Practically, this method is used to produce smaller shaped parts with a maximum of up to 10 kg. Preferably, using conventional technology for producing polyurethane foams, the components are continuously mixed in a mixing chamber with a low residence time and then cured during molding. To this end, the liquid or pasty mixture is poured, for example, into molds, applied to the surface or filled into the mixture with depressions, seams, cracks and the like.
    When mixed, the ratio between polyisocyanate and alkaline silicates can vary widely, for example from 90 to 10 up to 10 to 90. Preferably, the ratio between the polyisocyanate and alkaline silicate is between 7525 and 15-85. Optimum performance properties, especially high insulating ability, as well as high elasticity, stability when heated and difficult to flammable, get a mix ratio of 60-40 to 18-82. According to the invention katsshizatory. Tertiary amines, for example, triethylamine, tributylamine, N-methyl-morpholine, N-ethyl morpholium, M-cocomorpholine, N, N, N, N tetramethylethylenediamine, 1,4-diaza-bicyclo- (2.2, 2) -octane, M-methyl-M-dimethylaminoethylipiperazine, N, N-dimethylbenzylamine, bis-, N-diethyl aminoethyl-adipate, K, M-diethylbenzyl amine, pgntamethyldistilenetriamine, N, N-dimethylcyclohexterate, and N-N-dimethylcyclohexaneterate, n-diethylbenzyl amine, n-diethyl aminoethyl-adipate, K, M-diethylbenzyl amine; , n-tatramethyl-1,3-butanediamine, N, N-dimethyl-1b-phenylethylamine, 1, 2-dimethylimidazole, 2-methylimidazole. Tertiary amines possessing an active with respect to isocyanat hydrogen atom groups, for example, triethanolamine, triisopropanolamine, H-methyl-diethanolamine, -ethyl-diethanolamine, N, H-dimethyl-ethanolamine, and their interaction products with alkylene oxides, like propylene oxide and / or ethylene oxide, organosilicon amines with carbon-silicon-bonds. For example, 2,2,4-trimethyl-2-silimilorphine, 1,3-diethylaminomethyl-tetramethyldisiloxane. Nitrogen-containing bases such as tetragshlylammonium hydroxide, as well as alkali metal hydroxides, are also used as catalysts. as sodium hydroxide f alkali metal enolates, such as sodium phenol, or alkali metal alkoxides, such as sodium methoxide. Also, hexahydrotriazines can be used as catalysts. Organic compounds of metals can also be used as catalysts, in particular tin compounds, such as lipo (II) carboxylic acids, ka tin acetate- (I), tin octoate (And ethylhexoate tin- (II) and ola vaca- laurate (to and salts of dialkyltin carboxylic acids, for example, dibutyl polio diacetate, dibutyl tin dilaurate, dibutyl tin maleate, or dioctyl tin diacetate. Catalysts are usually used in an amount of 0.001 to 1 wt.% based on the amount of the compound, as a percentage reactive with respect to Hydrogen atoms with molecular weights of 400 to 10,000 are used for isocyanates. Surface-active additives (emulsifiers and foam stabilizers) can also be used simultaneously. Sodium salts of castor oil or fatty acid sulfates or amines with fatty acids can be used as emulsifiers. oleate diethylamine or diethanolamine stearinate, as well as alkali metal salts and ammonium sulfonic acid salts, for example dodecylbenzenesulfonic acid or dinaphthylmethanedisulfonic acid, or also fatty acids like ricinoleic acid, and whether polymeric fatty acids. The water-soluble polyether siloxane is primarily used as a foam stabilizer. These compounds are generally constructed in such a way that a copolymer of ethylene oxide and propylene oxide is bound to a polydimethylsiloxane residue. According to the invention, reaction inhibitors that react as acid substances, like hydrochloric acid or organic acid halides can be used, then cell regulators — paraffins or fatty alcohols or dimethylpolyLisiloxanes, as well as pigments or dyes and flame retardants: tris-chloroethylphosphate, or aluminum phosphate and aluminum polyphosphate, stabilizers against the influence of weather conditions and aging, emollients (plasticizers) and fungistatic and bacteriostat-. Ingredients, fillers such as barium sulphate, diatomaceous earth, carbon black or floated chalk. The introduction of flame retardants, in particular halogenated paraffins and inorganic salts of phosphoric acid, metaphosphoric acid or polyphosphoric acid, is of particular importance. The production of foams is carried out in such a way that, in a periodically or continuously operating mixer, the described reaction components are mixed with each other in one stage or in several stages and the resulting mixture of whole outside the mixer is subjected to foaming and solidification in forms. In this case, the components of the reaction temperature of about 0-200 ° C, preferably 30-160 ° C can be achieved either by the fact that one or several reaction components are preheated before the mixing process, or heated in a mixing apparatus, or the prepared reaction mixture is heated after mixing . Combinations of one or another variant of the method for adjusting the reaction temperature are also suitable. In most cases, during the reaction itself, sufficient heat is released, so that the reaction temperature after starting the reaction or foaming can rise to a value above 30 ° C. Especially valuable plastics are obtained when curing occurs at temperatures above 20 ° C, in particular 30-100 ° C. With combinations of polyisocyanates with a 10-40% NCO group of solutions of alkali metal silicates without external heat input, so much heat is generated from outside that the water containing it begins to evaporate. Temperatures may be reached inside the foam blocks. Under these conditions, particularly pronounced α-interactions or particularly close bonding between the inorganic and organic polymers occur, so that the materials are obtained as a result, on the one hand, they are hard, but on the other hand highly elastic and resistant to impact. kink Since the amount of heat released during the reaction between the components is not enough, the mixture can be immediately subjected to elevated temperature, e.g., 40-100 ° C. In special cases, it is also possible to wear out at a temperature of atmje up to pressure, so that when the material leaves, the stress relieves from foaming. At elevated temperatures, it is also possible to work with high boiling foaming agents, for example, hexane, di chloroethane, trichlorethane, carbon tetrachloride, light gasolines as additives. Containing water in a mixture can also function as a blowing agent. Further, thin metal powders, such as calcium, magnesium, aluminum, or zinc, due to the evolution of hydrogen with sufficiently alkaline water glass, can serve as a blowing agent, and they simultaneously have a curing and reinforcing effect. Foams can also be produced with inert gases, especially air. For example, one of the two reaction components can be pre-foamed with air and then mixed with the other. It is also possible to achieve a mixture of components, for example, by means of compressed air, so that foam is directly formed, which is then cured when placed in a mold. The properties of the resulting foams, for example, their density in a wet state, depend somewhat on this recipe on the mixing process, for example, the shape and speed of the agitator, the structure of the mixing chamber, etc., as well as on the selected reaction temperature at the start of foaming. The density in the wet state varies from about 0.005 to 0.6 g / cm, most often the density of moist fresh foams is obtained from 0.02 to 0, 4 g / cm. Dried foams can have an open cellular or closed cellular character, most often they have an open cellular character and have densities from 0.01 to 0.2 g / cm. According to a preferred embodiment, the solution of the polyisocyanate in the liquid blowing agent is mixed with an aqueous solution of alkali metal silicate and thus, when the curing agent is foamed. Instead of foaming agents, inorganic or organic finely dispersed hollow bodies can be used to produce foams, like bloated hollow spheres of plastic, straws, etc. Thus, the available pawls can be used in a dry or wet condition, under certain conditions after the compression process or heat treatment, under pressure, as insulating materials, cavity fillers, packaging materials, builders1}} of the first materials with horse resistance. solvent and beneficial combustion behavior. They are also applicable as light structural elements, in the form of a multilayer structure, for example, with metal coating layers, in the construction of houses, the automotive industry. Of particular interest are light inorganic-organic foams produced by the proposed method with an apparent density of 10-80 kg / s. Foam plastics can be obtained in the form of continuous or discontinuous block materials, when produced using a double conveyor belt in the form of laminated or non-sheathed sheet material or also directly at the construction site by mixing. Light construction materials that are especially valuable for the construction sector in the construction sector can be prepared because loading of inorganic granules with low apparent densities, for example, expanded glass, expanded clay (expanded clay), expanded slate (slate) in pumice, etc. . churn along with the specified foams. Thus, it is possible to rationally manufacture elements of walls and facades that, based on the low content of organic parts in all multilayer material according to DIN 4102, reach a class (by burning) non-combustible building materials (A2. Reaction mixtures can also be dispersed in droplet form, for example gasoline , or during free fall, etc., to bring to foaming and curing, and foamed balls are formed. You can also add to the foaming reaction mixtures, while they are still flowable. chemical and / or inorganic, foaming or already foam particles, for example expanded clay,
    expanded glass, wood, microgels, cork, hollow balls of plastics, for example, of vinyl chloride polymers. polyethylene, polystyrenes or foam particles from or from pre-sulfonic, polyepoxides, polyurethanes, polyureas, poly formaldehyde, polyphenol formaldehyde, polyimides, or foaming by shaking these particles in the reaction mixtures, and thus obtaining insulating materials that benefit tny behavior when burning.
    If in a mixture containing, under known conditions, inorganic additives of aqueous solutions of silicates and. hardeners at a given temperature At the same time, a foaming agent, such as (halogen) hydrocarbon, is added at the same time to evaporating or evolving gases, the resulting liquid mixture can be used not only for the manufacture of homogeneous foams or other foamed or non-foamed foam fillers, and it can also be foamed together with canvas, fabric, mesh, structural elements or other permeable foam structures placed in it, while obtaining materiashy are laminated with special properties, such advantageous behavior during combustion are applicable under certain conditions directly as structural elements in the construction sector, in the manufacture of furniture or automotive and aircraft
    The proposed foams can be admixed to the soil in the form of lumps under certain conditions, together with fertilizers and plant means, in order to improve the agrarian consistency of the soil, but water-containing foams can be used as a substrate for propagating sprouts, cuttings and plants or cut flowers. By spraying the mixtures onto impassable or loose areas, such as dunes or swamps (tracts), tangible reinforcement can be achieved, which after a short time is passable or protects against erosion.
    It is of interest to spray the proposed reaction mixtures in case of fires and catastrophes on the protected objects, and the water containing on the surface of the protected body does not drain or cannot evaporate quickly, thereby achieving particularly active protection against burning or heat or radiation, since hardened mixture, pok
    it still contains water, it can be insignificantly heated above 100 ° C, or it absorbs IR or cheek radiation.
    On the basis of a good sprayability of the mixture by the fact that they are sprayed, for example, on fabric, other planes, gratings or only on walls, they can form protective partitions and protective layers during mining, in accidents, etc.
    Foam mixtures can also be used in the construction of above-ground and underground structures, in road construction for the manufacture of walls, seals, seals, plastering, making bases for insulation, finishes, as coating materials for a seamless floor and materials for lining. It is also possible to use them as adhesives or mortars or molding masses (casting slips) under known conditions in a filled form, and inorganic or organic fillers are taken into account.
    Due to the fact that the hardened foams offered, after drying, can have significant porosity, they are suitable as dryers, since they can again absorb water. However, they can also carry biologically active substances or be used as catalysts carriers or as filters and absorbents.
    Foams in the water-containing or dried or impregnated state can be further varnished, metized, coated, laminated, coated, coated on them by spraying, gluing or flocking. Molded articles can be further molded in a water-containing or dried state, for example, by milling, sawing, planing, polishing and other processing methods.
    Examples of polyisocyanates used.
    Example 1. A distillate of an anosine-formaldehyde condensate phosgenation product consisting of 90 wt.% 4,4-diphenyl methane diisocyanate, 8 wt.% 2,4-diphenyl methane diisocyanate, and 2 wt.% 3-core polyphenyl polymethylene polyisocyanates, viscosity at 7 centipoise, at crystalline temperature, partially crystallization; NSO-content 33 wt.%.
    Example 2. So much diisocyanato-diphenylmethane is distilled off from the crude product of the phosgenation of aniline-formhiredehyde condensate, that the residue after distillation at 25 ° C has a viscosity of 50 centipoise (2-part of 68% by weight, 3- part of 16% by weight 7 the part with a higher content of nuclei polyisocyanates 16 wt.% KSO-content 32 wt.%).
    Example 3. Accordingly, the resulting polyisocyanate with a viscosity of 100 centipoise at 25 ° C (2-sod part 59 wt.%, 3-sod part 21.3 wt.% 7 dollars multi-nuclear polyisocyanates 19.0 wt.%, NCO content ; 1.4 wt.%).
    P. 4. Mer. 4. Correspondingly, a paramilitary polyeiocyanate with a viscosity of 200 qaHTHnya3 with (2-sod part 44.3 wt.%, 3-sod part 23.5 wt.%; A fraction of many nuclear polyisocyanates 32.2 wt. %, NCO-content 31.4. Weight.%),
    Example 5. Accordingly, the resulting polyisocyanate with a viscosity at 250–400 centipoise (2-sod part 45 wt.%, 3-sod part 22.3 wt.%; Share, many nuclear polyisocyanates 32.6 wt.%; NCO- content 31.0 wt.%)
    Example 6. Accordingly, the resulting polyisocyanate with a viscosity at 25s 800 centipoise (2-sod part 40.6 wt.%; 3-sod part 27.2 wt.%, The proportion of multi-core polyisocyanates 32.2 wt.%; Ncb content 30.5 wt.%).
    Example 7. Polyisocyanate C 6 and polyisocyanate P 8 are mixed in such a way that a polyisocyanate with a viscosity of 1100 centipoise at 25 s is obtained from them.
    Example 8. Accordingly, the resulting polyisocyanate with a viscosity at 25 s is 1700 centipoise (2-sod part 40.3 wt.%; 3-sod part 34.0 wt.%; Share of many nuclear isocyanates 25.7 wt.%; NCO- content of 30.4 wt.%).
    Example 9. Semi-prepolymer obtained from 1000 parts by weight polyisocyanate P 5 and 15 weight.h. butanediol -
    1,4., ..
    Viscosity at 940 cps; NSO-content of 28.2 wt.%.
    Example 10. A semi-prepolymer obtained from 1000 parts by weight of ziolisocyanate P 5 and 30 parts by weight hexanedol — 1.6 Viscosity at 30,000 centipoise, the NCO content is 27 wt.%.
    Example 11. Semi-prepolymer, irradiated from 1000 ec. polyisocyanate P 5 and 15 web.h, hexanediol 1,6. Viscosity at 1400 centipoise} NCO content of 28.6 wt.%.
    Example 12. Semi-prepolymer, obtained from 1000 parts by weight polyisocyanate P 5 and 30 weight.h. glycerol. Viscosity at 25s 7500 centipoise, NCO content of 26.2 wt.%.
    Example 13. The product of the interaction of 100 weight.h. P 3 with 1 weight.h. water. Viscosity at 19900 Saitipuae; The NCO content is 26.7 wt.%.
    Example 14. The polyisocyanate P 3 is heated for 2 hours at. Get
    polyisocyanate with a viscosity of 1450 centipoise at 25 s and an NCO content of 24.2 wt.%.
    Example 15. Isomers and 80% by weight of 2,4-toluene diisocyanate and 20% by weight of 2,6-toluene diisocyanate are reacted with water under biuretizing conditions. The viscosity at 25 ° C is 6500 centipoise, the NCO content is 32.5 wt.%.
    Example 16. A solid technical residue after distillation, which is obtained by the distillation of technical mixtures of toluylene diisocyanates. NCO-content of 17 wt.%. The monomer content is about 10% by weight.
    Example 17. Liquid technical residue after distillation, which is obtained by distillation of 1,6-hexamethylene diisocyanate. Viscosity at 25 ° C 95 centipoise, NCO content 35% by weight. about
    Example 18. 2250 weight.h. P 17 and 250 weight.h. finely milled P 16 is heated together with stirring for 5 hours at, and P 16 dissolves in P 17. The resulting U 18 polyisocyanate has a viscosity of 800 centipoise with and M CO content of 31.9% by weight.
    Example 19. Received respectively P 18 polyisocyanate from 2000 weight.h. P 17 and 500 weight.h. P 16. Viscosity 1800 centipoise at 25 ° C; The NCO content is 30.6 wt.%.
    P p and measures 20. Received respectively P 18 polyisocyanate from 1750 weight.h. P 17 rt 750 weight.h. P 16. Viscosity 6,200 cps with an NCO content of 29.2 wt.%.
    Examples 1-14. With a constant formulation, which in terms of the composition of the main components, as well as the applied activator, corresponds to Example 1, polyisocyanates of different viscosity and functionality are used and processed under the same conditions. The main recipe is as follows: 250 weight.h. liquid glass based on sodium silicate (48% solids, molar ratio NajO: SiOj, 1: 2, 1.5 parts by weight of stabilizer (polyether polysiloxane). 4 parts by weight of 1-min catalyst (consisting of 75 parts by weight N, N-dimethyl-aminoethanol and 25 parts by weight of diazabicyclo-octane) 100 parts by weight of polyisocyanate (component t), 25 parts by weight of trichlorofluoromethane (component II).
    Components I and 1.1 are mixed, then combined, mixed vigorously with a high-speed mixer for 15 seconds and then poured into paper bags, where the reaction mixture after a short time begins to foam and, under the action of heat, cures into an organic organic foam. Reaction time and
    The physical properties of the foams obtained are presented in Table. one.
    The following symbols are entered:
    tg is the mixing time, the mixing time of the mixture of components I and I;
    1c is the holding time, the time from the beginning of mixing to the beginning of foaming;
    1d setting time, the time from the start of mixing to the beginning of curing;
    tg is the rise time, the time from the start of mixing to the end of the foaming process.
    Bulk density and compressive strength are always determined a day after it is produced,
    As follows from Examples 1-4 of Table 1, the foam mixture weakens (the foam settles), since the viscosity of the polyphenyl-fullmethylene polyisocyanates used is below 400 centipoise at (P 1 - P 4). Schlc-viscous polyphenyl-polymethylene-polyisocyanates P 5 - P 8 give inorganic-organic foams, which, at about the same bulk weight, have the higher limits of compressive strength, as shown by a more fine-pore and more regular pattern of pores (cells), than taller viscous and more highly funciated polyisocyanate applied.
    The advantage of using highly viscous polyisocyanates (P 6 - P 8) is clearly manifested in the TCNL that these polyisocyanates of approximately the same chemical structure give, as well as more low P 5 foams. strata layers with a lower bulk density have significantly higher compressive strengths.
    The products of the interaction of P 5 with insignificant amounts of low molecular weight diols (P 9 - P 11), in which case the viscosity is significantly increased compared with P 5, however, the functionality can only be slightly higher, leading to foams with improved properties.
    Examples 9-11. The properties of foams are dramatically improved if a polyisocyanate is used as a ps-prepolymer (for example P12), in which both the functionality and the viscosity are increased as it is. takes place in example 12.
    Impurities 13 and 14 show that the unsuitable low viscosity polyisocyanate (P 3) itself can be transformed by simple heating (P 14) or by reacting with insignificant amounts of water (P 13) into a highly viscous polyisocyanate from which Inorganic / organic foams are required.
    Examples 15-23. 200 weight.h. liquid glass based on sodium silicate (44% solids, molar ratio of Na,: SiO, j 1: 2), (component, 1.5 parts by weight of stabilizer according to examples 1-14. 2 parts by weight of amine catalyst according to Examples 1-14 are 100 parts by weight of polyisocyanate (P 1 P 8, P 14) (component II) 5 parts by weight of diphenyl cresyl phosphate 40 parts by weight of trichlorofluoromethane.
    0
    The mixing of the components as well as the preparation of foams is carried out according to examples 1-14. The results are presented in table. 2, applied abbreviations in which correspond to such table. 1. In this series of examples it is also clearly shown that polyisocyanates with a viscosity of more than 400 centipoise are superior to the corresponding low molecular weight types. With approximately the same volumetric weight, the resulting inorganic-organic foams receive products that with increasing viscosity of polyisocyanates show higher viscosities, a more regular and thinner cellular structure, as well as higher compressive strength. (Examples are comparative).
    Compared with those listed in table 1
    0 examples are given in table. 2 ne The noplasts are distinguished by higher viscosities. This is explained, in addition to the changed composition of the main components, and additionally jointly used diphenyl cresyl phosphate used as a flame retardant. i
    When using polyisocyanates P 1 - P 4, which have a viscosity below 400 centipoise, if 0 the mixture becomes weaker, these polyisocyanates, although they have more than 2 functions, are unsuitable for the method of the invention due to their low viscosity.
    Polyisocyanates P 5 and P 8, which
    5 have the same kind of chemical structure and, along with slightly increased functionality, are primarily characterized by a viscosity of f / –400 centipoise at 2500, suitable for obtaining inorganic-organic foams. Moreover, as examples 19-22 show, with increasing viscosity of polyisocyanates, foams are obtained with a more regular, highly porous (cellular) structure, as well as with greatly improved compressive strengths with almost the same bulk weight. If Esli compare Example 19 with Example 22, then the compressive strength even doubles.
    Example 23 shows that a low-quality, in itself unsuitable polyisocyanate (P 3) can be converted by heat treatment into a high quality juice suitable according to the invention, which can be processed into a suitable foam plastic.
    Example 24. 200 weight.h. liquid glass based on sodium silicate, according to Example 1.2 part by weight. amine catalyst according to example 1 (component I) 100 weight.h. polyisocyanate P 15, 1 weight.h. stabilizer (prliphiropolyoxane), 10 weight.h. diphenylcresyl phosphate, 40 parts by weight, trichlorofluoromethane (component II).
    The preparation of foams is carried out according to examples 1-14.
    1d 15 s
    H 30 s
    1d 50 s
    tg 60 s
    A highly porous brittle, inorganic-organic foam with a regular cellular structure is obtained, which, in its fresh state, has a bulk weight of 33 kg / m.
    Example 25. 400. weight.h. liquid glass based on sodium silicate according to example 1, 4 weight.h. amine catalyst according to example 1 (component I) 100 weight.h. polyisocyanate P 8,0,5 weight.h. stabilizer according to example 24, 40 weight.h. trichlorofluoromethane (component II).
    The preparation of foams is carried out according to examples 1-14.
    tg 15 s
    t, 45 s
    H 65 s
    tg 115 s
    A solid, inorganic-organic foam with an average pore size and a regular cheissy structure with a bulk weight of 81 kg / m and a subject of compressive strength of 0.6 kgf / cm is obtained. Based on the content of the high inorganic part, this foam has an excellent fire-resistant behavior and can easily be classified as Class B 1 (difficult to ignite) according to DIN 4102.
    Example 26. 100 weight.h. liquid glass based on sodium silicate according to example 1, 2 parts by weight of amine catalyst according to example 1 (component I), 300 parts by weight polyisocyanate P 8, 1 weight.h. stabilizer according to example 24, 20 weight.h. trichlorofluoromethane (component It).
    The preparation of the foam is carried out according to Example 1-14.
    to 15 s
    tR Part 60 from 90 with t
    ts. 95 s
    A highly porous inorganic-organic foam with a regular cellular structure is obtained, which immediately after production has a bulk weight of 12 kg / m and a compressive strength of 0.2 kgf / cm. Because of its low apparent density, this foam is particularly suitable as a cheap insulating foam. 5 Example 27. 200 parts by weight, sodium silicate-based liquid glass according to example 1, 2 parts by weight amine catalyst according to example 1 (component 1) 100 weight.h. Q liisocyanate P 8, 0.5 weight.h. stabilizer according to example 24, 5 weight.h. diphenylcresyl phosphate, 3 weight.h. Chlorinated paraffin mixture 40 wt.h. trichlorofluoromethane (component 1 I), 100 weight.h. 40% aqueous solution of dipotassium hydrophosphate (component tit).
    The components are first mixed well on their own, then vigorously mixed using a high-speed
    0 mixers of component JI are sequentially added to component I and component 111. After 15 minutes of stirring, the reaction mixture is poured into paper bags, where it is
    55 s (calculated from the moment the components are joined) begins to foam and after 135 s (calculated from the moment the components are combined) solidifies into a solid, inorganically .j organic foam with a regular cellular structure and fine pore size. One day after preparation, the volumetric weight and (Compressive strength limit. Bulk weight 37 kg / m) are determined. The npo4HocTk limit in compression is 0.3 kgf / cm.
    The resulting foam is particularly suitable for use as an insulation, in which at the same time good non-combustibility is required. The plates manufactured according to the specified recipe stand the test for burning in the mine according to DIN 4102 and were classified as non-flammable (B1). Examples 28-41. The composition, reaction time, as well as the volume weight and the compressive strength of the obtained inorganic-organic foams are presented in table. 3. The preparation of foams is carried out according to examples 1-14, and the abbreviations used are as shown in Table 2. 1. All the mixtures of substances used are specified in g. Solid inorganic-organic foams with a regular cellular structure and a pore size from medium to
    coarse. with a bulk weight of 120-250 kg / m, which, on the basis of high strength and good behavior during combustion, are particularly well suited
    0 for the manufacture of lightweight, self-supporting, pre-fabricated | 1 "lx building parts with excellent thermal insulation properties.
    Table 1
    irregular
    21P 7 15 45 105 145 30
    22P 8 15 40 90 130 28
    23P 14 15 65 115 130 35 Note
    Continued table. 2
    0.34 Viscous, medium porous, regular
    0.54 Viscous, finely porous, regular
    0,60 V zko-fragile, medium porous, regular
    T and blitz
    O 1) Emulsifier, 50% aqueous solution of sodium sulfate, sulfochlorinated paraffin mixture 2) tj. - tt 3) The volume and weight of the compressive strength were determined after 1 day after shaking foam. 2,185,000 claims A method for producing foams by reacting an aqueous solution of alkali metal silicate with an isocyanate component in the presence of. catalyst and foam stabilizer, characterized in that, in order to improve the physicomechanical properties of the final product, as an isocyanate component. use the product of the phosgenation of an annlin-formaldehyde condensate with a viscosity at 25 ° C equal to 400,922 10,000 cps, preferably 50010000 spe, and with an average functionality equal to more than 2, and the weight ratio of the isocyanate component to the silicate aqueous solution is from 70:30 to 20:80. Sources of information taken into account in the examination 1. Unaccepted for Germany 1770384, cl. 39 in 31/17, published 1971. 2. Unaccepted for Germany No. 2227147, cl. 39 on 31/06, published 1973 (prototype).
    权利要求:
    Claims (2)
    [1]
    Claim
    A method of producing foams by reacting an aqueous solution of an alkali metal silicate with an isocyanate component in the presence of a catalyst and a foam stabilizer, characterized in that, in order to improve the physicomechanical properties of the final product, an aniline-formaldehyde condensate phosgenation product with a viscosity of 25 ° C, equal to 40010000 SPZ, mainly 50010000 SPZ, and with an average functionality equal to more than 2, and the weight ratio of the isocyanate component to an aqueous solution of silicate is from 70:30 to 20:80. Sources of information taken into account during the examination
    1. Unapproved application of Germany No. 1770384, cl. 39 at 8 31/17, published 10 1971 '
    [2]
    2. Unapproved application of Germany
    H 2227147, cl. 39 6 31/06, published in 1973 (prototype).
    类似技术:
    公开号 | 公开日 | 专利标题
    SU850009A3|1981-07-23|Method of preparing foam materials
    US4052347A|1977-10-04|Inorganic-organic compositions
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    同族专利:
    公开号 | 公开日
    AU1217776A|1977-09-22|
    AT352403B|1979-09-25|
    US4129696A|1978-12-12|
    RO70545A|1981-07-30|
    FR2304637A1|1976-10-15|
    DD125759A5|1977-05-18|
    NO760776L|1976-09-21|
    HU176469B|1981-03-28|
    DK121076A|1976-09-21|
    BR7601701A|1976-09-21|
    IT1057350B|1982-03-10|
    JPS51119095A|1976-10-19|
    CH628655A5|1982-03-15|
    ATA201776A|1979-02-15|
    DE2512170B2|1980-11-06|
    DE2512170C3|1981-06-11|
    BE839710A|1976-09-20|
    IE42661L|1976-09-20|
    CA1078984A|1980-06-03|
    GB1477623A|1977-06-22|
    DE2512170A1|1976-09-23|
    PL105039B1|1979-09-29|
    ES446182A1|1977-06-01|
    JPS579373B2|1982-02-20|
    IE42661B1|1980-09-24|
    FR2304637B1|1980-05-30|
    NL7602932A|1976-09-22|
    SE7602706L|1976-09-21|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR1419552A|1958-10-23|1965-12-03|New flame retardant and insulation product, and its manufacturing process|
    FR1362003A|1963-04-13|1964-05-29|Method of manufacturing an adherent insulating material and the product thus obtained|
    AT267888B|1966-07-29|1969-01-27|Marquet & Cie Noel|Process for the production of new polyester-based foams with improved properties|
    GB1186771A|1967-05-12|1970-04-02|Conteki Dev Ltd|Silicious Products|
    US3634342A|1967-08-28|1972-01-11|Martin Marietta Corp|Depottable polyurethane foam|
    US3975316A|1972-05-04|1976-08-17|Thiokol Corporation|Curing liquid polyurethane prepolymers|
    US4072637A|1972-06-14|1978-02-07|Blount David H|Process for the production of polyurethane resins and foams utilizing silico-formic acid|
    DE2310559C3|1973-03-02|1975-09-11|Bayer Ag, 5090 Leverkusen|Foam concrete, a process for its manufacture and its use for the manufacture of building elements|
    DE2325090C3|1973-05-17|1980-11-06|Bayer Ag, 5090 Leverkusen|Process for the production of an inorganic-organic polymer-polysilicic acid composite material in the form of a colloidal xerosol|
    DE2359612C3|1973-11-30|1980-06-19|Bayer Ag, 5090 Leverkusen|Process for the production of inorganic-organic, present as colloidal xerosol, polyurea-polysilicic acid composite material of high strength, elasticity, heat resistance and flame resistance|
    DE2359611C3|1973-11-30|1981-09-17|Bayer Ag, 5090 Leverkusen|Process for the preparation of fillers bound by isocyanate-based resins|
    DE2359606C3|1973-11-30|1980-01-17|Bayer Ag, 5090 Leverkusen|Process for the production of an inorganic-organic polymer-polysilicic acid gel composite material in the form of a colloidal xerosol|
    US4057519A|1974-09-05|1977-11-08|H. H. Robertson Company|Sodium silicate extended polyurethane foam|USRE31340E|1970-09-11|1983-08-09|Process for the production of polysolid|
    US4185147A|1970-09-11|1980-01-22|Blount David H|Production of amino-silicate compounds, condensation resinous products and foam|
    DE2734691A1|1977-08-02|1979-02-08|Bayer Ag|PROCESS FOR THE PRODUCTION OF INORGANIC-ORGANIC PLASTICS|
    DE2734690A1|1977-08-02|1979-02-08|Bayer Ag|PROCESS FOR THE PRODUCTION OF INORGANIC-ORGANIC PLASTICS|
    US4273879A|1978-03-31|1981-06-16|Minnesota Mining And Manufacturing Company|Intumescent fire retardant composites|
    USRE31946E|1979-03-06|1985-07-16|Bergwerksverband Gmbh|Process for consolidating and sealing off geological and artificially deposited rock and earth formations|
    DE2908746C2|1979-03-06|1983-08-11|Bayer Ag, 5090 Leverkusen|Process for consolidating and sealing geological and poured rock and earth formations|
    US4243757A|1979-04-12|1981-01-06|Blount David H|Process for the production of alkali metal-cellulose-silicates and their reaction products|
    US4220757A|1979-04-12|1980-09-02|Blount David H|Process for the production of alkali metal-cellulose-silicates and their reaction products|
    US4273908A|1979-05-07|1981-06-16|Blount David H|Process for the production of poly (polyisocyanate-polyol-alkali metal silicate solid|
    US4242497A|1980-01-10|1980-12-30|Blount David H|Production of amino-silicate compounds, condensation resinous products|
    EP0044832A4|1980-02-04|1982-07-06|David H Blount|Production of polysolid or cellular solid utilizing alkali metal silicates.|
    EP0067990A1|1980-12-30|1983-01-05|BLOUNT, David H.|Process for the production of alkali metal poly ester silicate resinous products|
    DE3227580A1|1982-07-23|1984-01-26|Basf Ag, 6700 Ludwigshafen|STABLE WATER GLASS SOLUTIONS, METHOD FOR THE PRODUCTION AND USE THEREOF FOR ORGANOSILICATE FOAMS AND A PRODUCTION METHOD THEREFOR|
    DE3421086C2|1984-06-06|1987-09-10|Kvt Kunststoffverfahrenstechnik Gmbh & Co|
    DE3421085C1|1984-06-06|1985-10-31|F. Willich GmbH & Co, 4600 Dortmund|Process for solidifying and sealing coal and / or rock and earth formations|
    US4904522A|1988-07-26|1990-02-27|Mobay Corporation|Process for the production of fiberglass mats|
    DE4026702A1|1990-08-24|1992-02-27|Bayer Ag|METHOD FOR PRODUCING HARD POLYURETHANE FOAMS|
    JP2603367B2|1991-01-22|1997-04-23|株式会社常盤電機|Coating composition|
    DE4121153C2|1991-06-26|2000-01-13|Polinvent K F T|Polysilicic acid-polyisocyanate materials, composite materials and foams and a process for their production|
    US5985947A|1998-12-23|1999-11-16|Hagen; Peter|Extruded foamed silicone rubber composition and method for making same|
    KR20040034754A|2002-10-15|2004-04-29|김부남|The manufacturing method of polyurethane sponge mixing activated carbon|
    CA2523469A1|2003-05-15|2004-11-25|Huntsman International Llc|Polyisocyanate-based adhesive formulation for use in sandwich panels|
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    ITMI20061325A1|2006-07-07|2008-01-08|C N R Consiglio Naz Delle Ricerche|AN INORGANIC EXPANDING-BENDING HYBRID MATERIAL WITH DENSITY AND CONTROLLED MORPHOLOGY METHOD FOR ITS PREPARATION AND ITS USE|
    US7678840B2|2006-11-28|2010-03-16|Bayer Materialscience Llc|Reduction of MDI emissions in cavity filling NVH polyurethane foams|
    WO2010102284A2|2009-03-06|2010-09-10|Parker Anthony A|Protein-containing emulsions and adhesives, and manufacture and use thereof|
    CA2753896C|2009-03-06|2018-08-28|Biopolymer Technologies, Ltd.|Protein-containing foams, manufacture and use thereof|
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    US20150044483A1|2011-09-09|2015-02-12|Biopolymer Technologies, Ltd.|Protein-containing adhesives, and manufacture and use thereof|
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    DE102015000393A1|2014-01-21|2015-07-23|Frank Becher|Process for the preparation of closed-cell products with hollow cells, by means of which the pressure in the cells can be increased or reduced in a controlled manner during foaming, and also products which are produced by this process|
    NL2014985B1|2014-06-20|2016-12-06|Ceves-Vergeer B V|Dry mortar mixture with grains of expanded glass.|
    CN106007505B|2016-05-20|2018-01-26|河北建筑工程学院|A kind of polyurethane foamed concrete and preparation method thereof|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE2512170A|DE2512170C3|1975-03-20|1975-03-20|Process for the production of optionally foam-shaped, hard inorganic-organic composite material|
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