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
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4833—Polyethers containing oxyethylene units

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, 2 359 608, 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 the inorganic components, have above all improved fire resistance compared to purely 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 / 0 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 has for its object to avoid the disadvantages described above and to produce inorganic-organic plastics, even with high amounts of organic components, without any problems.
• the final dispersion has a viscosity range of 100-4000 cP before the start of curing at room temperature and consists of 10-50% by weight of inorganic aqueous phase and 90-50% by weight of organic phase.
• the process according to the invention can be carried out continuously or preferably batchwise.
• the stable primary dispersion consisting of polyisocyanate, aqueous basic solution or suspension and, if appropriate, further additives such as activators, emulsifiers and blowing agents prepared and then the addition of the organic compound (component c)) made.
• 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, and the mixing with the organic compound (component c)) takes place continuously in a downstream mixing head.
• the discontinuous variant is recommended when using such organic compounds as component c), which e.g. gel aqueous alkali silicate solutions spontaneously.
• component c organic compounds
• polyisocyanate and e.g. aqueous alkali silicate produced a stable primary dispersion and then added component c).
• Organic compounds according to component c) which do not gel or only very slowly gel aqueous alkali silicates can be used either by the continuous or by the batch process.
• the individual components are mixed, for example, in the order that a spatial and temporal dispersion is first prepared from components a) and b), optionally with the addition of all or part of component d), using a mixing unit and component c) for this dispersion in a spatially and temporally arranged mixing unit, optionally with the addition of all or part of component d).
• 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 ethylene 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-isocyantomethylcyclohexane (DT-AS 1 202 785, US Pat.
• DT-AS 1 202 785 1-isocyanto-3,3,5 trimethyl-5-isocyantomethylcyclohexane
• polyisocyanates prepared by telomerization reactions, as described, for example, in US Pat. No. 3,654,106, Polyisocyanates containing ester groups, as are mentioned, for example, in British Pat. Nos. 965,474 and 1,072,956, in US Pat. No. 3,567,763 and in DT Pat. No. 1,231,688, reaction products of the above-mentioned isocyanates with acetals according to the 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-tclylene 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, Polyisocyanates containing urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups (“modified polyisocyanates").
• TDI 2,4- and 2,6-tclylene diisocyanate as well as any mixtures of these isomers
• CAMDI aniline-formaldehyde condensation and subsequent phosgenation
• carbodiimide groups Polyisocyanates containing urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups
• 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), Car polyisocyanates containing boxylate 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 polyphenyl polymethylene polyisocyanates of how they are produced by aniline-formaldehyde condensation and subse- ß end phosgenation ( "crude MDI") and from the obtainable therefrom by distilling off of two-core products distillation residues in generally have a viscosity between 50 and 50,000 P / 25 ° C, an NCO content of 28-33 weight percent and a functionality> 2.
• basic components are furthermore aqueous basic solutions or suspensions with an inorganic solid content 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.
• aqueous basic solutions or suspensions are often also used 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 glasses”.
• Raw technical solutions can also be used, which can additionally contain, for example, calcium silicate, magnesium silicate, borates and aluminates.
• Preferably, however, 32-54% by weight sodium silicate solutions are used, with a molar ratio Na 2 0 / Si0 2 of 1: 1.6 to 1: 3.3.
• Component c) is to be understood as meaning (preferably liquid at room temperature) organic compounds which, in addition to at least one isocyanate-reactive hydrogen atom, have at least one nonionic-hydrophilic group.
• the nonionic-hydrophilic groups are primarily hydrophilic polyether groups.
• Polyether groups which are composed of ethylene oxide and / or propylene oxide are preferred.
• Suitable organic compounds which, in addition to a hydrogen atom which is reactive toward isocyanate, have at least one nonionic-hydrophilic group are, in particular, polyethers which are made up of alcohols with a functionality of 1-3 and ethylene oxide and / or propylene oxide and have terminal OH groups .
• the hydrophilic center can also be introduced into the organic compound by incorporating a glycol such as tri- and tetraethylene glycol.
• polyether groups produced differently can also have organic compounds are used, provided they contain - in addition to at least one reactive H atom - hydrophilic groups, for example monofunctional polyethers based on monoalcohols and ethylene oxide.
• the proportion of ethylene oxide in the polyether should preferably be at least 10% by weight.
• Nonionic-hydrophilic compounds suitable according to the invention are furthermore polycarbonates based on ethylene glycol, propylene glycol, tetraethylene glycol.
• Formose can also be used here, as it is e.g. in DT-OS 2 639 084, 2 639 083, 2 714 084, 2 714 104, 2 721 186 and 2 721 093.
• compounds are also suitable which have a hydrophilic polyester segment, e.g. Contain tr-ethylene glycol or diethylene glycol and succinic acid or oxalic acid.
• a hydrophilic polyester segment e.g. Contain tr-ethylene glycol or diethylene glycol and succinic acid or oxalic acid.
• Polyethers which are composed of amines with a functionality of 1-4 and ethylene oxide and / or propylene oxide and have terminal OH groups are also particularly suitable for the batch process.
• volatile organic substances are optionally used as blowing agents.
• suitable organic blowing agents are acetone, ethyl acetate, halogen-substituted alkanes such as methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, chlorodifluoromethane, dichlorodifluoromethane, butane, hexane, heptane or diethyl ether.
• a blowing effect can also be achieved by adding at temperatures above room temperature with elimination of Gases, for example nitrogen, decomposing compounds, for example 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 often also 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-ethylmorpholine, 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-3-phenyle
• 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.
• 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.
• 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 can also be used (Emulsifiers and foam stabilizers) can also be used.
• Suitable emulsifiers are, for example, the sodium salts of castor oil sulfonates, sodium salts of sulfonated paraffins or also of fatty acids or salts of fatty acids with amines such as oleic acid diethylamine or stearic acid diethanolamine.
• 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-readable 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 which may be used according to the invention sensors and cell regulators, reaction retarders, stabilizers; Flame retardant substances, plasticizers, dyes and fillers as well as fungistatic and bacteriostatic substances as well as details on the use and mode of action of these additives are in the plastic manual, Volume VII, edited by Vieweg and Höchtlen, Carl-Hanser-Verlag, Kunststoff 1966, e.g. on the p 103 to 113.
• the reaction components are preferably mixed at room temperature.
• dispersions are generally obtained which, with an increasing proportion of organic components and changing the W / O phase structure, undergo unstable dispersion states which, after hardening, can result in disturbances in the structure of the inorganic-organic plastic.
• the process products find the application known for organic-inorganic plastics, e.g. as sound and heat insulation materials, as building material, as concrete and joint sealing compounds.
• Components II and III were premixed.
• Component I was 10 sec. mixed to achieve the primary dispersion with a high-speed stirrer, the mixture component (II + III) was then within 5 seconds. added with stirring. After 20 seconds Total mixing time, the reaction mixture was poured into a paper packet, started after 30 seconds. to foam up and was after 85 sec. stiffens.
• a tough-elastic, inorganic-organic lightweight foam with a bulk density of 48 kg / m and a compressive strength of 0.07 [MPa] was obtained.
• Example 1 A conventional, simultaneous mixing of the three components according to Example 1 leads to a foam which is not practical, with foam disorders and defoamed, wet floor zone.
• Foaming was carried out according to Example 1. The foaming process continued after 28 seconds. on, after 75 sec. the reaction mixture had solidified.
• Example 2 was repeated with an additional 3 g of polyether C 3 in component II.
• a light foam was obtained with the following data:.
• Foaming was carried out according to Example 1.
• a tough, elastic, inorganic-organic lightweight foam was obtained with the values: t R : 20 sec .; t L : 34 sec .; t A : 140 sec .;
• Components II and III were mixed.
• Component I was 10 sec. mixed to achieve the primary dispersion with a high-speed stirrer, the mixture component (II + III) was then within 5 seconds. added with stirring. After 20 seconds Total mixing time, the reaction mixture was poured into a paper packet, started after 37 seconds. to foam up and was frozen after 40 seconds.
• a tough, elastic, inorganic-organic lightweight foam with a bulk density of 48 kg / m 3 and a compressive strength of 0.09 [MPa] was obtained.
• Components II and III were premixed.
• Component I was 10 sec. mixed to achieve the primary dispersion with a high-speed stirrer, the mixture component (II + III) was then within 5 seconds. added with stirring. After 20 seconds Total mixing time, the reaction mixture was poured into a paper packet, started to foam after 34 seconds and was after 90 seconds. stiffens.
• a tough, elastic, inorganic-organic lightweight foam was obtained with a bulk density of 47 kg / m and a compressive strength of 0.10 [MPa].
• a conventional, simultaneous mixing of all three components leads within 20 seconds. to an inhomogeneous, highly viscous, non-foamable reaction mixture.
• Example 19 components I + II were premixed with a high-speed stirrer, component III was then within 5 seconds. added with stirring. After 30 seconds intensive mixing, the reaction mixture was poured into a wooden box mold of approx. 55 dm 3 , started after 48 sec. to foam up and was after 70 sec. stiffens. A hard inorganic-organic foam with a bulk density of 169 kg / m and a compressive strength of 0.57 [MPa] was obtained.
• a dispersion of water glass (50% solids content) and polyisocyanate A 1 is prepared, which is then mixed with a mixture M of the following composition in a second stirrer:
• the product flows are set to the following values: water glass 8000 g / min, polyisocyanate 8040 g / min., 4920 g / min. the mixture M. Both mixing units have stirrers in a 300 ml mixing chamber at 3000 rpm. The promotion takes place via standard gear pumps.
• a uniformly fine-cell foam with a bulk density of 14 kg / m 3 is obtained , which can be produced continuously without difficulty at heights of up to 80 cm and a width of 100 cm.
• Example 24 With product streams of the same size as in Example 24, a dispersion of water glass and isocyanate is first produced in a mixing unit as in Example 24, which is fed to a static mixer and mixed with the mixture M there. An equally good foam is obtained as in Example 24.

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• Chemical & Material Sciences (AREA)
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• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• 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 DE19772734690 patent/DE2734690A1/de not_active Withdrawn
• 1978
  • 1978-07-26 EP EP78100505A patent/EP0000580B1/fr not_active Expired
  • 1978-07-26 DE DE7878100505T patent/DE2860168D1/de not_active Expired
  • 1978-07-28 IT IT50515/78A patent/IT1106860B/it active
  • 1978-08-01 US US05/930,123 patent/US4198487A/en not_active Expired - Lifetime
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