WO2000056810A1 - Mousses contenant une charge - Google Patents

Mousses contenant une charge Download PDF

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Publication number
WO2000056810A1
WO2000056810A1 PCT/EP2000/002249 EP0002249W WO0056810A1 WO 2000056810 A1 WO2000056810 A1 WO 2000056810A1 EP 0002249 W EP0002249 W EP 0002249W WO 0056810 A1 WO0056810 A1 WO 0056810A1
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WO
WIPO (PCT)
Prior art keywords
acid
temperature
weight
filler
foams
Prior art date
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PCT/EP2000/002249
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German (de)
English (en)
Inventor
Hermann Kluth
Robert Graf
Maria-Elisabeth Kaiser
Wolfgang Ernst
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Cognis Deutschland Gmbh
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Filing date
Publication date
Application filed by Cognis Deutschland Gmbh filed Critical Cognis Deutschland Gmbh
Priority to EP00920499A priority Critical patent/EP1171518A1/fr
Priority to AU41053/00A priority patent/AU4105300A/en
Priority to CA002367730A priority patent/CA2367730A1/fr
Publication of WO2000056810A1 publication Critical patent/WO2000056810A1/fr
Priority to NO20014602A priority patent/NO20014602L/no

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Classifications

    • 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
    • C08J9/0066—Use of inorganic compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/14—Macromolecular materials
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L5/00—Devices for use where pipes, cables or protective tubing pass through walls or partitions
    • F16L5/02—Sealing
    • F16L5/04—Sealing to form a firebreak device
    • 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
    • C08G2101/00—Manufacture of cellular products
    • 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
    • C08J2375/04—Polyurethanes

Definitions

  • the present invention is in the field of filler-containing foams and relates to foams with increased fire resistance.
  • Foams are used in the construction industry primarily for cold and thermal insulation. Such foams are usually manufactured industrially and delivered to the construction site in sheet form. The foams mainly used as insulation materials are generally not used in places in construction that are of particular importance in terms of fire protection, in particular component openings (joints) and line penetrations (cables and pipes) in the area of ceilings and walls. The fire behavior and fire resistance of such foams are therefore of great importance. Fire resistance, in particular the time during which a component may prevent the fire from passing through, is crucial.
  • the object of the present invention was therefore to develop foams which are distinguished by improved fire resistance.
  • the desired high fire resistance should be achieved both for so-called local foams, which are made directly from two components on / in the building, and for one-component foams, which are usually applied in aerosol cans, as well as for prefabricated foams.
  • the handling and processing of such a foam should also enable it to be used directly on site. This requires above all a production without or with only slight heating of the starting mixtures.
  • good shelf life of the products is of great interest.
  • the invention relates to filler-containing foams which can be obtained, for example, by reacting
  • the foams obtainable in this way have excellent fire resistance, which can be demonstrated in tests in accordance with DIN 4102, Part 2 and at the same time have essential positive properties such as low weight, simple workability and deformability under pressure.
  • the foams containing filler according to the invention are suitable to be used in the form of two-component foams directly on site. This works at temperatures from 0-40 ° C without heating the components beforehand.
  • the compositions according to the invention furthermore have good storage stability, they are furthermore very suitable for processing by the RIM technique. For this purpose, the components are quickly metered and mixed and the mixture is injected into the mold (tool or cavities), in which it hardens in seconds to minutes, depending on the temperature of the mold or the reaction mixture.
  • Foams are understood to mean materials whose essential constituents consist of macromolecular organic compounds, which contain open and / or closed pores distributed over their entire mass and whose bulk density is lower than that of the framework substance.
  • Multifunctional isocyanates are understood to mean materials whose essential constituents consist of macromolecular organic compounds, which contain open and / or closed pores distributed over their entire mass and whose bulk density is lower than that of the framework substance.
  • polyfunctional isocyanates are used as component (I), which are selected from the group of aliphatic, cycloaliphatic, aromatic polyfunctional isocyanates and oligomerized products with NCO groups produced therefrom.
  • the viscosity of the multifunctional isocyanates is usually at 25 ° C ⁇ 5000 mPas, measured according to DIN-53211.
  • multi-functional is meant a functionality of the isocyanate component of greater than 1.5.
  • the isocyanate component can also be a mixture of isocyanates, although strictly monofunctional isocyanates can also be used, e.g. Phenyl isocyanate.
  • the suitable polyfunctional isocyanates preferably contain an average of 2 to at most 5, preferably between 2.3 and 4, NCO groups.
  • suitable isocyanates are phenyl isocyanate, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), hydrogenated MDI (H- ⁇ MDI), xylylene diisocyanate (XDI), m- and p-tetramethylxylylene diisocyanate (TMXDI),
  • Sulfur-containing polyisocyanates are obtained, for example, by reacting 2 mol of hexamethylene diisocyanate with 1 mol of thiodiglycol or dihydroxydi- hexyl sulfide.
  • Other important diisocyanates are trimethylhexamethylene diisocyanate, 1,4-diisocyanatobutane, 1,12-diisocyanatododecane and dimer fatty acid diisocyanate.
  • interesting partially blocked polyisocyanates which enable the formation of self-crosslinking polyurethanes, e.g. dimeric tolylene diisocyanate, or partially or completely reacted polyisocyanates with, for example, phenols, tertiary butanol, phthalimide, caprolactam.
  • the isocyanate component partially contains dimer fatty acid isocyanate.
  • Dimer fatty acid is a mixture of predominantly C3g-dicar- bonic acids, which is produced by thermal or catalytic dimerization of unsaturated C ⁇ -monocarboxylic acids, such as oleic acid, tall oil fatty acid or linoleic acid. Such dimer fatty acids have long been known to the person skilled in the art and are commercially available.
  • the dimer fatty acid can be converted into dimer fatty acid isocyanates.
  • Technical dimer fatty acid diisocyanate has on average at least two and less than three isocyanate groups per molecule of dimer fatty acid.
  • the isocyanate component (I) preferably consists of more than 30% by weight, based on the total amount of isocyanates, in particular at least predominantly, preferably completely, of aromatic isocyanates such as MDI.
  • a polymer MDI with a functionality of 2.3 to 3.0 is particularly preferred.
  • aromatic isocyanates are preferred, as are oligomerized NCO-terminal adducts from the above-mentioned isocyanates and polyols, polyamines or amino alcohols.
  • aliphatic and cycloaliphatic isocyanates are able to react quickly and completely even at room temperature.
  • Particularly preferred as aliphatic polyisocyanates are trimerizates of hexamethylene diisocyanate and isophorone diisocyanates, in which the monomer HDI or IPDI was brought to a content of less than 0.5%, and in particular less than 0.1%, by thin-layer distillation of the trimerate solution.
  • the equivalent ratio of isocyanate groups (NCO) to groups with active hydrogen (AKH) should be 2: 1 to 0.5: 1, preferably 1.5: 1 to 0.6: 1. If, in addition to the described reactions with compounds with active hydrogen, trimerization of excess isocyanate groups is desired, the ratio of NCO: active hydrogen can also be up to 5: 1.
  • the vapor pressure of the multifunctional isocyanates is usually a maximum of 0.0002 mbar at 25 ° C.
  • the multifunctional isocyanates are generally present in component (I) in amounts between 70 and 100% by weight, based on the total amount of component (I), in particular between 85 and 98% by weight.
  • the carboxylic acids to be used as component a) of component (II) are understood to be acids which contain one or more carboxyl groups (-COOH).
  • the carboxyl groups can with saturated, unsaturated and / or branched alkyl or cycloalkyl radicals or with aromatic residues. You can add other groups such as ether, ester, halogen, amide,
  • Liquids can be easily incorporated at room temperature, such as native fatty acids or
  • Fatty acid mixtures COOH-terminated polyesters, polyethers or polyamides, dimer fatty acids and
  • Trimer fatty acids incompletely esterified mixtures of aliphatic dicarboxylic acids and aliphatic polyols, preferably based on polyether.
  • Specific examples of the carboxylic acids according to the invention are: acetic acid, Valerian, Capron, Capryl, Caprin, Laurin,
  • Linolenic and Gadoleic Acid The following may also be mentioned: adipic acid, sebacic acid,
  • Tetrachlorophthalic acid oxalic acid, muconic acid, succinic acid, fumaric acid, ricinoleic acid, 12-
  • esters of polycarboxylic acids or carboxylic acid mixtures which have both COOH and OH groups can also be used, such as esters of TMP [C 2 H.-C (CH 2 OH) 3 ], glycerol, pentaerythritol, sorbitol,
  • carboxylic acids also includes hydroxycarboxylic acids and polyhydroxycarboxylic acids.
  • Hydrocarboxylic acids are to be understood as monohydroxymonocarboxylic acids, monohydroxypolycarboxylic acids, polyhydroxymonocarboxylic acids and polyhydroxypolycarboxylic acids with 2 to 600, preferably with 8 to 400 and in particular with 14 to 120 C atoms, which contain 1 to 9, preferably 2 to 3, hydroxyl groups or carboxyl groups on one HC residue, especially an aliphatic residue.
  • the polyhydroxy monocarboxylic acids and the polyhydroxy polycarboxylic acids are combined to form the polyhydroxy fatty acids.
  • Polyhydroxy fatty acids which can be used according to the invention can expediently be prepared by first epoxidizing esters of unsaturated fatty acids and then using bases or acid catalysis with an excess of a hydrogen-active compound, in particular i) a hydroxyl-containing compound, for example a hydroxycarboxylic acid, an aliphatic polyol or ii) compounds containing carboxyl groups, in particular polyvalent carboxylic acids and / or iii) water with ring opening and, if appropriate, transesterification.
  • the reaction mixture is then treated at temperatures between 20 ° C and '60 ° C with an alkali metal hydroxide and then saponified at temperatures between 80 ° C and 110 ° C to the polyhydroxy fatty acids.
  • hydroxycarboxylic acids the aliphatic polyols and / or water are used stoichiometrically or in deficit when opening the epoxy ring, crosslinking reactions also occur, in which polyhydroxy polyfatty acids are formed, which in the sense of the invention also fall under the term polyhydroxy fatty acids.
  • the polyhydroxy fatty acids according to the invention are preferably derived from naturally occurring fatty acids. Therefore, they usually have an even number of carbon atoms in the main chain and are not branched. Those with a chain length of 8 to 100, in particular 14 to 22, carbon atoms are particularly suitable.
  • natural fatty acids are mostly used as technical mixtures. These mixtures preferably contain a part of oleic acid. They can also contain other saturated, monounsaturated and polyunsaturated fatty acids. In principle, mixtures of different chain lengths can also be used in the preparation of the polyhydroxyfatty acids or polyhydroxyalkoxyfatty acids which can be used according to the invention and which may also contain saturated portions or else polyhydroxyalkoxycarboxylic acids with double bonds.
  • the pure polyhydroxy fatty acids are suitable here, but also mixed products obtained from animal fats or vegetable oils which, after preparation (ester cleavage, purification stages), contain monounsaturated fatty acids> 40%, preferably> 60%.
  • monounsaturated fatty acids > 40%, preferably> 60%.
  • these are commercially available natural raw materials such as beef tallow with a chain distribution of 67% oleic acid, 2% stearic acid, 1% heptadecanoic acid, 10% saturated acids with chain length C12 to C16, 12% linoleic acid and 2% saturated acids> C18 carbon atoms or e.g. the oil of the new sunflower (NSb) with a composition of approx.
  • Polyhydroxyfatty the invention derive from monounsaturated fatty acids, such as 4,5-tetradecenoic, 9,10-tetradecenoic, 9,10-pentadecenoic acid, 9,10 hexadecenoic, 9,10-heptadecenic, '6,7-octadecenoic , 9,10-octadecenoic acid, 11,12-octadecenoic acid, 11, 12-eicosenoic acid, 11, 12-docosenoic acid, 13,14-docosenoic acid, 15,16-tetracosenoic acid and 9,10-ximenoic acid.
  • oleic acid (9,10-octadecenoic acid) is preferred. Both ice and trans isomers of all the fatty acids mentioned are suitable.
  • polyhydroxy fatty acids which are derived from less frequently occurring unsaturated fatty acids, such as decyl-12-enoic acid, stilingic acid, dodecyl-9-enoic acid, ricinoleic acid, petroselinic acid, vaccenic acid, elaostearic acid, punicic acid, licanoic acid, parinaric acid, gadoleic acid, arachidonic acid 5-eicosenoic acid, 5-docosenoic acid, cetoleic acid, 5,13-docosadienoic acid and / or seiacholeic acid.
  • Polyhydroxy fatty acids which have been prepared from isomerization products of natural unsaturated fatty acids are also suitable.
  • the polyhydroxy fatty acids produced in this way differ only in the position of the hydroxy or hydroxyalkoxy groups in the molecule. They are generally in the form of mixtures.
  • Naturally occurring fatty acids are preferred as starting components in the sense of natural raw materials in the present invention, but this does not mean that synthetically produced carboxylic acids with corresponding C numbers are not suitable.
  • Polyunsaturated fatty acids are also suitable, e.g. Linoleic acid, linolenic acid and ricinic acid.
  • Cinnamic acid is a concrete example of an aromatic carboxylic acid and tartaric acid and citric acid are examples of a polycarboxylic acid.
  • the hydroxyalkoxy radical of the polyhydroxy fatty acids is derived from the polyol which has been used for the ring opening of the epoxidized fatty acid derivative. Preference is given to polyhydroxy fatty acids whose hydroxyalkoxy group is derived from preferably primary difunctional alcohols having up to 24, in particular up to 12, carbon atoms.
  • Suitable diols are propanediol, butanediol, pentanediol and hexanediol, dodecanediol, preferably 1,2-ethanediol, 1,4-butanediol, 1,6-hexanediol, polypropylene glycol, polybutadiene diol and / or polyethylene glycol with a degree of polymerization of 2 to 40 particularly suitable as diol compounds polypropylene glycol and / or polytetrahydrofuran diol and their mixed polymerization products. This applies in particular if these compounds each have a degree of polymerization of about 2 to 20 units.
  • triols or higher alcohols for example glycerol and Trimethylolpropane and their adducts of ethylene oxide and / or propylene oxide with molecular weights up to 1,500. Polyhydroxy fatty acids with more than 2 hydroxyl groups per molecule are then obtained.
  • a hydroxycarboxylic acid can also be used instead of a polyol as the compound containing hydroxyl groups, e.g. Citric acid, ricinoleic acid, 12-hydroxystearic acid, lactic acid. Ester groups then arise instead of ether groups.
  • amines, hydroxyl-bearing amines or amine carboxylic acids can also be used to open the ring.
  • dihydroxy fatty acids in particular from diols, are preferred. They are liquid at room temperature and can be easily mixed with the other reaction participants.
  • dihydroxy fatty acids are understood to mean both the ring opening products of epoxidized unsaturated fatty acids with water and the corresponding ring opening products with diols and their crosslinking products with further epoxy molecules.
  • the ring opening products with diols can also be referred to more precisely as dihydroxyalkoxy fatty acids.
  • the hydroxyl groups or the hydroxyalkoxy group are preferably separated from the carboxy group by at least 1, preferably at least 3, in particular at least 6, CH 2 units.
  • Preferred dihydroxy fatty acids are:
  • epoxidized carboxylic acid esters for example epoxidized fatty acid methyl, ethyl, propyl or glycerol esters
  • water and / or the polyols from which the hydroxyalkoxy group is to be derived under ring opening and, if desired, transesterification conditions can be used for this.
  • a basic or acidic catalyst - for example a strong mineral acid - and at a reaction temperature between 80 ° C and 120 ° C or basic at 200 ° C
  • epoxidized fatty acid derivative continuously or in portions.
  • the progress of the reaction can be monitored by titration of the residual epoxide content or by means of spectroscopic methods.
  • the catalyst is destroyed by neutralization.
  • the resulting polyhydroxy fatty acid esters can, if necessary, be freed from excess reactant by distillation.
  • the saponification of the polyhydroxy fatty acid esters to form the polyhydroxy fatty acids is usually carried out.
  • the saponification is preferably carried out at temperatures between 40 ° C and 120 ° C in the presence of water with basic catalysis.
  • Suitable bases are the hydroxides of the alkali and / or alkaline earth metals and tertiary amines.
  • the polyhydroxy fatty acids are obtained as salts (soaps) and can be obtained by adding strong acids, for example hydrochloric acid or sulfuric acid. It is possible to clean the reaction products by simple or, if desired, multiple washing with water. In principle, it is also possible to split the esters, in particular the triglycerides, with water in the absence of catalysts.
  • Alcohols as substances b) of component (II) are to be understood as hydroxyl derivatives of aliphatic and alicyclic saturated, unsaturated and / or branched hydrocarbons. Both 1- and 2- or higher alcohols can be used. In addition to monohydric alcohols, this also includes the low molecular weight chain extenders or crosslinkers with hydroxyl groups which are known per se from polyurethane chemistry.
  • low molecular weight range examples from the low molecular weight range are pentanol, 2-ethylhexanol, 2-octanol, ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, 2,3-butylene glycol, hexamethylene diol, octamethylene diol, neopentyl glycol, 1,4-bishydroxymethylcyclohexane, 2-methyl-1,3 -Propanediol, hexanetriol- (1,2,6), glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, formite, methylglycoside, butylene glycol, the reduced dimer and trimer fatty acids and higher polyethylene, polypropylene and polybutylene glycols.
  • the term “alcohols” in the context of polyurethane chemistry is also to be understood to mean organic polyhydroxyl compounds (polyols) which are known per se.
  • polyols organic polyhydroxyl compounds
  • Such polyhydroxy polyethers are known per se by alkoxylation of suitable starter molecules, for example water, propylene glycol, glycerol, trimethylolpropane, sorbitol, cane sugar, amino alcohols such as ethanolamine or diethanolamine or lipatic amines such as n-hexylamine or 1,6-diaminohexane or any mixtures of such starter molecules.
  • Suitable alkoxylating agents are, in particular, propylene oxide and optionally ethylene oxide.
  • the usual polyester polyols in the molecular weight range from 400 to 10,000 are also suitable for foam production. if you 2 bi s contain 6 hydroxyl groups.
  • Suitable polyester polyols are the known reaction products of Excess amounts of polyhydric alcohols of the type already exemplified as starter molecules with polybasic acids such as succinic acid, adipic acid, phthalic acid, tetrahydrophthalic acid, dimer and trimer fatty acid or any mixture of such acids.
  • Polycarbonate polyols are also suitable.
  • polyether and polyester polyols with an OH number greater than 200, in particular greater than 250 and a functionality between 2.5 and 4.5 is particularly preferred. Mixtures of polyhydroxy compounds with low and higher molecular weights are particularly suitable for this.
  • polyvalent primary or secondary amines can also be used as chain building blocks, as can aminocarboxylic acids and low molecular weight protein compounds.
  • polyoxyethylene, polyoxypropylene and polyoxybutylene diamine with molecular weights up to 5,000 or glycine, alanine, valine, leucine, cysteine, cystine, aspartic acid, glutamic acid, tyrosine, tryptophone, eta-amino-caproic acid, 11-amino -undecanoic acid, 4-amino-butyric acid, mono- and -di-amino-naphthoic acid.
  • Carboxylic acids with at least 2 carbon atoms, in particular with 5 to 400 carbon atoms, are preferred.
  • dicarboxylic acid with polyether diols and / or polyether triols as they are available, for example under the name SOVERMOL ® (Henkel KGaA).
  • SOVERMOL ® Hexkel KGaA
  • carboxy polyols generally have a hydroxyl number (OH number) of 200-400, in particular 250-350, and an acid number (SZ number) of 100-200, in particular 100-150.
  • component (I) and / or component (II) contain, as further constituents, catalysts and / or foam stabilizers and / or liquid fire retardants and / or silicon dioxide.
  • Silicon dioxides whose average particle size is smaller than 100 nm can be used as further constituents of components (I) and / or (II).
  • pyrogenic silicas can be used here, under this name are summarized highly disperse silicas that are produced by flame hydrolysis. These are usually available as agglomerates with a size of 1-50 ⁇ m.
  • precipitated silicas is preferred; in particular, finely divided silicas are preferred, the primary particle size of which is 5-100 nm.
  • concentrations of the silicon dioxide are generally between 0.5 and 5.0% by weight, in particular between 1.0 and 4.0% by weight, based on the total amount of the respective component (I) or (II).
  • catalysts for accelerating the NCO-COOH reaction substances can be used which have a high nucleophilicity due to their ability to stabilize positive charges. This property is already present to a considerable extent with aliphatic tertiary amines, especially with a cyclic structure. Also suitable among the tertiary amines are those which additionally carry groups which are reactive toward the isocyanates, in particular hydroxyl and / or amino groups. Specifically:
  • heteroaromatics are preferably used, in particular if they have at least one nitrogen atom in the ring and further heteroatoms or functional groups which have a positive inductive and / or positive mesomeric effect (HR Christen, Fundamentals of Organic Chemistry, 4th ed. 1977, p. 378 ff) included. So practice e.g. Alkyl groups a weak positive inductive (+ I) effect. Amino groups can produce a strong positive mesomeric (+ M) effect due to the lone pair of electrons. Preferred catalysts are therefore heteroaromatic amines which carry substituents with + I and / or + M effects, in particular further heteroatoms, and therefore
  • n can stabilize positive charges particularly well.
  • These include: derivatives of pyrrole, indolizine, indole, isoindole, benzotriazole, carbazole, pyrazole, imidazole, oxazole, isooxazole, isothiazole, triazole, tetrazole, thiazoles, pydridine, quinoline, isoquinoline, acridine, phenantridine, pyridrains, pyrimidines, pyrimidines Triazines and compounds containing corresponding structural elements.
  • the catalysts can also be in oligomerized or polymerized form, for example as N-methylated polyethyleneimine.
  • 1-Methylimidazole, 2-methyl-1-vinylimidazole, 1-allylimidazole, 1-phenylimidazole, 1, 2,4,5-tetramethylimidazole, 1 (3-aminopropyl) imidazole, pyrimidazole, 4-dimethylamino-pyridine, 4 are particularly suitable - pyrrolidinopyridine, 4-morpholino-pyridine, 4-methylpyridine and N-dodecyl-2-methylimidazole.
  • Preferred catalysts are amino-substituted pyridines and / or N-substituted imidazoles.
  • organometallic compounds such as tin (II) salts of carboxylic acids, strong bases such as alkali hydroxides, alcoholates and phenolates, e.g. Di-n-octyl tin mercaptide, dibutyl tin maleate, diacetate, dilaurate, dichloride, bisdodecyl mercaptide, tin ll acetate, ethyl hexoate and diethyl hexoate or lead phenyl ethyl dithiocarbaminate.
  • organometallic compounds such as tin (II) salts of carboxylic acids, strong bases such as alkali hydroxides, alcoholates and phenolates, e.g. Di-n-octyl tin mercaptide, dibutyl tin maleate, diacetate, dilaurate, dichloride, bisdodecyl mercaptide, tin
  • the organometallic catalysts can also be used alone if certain carboxylic acids are used, namely hydroxy and amino carboxylic acids.
  • DABCO, TMR-2 etc. from Air Products may be mentioned as the trimerization catalyst, which are quaternary ammonium salts dissolved in ethyl glycol.
  • the above-mentioned starting materials and catalysts are used in the following proportions: 0.1 to 5, preferably 0.1 to 2 equivalents of a mixture of carboxylic acid and alcohol and 0.0001 to 0.5, preferably 0.001 to 0.1, are added to one equivalent of isocyanate Equivalents of amine, where the alcohol: acid ratio can be 20: 1 to 1:20. If catalysts are used which still carry groups which are reactive towards the isocyanates, in particular OH and NH groups, these catalysts can be used in a substantially higher concentration since they themselves contribute to the molecular weight build-up. In this case, from 0.001 to 2.0 equivalents of amine are possible.
  • the amines should preferably be used in a concentration of 0.05 to 15, in particular 0.5 to 10,% by weight, based on the sum of hydroxycarboxylic acid and isocyanate .
  • siloxane-oxyalkylene copolymers are used as foam stabilizers.
  • substances are generally used, such as are described in, for example, the Kunststoff-Handbuch, Volume 7, Polyurethane, Carl Hanser Verlag, Kunststoff, 3rd edition, 1993, pages 104-127 to which express reference is made here.
  • Silicone-free stabilizers can also be used, e.g. LK-221 (OHZ: 40.5), LK-332 (OHZ: 35) and LK-443 (OHZ: 44) from Air Products.
  • the use concentration of the foam stabilizers is 0.1-5.0% by weight, based on the sum of isocyanate and isocyanate-reactive compounds (polyols + carboxypolyols).
  • Components (I) and / or (II) can further contain fire retardants which are liquid at room temperature.
  • fire retardants include, in particular, bromine, chlorine and phosphorus-containing fire protection agents, such as those mentioned in the publication series of the Federal Institute for Occupational Safety and Health Hazardous Working Materials - GA 24 ", HM Berstermann: Substitutes for Antimony Trioxide, 1996, Table 8.4, to which expressly here
  • liquid fire retardants can be used in amounts of 0 to 30% by weight, preferably 15 to 25% by weight, in each case based on the total amount of
  • component (I) contains
  • auxiliaries 0 to 30% by weight, in particular 2 to 20% by weight, of auxiliaries.
  • The% by weight is given in relation to the total weight of component (I). It is essential for the selection of the auxiliary substances that they do not react with the polyfunctional isocyanates, that is, they represent an inert component.
  • the auxiliaries can in particular be selected from the group consisting of catalysts, foam stabilizers, liquid fire retardants and silicon dioxide.
  • substances which are suitable for adjusting the density of component (I) can be used as auxiliary substances.
  • Microporous, high-temperature-resistant fillers, as described as component c-2, are particularly suitable.
  • the addition of micropore-forming, high-temperature-resistant fillers as auxiliaries to component (I) has no influence on the amount of these substances, as used in the filler mixture of component (II). Barium sulfate, for example, is still suitable for density regulation.
  • component (II) contains water as further constituents.
  • component (II) To support foam formation, small amounts of water can be added to component (II), the addition is generally between 0.2 and 2.0%, and can be selected depending on the required density of the expanded fire-retardant foams. Quantities of 0.5-1.5% by weight, based on the sum of the substances of component (II), are preferred.
  • Mineral substances such as calcium carbonate, calcium sulfate, clay, aluminum oxide, aluminum silicate and magnesium oxide are suitable as inorganic, high-temperature-resistant fillers (c-1).
  • Natural aluminum silicates such as kaolin, mica, feldspar and mixtures thereof are preferred.
  • These fillers are generally used in finely ground form, an average size of 1 to 20 ⁇ m being particularly preferred. Usual amounts are 20 to 90% by weight based on the total amount of filler, the use of 40 to 80% by weight is particularly preferred.
  • microporous, high-temperature-resistant fillers are added in order to close not only the pores formed when the foam is foamed, but also thermostable pores in the product produce. This is of particular importance since the pores formed when the foam is foamed have organic, thermally decomposable cell walls which are destroyed at temperatures above the decomposition point of the foam (> 200 ° C.).
  • the added, high-temperature-resistant fillers are distinguished by the fact that they form pores which are stable even at temperatures above this decomposition temperature. You get the thermal insulation ability of the molded parts over wide temperature ranges up to approx. 1200 ° C.
  • Suitable fillers are, for example, expanded pearlite and vermiculite, expanded clay, aluminum silicate, glass and / or fly ash hollow spheres, aerated concrete and expanded water glass.
  • the microporous, high-temperature-resistant fillers can be used as individual substances, but the use in mixtures is preferred.
  • Particularly preferred are microporous fillers, the surface of which has been deactivated by suitable polymers or monomers in such a way that the surface is no longer alkaline, so that the fillers modified in this way give mixtures of high storage stability, particularly when mixed with aromatic polyfunctional isocyanates.
  • fillers are usually used in a grain size of 0.0001 to 10 mm, preferably 0.0001 to 2 mm, in particular 0.001 to 1.0 and particularly 0.002 to 0.5 mm.
  • Preferred amounts of the microporous, high-temperature-resistant fillers are 2 to 40% by weight, in particular 2.5 to 30% by weight, based on the total amount of filler.
  • Substances or mixtures which expand their volume in the temperature range from 100 to 1000 ° C., in particular at 200 to 900 ° C., by 2 to 100 times, in particular 10 to 50 times, are used as thermally activatable swelling agents. This expansion compensates for the loss of volume that occurs when the binder is destroyed at its decomposition temperature.
  • the thermally activatable swelling agents thus contribute significantly to the integrity of the molded parts at high temperatures.
  • Such swelling agents are, for example, native vermiculite and native pearlite, expanded graphite, sodium or potassium water glass.
  • mixtures of substances which are capable of releasing phosphoric acid and / or oligophosphoric acid and / or polyphosphoric acid consist of carbon-containing substances with esterifiable hydroxyl groups and substances and mixtures which are capable of releasing a non-combustible gas at elevated temperature can be used as the thermally activatable swelling agent.
  • the latter mixtures can also be used in microencapsulated form.
  • Swelling agent mixtures whose swelling action occurs at different temperatures are preferably used. This is the case, for example, with a mixture of native vermiculite and native pearlite: while native vermiculite already expands at temperatures of 250 to 300 ° C, this effect only occurs at 900 to 1000 ° C with native pearlite.
  • the swelling agents are usually used in a grain size of 0.0001 to 8 mm, a grain size of 0.0001 to 3 mm is preferred.
  • Preferred amounts of the thermally activatable swelling agents are 1 to 30% by weight, in particular 2 to 20% by weight, based on the total amount of filler.
  • the filler mixture (c) contains, as further constituents, adhesives and / or grinding aids and / or anti-caking agents.
  • Suitable adhesives are inorganic adhesives, in particular high-temperature resistant inorganic adhesives.
  • Suitable adhesives for the relevant temperature range (above the decomposition temperature of the foam) are, for example, phosphates, borates and mixtures thereof.
  • both monophosphates and oligo- and polyphosphates in particular melamine phosphate, melamine diphosphate, guanidine phosphate, monoammonium phosphate, diammonium phosphate, potassium triphosphate, sodium hexametaphosphate and ammonium polyphosphate, are suitable.
  • borates of the alkali and alkaline earth metals borates of zinc are preferred for the borates. Mixtures of these adhesives which have their effect over a wide temperature range are preferred.
  • the adhesive is usually used in finely ground form, with a grain size of 0.1 to 1000 ⁇ m, in particular 1 to 100 ⁇ m is preferred.
  • Preferred amounts of the adhesives are 0.1 to 35% by weight, in particular 1 to 25% by weight, based on the total amount of filler.
  • Grinding aids and / or anti-caking agents can be used for problem-free production, storage and metering of the fillers used.
  • Apatites and / or stearates in particular potassium and aluminum stearates, can be used for this purpose.
  • An advantage of using stearates is the fact that they develop an adhesive effect at low temperatures.
  • the grinding aids and / or anti-caking agents are generally added to the mixtures in finely ground form during the grinding process and / or during the mixing process. As a rule, they are used in a grain size of 0.1 to 200 ⁇ m, preferably 1.0 to 50 ⁇ m.
  • Preferred amounts of the grinding aids and / or anti-caking agents are 0.01 to 10% by weight, in particular 0.1 to 5% by weight, based on the total amount of filler.
  • thermally activatable swelling agents 0.1 to 35% by weight of adhesives
  • micropore-forming, high-temperature-resistant fillers 0.01 to 10% by weight of grinding aids and / or anti-caking agents with the proviso that the information is 100% by weight.
  • microporous, high temperature resistant fillers 2.5 to 30 wt .-% microporous, high temperature resistant fillers
  • the filler mixtures are usually added to component (II) in amounts of 5 to 35% by weight, based on the total amount of component (II), in particular in amounts of 15 to 25% by weight.
  • composition (II) 20-50% by weight carboxylic acids 0-20% by weight polyols
  • auxiliaries selected in particular from the group consisting of catalysts, foam stabilizers, liquid fire retardants and silicon dioxide.
  • the percentages by weight are based on the total weight of component (II).
  • additives such as pigments, plasticizers, cell regulators, anti-aging agents, bitter substances and fungicides can also be added to components (I) and / or (II).
  • the present invention further relates to a process for the production of foams containing filler, characterized in that components (I) and (II) are initially introduced separately and the foam is produced by mixing (I) and (II).
  • Components (I) and (II) are usually used in a volume ratio of 1: 2 to 2: 1, preferably in a ratio of 1: 1.
  • the present invention includes the knowledge that the foams can be produced at a temperature of 0-40 ° C, in particular 5-30 ° C. In particular, heating of components (I) and (II) before mixing is not necessary or only to a small extent.
  • the present invention includes the finding that production at room temperature is particularly successful in the presence of catalysts.
  • components (I) and (II) are in a cartridge system.
  • the liquid ingredients are first under a slow-running agitator, max. 1000 rpm mixed.
  • the fillers are then mixed into the homogeneous liquid phase, the stirring speed in particular when incorporating the microballoons into component (I) or (II) must be selected such that the hollow balls are not destroyed to any appreciable extent.
  • the finely divided silicon dioxide is mixed in, as a result of which the component (I) and / or (II) is adjusted to the desired viscosity.
  • the foams according to the invention are particularly suitable for producing fire protection foams.
  • they show good insulation properties, so that they can be used as insulation and insulating materials. Examples
  • a mixture of 1 part by volume of component (I) and one part by volume of component (II) is filled into a coaxial cartridge and injected by means of a cartridge gun via a static mixer into a masonry opening containing a pipe leadthrough.
  • the foam has a bulk density of approx. 55.0 g / l.
  • Example 1 was repeated using a filler mixture according to Table 2.
  • Ammonium polyphosphate 3.0 0-100 microporous, expanded perlite 6.0 0-3000 high temperature resistant filler
  • Example 1 was repeated using a filler mixture according to Table 3.
  • Adhesive ammonium polyphosphate 5.0 0.001-100 microporous, aluminum silicate hollow spheres 9.4 0.001-2000 high temperature resistant filler
  • the PU foams obtained according to Examples 1 to 3 were used for the decay of 30 mm wide, perpendicular joints in 150 mm thick concrete walls in component thickness. If these wall components are exposed to a fire test in accordance with DIN 4102, Part 2, the joints have a fire resistance of at least 90 minutes.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Polymers & Plastics (AREA)
  • General Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne des mousses contenant une charge et leur procédé de production. Les mousses selon l'invention conviennent comme matière calorifuge et comme mousses ignifuges.
PCT/EP2000/002249 1999-03-22 2000-03-14 Mousses contenant une charge WO2000056810A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP00920499A EP1171518A1 (fr) 1999-03-22 2000-03-14 Mousses contenant une charge
AU41053/00A AU4105300A (en) 1999-03-22 2000-03-14 Foams containing a filler
CA002367730A CA2367730A1 (fr) 1999-03-22 2000-03-14 Mousses contenant une charge
NO20014602A NO20014602L (no) 1999-03-22 2001-09-21 Skum som inneholder et fyllstoff

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19912988.6 1999-03-22
DE1999112988 DE19912988C1 (de) 1999-03-22 1999-03-22 Füllstoff enthaltende Schaumstoffe

Publications (1)

Publication Number Publication Date
WO2000056810A1 true WO2000056810A1 (fr) 2000-09-28

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PCT/EP2000/002249 WO2000056810A1 (fr) 1999-03-22 2000-03-14 Mousses contenant une charge

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Country Link
EP (1) EP1171518A1 (fr)
AU (1) AU4105300A (fr)
CA (1) CA2367730A1 (fr)
DE (1) DE19912988C1 (fr)
NO (1) NO20014602L (fr)
WO (1) WO2000056810A1 (fr)
ZA (1) ZA200107780B (fr)

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NL1019919C2 (nl) * 2002-02-07 2003-08-08 Beele Eng Bv Doorvoerinrichting voor het afdichtend doorvoeren van een kabel, buis, leiding en dergelijke door een opening van een wand.
WO2006075964A1 (fr) 2005-01-17 2006-07-20 Gyros Patent Ab Procede permettant de co-transporter un reactif avec une substance macromoleculaire amphiphile dans un conduit de transport microfluidique
CN110156950A (zh) * 2019-05-30 2019-08-23 杨开芳 一种环保型阻燃聚氨酯泡沫材料的制备方法
CN110423326A (zh) * 2019-07-01 2019-11-08 陕西科技大学 一种改性硫酸钙晶须/聚氨酯复合发泡材料及其制备工艺
CN111196869A (zh) * 2018-11-19 2020-05-26 北京市建筑工程研究院有限责任公司 一种混凝土用三维微孔透气模板及其制备方法

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DE10060513A1 (de) * 2000-12-06 2002-06-20 Illbruck Gmbh Kartuschenset zur Ausbringung von Ortschaum
DE10361070A1 (de) * 2003-12-23 2005-07-28 Nadine Wenzler Verfahren zur Herstellung eines Polyurethanschaumes
DE102004033246B4 (de) * 2004-07-08 2006-10-19 Helmut Vierk Verfahren zur Befüllung und Ausfüllung von Hohlprofilen
DE102005054375B4 (de) * 2005-11-15 2016-05-12 Hanno-Werk Gmbh & Co. Kg Schwer brennbares oder nicht brennbares Schaumstoffprofil zur brandschützenden Abdichtung von Bauöffnungen
WO2008105843A1 (fr) * 2007-02-26 2008-09-04 Bayer Materialscience Llc Mousse hybride de polychlorure de vinyle/polyuréthanne à propriétés de combustion améliorées
US7601762B2 (en) 2007-02-26 2009-10-13 Bayer Materialscience Llc Polyvinylchloride/polyurethane hybrid foams with improved burn properties and reduced after-glow
US7601761B2 (en) 2007-02-26 2009-10-13 Bayer Materialscience Llc Rigid polyurethane foams with increased heat performance
CN100447470C (zh) * 2007-06-01 2008-12-31 华东理工大学 一种膨胀型防火套管及制备方法
EP2061126B1 (fr) * 2007-11-19 2012-08-01 Volker Rodenberg Passage de câble ignifuge
DE102009018635A1 (de) 2008-04-18 2009-10-22 Dracowo Forschungs- Und Entwicklungs Gmbh Duroplastische Schaumstoffe auf Basis nativer Epoxide, Verfahren zu deren Herstellung sowie Halbzeuge
KR20150020540A (ko) * 2012-06-06 2015-02-26 더블유.알. 그레이스 앤드 캄파니-콘. 콘크리트 구조물의 방수를 위한 폴리우레탄계 방수 조성물
RU2641755C2 (ru) 2012-09-24 2018-01-22 Басф Се Система и способ получения in situ-пеноматериала
CN103771695A (zh) * 2014-01-22 2014-05-07 袁利民 一种垃圾焚烧飞灰无害化处理及利用方法
CN104944894A (zh) * 2015-06-16 2015-09-30 安徽天元电缆有限公司 一种信号电缆填充料
KR20180074724A (ko) 2015-10-20 2018-07-03 바스프 에스이 동일 반응계 포움의 제조 시스템 및 방법

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EP0679669A1 (fr) * 1994-04-25 1995-11-02 Bayer Ag Polyuréthanes et/ou polyuréthanepolyurées éventuellement cellulaires, procédé de leur préparation et leur utilisation
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DE19702760A1 (de) * 1997-01-27 1998-07-30 Joachim Gluske Fa Brandhemmender Polyurethanschaum

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL1019919C2 (nl) * 2002-02-07 2003-08-08 Beele Eng Bv Doorvoerinrichting voor het afdichtend doorvoeren van een kabel, buis, leiding en dergelijke door een opening van een wand.
WO2003067136A1 (fr) 2002-02-07 2003-08-14 Beele Engineering B.V. Dispositif d'isolation destine a boucher de maniere etanche le passage pour un cable, un tuyau, une conduite ou analogue dans un mur
JP2005517143A (ja) * 2002-02-07 2005-06-09 ビール エンジニアリング ビー．ブイ． 壁の開口部を通過するケーブル、パイプ、導管などの通路をシールするためのブッシュ装置
WO2006075964A1 (fr) 2005-01-17 2006-07-20 Gyros Patent Ab Procede permettant de co-transporter un reactif avec une substance macromoleculaire amphiphile dans un conduit de transport microfluidique
CN111196869A (zh) * 2018-11-19 2020-05-26 北京市建筑工程研究院有限责任公司 一种混凝土用三维微孔透气模板及其制备方法
CN110156950A (zh) * 2019-05-30 2019-08-23 杨开芳 一种环保型阻燃聚氨酯泡沫材料的制备方法
CN110423326A (zh) * 2019-07-01 2019-11-08 陕西科技大学 一种改性硫酸钙晶须/聚氨酯复合发泡材料及其制备工艺

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CA2367730A1 (fr) 2000-09-28
AU4105300A (en) 2000-10-09
DE19912988C1 (de) 2000-08-17
ZA200107780B (en) 2002-12-20
NO20014602D0 (no) 2001-09-21
EP1171518A1 (fr) 2002-01-16
NO20014602L (no) 2001-11-20

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