EP0055256A1 - Verfahren zur herstellung von polyisocyanat-polyester-silikat-kunststoffen - Google Patents

Verfahren zur herstellung von polyisocyanat-polyester-silikat-kunststoffen

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Publication number
EP0055256A1
EP0055256A1 EP81900762A EP81900762A EP0055256A1 EP 0055256 A1 EP0055256 A1 EP 0055256A1 EP 81900762 A EP81900762 A EP 81900762A EP 81900762 A EP81900762 A EP 81900762A EP 0055256 A1 EP0055256 A1 EP 0055256A1
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weight
component
water
polyisocyanate
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French (fr)
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David H. Blount
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Classifications

    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • 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
    • C08G18/088—Removal of water or carbon dioxide from the reaction mixture or reaction components
    • C08G18/0885—Removal of water or carbon dioxide from the reaction mixture or reaction components using additives, e.g. absorbing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
    • C08G18/4692—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing silicon
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/68—Unsaturated polyesters
    • 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

Definitions

  • a polyisocyanate is reacted with an unsaturated polyester containing a vinyl, monomer and a water-binding agent, then cured with water, containing an oxidated silicon compound and an initiator such as peroxide to produce a solid or cellular solid inorganic-organic plastic.
  • This invention relates to a process for the production of a polyisocyanate-polyester-silicate which has high strength, elasticity, wear resistance, good thermo stability and good fire-resistant characteristics.
  • This inorganic-organic plastic may be produced as a solid or a. cellular solid.
  • the solid inorganic-organic plastic has the physical properties similar to polyester plastics such as high strength, wear resistance and water resistance, but is less expensive due to the high percentage of the water-binding agent that may be used. Its fire resistant characteristics has been greatly improved.
  • the cellular solid inorganic-organic plastic has high strength and rigidity, but has elasticity, good wear resistance, water resistance good thermal- and sound insulation properties similar to the polyurethane rigid foams, but is less expensive, due to the high percentage of the unsaturated polyester resin and water-binding agent used. It has much improved flame-resistant characteristics and water-resistant characteristics.
  • the polyisocyanate-polyester-silicate plastics which are produced by the process of this invention are characterized by high strength, elasticity, dimensional stability and flame resistance. They are produced by mixing: (a) an organic polyisocyanate, preferably aromatic or polyisothiocyanate; (b) an unsaturated polyester resin (a solution of an unsaturated linear polymer and a liquid monomer that is capable of copolymerizing with the linear polymer);
  • an initiator such as an organic peroxide
  • the proportion, by weight, of component (a) to component (b) is preferably from 70:30 to 20:80.
  • the quantity of component (c) needs to be only a catalytic amount which varies with each initiator.
  • the quantity of component (d) may vary greatly from 0% up to 200%, by weight, based on components (a) , (b) and (e) .
  • the quantity of component (e) may vary greatly from 10% to 100%, by weight based on components (a) and (b) .
  • novel inorganic-organic plastics are produced when a curing agent such as water containing an oxidated silicon compound is combined with a mixture of:
  • Any suitable organic polyisocyanate or polyisothiocyanate may be used. It is generally preferred to use commercially readily available polyisocyanates, e.g., tolylene-2,4- and -2,6-diisocyanate and any mixtures of these isomers, (“TDI”) , polyphenyl-polymethylene-isocy- anates obtained by aniline-formaldehyde condensation followed by phosgenation (“crude MDI”) , and polyisocyanates which contain carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups, imide groups or biuret groups, ("modified poly isocy-anates").
  • TDI tolylene-2,4- and -2,6-diisocyanate and any mixtures of these isomers
  • CAMDI polyphenyl-polymethylene-isocy- anates obtained by aniline-formaldehyde condensation followed by phos
  • Suitable organic polyisocyanates may be used according to the invention, including aliphatic, cycloali phatic, araliphatic, aromatic and. heterocyclic polyisocyanates such as those descrived, e.g., by W.
  • perchlorinated arylpolyisocyanates such as those described, e.g., in German Auslegeschrift No. 1,157,601; polyisocyanates which contain carbodiimide groups as described in German Patent No. 1,092-007; the diisocyanates described in U. S, Patent No. 3,492,330; polyisocy.anates which contain allophanate groups as described, e.g., in British Patent No. 994,890, in Belgian Patent No. 761,626 and in published Dutch Patent Application No. 7,102-524; polyisocyanates which contain isocynurate groups as described e.g., in German Patents Nos.
  • polyisocyanates prepared by telomerization reactions as described e.g., in 3elgian Patent No. 723,640, polyisocyanates which contain ester groups such as those mentioned, e.g., in British Patents Nos. 956,474 and 1,086,404 and in U. S. Patents Nos. 3,281,378 and 3,567,763, and reaction products of the above-mentioned isocyanates with acetals according to German Patent No. 1,072,385.
  • distillation residues which are obtained from the commercial production of isocyanates and still contain isocyanate groups may also be used, optionally dissolved in one or more of the above-mentioned polyisocyanates. Mixtures of the above-mentioned polyisocyanates may also be used.
  • Organic polyisocyanates wich are modified with ionic groups, for example, with carboxyl and/or carboxylate groups and/or sulphonic acid groups and/or sulphonate or sulphonate groups may be used with the above-mentioned organic polyisocyanates.
  • a certain proportion of non-ionic hydrophilically-modified organic polyisocyanates may, of course, also be included.
  • Reaction products of from 50 to 99 mols of aromatic diisocyanates with from 1 to 50 mols of conventional organic compounds with a molecular weight of, generally, from about 400 to about 10,000 which contain at least two hydrogen atoms capable of reacting with isocyanates may also be used.
  • organic polyhydroxyl compounds in particular compounds which contain 2 to 8 hydroxyl groups, e.g., polyesters, polyethers, polythioethers, polyacetals, polycarbonates or polyester amides containing at least 2, generally from 2 to 8, but preferably 2 to 4, hydroxyl groups of the kind known for producing homogenous and cellular polyurethanes.
  • the hydroxyl group containing polyesters may be, for example, reaction products of polyhydric alcohols, preferably dihydric alcohols, with the optional addition of trihydric alcohols; and polybasic, preferably dibasic carboxylic acids.
  • polyhydric alcohols preferably dihydric alcohols, with the optional addition of trihydric alcohols
  • polybasic, preferably dibasic carboxylic acids instead of the free polycarboxylic acids, the corresponding polycarboxylic. acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or their mixtures may be used for preparing the polyesters.
  • the polycarboxylic. acids may be aliphatic, cycloaliphatic, aromatic and/or heterocyclic and may be substituted, e.g., with halogen atoms and my be unsaturated.
  • Examples include: succinic acid, adipic acid, suberic acid, azelaic acid, phthalic acid, sebacic acid, isophthalic acid, trimellitic acid, phthalic acid anhydride, tetrahydrophthalic acid anhydride, tetrahydrophthalic acid anhydride, hexahydroththalic acid anhydride, tetrachlorophthalic acid anhydride, endomethylene tetrahydrophthalic acid anhydride, gl ⁇ taric acid anhydride, maelic acid,maleic acid anhydride, fumari ⁇ acid, dimeric and trimeric fatty acids such as oleic acid, optionally mixed with monomeric fatty acids, dimethyl terephthalate and bis-glycol terephthalate.
  • Any suitable polyhydric alcohol may be used such as, for example, ethylene glycol; propylene-1, 2- and -1,3-glycol; butylene-1, 4- and -2,.3-glycol; hexane-1, 6-diol; octane 1,8-diol; neopentyl glycol; cyclohexanedimethanol- (1/ 4-bis-hydroxymethycyclohexane) ; 2-methyl-propane-1, 3-diol; glycerol; trimethylol propane; hexane-1, 2-6-triol; butane-1, 2, 4-triol; trimethylol ethane; pentaerythritol; quinitol; mannitol and sorbitolmethyglycoside; diethylene glycol; triethylene glycol; tetraethyleneglycol; polyethylene glycol ⁇ ; dipropylene glycol; polypropylene glycols; dibut
  • the polyethers with at least 2, generally from 2 to 8, and preferably 2 to 3, hydroxyl groups, used according to the invention, are known and may be prepared, e.g., by the polymerization of epoxides, e.g., ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin, each with itself, e.g., in the presence of BF 3 , or by addition of these epoxides, optionally as mixtures or successively to starting, components which contain reactive hydrogen atoms such as alcohols, or amines, e.g., water, ethylene glycol, propylene-1, 3- or -1,2-glycol, trimethylol propane 4,4 ' -dihydroxydiphenylpropane, aniline, ammonia, ethanolamine or ethylenedi-amine.
  • epoxides e.g., ethylene oxide, propylene oxide, butylene
  • Sucrose polyethers such as those described, e.g., in German Auslege- schriften Nos. 1,176,358 and 1,064,938, may be used according to the invention. It is frequently preferred to use polyethers which contain predominantly primary OH groups (Up to 90% by weight, based on the total OH group content of the polyether). Polyethers modified with vinyl polymers such as those which may be obtained by polymerizing styrene or acrylonitrile in the presence of polyethers (U. S. Patent Nos. 3,383,351; 3,523,093 and 3,110,695 and German Patent No. 1,152,536), and polybutadienes which contain OH groups are also suitable.
  • polythioethers are meant, in particular the condensation products of thiodiglycol with itself and/or with other glycols, dicarboxylic acids, formaldehyde, aminocar- boxylic acids or amino alcohols.
  • the products obtained are polythio-mixed ethers, polythioether esters or poly thioether ester amides, depending on the co-component.
  • the polycarbonates with hydroxyl groups used may be of the known kind, e.g., those which may be prepared by reacting diols, e.g., propane-1, 3-diol; butane-1,4- diol and/or hexane-1, 6-diol, or diethyleneglycol, triethylene glycol or tetraethylene glycol, with diarylcarbonates, e.g., diphenylcarbonate or phosgene.
  • diols e.g., propane-1, 3-diol
  • butane-1,4- diol and/or hexane-1, 6-diol or diethyleneglycol, triethylene glycol or tetraethylene glycol
  • diarylcarbonates e.g., diphenylcarbonate or phosgene.
  • the polycetals used may be, for example, the compounds which may be obtained from glycols,. e.g., diethy lene glycol, triethylene glycol, 4,4 '-dihydroxydiphenyl- dimethylmethane, hexanediol, and formaldehyde.
  • Polyacetals suitable for the invention may also be prepared by the polymerization of cyclic acetals.
  • the polyester amides and polyamides include, e.g., the predominantly linear condensates obtained from polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyvalent saturated and unsaturated amino alcohols, diamines, polyamines and mixtures thereof.
  • Polyhydroxyl compounds which already contain urethane or urea groups, modified or unmodified natural polyols, e.g., castor oil, carbohydrates and starches, may also be used. Additional products of alkylene oxides with phenolformaldehyde resins or with urea-formaldehyde resins are also suitable for the purpose of the invention.
  • the polyi ⁇ ocy-anate or the prepolymer which contains NCO groups has a viscosity above 2000 cP at 25 C, it may be advantageous to reduce the viscosity thereof by mixing it with a low-viscosity organic polyisocyanate and/or an inert blowing agent or solvent.
  • Any suitable unsaturated polyester resin may be used according to the invention. It is generally preferred to use commercially readily available unsaturated polyester polymers which usually contain a polymerable organic compound and a catalyst to catalyze the initiator (Component e) .
  • unsaturated polyester polymers and/or resins are well known in the arts, and a detailed description of their production will not be given in this Specification. Suitable unsaturated polyester polymers and/or resins are described, e.g., by Brage Golding, in Polymers and Resins, 1959, published by the Van Nostrand Company, Inc., Princeton, New Jersey, Toronto, London and New York, pages 283 to 313.
  • polyester, polyester resin or unsaturated polyester resin technically refer to a solution of an unsaturated linear polymer in a liquid monomer that is capable of copolymerizing with the linear polymer.
  • Most polyester resins consist of a solution of an allyl resin, prepared, for example, from propylene glycol, maleic acid, and adipic acid, or from diethylene glycol, tetrahydrophthalic anhydride and fumaric acid, in 30% of its weight of styrene.
  • An inhibitor such as quaternary ammonium salt, is added to prevent polymerization before use.
  • an initiator such as a perioxide initiator, e.g., benzoyl peroxide or t-butylhydroperoxide together with a catalyst such as cobalt or managanese salt as a promoter, is added.
  • a perioxide initiator e.g., benzoyl peroxide or t-butylhydroperoxide together with a catalyst such as cobalt or managanese salt as a promoter
  • a catalyst such as cobalt or managanese salt as a promoter
  • Reagents that add to the double bond of other ⁇ , ⁇ -unsaturated acids also add to maleic and fumaric acids and their derivatives. ⁇ , ⁇ -unsaturated acids are readily available.
  • the most important ⁇ , ⁇ -unsaturated compounds from a technical viewpoint are acrylonitrile, methyl acrylate and methyl methacrylate.
  • the ⁇ , b -unsaturated acids are usually made by the oxidation of an ⁇ , ⁇ -unsaturated aldehyde.
  • ⁇ , ⁇ -unsaturated esters and nitriles react with these reagents with even greater ease and ⁇ , ⁇ -unsaturated acids, especially when the reaction is catalyzed by bases.
  • the ⁇ -aryl-substituted ⁇ , ⁇ -unsaturated acids may be obtained by the Perkin Synthesis (an aldol-type addition of anhydrides to aromatic aldehydes).
  • ⁇ , ⁇ -unsaturated acids are described, e.g. , in Textbook of Organic Chemistry by Carl R. Noller and published by W. D. Saunders Co., Philadelphia and London, 1966, pages 202, 463, 618 and 619.
  • an unsaturated polyester resin will be used, that is, a solution of an unsaturated linear polymer in a liquid monomer that is capable of copolymerizing with the linear polymer.
  • the unsaturated polyester resins are also known as contact and low-pressure laminating resins.
  • the polyester resin is usually a linear, unsaturated polyester and the combination of the unsaturated ester and the unsaturated vinyl-type monomer, i.e., the final product, is an unsaturated polyester resin.
  • Long-chain unsaturated polyester resins may be made from dibasic acids and dihydric alcohols. Either the dibasic acid or the dihydric alcohol may be unsaturated. Usually a combination of saturated and unsaturated dibasic acids and dihydric alcohols is used to produce the unsaturated polyester resin. Either or both of the dibasic acid and dihydric alcohol may be unsaturated. Instead of the dibasic acids, the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols, or their mixtures, may be used for preparing the unsaturated polyester resins.
  • Suitable dibasic acids may be aliphatic, cycloaliphatic, aromatic and/or heterocyclic and may be substituted, e.g., with halogen atoms. Examples of dibasic acids are listed with the polycarboxylic acid in Component (a) . Any suitable unsaturated dibasic acid may be used such as maleic acid, maleic acid anhydride, fumaric acid, itaconic acid and mixtures thereof.
  • Polymerable oils may also be utilized in the production of unsaturated polyester resins.
  • Polymerable oils include, but are not limited to, unsaturated fatty acids (or their esters), tung oil, linseed oil, heated linseed oil, soya bean oil, dehydrated castor oil and mixtures thereof.
  • Other oils such as castor oil, tall oil, cottonseed oil, sunflower oil, fish oil, perilla oil, oiticica oil or safflower oil may be utilized with unsaturated polycarboxylic acid, carboxylic acid anhydrides and polyhydroxyl compounds.
  • Suitable dihydric alcohols are listed in Component (a) in the list of polyhydric alcohols.
  • Saturated glycols such as ethylene glycol, propylene glycol and diethtlene glycol are usually used with the unsaturated dibasic acids.
  • the unsaturated polyester resins may contain free hydroxyl groups and/or carboxyl groups may be used in this invention.
  • Suitable unsaturated alcohols such as allyl alcohol may be reacted with dibasic acids such as phthalic anhydride, succinic acid, maleic acid, maleic acid anhydride, itaconic acid and fumaric acid to produce allyl esters which may be polymerized alone or with--other polymerizing monomers. Allyl esters such as diethylene glycol bis (allyl carbonate), diallyl maleate, diallyl fumarate, diallyl phthalate, diallyl benzene phosphonate, allyl itacontate, and methallyl methacrylate may be used in this invention.
  • Triallyl cyanurata may be reacted with unsaturated polyester resins to produce resins and may be used as the polymerizing monomer.
  • allyl-type alcohols which are alcohols having a double bond of aliphatic character between two carbon atoms, one of which in turn is attached directly to an alcoholic hydroxyl group, as represented by the general structural formula: Alcohols embodying this structure may properly be termed "beta, gamma-olefinic monohydric alcohols.” Allyl-type alcohols, having a terminal methylene group attached by an olefinic double bond to a carbon atom, which is attached directly to a saturated carbinol carbon atom, are represented by the formula:
  • Allyl-type alcohols include, but are not limited to, allyl alcohol, methallyl alcohol, ethallyl alcohol; chloroallyl alcohol, buten 1-ol-3; penten-1-ol-3; hexen-1-ol-3; 3-methyl-buten-1-ol-3; 3-methyl-penten-1-ol-3; 2-methyl-buten-1-ol-3; 2-methyl-penten-1-ol-3; 2, 3-dimethyl-buten-1—ol-3; hepten-1 ol 3 etc. Any suitable polymerizing monomer may be used with the unsaturated polyester resin such as, but not limited to, vinyl monomers, triallyl cyanurate, allyl esters and mixtures thereof.
  • Styrene is the preferred polymerizing monomer and may be used alone or in combination with vinyl toluene, acrylic and methacrylic esters, and vinyl acetate.
  • vinyl monomers may be used, such as acrylic acid compounds and esters, vinyl toluene, divinyl benzene, acrylonitrile, methacrylonitrile, etc.
  • Inhibitors such as p-tert-butyl catechol, hydro-quinone, p-nitroso .dimethjrianiline, or similar compound, which will increase the lifetime of the unsaturated polyester resin, may be added to the unsaturated polyester resin.
  • Activators and promoters used in conjunction with the initiators such as cobalt, in the form of its ethyl hexan ⁇ ate or naphthenate salt, is a good, generalpurpose activator for use with ketone peroxides, which may be added to the unsaturated polyester resin. Concentrations as low as 30 ppm of cobalt metal will activate a system. Other activators may be added to the unsaturated polyester resins such as tertiary dialkyl aryl amines, e.g., diethyl aniline, and aliphatic thiols, e.g., lauryl mercaptan when acyl peroxides are used.
  • Any suitable initiator which will promote the copolymerization of a aolution of an unsaturated linear polymer in a liquid monomer may be used in this invention.
  • the controlled polymerization of an unsaturated polyestermonomer mixtures to yield fully cured solids usually requires the use of an initiator.
  • the unsaturated polyester monomer may be cured by the polyisocyanate. and water when an excess of polyisocyanate is used, but it is preferable to use an initiator to cure unsaturated polyester resin.
  • Any suitable free-radical initiator such as peroxides, azo compounds, alkali metal sulfates, ammonium persulfate and mixtures thereof, may be used.
  • Thermal arid photopolymerization may be used in certain cases.
  • Suitable organic peroxide initiators include, but are not limited to, acetyl benzoyl peroxide, peracetic acid, methyl ethyl ketone peroxide, cyclohexanone peroxide, cyclo hexyl hydro peroxide, 2, 4-dichlorobenzoyl peroxide, cumen hydroperoxide, tert-butyl hypoperoxide, methyl amyl ketone peroxide, lauroyl peroxide, benzoyl peroxide, tert-butyl perbenzoate, di-tert-butyl diperphthalate and mixtures therof.
  • Promoters used with acyl peroxide include tertiary dialkyl aryl amines, such as diethyl aniline and aliphatic thiols, as, for example, lauryl mercaptan. Con centrations used are most often in the range of 0.05% to 0.5% of active substances. Promoters usually are strong reducing agents and initiators are strong oxidizing agents.
  • Suitable alkali metal persulfates include potassium and sodium persulfate. Redox systems may also be utilized in this invention.
  • Water-binding components may be used according to the invention which include organic or inorganic water-binding substances which have, first, the ability to chemically combine, preferable irreversibly, with water and, second, the ability to reinforce the polyisocyanate-polyester-silicate plastic and products of the invention.
  • the most preferred water-binding component of the invention holds the water chemically bound until heated sufficiently as in a fire. Thus, in a fire, the water is released and extinguishes the fire.
  • water-binding component is used herein to identify a material, preferably granular or particulate, which is sufficiently anhydrous to be capable of absorbing water to form a solid or gel such as mortar or hydraulic cement.
  • This component may be a mineral or compound which is anhydrous, such as CaO and CaSO 4 , but may exist as a partial hydrate.
  • the water-binding components preferably used are inorganic materials such as hydraulic cements synyhetic anhydrite, gypsum or burnt lime. It is preferred that the water-binding component contain an oxidated silicon compound or that one should be added with the component.
  • Suitable hydraulic cements are, in particular, Portland cement, quick-setting cement, blast-furnace Portlanc cement, mild-burnt, cement, sulphate-resistant cement, brick cement, lime cement, gypsum cement, pozzolan cement and calcium sulphate cement.
  • any mixture of fine ground lime, alumina and silica that will set a hard product by admixture of water, which combines chemically with the other ingredients to form a hydrate may be used.
  • the most preferred forms of water-binding agents to be used according to the invention are those materials which are normally known as cement.
  • Component (e) contains the curing agent and/or activators :
  • alkali metal silicate such as sodium and/or potassium silicate
  • Crude commercial alkali metal silicate may contain other substances, e.g., calcium silicate, magnesium silicate, boarates or aluminates and may also be used.
  • the curing agent contains 0.001% to 10% by weight of an activator (catalyst) such as: (a) tertiary amines, e.g., triethylamine, tributylamine, N-methyl-morpholine;
  • an activator such as: (a) tertiary amines, e.g., triethylamine, tributylamine, N-methyl-morpholine;
  • N-cocomorpholine N,N,N' , N' -tetramethyl ethylenediamine; 1 , 4-diazo-biscycle- (2,2,2) -octane; N-methyl-N' dimethyla minoethyl piperazine; N,N-dimethylbenzyl amine; bis (N, N—diethylaminoethyl)- adipate; N, N-diethylbenzylamine;pentameth yldiethylenetriamine; N, N-dimethyl- cyclohexylamine; N,N,N ' ,N ' -tetramethyl- 1, 3-butanediamine; N,N-dimethyl-beta phenylethyl.amine and 1 , 2-dimethylimi dazole.
  • Suitable tertiary amine activators which contain hydrogen atoms which are reactive with isocyanate groups include, e.g., triethanolamine; triisopanolamine; N,N-dimethylethanolamine; N-methyl diethanolamine; N-ethyldiethanolamine, and their reactive products with alkylene, e.g., propylene oxide and/or ethylene oxide.
  • Organo-metallic compounds preferably organo—tin compounds such as tin salts of carboxylic acid, e.g., tin acetate, tin octoate, tin ethyl hexoate, and tin laurate; and the dialkyl salts of carboxylic acids, e.g., dibutyl tin dia cetate, dibutyl tin dilaurate dibutyl tin m-aleate or dioctyl tin diacetate.
  • organo—tin compounds such as tin salts of carboxylic acid, e.g., tin acetate, tin octoate, tin ethyl hexoate, and tin laurate
  • dialkyl salts of carboxylic acids e.g., dibutyl tin dia cetate, dibutyl tin dilaurate dibutyl tin
  • Silaamines with carbon-silicon bonds as described, e.g., in British Patent No. 1,090,589, may also be used as activators, e.g., 2,2,4-trimethyl-2-silamorpholine or 1, 3-diethylaminoethyl-tetramethyl-di siloxane.
  • the activators may be added separately from the water to promote the reaction, of the polyisocyanate with an active hydrogen.
  • emulsifiers and foam stabilizers may also be used according to the invention.
  • Suitable emulsifiers are, e.g., the sodium salts of ricinoleic sulphonates or of fatty acids diethylamine or stearic acid diethanolamine.
  • Other surface-active additives are alkali metal of ammonium salts of sulphonic acids, e.g., dodecylbenzene sulphonic acid or dinaphthyl methane disulphonic acid, or fatty acids, e.g., ricinoleic acid, or polymeric fatty acids.
  • the commercially available soaps and detergents may be used.
  • the foam stabilizers used are mainly water-soluble polyester siloxanes. These compounds generally have a polydimethylsiloxane group attached to a copolymer of ethylene oxide and propylene oxide. Foam stabilizers of this kind have been described, e.g., in U. S. Patent No. 3,629,308. These additives are preferably used in quantities of from 0% to 20%, based on the reaction mixture.
  • the surfact-ants may be used in this invention such as sodium dioctyl sulfosuccinate, potassium dioctyl sulfosuccinate and dioctyl calcium sulfosuccinate.
  • the oxidated silicon compounds which are used in this invention may be added to any of the active components of this invention. They may be pre-reacted with the polyisocyanate to produce polyisocyanate silicate prepolymers as in the process of U. S. Patent Nos. 4,072,637 and 4,097, 424; They may be added to unsaturated polyesters; they may be added to the water-binding agent and/or be a part of the water-binding agent such as the oxidated silicon compound in hydraulic cement; they may be added to the curing agent in the form of a solution or in a suspension.
  • the oxidated silicon compounds may be reacted with alcohols and polyols to produce organic hydroxyl silicate compounds, as produced by the process in U. S. Patent No. 4,089,883.
  • the oxidated silicon compound may be first reacted with a polyhydroxy alcolol and a polycarboxylic acid and/or organic acid anhydride as in U. S. Patent No. 4,125, 498.
  • Suitable oxidated silicon compounds which may be used include, but are not limited to, silica, e.g., hydrated silica, silicoformic acid and silica sol, alkali metal silicates, alkaline earth metal silicates, natural silicates containing free silicic acid groups and mixtures thereof.
  • the amount of oxidated silicon compound which may be used in the invention is quite varied because it will react with the available NCO groups, may be a part of the water-binding component, and any exc ess may be used as a filler.
  • the oxidated silicon acid will also react with free hydroxyl and carboxyl groups in the polyester resin.
  • the oxidated silicon compound content as compared with the total organic content, may vary within wide limits, e.g between 99:1 and 1:99, preferably between 70:30 and 20:80 parts, by weight.
  • acid-liberating hardeners may be added to the reaction mixture to react with the alkali metal group to form a salt.
  • Halogen or phosphorus-containing compounds are preferred. Any suitable salt-forming group may be used such as alkylating agents, and inorganic or organic acids are suitable. Sufficient amount is added to react with the alkali metal group to produce an alkali metal salt.
  • the organic polyisocyanate may contain groups of the kind which form salt groups in the presence of alkali silicate, for example: -COOH, -SO 2 H, -SO 2 -NH-SO 2 , -CO-NH- CO, and also phenolic OH-groups. Two or more of the aforementioned groups can also be present.
  • Suitable hardeners include mineral acids, hydrogen-containing salts of mineral acids, organic acids, polyfunctional alkylating agents, monofunctional alkylating agents, e.g., methyl chloride, ethyl chloride, dimethyl sulfate, diethyl sulfate, etc. Further examples of acidliberating hardeners may be found in DAS No. 1,205,087; Dutch Auslegeschrift No. 67/03743; German Patent No. 1,178,586; and U. S. Patent No. 3,450,592. Various Salt-binding agents may also be used in combination.
  • polyisocyanate-polyester-silicate plastic products The process for the production of polyisocyanate-polyester-silicate plastic products is simple. It is merely necessary for the components to come togeth er.
  • an organic polyisocyanate, an unsaturated polyester, a catalytic amount of an initiator, optionally a water-binding agent containing an oxidated silicon compound, and a curing agent such as water are mixed simultaneously, after which the mixture generally hardens in a short period of time.
  • an oxidated silicon compound will react chemically with a polyisocyanate compound to produce a polyisocyanate silicate prepolymer, and the polyisocyanate reacts with the unsaturated polyester resin to produce a polyurethane silicate prepolymer.
  • the prepolymer is cured by the use of an initiator to react the polymerizing monomer with the unsaturated polyester part of the prepolymer and a curing catalyst, such as water, to react with the free isocyanate groups and with the water-binding component.
  • the preferred method to produce polyisocyanate-polyester inorganic-organic plastic is to mix Component (b) (an unsaturated linear polymer in a liquid monomer that is capable of copolymerizing with the linear polymer), Component (a) (organic polyisocyanate) and Compcnent (d) (a water-binding agent) , then to add Component (c) (an initiator) while agitating. To this mixture, Component (e) (curing agent) is added while agitating and the mixture cures in a short period of time into a solid or cellular solid.
  • the components may be mixed in any suitable manner, they may be mixed simultaneously; Components (a) and (b) may be premixed, then Components (c) , (d) and (e) added simultaneously; Components (b) , (d) and (e) may be premixed, then Components (a) and (c) added; Component (d) may be added to Component (a) , (b) and/or (e) ; the curing agent may contain surface-active additives from 0% up to 20% by weight, based on the mixture, to improve the emulsifying of water into the mixture and to aid in regulating and stabilizing the foam.
  • Components (a) , (b) and a portion of Component (d) are premixed to produce a polyurethane silicate prepolymer.
  • the prepolymer may be stored; then when ready to use, (Component (c) is added and thoroughly mixed with the prepolymer; then Component (e) is mixed with the rest of Component (d) and rapidly and thoroughly mixed with the prepolymer. The mixture cures in a short time to produce a solid or cellular solid product.
  • the reactions of this invention may take place under any suitable physical conditions. While many of the reactions will take place acceptably at ambient temperature and pressures, in some cases, better results, may be obtained at somewhat elevated temperature and pressure.
  • the reactions are somewhat exothermic and may elevate the temperature of the mixture.
  • the reactants are preferably mixed at room temperature, though any suitable temperature in the range of 0o c to 150o C may be employed, preferably between 20o C and about 100o C. In certain cases where the temperature of the mixture does not rise sufficiently to activate the initiator, it may be necessary to heat the mixture.
  • the ratios of the essential reactants which lead to the inorganic-organic plastic products of the invention may vary broadly speaking, within ranges as follows: a. from 20 to 70 parts by weight of the organic polyisocyanate; b. from 30 to 80 parts by weoght of the unsaturated polyester resin; c. a catalytic amount of an initiator; the amount varies with each initiator; d. from 0% up to 200% by weight, of a water- binding agent, based on the Components (a) and (b) ; e. from 10% to 100% by weight of a curing agent, based on Components (a) , (b) and (d) ; f.
  • the hardening process proceeds more rapidly when the hardening process is carried out at temperatures above 40° C.
  • temperatures above 40° C.
  • Temperatures up to 110° C may be reached inside the foam products.
  • the products are usually as hard as stone, but, on the other hand, are highly elastic and, hence, highly resistant to impact and breakage. If the quantity of heat is liberated during the reaction between the components is not sufficient to obtain optimum properties, mixing can readily be carried out at elevated temperatures, for example, temperatures of from 40° C to 100° C.
  • mixing can also be carried out under pressure at temperatures above 100° C, up to about 150° C, in a closed container so the expansion occurs, accompanied by foam formation, as the material issues from the container.
  • the reaction of polyisocyanages with oxidated silicon compound is endothermic, and if the reaction of the polyisocyanate with the curing agent does not produce enough heat, an external source of heat is required to heat the reaction mixture to above 30° C, preferably above 40° C, in order to decrease the curing time.
  • production of the foams in. accordance with the invention is carried out by mixing the described reaction components together, either in one stage or in several stages in a batch-type or a continuous mixer, and allowing the resulting mixture to foam and harden in molds or on suitable substrates, generally outside the mixer.
  • the necessary reaction temperature amounting to between 0° C and 150° C and preferably between 20° C and 130° C, can either be achieved by preheating one or more reaction components before the mixing process or by heating the mixer itself or by heating the reaction mixture prepared after mixing. Combinations of these or other procedures for adjusting the reaction temperature are, of course, also suitable. In most cases, sufficient heat is generated during the reaction itself so that, after the beginning of the reaction or foaming, the reaction temperature can rise to levels above 100° C.
  • the properties of the resulting foams for example, their moist density, is governed to some extent by the parameters of the mixing process, for example, the shape and rotational speed of the stirrer, the shape of the mixing chamber, etc., and also the reaction temperature selected for initiating foaming.
  • the moist, fresh foam usually has a density of approximately 0.1 g/cc to 1.3 g/cc.
  • the dried foams can have closed or open cells, but are open-celled in most cases.
  • the compression strength obtained according to the invention depends to a large extent on the proportions in which the starting components are mixed and the resulting density, e.g., densities of between 200 and 600 kg/m 2 , and compression strength of 10 to 100 kg.
  • wt/cm 2 are obtained.
  • production of the solid products in accordance with the invention is carried out by mixing the described reaction components together, either in one stage or in several states, in a batch-type or continuous mixer, and allowing the resulting mixture to harden in molds or on suitable substrates, generally outside the mixer.
  • the necessary reaction temperature amounts to between about 0° C to 150° C, preferably between 20° C and 150° C.
  • the temperature necessary during the curing stage mainly depends on the temperature range in which the initiator functions properly.
  • the desired temperature may be obtained by the use of an outside heat source; usually ambient temperature is satisfactory.
  • the products produced are as hard as stone, but are elastic and highly resistant to impact and breakage.
  • the proportions of the components may be adjusted to obtain the desired product, from a solid to a highly cellular solid.
  • a higher percentage of the goly isocyanate is used, there are free NCO groups to react with the curing agent, water, to produce CO 2 .
  • Pores are produced in the product by the evolved CO 2 .
  • the CO 2 is rapidly evolved and escapes before the product hardens so that a solid product can be produced nearly completely free of air cells.
  • the curing time generally increases with additives.
  • an alkali metal silicate and/or silica may be added to the curing agent or polyisocyanate.
  • the NCO groups react with the polyester, the oxidated silicon compound in the water-binding component and with the alkaline metal group in the water-binding component and/or the alkali metal group in the curing agent; therefore, there is no free CO 2 produced for foaming.
  • a blowing agent may be added to the mixture.
  • foaming is directly accompanied, by hardening, for example, by preparing the reaction mixture in a mixing chamber and simultaneously adding the readily- voltatile blowing agent such as , for example, dichlorodifluoromethane, trichlorofluoromethane, butane, isobutylene or vinyl chloride, so that, providing it has a suitable temperature, the reaction mixture issuing from the mixing chamber simultaneously foams through evaporation of the blowing agent and hardens to its final foam under the effect of the organic polyisocyanate and initiator.
  • Said foam optionally contains emulssifiers, foam stabilizers and other additives.
  • the initially still-liquid reaction mixture can be expanded into a foam by the introduction of gases, optionally under pressure, such as air, methane, CF 4 , noble gases.
  • gases optionally under pressure, such as air, methane, CF 4 , noble gases.
  • the resulting foam is introduced into the required mold and hardened therein.
  • the mixture of polyisocyanate, polyester and water-binding agent, optionally containing foam stabilizers at the surfactants, foam formers, emulsifiers and, if desired, other organic or inorganic fillers or diluents may initially be converted into a foam by blowing gas and the resulting gas may subsequently be mixed in the mixer with other components and, if desired, with the curing agent, the resulting mixture being allowed to harden.
  • the curing agent may be preheated and added to the mixture of polyisocy-anate, unsaturated polyester resin, water-binding agent, liquid expanding or blowing agent and thus hardened while foaming.
  • blowing agents it is also possible to use inorganic or organic finely-divided hollow bodies such as expanded hollow beads of glass or plastics, expanded clay, straw and the like, for producing foams.
  • the foams obtainable in this way can be used in either their dry or their moist form, if desired, after a compacting or tempering process, optionally carried out under pressure. They will be useful as thermal- and sound-insulating materials for cavity filling, for packaging material and for building materials with outstanding resistance to solvents and favorable flame behavior. They can also be used as lightweight bricks or in the form of sandwich elements, for example, with metal-covering layers in house, vehicle and aircraft construction. They may be produced in the form of sheets which are used for siding on . houses.
  • reaction mixtures can also be dispersed in the form of droplets, for example, in petrol, or foamed and hardened during free fall or the like, resulting in the formation of foamed beads.
  • the polyisocyanate, unsaturated polyester, water-binding component, initiator and curing agent are simultaneously added; then, at a predetermined temperature, the blowing agent such as halogenated hydrocarbon, which is capable of evaporation or of gas formation at these temperatures, is added to the mixture.
  • the blowing agent such as halogenated hydrocarbon, which is capable of evaporation or of gas formation at these temperatures, is added to the mixture.
  • the initial liquid mixture formed can be used not only for producing uniform foams or non-uniform foams containing foamed or unfcamed fillers, but can also be used to foam through any given. webs, woven fabrics, lattices, structural elements or other permeable structures of foamed materials, resulting in the formation of composite foams with special properties, for example, favorable flame behavior, which may optionally be directly used as structural elements in the building of furniture or vehicles and in the aircraft industries.
  • the so-called pot life during which the mixture remains in a workable state depends mainly on the chemical nature of, and proportions of, the components used.
  • the pot life may vary from 0.2 seconds to about 15 hours.
  • Mixing of components is generally carried out immediately before the molding or shaping process.
  • the so-called pot life also varies with the stage at which the initiator is added, the temperature, the concentration of the initiator, the type of initiator and. whether or not a catalyst is used with the initiator.
  • the water-binding component's curing is greatly affected by the temperature.
  • the process according to the invention is provided with a number of potential uses, either as porous or as homogeneous materials. Accordingly, a few fields of application are outlined by way of example in the following.
  • the possibility of leaving the water present in the hardened mixtures as a required, constituent of the foam, or of protecting the foam against the elimination of water by suitably coating or covering the foam with a water- impermeable layer, or of removing all or part of the water by suitable drying techniques for example, in a heating cabinet or oven with hot air, infrared heating, ultrasonic heating or high-frequency heating
  • suitable drying techniques for example, in a heating cabinet or oven with hot air, infrared heating, ultrasonic heating or high-frequency heating
  • the foaming reaction mixture or the reaction mixture containing the blowing agent can be coated, for example, onto any given warm, cold or even IR- or HF-irradiated substrate, or, after passing through the mixer, can be sprayed with compressed air or applied by the airless process onto these substrates on which it can foam and harden to give a filling or insulating and protective coating.
  • the foaming reaction mixture can also be molded, cast or injection-molded in cold or heated molds, being allowed to harden in these molds which maybe relief or solid or hollow molds. Application can be made by centrifugal casting at room temperature or at temperatures of up to 200° C and, if desired, under pressure.
  • Strengthening elements may be used, whether in the form of inorganic and/or organic or metallic wires, fibers, webs, foams, woven fabrics, skeletons, etc. This can be done, for example, by the fiber-mat impregnating process or by processes in which reaction mixtures and strengthening fibers are applied together to the mold, for example, by means of a spray unit.
  • the moldings obtainable in this way can be used as structural elements, for example, in the form of optionally foamed sandwich elements produced wither directly or subsequently by lamination with metal, glass, plastics, etc., in which case the favorable flame behavior of the foams in either their moist or dry. form is of particular advantage.
  • they can also be used as hollow bodies, being employed, for example, as containers for products that may have to be kept moist or cool, as filter materials, or exchangers, as supports for catalysts or active substances , as decorative elements, as parts of furniture and as cavity fillings. They can also be used as high-stress lubricants and coolants or as carriers, therefore, for example, in the extrusion of metals. They can also be used in the field of pattern and mold design, and also in the production of molds or casting metals.
  • the foams obtainable by the process of this invention can be used in either their dry or their moist form, if desirable after compacting or tempering process, optionally carried out under pressure; as insulating materials, cavity fillings, packaging materials, building materials with outstanding resistance to solvents and with favorable flame behavior.
  • the reaction mixture may be sprayed onto impassable or loose terrain such as, for example, sand dunes or marshes, to obtain effective consolidation which scon becomes passable and offers protection against erosion. It is also advantageous to spray the proposed reaction mixtures onto articles which are to be protected in the event of fire or accident.
  • the mixtures can form effective protective walls and protective layers in mines when sprayed onto woven fabrics or other surfaces, lattices or even only onto walls.
  • the mixtures can be used in construction engineering, civil engineering and road building, for erecting walls and igloos, making seals, filling joints, plastering, flooring, insulation, decoration, boat or ship construction, and as a coating for metals, wood, concrete, plastics, etc., screed and covering material. They can also be used as adhesives or mortars, and as casting compositions which are optionally filed with inorganic or organic fillers. They can be useful as auxiliaries which may, if desired, be used in, or subsequently introduced into, the reaction mixture, such as emulsifiers, surfactants, dispersants, hydrophobizing substances, odorants, etc.
  • the process according to the invention is particularly suitable for in situ foaming on the building site.
  • any types of hollow molds of the kind made by formwork in the usual way, can be cast or can be filled with foam.
  • the reaction mixture can also be used to fill cavities, gaps, or cracks, giving a firm bond between the joined materials.
  • Insulating internal plasters can also be readily produced by spraying on the reaction mixture.
  • the materials obtained can be used instead of wood or hard-fiver boards. They can be sawed, rubbed down, planed, nailed, drilled or milled. In this way, they can be worked and used in a number of different ways.
  • the foams can be subsequently lacquered, metallized, coated, laminated, galvanized, subjected to vapor deposition, bonded or flocked in either their moist or dry form or in impregnated form.
  • the optionally filled molding can be further modified in their properties by thermal aftertreatment, oxidation processes, hot-pressing, sintering processes, surface melting or other consolidation processes.
  • Suitable mold materials include inorganic and/or organic foamed or unfoamed materials such as metals, for example, iron, nickel, fine steel, lacquered or, for example, teflon-coated aluminum, porcelain, glass, wood, plastics such as PVC, polyethylene, epoxide resins, ABS, polycarbonates, etc.
  • the foams or solid products obtainable in accordance with the invention can be surface-treated or, where they are in the form of substantially permeable structures, such as substantially opencell foams or porous materials, can even be treated by centrifuging, vacuum treatment, blowing air through or by rinsing with (optionally heated) liquids or gases which remove the water present, such as methanol, ethanol, acetone dioxan, benzene, chloroform and the like.
  • the foams or solid products can be dried with air, CO 2 or super-heated steam.
  • the moist or dry products can also be aftertreated by rinsing or by impregnating with aqueous or non-aqueous acid, neutral or basic liquids or gases such as hydrochloric acid, phosphoric acid, formic acid, acetic acid, ammonia, amines, organic or inorganic salt solutions, lacquer solutions, solutions of polymerizable or already polymerized monomers, dye solutions, galvanizing baths, solutions of catalysts or catalyst preliminary stages, odorants and the like.
  • aqueous or non-aqueous acid neutral or basic liquids or gases
  • neutral or basic liquids or gases such as hydrochloric acid, phosphoric acid, formic acid, acetic acid, ammonia, amines, organic or inorganic salt solutions, lacquer solutions, solutions of polymerizable or already polymerized monomers, dye solutions, galvanizing baths, solutions of catalysts or catalyst preliminary stages, odorants and the like.
  • the new composite materials are particularly suitable for use as structural materials because they show tensile and compressive strength, are tough, rigid and, at the same time, elastic. They show high permanent dimen ⁇ sional stability when hot and are substantially nonflammable.
  • the unfoamed reaction mixture may be utilized in production of many products similar to those produced by the polyester resins, such as boats, construction panels, automobile parts and bodies, airplane structural parts, furniture, solid art objects, cavity-filling, plastering material, road building material, coating material for metals, wood, plastics, concrete, etc., adhesive material, mortar, walls, sealant, flooring, etc.
  • the unfoamed reaction mixture may be sprayed on or be applied by a tool such as a trowel or brush to layers of fiberglass cloth or multiple layers of wire mesh, such as chicken wire in order to produce items such as boats of which the hulls have good tensile and compressive strength, are rigid and, at the same time, elastic, show high permanent dimensional stability and good salt water resistance.
  • a boat hull made of the materials of this invention, which have equal thickness and reinforcing materials, is very similar in strength and durability to a hull made of polyester boat resin. This material will produce a boat of much less weight compared to a ferro-cement boat, while using equivalent reinforcing material.
  • a strong, light-weight wall which may be used in construction can be produced by pouring or spraying the unfoamed reaction mixture in a mold to make the outer surface, then pouring or spraying a foamable or foaming-reaction mixture for the core. When foaming is complete, an outer layer of the unfoamed reaction mixture is poured or sprayed on the foam and is finished in the desired texture or design. The thickness of the various layers may be varied to produce the desired strength.
  • Fillers in the form of particulate or powdered materials can be additionally incorporated into the mixture of organic polyisocyanates, unsaturated polyester resin and water-binding agent and/or curing agent.
  • Suitable fillers include solid, inorganic or organic, substances, for example, in the form of powders, granulates, wire, fibers, dumb bells, crystallites, spirals, rods, beads, hollow beads, foam particles, webs, pieces of woven fabric, knit fabric, ribbons, pieces of film, etc., for example, of dolomite, chalk, alumina, asbestos, basic silicas, sand, gravel, talcum, iron oxide, aluminum oxide and oxide hydrate, zeolites, calcium silicates, basalt wool or powder, glass fibers, C-fibers, graphite, carbon black, Al-, Fe-, Cu-, Ag-powder, molydenum sulphite, steel wool, bronze or copper cloth, silicon powder, expanded clay particles,hollow glass beads, glass powder, lava and
  • suitable organic polymers the following, which can be present, for example, in the form of powders, granulates, foam particles, hollow beads, foamable or unfoamable particles, fibers, ribbons, woven fabric, webs, etc., are mentioned purely by way of example; polystyrene, polyethylene, polypropylene, polyacrylonitrile, polybutadiene, polyisoprene, polytetrafluorethylene, aliphatic and aromatic polyesters, melamine-urea or phenol resins, polyacetal resins, polyepoxides, polyhydantoins, polyureas, polyesters, polyurethane,polyimides, polyamides, polyethers, polysulphones, polycarbonates, and, of course any copolymers as well. Inorganic fillers are preferred.
  • the composite materials according to the invention can be filled with considerable quantities of fillers without losing their valuable property spectrum.
  • the amount of fillers can exceed the amount of Components (a) , (b) , (c) and (d) .
  • coarse fillers can be used in wet form; powdered fillers such as, e.g., chalk, alumina, dolomite, calcium hydroxide, magnesium carbonate, sand and calcium carbonate, can be used also as an aqueous suspension.
  • Expanded clay may be used as a water-binding agent in this invention and will produce a polyisocyanate- polyester-silicate plastic which is strong, light weight, high concrete and may be used, for example, as panels in the construction field.
  • the object of the present invention is to provide a novel process to produce polyisocyanate-polyester- slicate plastics. Another object is /to produce novel polyisocyanate-polyester-silicate plastic products. Still another object is to produce novel, fine cellular, solid products of relatively low cost, light weight, high strength, with good flame resistance and dimensional stability when heated. Another object is to produce novel solid polyisocyanate-polyester-silicate plastics. Another object is to produce solid or cellular solid products that may be used for sound and thermal insulating, structural purposes, shock-resistant packaging, coating for wood, metals and plastics, adhesives, casting materials, putty, etc.
  • Example 1 Component (a): Tolylene-2,4-diisocyanate; Component (b) : unsaturated polyester resin containing 2 mols of phthalic anhydride, 1 mol of maleic anhydride and 3.5 mols of propylene glycol, and 30% styrene with 0.005 to 0.01 part by weight of cobalt naphthenate; Component (c) : 0.01 parts by weight of methyl ethyl ketone peroxide; Component (e) : water containing 40% silica sol and
  • Example 2 Component (a) : diisocyanatediphenylmethane; Component (b) : unsaturated polyester resin containing about 2 mols of adipic acid, 1 mol of fumarie acid, 0.5 mol of ethylene glycol and 1.5 mols of propylene glycol, 20% styrene, 10% methyl methacrylate and 50 to 100 ppm of cobalt metal in the form of cobalt naphthenate. Component (c) : methyl ethyl ketone peroxide; Component (d) : Portland cement;
  • Component (e) water containing 0-01% triethyl amine, 3% sodium salt of a sul phochlorinated C 10 -C 14 paraffin mixture.
  • About 1 part by weight of Component (a) , 3 parts by weight of Component (b) , 0.005 to .02 part by weight of Component (c) and 1 part by weight of Component (d) are mixed; then 0.5 part by weight of Component (e) is thoroughly mixed, and in about 1 to 3 minutes, the mixture exapands 3 to 10 times its original volume to produce a tough, rigid, cellular solid plastic.
  • Example 3 Component (a) : tolylene diisocyanate (80% 2,4— isomer and 20% 2,6-isomer); Component (b) : unsaturated polyester resin containing diallyl phthalate, 20% styrene, 10% vinyl acetate and 100 ppm of cobalt metal in the form of cobalt naphthenate; Component (c) : methyl ethyl ketone peroxide; Component (d) : gypsum mixed with 50% hydrated silica; Component (e) : water containing 2% soap, 0.1% diethylenetriamine, 20% sodium silica; Additives: tris- (chloro-ethyl phosphate); Blowing agent; trichlorofluoromethane;
  • Component (a) 20% solution of TDI residue in MDI (MCO content 30% viscosity 1900 centipoisas);
  • Component (b) unsaturated polyester resin produced by reacting 2 mols of sebacic acid, 1 mol of fumaric acid and 3.5 mols of diethylene glycol, and containing 15% styrene, 5% vinyl acetate, 5% methacrylic acid and 0.01% cobalt naphthenate;
  • Component (c) methyl amyl ketone peroxide
  • Component (d) calcium oxide containing 25% Portland cement
  • Component (e) water containing 10% sodium silicate; 5% magnesium oxide, 0.1% triethyl amine;
  • Component (a) 2 parts, by weight of diisocy-anate- diphenylmethane, distilled from crude phosgenation product of an aniline- formaildehyde condensate until the distillation residue has a viscosity of about 600 cP at 25° C with an NCO content of 29 to 30% by weight.
  • Component (b) 4 parts by weight of an unsaturated polyester produced by reacting 2 mols of adipic acid, 0.5 mol of phthalic anhydride, 1 mol of fumaric acid and 4 mols of propylene glycol and containing 10% triallyl cyanurate, 10% divinyl benzene, 10% styrene and about 100 ppm of cobalt in the form of cobalt hexanoate.
  • Component (c) 0.02 parts by weight of methyl ethyl ketone peroxide.
  • Component (d) 2 parts by weight of rapid-setting cement. Blowing agent; 0.6 part by weight of chloroform. MIXTURE II:
  • Component (e) 2 parts by weight of water containing
  • Example 6 Component (a) : 1 part by weight of tolylene diisocyanate, 0.5 part by weight of sulphonated diisocyanate- diphenyImethane; Component (b) : 4 parts by weight of a commercial unsaturated polyester boat resin containing styrene and cobaltcatalyst Component (e) : 1 part by weight of water containing 30% sodium silicate and 15% silica sol; Component (c) : catalytic amount of methyl ethyl ketone peroxide; Additives: 0.05 part by weight of sodium dioctyl sulfosuccinate, 0.01 part by weight of triethylamine and 0.1 part by weight of glass fibers (3 to 5 mm.
  • the components and additives are mixed simultaneously for 0.5 to 3 minutes, and a soft, workable mass is obtained.
  • the mass is pressed into a mold at a temperature of 40° C to 60° C. hardens into a hard, tough product within 30 minutes.
  • Example 7 Component (a) : 1 part by weight of 4-methyl-m- phenylene diisocyanate; Component (b) : 4 parts by weight of a commercial unsaturated polyester laminating resin containing a catalyst; Component (c) : 0.05 part by weight of methyl ethyl ketone peroxide; Component (d) : 6 parts by weight of Portland cement; Component (e) : 3 parts by weight of water containing 30% silica and 1% of sodium dodecylbenzene sulphonate; The components (a) (b) , (c) and (d) are mixed, then Component (e) is added and thoroughly mixed to form a very thick liquid or soft, workable mass.
  • the mixture is then spread with a brush or trowel between layers of fiberglass cloth and hardens in 15 minutes to 1 hour at ambient temperature, becoming very strong and rock hard in 1 to 12 hours, depending on the temperature and the amount of initiator used.
  • this composition appears to be just as strong.
  • Example 8 Component (a) : 1 part by weight, of methylenedi-p- phenylene diisocyanate; Component (b) : 3 parts by weight of a commercial unsaturated polyester casting resin ("Titan Casting Resin"); Component (c) : 0.01 part by weight of an initiator
  • Component (a) 1 part by weight of a 30% solution of TDI residue in MDI (NCO content of about 30%, viscosity cP) ;
  • Component (b) 4 parts by weight of a commercial unsaturated polyester boat resin containing a catalyst; (Al Paint and Varnish Co., Torrance, Calif.)
  • Component (c) catalytic amount of methyl ethyl ketone; Component (d) : 5 parts by weight of sulphate resistant cement; 3 parts by weight of sharp sand; Component. (e) : 2 parts by weight of water containing
  • Component (a) 1 part by weight of tolylene diisocyanate; Component (b) : 3 parts by weight of the unsaturated polyester as in Example 4; Component (c) : 0.05 part by weight of potassium persulfate; Component (e) : 1 parts by weight of water containing
  • Example 11 Component (a) : 2 parts by weight of tolylene diisocyanate; Component (b) : 3 parts by weight of an unsaturated polyester resin containing diallyl phthalate and equal parts by weight of diethylene glycol bis (allyl carbonate) ; 20% aerylonitrile and 10% methyl methacrylate; Component (c) : 0.05 parts by weight of potassium persulfate; Component (d) : 4 parts by weight of Portland cement; Component (e) : 2 parts by weight of water containing 30% sodium silicate, 1% triethylamine and 1% sodium docytl sulfosuccinate; Additive: 0.1 part by weight of vermiculite;
  • Components (a) , (b) , (c) , (d) and methyl chloride are mixed, then Component (e) and vermiculate are added, the mixture being vigorously agitated for about 15 to 30 seconds before it is poured into a mold. It solidifies in a few minutes, then forms a hard, tough, solid plastic product in 3 to 12 hours.
  • Component (a) tolylene diisocyanate
  • Component (c) a catalytic amount of methyl ethyl ketone peroxide
  • Component (e) water containing 10% potassium silicate, 10% silica sol, 1% triethylamine and 2% detergent
  • Component (e) water containing 10% potassium silicate, 10% silica sol, 1% triethylamine and 2% detergent
  • the mixture is agitated for 15 to 30 seconds, and expands 3 to 10 times its original volume to produce a tough, rigid, cellular solid product.
  • Example 13 About 1 part by weight of Component (a) , listed in examples below, 2 parts by weight of Component (b) , listed in samples below, 3 parts by weight of Portland cement (Component (d) ) and a catalytic amount of Component (c) (methyl ethyl ketone peroxide) are mixed; then 2 parts by weight of water containing 30% sodium silicate, 1% triethylenetetramine (Component (c) and 0.1. part by weight of a blowing agent (methylene chloride) are added and vigorously agitated for 15 to 30 seconds. The mixture then expands 1 to 10 times its original volume and in a short time, solidifies to form a tough, cellular solid product.
  • Component (a) listed in examples below, 2 parts by weight of Component (b) , listed in samples below, 3 parts by weight of Portland cement (Component (d) ) and a catalytic amount of Component (c) (methyl ethyl ketone peroxide) are mixed; then 2 parts by weight
  • Example 13 About 1 part by weight of Component (a) , listed in examples below, 2 parts by weight of Component (b) , listed n examples below, 3 parts by weight of Portland cement (Component (d) ) and a catalytic amount of Component (c) (methyl ethyl ketone peroxide) are mixed; then 2 parts by weight of water containing 30% sodium silicate, 1% triethylenetetramine (Component (e) ) and 0.1 part by weight of a blowing agent (methylene chloride) are added and vigorously agitated for 15 to 30 seconds. The mixture then expands 1 to 10 times its original volume and in a short time, solidifies to form a tough, cellular solid product.
  • Component (e) methyl ethyl ketone peroxide
  • Example 14 About 2 parts by weight, of Component (a) (tolylene diisocyanate), 0.5 part by weight of a polyhydroxyl compound listed. (Additive Component), 2 parts by weight of Component (b) containing 50% diallyl phthalate, 10% diallyl furmarate, 10% diallyl benzene phosphonate, 10% methallyl methacrylate and 20% styrene containing 0.5% diethyl aniline), 0.05 part by weight of Component (c) (acetyl benzoyl peroxide) and 1 part by weight of Portland cement (Component (d) ) are mixed, then agitated for about 30 minutes; then a mixture of 2 parts by weight of water, containing 2 parts by weight of Portland cement and 0.001 part by weight of tin acetate, is added and agitated for 15 to 30 seconds. The mixture expands 2 to 5 times its original volume and solidifies in a short period of time, thereby pro ⁇ ducing a rough, cellular solid product.
  • Organic polyhydroxyl compounds used in the example are: polyethylene glycol (average molecular weight 480) , polypropylene glycol (average molecular weight 600) , dibutylene glycol, epichlorohydrin polymer, saturated polyester resin (4 mols glycerol, 2.5 mols adipic acid and 0.5 mol phthalic anhydride) , a polyester amide containing at least 2 hydroxyl groups per molecule (molecular weight 1400 to 1500) , a polycarbonate with at least 2 hydroxyl groups per molecule (diethylene glycol. and phosgene), an additional product of propylene oxide with phenoformaldehyde. resin, polyacetal (diethylene glycol and formaldehyde) , glycerol, butylene-1, 4-glycol, pentaerythritol, and polyether (tetrahydrofuran polymerized).
  • polyethylene glycol average molecular weight 480
  • polypropylene glycol
  • Example 15 Component (a) : 1 part by weight of tolylene diisocyanate, 0.25 part by weight of polypropylene glycol (molecular weight 500) ; Component (b) : 1 part by weight of unsaturated polyester resin (2 mols adipic acid, 1 mol fumaric acid, 3.25 mols of propylene glycol) containing 25% styrene and cobalt catalyst; Component (c) : catalytic amount of methyl ethyl ketone Component (e) : 3 parts of water containing 60% sodium silicate, 3% soap and 1% triethylamine; Hardener: listed below in the amount wherein the mols of the hardener are equal to the mols of the allali metal atoms.
  • Blowing agent 0.5 parts by weight of ethylene chloride.
  • Components (a) , (b) , (c) and the blowing agent are mixed; then Component (e) and the hardener are added simultaneously while agitating for a few seconds.
  • the mixture expands 3 to 10 times its original volume, thereby producing a rigid, cellular solid product.
  • Hardeners Acetic acid, formic acid, propionic acid, propionic acid chloride, methanesulphonic acid chlo ride, ethanesulphonic acid, 4-toluenesulphonic acid, tri methyl phosphite, triethyl phosphate, dimethyl phosphate, diethyl phosphite, diethylphosphate, phosphoric acid, thiophosphoric acid trimethylester, sodium dihydrogen phosphate , sodium hydrogen sulf ate , calcium hydrogen sul fate, propyl chloride, ethyl bromide, isopropyl iodide, benzyl chloride chloroacetic acid, dichloroacetic acid, sulphurous acid, sulphuric acid., hypophosphorous acid, phoshinic acid, phosphonous acid, phosphonic acid, oxalic acid, glycolic acid and p-xylylene dichloride.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
EP81900762A 1980-06-26 1980-06-26 Verfahren zur herstellung von polyisocyanat-polyester-silikat-kunststoffen Withdrawn EP0055256A1 (de)

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HUP0401557A2 (en) * 2004-08-06 2006-06-28 Polinvent Kft Polyisocyanate and waterglass based hybrid resin, composites containing them and production-process thereof
US11618814B2 (en) 2020-12-04 2023-04-04 Covestro Llc Elastomeric compositions containing a solid residue of isocyanate manufacturing
CN112745475A (zh) * 2020-12-17 2021-05-04 山东润义金新材料科技股份有限公司 建筑工程用纤维改性复合聚氨酯材料及其制备方法
CN120464185B (zh) * 2025-07-16 2025-11-21 山东一诺威聚氨酯股份有限公司 耐温微孔填充材料及其制备方法

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US4142030A (en) * 1973-11-30 1979-02-27 Bayer Aktiengesellschaft Inorganic-organic plastic
US4136238A (en) * 1974-12-21 1979-01-23 Metallgesellschaft A.G. Non-flammable and optionally electrically conductive organo-silicate polymers and process for preparing same

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