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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/14—Manufacture of cellular products
• • 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
  • C08G18/003—Polymeric products of isocyanates or isothiocyanates with epoxy compounds having no active hydrogen
• • 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
  • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
  • C08G18/022—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing isocyanurate 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
• • 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
  • C08G18/16—Catalysts
  • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
  • C08G18/1816—Catalysts containing secondary or tertiary amines or salts thereof having carbocyclic 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
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4825—Polyethers containing two hydroxy 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
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/0014—Use of organic additives
  • C08J9/0033—Use of organic additives containing sulfur
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
  • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
  • C08J9/143—Halogen containing compounds
  • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
  • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
• • 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
  • C08G2115/00—Oligomerisation
  • C08G2115/02—Oligomerisation to isocyanurate 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
  • C08G2170/00—Compositions for adhesives
  • C08G2170/60—Compositions for foaming; Foamed or intumescent adhesives
• • 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
  • C08G2350/00—Acoustic or vibration damping material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2203/00—Foams characterized by the expanding agent
  • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
  • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
  • Y10T428/249982—With component specified as adhesive or bonding agent
  • Y10T428/249983—As outermost component

Definitions

• the organic polyisocyanates may be reacted prior to blending with organic polyepoxides by adding catalysts and stopping them to form an intermediate containing isocyanurate groups.
• the reaction of the organic polyisocyanates with an intermediate containing isocyanurate groups can also be carried out after mixing with the organic polyepoxides.
• Conditioned resins are used in combination with blowing agents for the production of foams. There is no indication of the form in which the foaming should be made and which foaming agents should be used.
• storage-stable isocyanate-epoxy mixtures can be prepared.
• These reaction resin mixtures are i.a. suitable for the production of electrical insulation materials, transformers, capacitors or construction materials. It is stated that in the case of processing the mixtures in combination with blowing agents, it would also be conceivable to produce foams of high heat resistance. There is no indication under which conditions and with which blowing agents the foaming is to be made.
• No. 4,699,931 describes the preparation of isocyanurate foams containing oxazolidinone structures by reacting polyisocyanates with polyepoxides using catalysts, blowing agents and surface-active substances. To produce the foams, water or halogenated hydrocarbons, e.g.
• Difluorochloromethane trichlorofluoromethane, dichlorodifluoromethane, chlorotrifluoromethane, trichlorotrifluoroethane, dichlorofluoroethane, difluorotrichloroethane, tribromochlorofluorobutane and methylene chloride, and mixtures thereof.
• US Pat. No. 3,793,236 discloses isocyanurate foams containing oxazolidinone structures, which are prepared from oxazolidinone-containing prepolymers.
• inorganic foaming agents e.g. Water and boric acid
• hydrocarbons e.g. Pentane, hexane and heptane
• halogenated hydrocarbons e.g. Trichlorofluoromethane
• reactive organic blowing agents e.g. Nitroalkanes, aldoximes, acid amides, enolizable carbonyl compounds and nitrourea.
• US Pat. No. 3,849,349 describes polyolefin-modified isocyanurate foams containing oxazolidinone structures, which, in contrast to the one-shot process described in US Pat. No. 3,793,236, are prepared directly from polyisocyanate, polyepoxide and polyol.
• the blowing agents described correspond to the blowing agents disclosed in US 3,793,236.
• No. 4,129,695 describes the preparation of foams from polyisocyanates and polyepoxides, the foams having oxazolidinone and carbodiimide groups.
• CO 2 is liberated, which is known as Propellant is used.
• Possible additional blowing agents are water, butane, pentane, trifluorochloromethane, dichlorodifluoromethane and chlorofluoroethanes.
• Ammonium carbonate sodium bicarbonate, N, N'-dimethyl-N, N'-dinitrosoterephthalamide, para, para'-oxybis (benzenesulfonylhydrazide), azodicarbonamide, benzenesulfonylhydrazide, diazoaminobenzene, azodiisobutyronitrile, dinitrosopentamethylenetetramine and para-tert-butylbenzoylazide.
• the invention had the object of providing high-temperature-resistant foams having very good mechanical properties and very low thermal conductivity, which can be produced in a simple procedure, so that they can be produced in an industrial production in short mold occupancy times.
• halogenated hydrocarbons are particularly well suited as blowing agents to achieve low thermal conductivity.
• halogenated hydrocarbons in part, as the sole blowing agent and partly in combination with additional physical and / or chemical blowing agents, such as water as a CO2 releasing component.
• blowing agents have no outstanding influence on the quality of the high-temperature-resistant foams produced therewith.
• the reaction is particularly preferably carried out in the presence d) of a stabilizer from the group consisting of organic sulfonic acid esters, methyl iodide, dimethyl sulfate, benzenesulfonic anhydride, benzenesulfonyl chloride, benzenesulfonic acid, Trimethylsilyltrifluormethansulfonat, the reaction product of the reaction of benzene-sulfonic acid with epoxides, and mixtures thereof.
• a stabilizer from the group consisting of organic sulfonic acid esters, methyl iodide, dimethyl sulfate, benzenesulfonic anhydride, benzenesulfonyl chloride, benzenesulfonic acid, Trimethylsilyltrifluormethansulfonat, the reaction product of the reaction of benzene-sulfonic acid with epoxides, and mixtures thereof.
• the invention further provides a process for preparing the high-temperature-resistant foams according to the invention by reacting a) at least one organic polyisocyanate with b) at least one organic compound having at least two epoxide groups in an amount corresponding to an equivalent ratio of isocyanate groups to epoxide groups of 1 , 2: 1 to 500: 1, e) optionally in the presence of auxiliaries and additives characterized in that the reaction in the presence of 1,1,1,3,3-pentafluoropropane (HFC-245fa) as a blowing agent and optionally further chemical and / or physical blowing agents T) and a the isocyanate / epoxide reaction accelerating catalyst f) is carried out with foaming.
• HFC-245fa 1,1,1,3,3-pentafluoropropane
• a stabilizer selected from the group consisting of organic sulfonic acid esters, methyl iodide, dimethyl sulfate, benzenesulfonic anhydride, benzenesulfonyl chloride, benzenesulfonic acid, trimethylsilyltrifluoromethanesulfonate, the reaction product of
• the process for producing the high-temperature-resistant foams of the invention by (i) reacting a) at least one organic polyisocyanate in the presence c) of a tertiary amine as a catalyst to an intermediate product having isocyanurate groups, and
• step (ii) terminating the reaction under step (i) in a reaction of a maximum of 60% of the isocyanate groups of isocyanate a) by adding one of the amine amount c) at least equivalent amount d) of a stabilizer selected from the group consisting of organic sulfonic acid esters, methyl iodide, dimethyl sulfate, Benzenesulfonic anhydride, benzenesulfonyl chloride, benzenesulfonic acid, Trimethylsilyltrifluormethansulfonat, the reaction product of the reaction of benzene-sulfonic acid with epoxides and mixtures thereof and
• Another object of the invention is the use of high-temperature resistant foams according to the invention, optionally after tempering, as Cordschaum for cavities, as filling foam for electrical insulation, as the core of sandwich structures, for the production of construction materials for interior and exterior applications of any kind, for the production of construction materials for vehicle, ship, aircraft and rocket construction, for the production of aircraft interior and exterior components, for the production of insulation materials of any kind, for the production of insulation boards, pipe and container insulation, for the production of sound-absorbing materials, for use in engine compartments, for the production of grinding wheels and for the production of high-temperature insulation and flame retardant insulation.
• Another object of the invention is the use of the foamable mixtures before the end of foaming for high-temperature-resistant foam according to the invention for bonding substrates, for bonding steel and copper sheets, plastic sheets and polybutylene terephthalate sheets.
• Another object of the invention are cavities, electrical insulation, cores of sandwich structures, sandwich constructions, construction materials for interior and exterior applications of any kind, construction materials for vehicle, ship, aircraft and rocket construction, aircraft interior and exterior components, insulating materials of any kind, insulation boards, pipe and tank insulation, sound absorbing materials, engine room insulation and insulation materials, grinding wheels, high temperature insulation and flame retardant insulation, which are characterized by containing or consisting of the high temperature resistant foams of the present invention.
• Another object of the invention are adhesions of substrates, bonds of steel and copper sheets, plastic sheets and polybutylene terephthalate sheets, which are characterized in that they contain or consist of the high-temperature-resistant foams of the invention.
• the isocyanate component a) are any organic polyisocyanates of the type known per se from polyurethane chemistry. Examples which are suitable are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, as used, for example, by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, are described, for example, those of the formula
• Q is an aliphatic hydrocarbon radical having 2-18, preferably 6-10 C atoms, an aromatic hydrocarbon radical having 6-15, preferably 6-13 C atoms, or an araliphatic hydrocarbon radical having 8-15, preferably 8-13 C atoms, mean, eg 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.
• triphenylmethane-4,4 ', 4 "-triisocyanate polyphenyl-polymethylene polyisocyanates, as obtained by aniline-formaldehyde condensation and subsequent phosgenation (GB 874 430 and GB 848 671), m- and p - Isocyanatophenylsulfonyl isocyanates (US 3,454,606), perchlorinated aryl polyisocyanates, (US 3,277,138), carbodiimide group-containing polyisocyanates (US 3,152,162), norbornane diisocyanates (US 3,492,330), allophanate group-containing polyisocyanates, (GB 994 890 (US Pat.
• TDI 2,6-tolylene diisocyanate and any mixtures of these isomers
• polyphenylpolymethylene polyisocyanates as prepared by aniline-formaldehyde condensation and subsequent phosgenation ("crude MDI") and carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret-containing polyisocyanates ("modified polyisocyanates”), especially those modified polyisocyanates derived from 2,4- and / or 2,6-toluene diisocyanate or from 4,4'- and / or 2,4'-diphenyl-methane diisocyanate derived.
• modified polyisocyanates especially those modified polyisocyanates derived from 2,4- and / or 2,6-toluene diisocyanate or from 4,4'- and / or 2,4'-diphenyl-methane diisocyanate derived.
• Particularly preferred is the use of an isomer and / or homolog mixture of polyisocyanates of the diphenylmethane series with a content of 2,4'-diisocyanatodiphenylmethane of more than 20 wt .-%.
• polyisocyanate mixtures of the diphenylmethane series with a content of 2,4'-diisocyanatodiphenylmethane of more than 20 wt .-%, preferably from 30 to 70 wt .-%.
• the particularly preferred polyisocyanate component generally contains further isomeric or homologous polyisocyanates of the diphenylmethane series.
• the particularly preferred polyisocyanate component is generally either a mixture of 2, 4'-diisocyanatodiphenylmethane with 4,4'-diisocyanatodiphenylmethane and optionally 0 to 20% by weight, based on the total mixture of 2,2 '.
• Diisocyanate-diphenylmethane or is mixtures of these isomers with polynuclear polyphenyl polymethylene polyisocyanates. In the latter mixtures, a content of 10 to 60 wt .-% based on total mixture of such higher nuclear polyisocyanates is generally present.
• the first mentioned diisocyanate mixture enriched in 2,4'-isomers may be obtained, for example, by distilling off a diisocyanate mixture of the stated composition from a polyisocyanate mixture as obtained by phosgenation of aniline-formaldehyde. Condensates arise.
• the mixture which is likewise particularly preferably suitable and contains higher-nuclear polyisocyanates can be obtained, for example, by backmixing of the last-mentioned distillation product with phosgenation product depleted of 4,4'-diisocyanatodiphenylmethane, for example in accordance with DE-AS 1,923,214. It is also possible to use such a mixture, i. a polyisocyanate mixture whose content of 2,4'-diisocyanatodiphenylmethane corresponds to the information given, directly by appropriate
• the content of 2,4'-diisocyanatodiphenylmethane is above 20% by weight, based on the total mixture.
• the component b) containing epoxide groups is any aliphatic, cycloaliphatic, aromatic or heterocyclic compound having at least two epoxide groups.
• the preferred epoxides suitable as component b) have per molecule from 2 to 4, preferably 2 epoxide groups and an epoxide equivalent weight of 90 to 500 g / eq, preferably 170 to 220 g / eq.
• polyepoxides are polyglycidyl ethers of polyhydric phenols, for example catechol, resorcinol, hydroquinone, 4,4'-dihydroxydiphenylpropane (bisphenol A), 4,4'-dihydroxy-3,3'-dimethyldiphenylmethane, 4,4'-dihydroxydiphenyl methane (bisphenol F), 4,4'-dihydroxydiphenylcyclohexane, of 4,4'-dihydroxy-3,3'-dimethyl-diphenylpropane, of 4,4'-dihydroxydiphenyl, of 4,4'-dihydroxydiphenylsulfone (bisphenol S), of tris (4-hydroxyphenyl) methane, the chlorination and bromination products of the abovementioned diphenols, of novolaks (ie of reaction products of monohydric or polyhydric phenols with aldehydes, especially formaldehyde, in the presence of
• GB-PS 1 024 288) Mention may also be made of polyepoxide compounds based on aromatic amines and epichlorohydrin, for example N-di (2,3-epoxypropyl) aniline, ⁇ , ⁇ '-dimethyl-N, N'-diepoxypropyl-4,4'-diaminodiphenylmethane, N, N-diepoxypropyl-4-amino-phenyl-glycidyl ethers (see British Patents 772,830 and 816,923).
• glycidyl esters of polybasic aromatic, aliphatic and cycloaliphatic carboxylic acids for example phthalic acid diglycidyl ester, isophthalic acid glycidyl ester, terephthalic acid diglycidyl ester, adipic acid diglycidyl ester and glycidyl ester of reaction products of 1 mol of an aromatic or cycloaliphatic dicarboxylic acid anhydride and 1/2 mol of a diol or 1 / n Mol of a polyol with n hydroxyl groups or Hexahydrophthal Aciddiglycidylester, which may optionally be substituted with methyl groups.
• phthalic acid diglycidyl ester isophthalic acid glycidyl ester, terephthalic acid diglycidyl ester, adipic acid diglycidyl ester and glycidyl ester of reaction products of 1 mol of an aromatic or cycloaliphatic
• Glycidyl ethers of polyhydric alcohols for example of 1,4-butanediol (Araldite® DY-D, Huntsman), 1,4-butenediol, glycerol, trimethylolpropane (Araldite® DY-T / CH, Huntsman), pentaerythritol and polyethylene glycol can also be used.
• 1,4-butanediol Araldite® DY-D, Huntsman
• 1,4-butenediol 1,4-butenediol
• glycerol trimethylolpropane
• pentaerythritol and polyethylene glycol can also be used.
• triglycidyl isocyanurate ⁇ , ⁇ '-diepoxypropyloxyamide
• polyglycidyl thioethers of polyhydric thiols such as bismercaptomethylbenzene, diglycidyltrimethylene trisulfone
• epoxidation products of polyunsaturated compounds can be used, such as vegetable oils and their conversion products.
• Epoxidation products of di- and polyolefins such as butadiene, vinylcyclohexane, 1,5-cyclooctadiene, 1,5,9-cyclododecatriene, polymers and copolymers still containing epoxidizable double bonds, e.g.
• polymers of unsaturated monoepoxides for example of glycidyl methacrylate or allyl glycidyl ether.
• polyepoxide compounds or mixtures thereof are preferably used as component b):
• Liquid polyepoxides or low viscosity diepoxides such as bis (N-epoxypropyl) -aniline or vinylcyclohexanediepoxide can, in special cases, further reduce the viscosity of already liquid polyepoxides or convert solid polyepoxides into liquid mixtures.
• Component b) is used in an amount corresponding to an equivalent ratio of isocyanate groups to epoxide groups of from 1.2: 1 to 500: 1, preferably 3: 1 to 65: 1, "
• the catalyst component c) is any mono- or polyfunctional organic amines having tertiary amino groups.
• Suitable amines of the type mentioned generally have a molecular weight of up to 353, preferably from 101 to 185. Preference is given to those tertiary amines which are liquid at the reaction temperature of the first reaction stage.
• Suitable amines are triethylamine, tri-n-butylamine, dimethylcyclohexylamine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylethylenediamine, ⁇ , ⁇ -dimethylbenzylamine, triethylenediamine or dimethyloctylamine, N-methylmorpholine and bis- (N, N- dimethylaminoethyl) ether, preference is given to N, N-dimethylbenzylamine.
• the catalysts c) are used in an amount of 0.01 to 2, preferably 0.01 to 0.1 wt .-%, based on the total weight of component a) and b).
• the stabilizers d) are so-called catalyst poisons for the catalysts c)
• Suitable are any alkylating esters of organic sulfonic acids
• these sulfonic acid alkyl esters have a molecular weight of from 110 to 250 both aliphatic sulfonic acid alkyl esters, such as n-butanesulfonic acid methyl ester, n-Perfluorbutansulfonklamethylester or n-hexanesulfonic acid ethyl ester, and aromatic sulfonic acid alkyl esters, such as benzenesulfonate, ethyl ester or n-butyl ester, p-toluenesulfonate, ethyl ester or n-butyl ester, 1-naphthalenesulfonic acid methyl ester Methyl 3-nitrobenzenesulphonate or methyl 2-na
• Component d) is used at least in an amount equivalent to the tertiary amine nitrogen of component c).
• suitable chemical blowing agents T include, for example, water and / or phospholine oxide and / or formic acid.
• physical blowing agent T for example, hydrocarbons such as pentane, butane and / or hexane, but also halogenated hydrocarbons can be used.
• 1,1,1,3,3-pentafluoropropane (HFC-245fa) is the sole blowing agent.
• HFC-245fa 1,1,1,3,3-pentafluoropropane
• Suitable amines also include those which, in addition to the catalysis effect, also have a blowing effect.
• the catalyst component f) simultaneously acts as a blowing agent T.
• Preferred catalysts c) are dimethylbenzylamine, methyldibenzylamine, boron trichloride tert. - Amine adducts and N- [3 - (dimethylamino) propyl] formamide.
• Preferred auxiliaries and additives e) are the known foam stabilizers of the polyether siloxane type, mold release agents, e.g. Polyamide waxes and / or stearic acid derivatives and / or natural waxes, e.g. Carnauba wax.
• auxiliaries and admixtures e) which may be used are, for example, el) organic compounds of molecular weight range 62 to 8000 having at least 2, preferably 2 to 8 and preferably 2 to 3 alcoholic hydroxyl groups, as known per se as a synthesis component for polyurethane ,
• el organic compounds of molecular weight range 62 to 8000 having at least 2, preferably 2 to 8 and preferably 2 to 3 alcoholic hydroxyl groups, as known per se as a synthesis component for polyurethane
• simple polyhydric alcohols such as ethylene glycol, hexadiol-1, 6, glycerol or trimethylolpropane, dimethylsiloxane units containing polyols, eg. B. ether bis (dimethylhydroxymethyl-silyl); Ester group-containing polyhydroxyl compounds such as e.g.
• Castor oil or polyhydroxypolyester as obtained by polycondensation of excess amounts of simple polyhydric alcohols of the type just mentioned by way of example with preferably dibasic carboxylic acids or their anhydrides, e.g. Adipic acid, phthalic acid or phthalic anhydride are available or polyhydroxyl polyethers as by addition of alkylene oxides such as propylene oxide and / or ethylene oxide to suitable starter molecules such.
• Water, the just mentioned simple alcohols or amines with at least two amine NH bonds are accessible; Polyvalent amines such.
• DETDA Diethyltoluylenediamine
• the additives el) are used, if at all, in a maximum amount corresponding to an NCO / OH equivalent ratio, based on the isocyanate groups of component a) and the hydroxyl groups and / or amino groups of component el), of at least 2: 1, preferably at least 2.5: 1 corresponds.
• the amount of component a) must be such that the equivalent ratio of isocyanate groups of component a) to the sum of the epoxide groups of component b), hydroxyl groups and / or amino groups of component el) and optionally present in component b) hydroxyl ⁇
• auxiliaries and additives e) which may be used are e2) polymerizable, olefinically unsaturated monomers which are used in amounts of up to 100% by weight, preferably up to 50% by weight, in particular up to 30% by weight on the total weight of components a) and b) can be used.
• additives e2) are olefinically unsaturated monomers which do not have hydrogen atoms reactive with NCO groups, e.g. Diisobutylene, styrene, Ci-C i -alkylstyrenes such as ⁇ -methylstyrene, a-butylstyrene, vinyl chloride, vinyl acetate, maleimide derivatives such as e.g.
• styrene and / or (meth) acrylic acid-Ci-C i-alkyl esters are used, provided that the additives e2) are used at all.
• additives e2 With the use of additives e2), the concomitant use of conventional polymerization initiators, such as e.g. Benzoyl peroxide possible, but generally not required.
• conventional polymerization initiators such as e.g. Benzoyl peroxide
• auxiliaries and additives el) or e2) are generally not required.
• the additives mentioned by way of example under el) are preferred over the compounds exemplified under e2).
• auxiliaries and additives e) include, for example, e3) fillers such as quartz flour, chalk, microdol, alumina, silicon carbide, graphite or corundum; Pigments such as titanium dioxide, iron oxide or organic pigments such as phthalocyanine pigments; Plasticizers such as dioctyl phthalate, tributyl or triphenyl phosphate; incorporable compatibilizers such as methacrylic acid, ⁇ -hydroxypropyl ester, maleic acid and fumaric acid esters; Flame retardant substances such as exolith or magnesium oxide; soluble dyes or reinforcing materials such as glass fibers or glass cloths.
• fillers such as quartz flour, chalk, microdol, alumina, silicon carbide, graphite or corundum
• Pigments such as titanium dioxide, iron oxide or organic pigments such as phthalocyanine pigments
• Plasticizers such as dioctyl phthalate, tributyl or triphenyl phosphate
• suitable fillers are metallic fillers, such as aluminum, copper, iron and / or steel. The metallic fillers are used in particular in granular form and / or powder form.
• auxiliaries and additives e) which may be used are, for example, e4) olefinically unsaturated monomers having hydrogen atoms which are reactive toward NCO groups, for example hydroxyethyl methacrylate, hydroxypropyl methacrylate and aminoethyl methacrylate.
• auxiliaries and additives e) can be incorporated into the starting materials a) and b) before the process according to the invention is carried out and can also be added later.
• the starting materials a) and b) can be mixed with one another.
• the reaction mixture are then optionally further auxiliaries and additives e), the catalyst f), 1,1,1,3,3-pentafluoropropane (HFC-245fa) and optionally further blowing agent T) added, the whole intimately mixed and the foamable mixture in a poured open or closed mold.
• the method When using a known from polyurethane processing multi-component mixing head, the method is characterized by a high degree of flexibility. By varying the mixing ratio of the components a) and b) different foam qualities can be produced with one and the same starting materials. In addition, it is also possible to drive different components a) and various components b) in different proportions directly into the mixing head.
• the auxiliaries and additives e), the catalyst f), 1,1,1,3,3-pentafluoropropane (HFC-245fa) and optionally further blowing agents T) can be run separately or as a batch in the mixing head.
• HFC-245fa 1,1,1,3,3-pentafluoropropane
• optionally further blowing agent T foams with different density ranges can be produced.
• a stable reaction mixture is obtained by adding a stabilizer d) during the mixing of the starting materials a) and b) and, if appropriate, of the auxiliaries and additives e) or a part thereof.
• a stabilizer d during the mixing of the starting materials a) and b) and, if appropriate, of the auxiliaries and additives e) or a part thereof.
• the auxiliary auxiliary and additive e), the catalyst f), 1,1,1,3,3-pentafluoropropane (HFC-245fa) and optionally further blowing agents T) are optionally added to the stable reaction mixture, the whole intimately mixed and the foamable Mixture poured into an open or closed mold.
• This method is particularly advantageous if the mixing ratio of the components a) and b) should not be varied. There are no separate reservoir, metering and mixing head feeds for the components a) and b) necessary. 1 r
• the starting materials a) and c) and optionally the auxiliaries and additives e) or a part thereof can be mixed together and within the temperature range from 20 to 150.degree. C., preferably 60 to 130.degree to be reacted.
• the reaction is stopped by addition of the stabilizer / stopper d).
• the stable intermediate obtained in this case can, if appropriate, be mixed with intermediate component b) for any length of time, thereby obtaining a B-state which is liquid at room temperature. This can be fed, optionally after any intermediate storage for any length of the second stage of the process according to the invention.
• auxiliary agents and additives e), the catalyst f), 1,1,1,3,3-pentafluoropropane (HFC-245fa) and, if appropriate, further blowing agents T) are added to the B-state, the mixture intimately mixed and the foamable mixture is placed in an open or closed mold.
• This process offers the advantage of a higher viscosity B state to start the foaming reaction. Depending on whether and, if so, which auxiliaries and additives e) are added, a higher-viscosity B-state leads to improved foam properties. Subsequent mixing of the stable, partially reacted component a) with component b) offers the advantage of high flexibility since, as required, various components b) can be mixed with the partially reacted component a) to form various stable B states.
• the starting materials a) to c) and, if appropriate, the auxiliaries and additives e) or a part thereof may be mixed with one another and mixed within the temperature range from 20 to 150.degree.
• the resulting intermediate product represents a liquid B-state at room temperature and can be fed, optionally after any intermediate storage for any length of the second stage of the process according to the invention.
• the intermediate (B state) optionally further auxiliaries and additives e), the catalyst f), 1,1,1,3,3-pentafluoropropane (HFC-245fa) and optionally further blowing agent T) are added, the whole thing intimately mixed and the foamable mixture poured into an open or closed mold.
• This process also offers the advantage of a higher viscosity B state at the beginning of the foaming reaction. If component b) is not to be varied, this method is preferable in certain cases to that previously described.
• the generally low-viscosity components a) and b) can be easily mixed and used to produce the higher-viscosity B-state.
• the partially converted component a) depending on their nature and the degree of - 17 -
• the blowing process generally begins after a lying time of 10 seconds to 6 minutes and is usually completed after 2-12 minutes.
• the foams are fine-celled and even.
• a subsequent temperature treatment between 70 and 250 ° C, preferably 120 and 250 ° C, more preferably 180 and 220 ° C made after foaming in the final foamed state.
• Overfilling means filling a foamable mixture that in an open mold after complete foaming would occupy a larger volume than the internal volume of the mold.
• the foams of the invention have a low thermal conductivity, are flame retardant and have low dielectric losses, the moisture resistance and abrasion resistance and the processability in molds are excellent.
• the bulk densities were measured on foam cubes (5 x 5 x 5 cm) cut from the middle of the foams.
• the compressive strengths were measured according to DIN EN 826 on foam cubes (5 ⁇ 5 ⁇ 5 cm) cut from the middle of the foams.
• HFC-245fa Honeywell Fluorine Products Europe B.V.
• a comparison of the compressive strengths at approximately the same densities of the foams of Example 3 and Comparative Example 5 shows the enormous advantage of the HFC-245fa-driven foam according to the invention over the foam driven with Solkane® 365/227 93/7.
• the foam of the invention has a 37% higher compressive strength.
• a comparison of the compressive strengths of the foams of Example 2 and Comparative Example 4 shows the enormous advantage of the HFC-245fa-propelled foam of the invention over the Solkane® 141b-driven foam.
• the foam of the invention has at a 22% lower bulk density by 11%> higher compressive strength.
• the compressive strengths of a foam according to the invention were measured with a bulk density of 60 kg / m 3 at the indicated temperatures.
• Foams are obtained. Even at 180 ° C., the foam still has 75% of the compressive strength at room temperature.

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• 2012
  • 2012-04-27 EP EP12719344.9A patent/EP2705076A2/de not_active Withdrawn
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  • 2012-04-27 WO PCT/EP2012/057847 patent/WO2012150201A2/de active Application Filing
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