Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
  • C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
• • 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
  • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
  • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
  • C08G18/3895—Inorganic compounds, e.g. aqueous alkalimetalsilicate solutions; Organic derivatives thereof containing no direct silicon-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/775—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur sulfur
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica

Definitions

• Inorganic-organic plastics based on polyisocyanates and aqueous alkali silicate solutions are known; see e.g. DT-OS 1 770 384, 2 227 147, 2 359 606, 2 359 607, 2 359 606, 2 359 609, 2 359 610, 2 359 611, 2 359 612, DT-AS 2 325 090 and 2 310 559.
• plastics can be produced which, due to their inorganic content, have an improved fire resistance, especially compared to pure organic substances, and which, depending on the composition and reaction conditions, can be foamed or non-foamed, hard or soft, brittle or flexible. Due to the great variability of the properties, these inorganic-organic plastics offer a wide range of possible applications.
• the plastics resulting from a W / O type dispersion are particularly interesting. They have high mechanical strengths, even when exposed to moisture, because the hardened, coherent organic phase envelops and thus fixes the likewise hardened aqueous, inorganic, incoherent phase.
• the perfect coherent organic phase of these plastics also depends on the improved fire resistance of such systems due to the amount of water enclosed.
• the invention is based, to avoid the disadvantages described above and to produce inorganic-organic plastics, even with high amounts of inorganic components, the task.
• the final dispersion has a viscosity range of 600-6000 cP before the start of curing at room temperature and consists of 50-90% by weight of inorganic aqueous phase and 10-50% by weight of organic phase.
• the process according to the invention can be carried out continuously or preferably batchwise.
• the stable primary dispersion is first prepared from polyisocyanate, aqueous basic solution or suspension and, if appropriate, further additives, such as activators, emulsifiers and blowing agents, and then the inorganic compound (component c)) is added.
• the primary dispersion is generated in advance in a prechamber in accordance with the discontinuous mode of operation by means of a special mechanical arrangement; the mixing with the inorganic compound (component c)) takes place continuously in a downstream mixing head.
• mixing of the individual components e.g. carried out in the order that first a spatially and temporally from components a) and b), optionally with the addition of all or part of component d), a dispersion is produced with the aid of a mixing unit and to this dispersion in a spatially and temporally then arranged mixing unit, component c), if necessary with the addition of all or a part of component d), is added.
• the discontinuous variant is recommended when using such inorganic compounds as component c), which e.g. gel aqueous alkali silicate solutions spontaneously.
• component c e.g. gel aqueous alkali silicate solutions spontaneously.
• polyisocyanate and e.g. aqueous alkali silicate produced a stable primary dispersion and then added component c).
• Inorganic compounds according to component c) which do not or only very slowly gel aqueous alkali silicates can be used either by the continuous or by the batch process.
• Starting components (component a) to be used according to the invention are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, as described, for example, by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, for example acetylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate and any mixtures of these isomers, 1-isocyanto-3 , 3,5-trimethyl-5-isocyantomethyl-cpclonexan (DT-AS 1 202 785, US Pat.
• acetylene diisocyanate 1,4-tetramethylene diisocyanate
• polyisocyanates containing urethane groups as described, for example, in Belgian patent specification 752 261 or in American patent specification 3 394 164, have acylated urea groups de Polyisocyanates according to polyisocyanates according to DT-PS 1 230 778, polyisocyanates containing biuret groups, such as those in DT-PS 1 101 394 (US Pat. Nos.
• polyisocyanates prepared by telomerization reactions such as are described, for example, in US Pat. No. 3,654,106; polyisocyanates containing ester groups, such as are described, for example, in GB Pat. Nos. 965,474 and 1,072,956, in US Pat. No. 3,567,76 , 3 and in which DT-PS 1 231 688 are mentioned, reaction products of the above-mentioned isocyanates with acetals according to DT-PS 1 072 385, polyisocyanates containing polymeric fatty acid residues according to US Pat. No. 3,455,883.
• 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 the aforementioned polyisocyanates.
• polyisocyanates e.g. 2,4- and 2,6-toluyien diisocyanate as well as any mixtures of these isomers ("TDI"), polyphenyl-polymethylene polyisocyanates, such as those produced by aniline-formaldehyde condensation and subsequent phosgenation ("crude MDI”) and carbodiimide groups, Urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups containing pelyisocyanates ("modified polyisocyanates").
• TDI 2,4- and 2,6-toluyien diisocyanate as well as any mixtures of these isomers
• CAMDI aniline-formaldehyde condensation and subsequent phosgenation
• carbodiimide groups Urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups containing pelyisocyanates
• polyisocyanates containing ionic groups as described in DT-OS 2 227 147, for example sulfonated polyisocyanates (DT-OS 2 227 111, 2 359 614, 2 359 615), polyisocyanates containing carboxylate groups (DT-OS 2 359 613).
• nonionic-hydrophilic polyisocyanates as described in DT-OS 2 325 909, furthermore polyisocyanates containing polar groups according to DT-OS 2 359 608 and phenolic OH groups containing polyisocyanates as described in DT OS 2 359 616.
• polyisocyanates are preferably made from polyphenyl-polymethylene polyisocyanates, such as those produced by aniline-formaldehyde condensation and subsequent phosgenation ('crude MDI'), and from the distillation residues obtainable therefrom by distillation of two-core products, which generally have a viscosity between 50 and 50,000 P / 25 ° C, an NCO content of 28-33 percent by weight and a functionality> 2.
• aqueous basic solutions or suspensions containing are also used as starting components (component b)).
• inorganic solids of 20-80% by weight, preferably 30-70% by weight, especially aqueous alkali silicate solutions or alkaline stabilized silica sols, but also liquid-flowable basic suspensions of finely divided fillers.
• the aforementioned aqueous basic solutions or suspensions are often salted in combination.
• Aqueous solutions of alkali silicates are to be understood as the solutions of sodium and / or potassium silicate in water which are usually referred to as "water glass".
• Raw technical solutions which are e.g. Calcium silicate, magnesium silicate, borates and aluminates can be used.
• the molar ratio Me 2 O / SiO 2 (Me alkali metal, zR Na, K.) Is not critical and can vary within the usual limits; preferably it is 1: 1.6 to 1: 3.3. If the water content of the plastic initially obtained by reaction with the polyisocyanate plays a subordinate role because en does not interfere or because it can be easily removed by drying, then only weakly alkaline sodium silicate can be used, of which, for example, 20-35% by weight .-% solutions prepared. Preferably, however, 32-54% by weight silicate solutions are used which only have sufficient alkalinity to have the viscosity of less than 500 poise required for problem-free processing. Ammonium silicate solutions, for example solutions of guanidine silicate, can also be used, but these are less preferred. It can be real or colloidal solutions.
• concentration mainly depends on the wiped end product.
• Compact or closed-cell materials are preferably made with concentrated silicate solutions, which are adjusted to low viscosity if necessary by adding alkali hydroxide. In this way, 40-70% by weight solutions can be prepared.
• silicate solutions with a 30-35% by weight content are preferred for the production of light-pored foams in order to achieve low viscosities, sufficiently long reaction times and low densities. Even when using finely divided inorganic fillers in larger quantities, silicate solutions with a content of 30-35% are preferred.
• alkali metal silicate solutions which can be used according to the invention can be found in James G. Vail 'Soluble Silicates, their properties and uses', Reinhold Publishing Corporation, New York 1952.
• Flowable inorganic compounds are to be understood as component c), e.g. - In extreme cases - water or water-insoluble or sparingly soluble inorganic compounds which are brought into a flowable state and which have at least 50% by weight of a particle size of less than 50 microns (preferably 50% by weight of less than 10 microns).
• Inert mineral fillers or also hydraulic mineral binders are particularly suitable here, in particular aqueous suspensions of fillers which have a solids content of between 20 and 80% by weight. If the dry fillers already meet the particle size criteria according to the invention (at least 50% by weight less than 50 microns), they can be mixed directly with water to form a suspension. If the particles are coarser, an aqueous coarse suspension of the fillers can also be converted into a fine suspension usable according to the invention by known methods of wet grinding.
• Particularly preferred aqueous suspensions are those which are stable to sedimentation and show viscous, rapid flow behavior, as is known, for example, from paper coating slips. To produce such filler suspensions, it is therefore advantageous to use the methods known for the preparation of such coating slips.
• Suspensions which are produced with the addition of 0.05 to 20% by weight, based on filler, of one or more of the additives listed under 4.5 and 6 are particularly preferred. At the same time, although less economical from the point of view of economy, the use of surface-modified and thus hydrophilized fillers is, which generally eliminates the need for additives.
• the filler suspension is stabilized by organic additives, its amount should not exceed 5%, based on filler, in order not to deteriorate the fire behavior of the inorganic-organic plastics.
• suspensions contain additives according to 4 and / or 5. and / or 6 and are additionally produced according to the criteria mentioned under 1 and 3, this results in outstanding sedimentation-stable suspensions with flow behavior matched to the processing process.
• fillers are preferably used which have at least 90% by weight of a particle size of less than 20 microns and at least 50% by weight of a particle size of less than 10 microns.
• the filler suspension can also be prepared immediately before the addition, e.g. by metering dry fillers and water into a feed line to the mixing room in which the polyisocyanate is mixed with aqueous alkali silicate and by means of a mixing device, e.g. a screw within this feed line, the aqueous filler suspension is generated in situ.
• a mixing device e.g. a screw within this feed line
• hydraulic binders in particular cement
• cement generally requires suspension in water or aqueous alkali silicate immediately before processing with the isocyanate component, so that the setting process and any gelation process possibly caused by cement expediently take place in the finished plastic.
• the filler suspensions used preferably have a viscosity above 100 cP in order to ensure rheological behavior which is favorable for processing. On the other hand, they should be easy to flow and should in no way have crumbly consistency. A viscosity of 10,000 cP is preferably not exceeded. A good and very intimate relationship Mixing with the polyisocyanate in conventional processing equipment should be ensured. On the other hand, the content of fillers in the aqueous suspension should be as high as possible in order not to introduce more water than is absolutely necessary into the plastic. Depending on the particle size and the shape of the filler particles, the filler concentration is between 20 and 80%. A content of 30-70% is preferred. Lower concentrations generally have to be chosen if non-spherical fillers are also used, such as asbestos, talc, clays or special iron oxides. Component c) can also be identical to component b) in some cases.
• volatile organic substances are optionally used as blowing agents.
• organic blowing agents come e.g. Acetone, ethyl acetate, halogen-substituted alkanes such as methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, chlorodifluoromethane, dichlorodifluoromethane, butane, hexane, heptane or diethyl ether are also suitable.
• a blowing effect can also be achieved by adding compounds which decompose at temperatures above room temperature with the elimination of gases, for example nitrogen.
• Azo compounds such as azoisobutyronitrile can be achieved.
• the water contained in the aqueous basic solution or suspension can also take on the function of the blowing agent.
• Fine metal powders e.g. Calcium, magnesium, aluminum or zinc serve as a blowing agent through the development of hydrogen with sufficient alkaline water glass, while at the same time exerting a hardening and strengthening effect.
• catalysts are also often used.
• Suitable catalysts to be used include those of the type known per se, e.g. tertiary amines, such as triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholirl, N-cocomorpholine, N, N, N ', N'-tetramethyl-ethylenediamine, 1,4-diaza-bicyclo- (2.2 , 2) octane, N-methyl-N'-dimethylaminoethyl piperazine, N, N-dimethylbenzylamine, bis (N, N-diethylaminoethyl) adipate, N, N-diethylbenzylamine, bentamethyldiethylenetriamine, N, N-dimethylcyclohexylamine , N, N, N ', N'-tetramethyl-1,3-butanediamine, N, N-dimethyl-ß-
• Tertiary amines which have hydrogen atoms active against isocyanate groups are e.g. Triethanolamine, triisopropanolamine, 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 those e.g. in German Patent 1,229,290, in question, e.g. 2,2,4-trimethyl-2-silamorpholine, 1,3-diethylaminomethyl-tetramethyldisiloxane.
• Suitable catalysts are also nitrogen-containing bases such as tetraalkylammonium hydroxides, alkali metal hydroxides such as sodium hydroxide, alkali phenolates such as sodium phenolate or alkali metal alcoholates such as sodium methylate. Hexahydrotriazines can also be used as catalysts. According to the invention, organic metal compounds, in particular organic tin compounds, can also be used as catalysts.
• Preferred organic tin compounds are tin (II) salts of carboxylic acids such as tin (II) acetate, tin (II) acetate, tin (II) ethylhexoate and tin (II) laurate and the dialkyltin salts of carboxylic acids, such as e.g. Dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate or dioctyltin diacetate.
• carboxylic acids such as e.g. Dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate or dioctyltin diacetate.
• the catalysts are generally used in an amount between about 0.001 and 10% by weight, based on the amount of isocyanate.
• surface-active additives emulsifiers and foam stabilizers
• the emulsifiers are e.g. the sodium salts of castor oil sulfonates, sodium salts sulfonated paraffins or also of fatty acids or salts of fatty acids with amines such as oleic acid diethylamine or stearic acid diethanolamine in question.
• Alkali or ammonium salts of sulfonic acids such as dodecylbenzenesulfonic acid or dinaphthylmethanesulfonic acid or also 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 is linked to a polydimethylsiloxane radical. Such foam stabilizers are e.g. in U.S. Patent 2,764,565.
• reaction retarders e.g. acidic substances such as hydrochloric acid or organic acid halides
• cell regulators of the type known per se such as paraffins or fatty alcohols or dimethylpolysiloxanes as well as pigments or dyes and flame retardants of the type known per se, e.g. Tris-chloroethyl phosphate or ammonium phosphate and polyphosphate, inorganic salts of phosphoric acid, chlorinated paraffins, further stabilizers against aging and weather influences, plasticizers and fungistatic and bacteriostatic substances, fillers such as barium sulfate, diatomaceous earth, soot 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 fungistatic and bacteriostatic substances, and details on the use and action of these additives are given in the Plastics Manual, Volume VII by Vieweg and Höchtlen, Carl-Hanser-Verlag, Kunststoff 1966, e.g. on pages 103 to 113.
• the mixing of the reaction components is preferably carried out at room temperature.
• fillers which are preferably used as aqueous suspensions by the batch process according to the invention since they partially contain aqueous alkali silicates. Gelling spontaneously are: calcium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, chalk, lime, dolomite, calcium sulfate, gypsum and anhydride.
• fillers which can be mixed both by the batch and the continuous process are those which do not or only slowly gel aqueous alkali silicates and which are therefore suspended as an aqueous suspension or in aqueous alkali silicate, are used in the process according to the invention.
• Examples include: iron oxides, aluminum oxides, quartz powder, clays, asbestos, glasses in powder form, silicate minerals, and water cements such as red ribbon cement, fast-setting cement or alumina cement. From the quantitative ratios of 50-90% by weight of inorganic-aqueous phase and 10-50% by weight of organic phase, it can be seen that the quantitative ratio is not critical for the production of such plastics according to the invention.
• inorganic substances introduced using conventional mixing techniques, can initiate segregation processes and thereby prevent the production of technically useful inorganic-organic plastics. It is believed likely that such additives will gel the inorganic phase and / or that the organic and inorganic phase will not mix sufficiently due to the premature crosslinking reaction with the polyisocyanate.
• plastics according to the invention including foams, open up new possibilities in building construction and civil engineering as well as in the manufacture of finished parts and elements.
• Examples of possible applications include the manufacture of convertible elements in prefabricated buildings, lost formwork, roller shutter boxes, window sills, railroad and subway sleepers, curbs, stairs, the foaming of joints and the back-foaming of ceramic tiles.
• the foam concrete can also be used advantageously to bind gravel, marble, etc. You can get decorative panels such as those used as facade elements.
• Components II and III were premixed in accordance with Example 5 and subsequently quickly stirred into component I within 5 seconds. After 20 seconds of stirring, a highly viscous, non-pourable reaction mixture was obtained which did not foam. The solidified product was sandy and crumbly.
• Example 8 If the components from Example 8 were mixed at the same time, a highly viscous, non-pourable reaction mixture without foaming tendency was obtained after 30 seconds of stirring.

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• Chemical Kinetics & Catalysis (AREA)
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• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Polyurethanes Or Polyureas (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 1977
  • 1977-08-02 DE DE19772734691 patent/DE2734691A1/de not_active Withdrawn
• 1978
  • 1978-07-26 DE DE7878100504T patent/DE2860257D1/de not_active Expired
  • 1978-07-26 EP EP78100504A patent/EP0000579B1/fr not_active Expired
  • 1978-07-31 IT IT50543/78A patent/IT1105389B/it active
  • 1978-08-01 JP JP9324278A patent/JPS5428398A/ja active Granted
  • 1978-08-01 US US05/930,128 patent/US4276404A/en not_active Expired - Lifetime

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