DE3234038A1 - Optionally foamed intumescent compositions, and the use thereof - Google Patents

Abstract

Optionally foamed intumescent compositions obtained by reacting 1. polyisocyanates with 2. phosphorus-containing condensation products containing at least two hydroxyl groups and obtainable by condensation of optionally OH-containing primary or secondary monoamines and/or polyamines, carbonyl compounds and dialkyl phosphites, optionally with subsequent oxyalkylation, and 3. compounds containing at least two hydroxyl groups and having a mean OH number of from 150 to 500 and containing phosphorus, nitrogen, sulphur or halogen, and 4. optionally cyanuric acid and/or cyanuric acid derivatives, and 5. optionally water and 6. optionally further organic compounds containing hydrogen atoms which are reactive towards isocyanates, are used, for example, as cavity fillings, joint sealants, semifinished products, profile materials or coatings.

Description

Optionally foamed intumescent masses and their

Use If necessary, foamed intumescent materials are already available Subject of DE-OS 3 041 731 and German patent application P 31 09 352.3. These have a good intumescent effect when exposed to flame, which is the case for most Purposes.

However, there are areas of application, especially in the area of coatings with fire protection effect, where particularly good foaming is required in the event of fire becomes, that is, an even further increased ability to intumescence, which if possible with increased water resistance of the intumescent property should go hand in hand.

It has now been found that the intumescent properties of the aforementioned Surprisingly, intumescent materials can be significantly improved again if polyols containing phosphorus, nitrogen, sulfur or halogen are used.

Particularly good increases in intumescent properties are achieved with Use of halogen, in particular containing Br and / or Cl, at least two Polyethers containing hydroxyl groups with OH numbers from 150 to 500 were observed.

It could be expected that the fire behavior of intumescent materials on an organic basis through the use of e.g. halogen-containing polyethers would be improved, however it is unexpected and surprising that a significant Improvement of the foaming when exposed to a flame, i.e. the intumescent properties, is effected.

The subject of the invention are, if appropriate, foamed intumescent materials, obtained by reacting 1. polyisocyanates with 2. at least two hydroxyl groups containing phosphorus-containing condensation products, obtainable by condensation of primary or secondary aliphatic, optionally containing OH groups, cycloaliphatic, aromatic, araliphatic or heterocyclic mono- and / or Polyamines, carbonyl compounds and dialkyl phosphites, optionally below Oxyalkylating, and 3. having at least two hydroxyl groups Compounds with an average OH number of 150 to 500, which contain phosphorus, Contain nitrogen, sulfur or halogen, and 4. optionally cyanuric acid and / or Cyanuric acid derivatives and 5. optionally water and 6. optionally wide organic Compounds with isocyanate-reactive hydrogen atoms.

According to the invention, preference is given to intumescent compositions which are characterized by Reaction of 15 to 55 parts by weight of a polyisocyanate (1) with 100 parts by weight a mixture consisting of 10 to 45% by weight of at least two hydroxyl groups containing phosphorus-containing condensation products (2) and 20 to 55% by weight Polyols (3) and 0 to 60% by weight of cyanuric acid (derivatives) (4) and 0 to 10% by weight Water (5) and 0 to 25% by weight of other organic compounds with opposite Isocyanate reactive hydrogen atoms (6) have been obtained.

Intumescent materials are particularly preferred, characterized in that that polyphenylpolymethylpolyisocyanates are used as polyisocyanates, such as them by aniline-formaldehyde condensation and subsequent Phosgenation can be obtained, and also those having at least two hydroxyl groups Condensation products contain those of the formula (RO) 2 PO-CH2-N = (CHX-CHX-OH) 2, wherein in the formula R = C1-C8-alkyl or C1-C8-hydroxyalkyl and X = H or methyl mean.

Intumescent compositions preferred according to the invention are characterized in that that as component (3) at least two hydroxyl groups containing halogen Polyethers with average OH numbers from 150 to 500 can be used.

Particularly preferred intumescent materials according to the invention are those in their production as component (3) containing at least two hydroxyl groups, Polyethers containing chlorine and / or bromine with halogen contents of 10-55% by weight, preferably 25-45% by weight and with average OH numbers of 150-500, preferably 200 to 400 can be used.

According to the invention, intumescent compositions are very particularly preferred which are characterized in that as Component (3) addition products of ethylene oxide and / or epichlorohydrin-held on dibromoneopentyl glycol with halogen of 25-45% by weight and average OH numbers of 200-400 can be used.

The invention also relates to the use of the new intumescent materials as cavity fillings, joint seals, semi-finished products, profile materials and coatings with intumescent properties. The invention also relates to the use of the intumescent materials, obtained by reaction in forms or by subsequent deformation of the fully reacted Reaction mixtures for the production of moldings with intumescent properties.

Card, plastic, elastic or plastic-elastic intumescent materials, how they are obtained according to the invention, have a particular technical interest, because preforms made from it are particularly easy to insert into joints or cavities Press in or insert, glue in, nail in, leave because they are also for wrapping can be used by cables and pipes and their applicability due to vibrations of the application field is not impaired. Your considerable resistance to Access to water is also an interesting technical advantage.

The intumescent materials accessible according to the invention are natural flame retardant. When exposed to a flame, they foam up to more than ten times their own primordial initial volume and thereby form a fire-resistant Foam that shields the rear areas from further flames.

They can also be close to (i.e. mostly below) their foaming temperature processed thermoplastically. With suitable temperature control in the course of thermoplastic processing (e.g. by pressing, extrusion) into molded articles these can have a foamed or solid character. The thermoplastic behavior Under certain processing conditions it can also be used to modify molded parts E.g. panels made of foamed material are used, for example for cutting or Welding with other materials or for embossing or permanent deformation.

The intumescent compositions according to the invention surprisingly show one compared to the one available according to the German patent application P 31 09 352.3 Types much stronger foaming when exposed to flame, which is a clear advantage, e.g. in the case of sealing lips.

The production of the new intumescent materials can be carried out continuously or be worked discontinuously. The manufacture can be done by mixing the components or already premixed component mixtures take place on site and the reaction mixture mechanically or by hand into, for example, openings to be closed or heated or unheated molds going on or under pressure be poured in, where it then foams or hardens. You can with appropriate technical equipment sprayed onto the substrates to be protected, be spread or poured on. It is also to be considered that one with the reaction mixtures according to the invention initially semi-finished products, e.g. foams, Manufactures profiles or coatings and then processes them in a technically necessary manner Further processed, e.g. by cutting, hot forming, granulating, Milling or mixing, coating and gluing.

Process products in the form of solutions or dispersions can, for coating, printing or impregnating and soaking e.g. materials with textile properties such as cotton fabric, cotton fleece, glass and mineral fiber fleece and woven or knitted fabrics can be used. Made of such finished fabrics e.g. wraps with intumescent properties can be produced, or tarpaulins. By deforming and baking at 50-2000C, dimensionally stable, more or less hard molded parts, laminates and pipes, semi-finished products, etc.

produce.

By combining the reaction mixtures with foamed or massive inorganic or organic additives, such as polystyrene foam, polyurethane foam, Phenoplasts, aminoplasts or gravel or expanded clay, urea or phenolic resin foams, Glass foam glass fibers, wood, mineral wool, pumice, etc., can composites with special intumescent properties can also be obtained. The application of the intumescent compositions according to the invention for the production of fibers or wires respectively.

Woven, strands or fleeces made of organic or inorganic Materials reinforced molded parts or their use as a component in multilayer or sandwich structures are also to be considered; likewise the combination with other intumescent materials on an organic or inorganic basis.

The fillers used alone or in combinations are, in particular, aluminum oxide hydrates, Gypsum hydrates, chalk, kaolin, glass and solid or hollow beads made of silicate Material contemplated, e.g. so-called microballoons; Alumina hydrates are due their ability to dehydrate is preferred in addition to hollow beads.

For the production of the intumescent materials according to the invention used: 1. As starting components aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, such as those described by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, are described, for example those of the formula Q (NCO) n in the n = 2-4, preferably 2, and Q is an aliphatic hydrocarbon radical with 2-18, preferably 6-10, carbon atoms, a cycloaliphatic hydrocarbon radical with 4-15, preferably 5-10 carbon atoms, an aromatic hydrocarbon radical with 6-15, preferably 6-13 carbon atoms, or an araliphatic hydrocarbon radical with 8-1 D, preferably 8-13 C atoms, mean, e.g. ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and 1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,3, 5-trimethyl-5-isocyanatomethyl-cyclohexane (DE-Auslegeschrift 1 202 785, US Patent 3,401,190), 2,4- and 2,6-hexahydrotolylene diisocyanate as well as any mixtures of these isomers, hexahydro-1,3- and / or 1,4-phenylene diisocyanate, Perhydro-2,4'- and / or -4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers, diphenylmethane-2,4'- and / or -4,4'-diisocyanate, naphthylene-1,5-diisocyanate.

Furthermore, according to the invention, for example, are possible: triphenylmethane-4,4 ', r "-triisocyanate, Polyphenol-polymethylene-polyisocyanates, such as them by aniline-formaldehyde condensation and subsequent phosgation and, for example, in GB patents 874 430 and 848 671 are described, m- and p-Isocyanatophenylsulfonyl-isocyanate according to U.S. Patent @ 454,606, perchlorinated aryl polyisocyanates, e.g. DE-Auslegeschrift 1 157 601 (US Pat. No. 3,277,138) are described, Polyisocyanates containing carbodiimide groups, as described in DE patent 1 092 007 (US Pat. No. 3,152,162) and in German Offenlegungsschrift 2,504 400, 2,537,685 and 2,552,350, norbornane diisocyanates according to U.S. Patent 3,492,330, polyisocyanates containing allophanate groups, such as those described in UK Patent 994 890, BE patent specification 761 626 and NL patent application 7 102 524 polyisocyanates containing isocyanurate groups, such as those described in U.S. Patent 3 001 973, in DE patents 1 022 789, 1 222 067 and 1 027 394 as well as in the DE-Offenlegungsschriften 1 929 034 and 2004 048 are described, urethane groups containing polyisocyanates, as e.g.

in BE patent 752 261 or in US patents 3,394 164 and 3,644,457, polyisocyanates containing acylated urea groups according to DE patent specification 1 230 778, polyisocyanates containing biuret groups, for example, as described in U.S. Patents 3,124,605, 3,120,372, and 3,124,605 as well as in GB 889 050, by telomerization reactions manufactured polyisocyanates, as for example in the US patent pointing Polyisocyanates such as those described in GB patents 965,474 and 1,072,956 in in US Pat. No. 3,567,763 and DE Pat. No. 1,231,688, Reaction products of the above-mentioned isocyanates with acetals according to DE-Fatentschrift 1,072,385 and polymeric fatty acid esters-containing polyisocyanates according to the US patent 3,455,883.

It is also possible to use the technical isocyanate production resulting distillation residues containing isocyanate groups, if appropriate dissolved in one or more of the aforementioned polyisocyanates. Further it is possible to use any mixtures of the aforementioned polyisocyanates.

As a rule, those that are technically easily accessible are particularly preferred Polyisocyanates, e.g. 2,4- and 2,6-toluene diisocyanate and any mixtures of these isomeric ("TDI"), polyphenyl-polymethylene-polyisocyanates, as produced by aniline-formaldehyde condensation and subsequent phosgenation are produced ("crude MDI") and carbodiimide groups, Urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups containing polyisocyanates {"modified polyisocyanates"), 1 in particular those modified polyisocyanates, which are derived from 2,4- and / or 2,6-tolylene diisocyanate or derived from 4,4'- and / or 2,4'-diphenylmethane diisocyanate.

2. Phosphorus-containing condensation products containing at least two hydroxyl groups, such as, for example, by condensation of primary which may contain OH groups or secondary aliphatic, cycloaliphatic, aromatic, araliphatic or heterocyclic mono- and / or polyamines, carbonyl compounds and dialkyl phosphites, optionally with subsequent oxyalkylation, can be obtained. Such Condensation products are known per se, e.g. from DE-PS 1 143 022, US-PS 3 076 010, DE-AS 1 803 747 and DE-AS 1 928 265.

According to the invention, at least two hydroxyl groups are preferred phosphorus-containing condensation products containing those of the formula (RO) PO-CH2-N = (CHX-CHX-OH) 2r in which R = C1-C8-alkyl or C1-C8-hydroxyalkyl, preferably methyl, ethyl or Hydroxyethyl, and X = H or methyl, preferably H, are.

3. At least two, usually 2 to 8, preferably 2 to 4, hydroxyl groups containing compounds with an average OH number of 150-500, the phosphorus, Contain nitrogen, sulfur or especially halogen (or such atoms having groupings).

Such compounds are known per se. They are obtained, for example due to the addition of epichlorohydrin and / or epibromohydrin to corresponding starter molecules such as di- or polyfunctional carboxylic acids, amines or hydroxyl compounds, such as Trimethylolpropane, glycerine, ethylene glycol, water, neopentyl glycol, pentaerythritol, Mannitol, sorbitol, which in turn may contain phosphorus, nitrogen, or sulfur May contain halogen such as chlorine- or bromine-neopentylglycol, dibromoneopentylglycol, Calogenation products of polyols, esters of sulfuric acids with e.g. ethylene glycol, Bishydroxy thioethers, polymers and copolymers of cyclic ethylene sulfide, nitration products of polyalcohols or their nitric acid esters, nitrophenols or phosphoric acids.

If the starting molecule is already phosphorus, nitrogen, sulfur or halogen contains, the usual alkylene oxides such as ethylene oxide and / or can be used for alkoxylation Propylene oxide can be used. In addition to polyethers which are preferred, e.g. also polyester or polyester amides are possible. Addition products are of particular interest of ethylene oxide and / or epichlorohydrin to the relatively stable dibromoneopentyl glycol, which is optionally used in a mixture with other starters. For example are addition products of ethylene oxide and / or epichlorohydrin with dibromoneopentyl glycol with halogen contents of 25 to 45% by weight, average OH numbers of 200-400 and acid numbers below 1 are well suited according to the invention.

4. If necessary, cyanuric acid and / or its derivatives, i.e. cyanuric acid or compounds which understand themselves as cyanuric acid or isocyanic acid derivatives permit. Such are, for example, cyanamide, dicyanamide, dicyandiamide, guanidine and the like Salts, biguanide, urazole, urazole cyanurate, melamine cyanurate, cyanuric acid salts and Cyanuric acid esters and amides, especially melamine, because of its good accessibility is preferred.

The main body 2,4,6-triamino-s-triazine is preferably used as the melamine understood, but it is also, for example, through thermal treatment or conversion condensation products obtainable with formaldehyde should be considered.

-5. If necessary water, e.g. tap water, and 6. q if necessary further organic compounds -with hydrogen atoms reactive towards isocyanates, - the -different -from the under 3.

named compounds are.

These include: a) Compounds with at least two opposite isocyanates reactive hydrogen atoms with a molecular weight usually of 400 -10 000. This is preferably understood to mean compounds containing hydroxyl groups, into the- special compounds containing two to eight hydroxyl groups, especially those with a molecular weight of 1000 to 6000, preferably 1000 to 3000, e.g. at least two, usually 2 to 8, but preferably 2 to 4, hydroxyl groups comprising polyesters, polyethers, polyacetals, polycarbonates such as those used for production of homogeneous and of cellular polyurethanes are known per se.

The possible hydroxyl group-containing polyesters are e.g. reaction products of polyvalent, preferably divalent. and if necessary additionally trihydric alcohols with polybasic, preferably dibasic, carboxylic acids. Instead of the free polycarboxylic acids, the corresponding polycarboxylic anhydrides can be used or corresponding polycarboxylic acid esters vc-n lower alcohols or mixtures thereof used to manufacture the polyester.

The polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature.

Examples of such carboxylic acids and their derivatives are: Succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, Isophthalic acid, trimellitic acid, Phthalic anhydride, tetrahydrophthalic anhydride, Hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, Maleic acid, maleic anhydride, fumaric acid, dimerized and trimerized unsaturated Fatty acids, optionally mixed with monomeric unsaturated fatty acids, like oleic acid; Dimethyl terephthalate and bis-glycol terephthalate. The polyhydric alcohols are e.g. ethylene glycol, propylene glycol- (1,2) and - (1,3), Butylene glycol (1.4) and - (2.3), hexanediol (1.6), octanediol (1.8), neopentyl glycol, 1,4-bishydroxymethylcyclohexane, 2-methyl-1,3-propanediol, glycerine, trimethylolpropane, Hexanetriol (1,2,6), butanetriol (1,2,4), trimethylolethane, pentaerythritol, quinite, Mannitol and sorbitol, formitol, methyl glycoside, also diethylene glycol, triethylene glycol, Tetraethylene glycol and higher polyethylene glycols, dipropylene glycol and higher polypropylene glycols as well as dibutylene glycol and higher polybutylene glycols in question.

The polyesters can have a proportion of terminal carboxyl groups. Also polyesters made from lactones, e.g.

S-caprolactone, or from hydroxycarboxylic acids, e.g.

O -hydroxycaproic acid can be used.

b) Also the at least two in question according to the invention usually two to eight, preferably two to three, hydroxyl groups Polyethers are those of the type known per se and are made, for example, by polymerization from Epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, Styrene oxide or with itself, e.g. in the presence of Lewis catalysts such as BF3, or by adding these epoxides, preferably ethylene oxide and propylene oxide, optionally in a mixture or in succession, of starting components with reactive ones Hydrogen atoms such as water, alcohols, ammonia or amines, e.g. ethylene glycol, Propylene glycol- (1,3) or - (1,2), trimethylolpropane, glycerine, sorbitol, 4,4'-dihydroxydiphenylpropane, Aniline, ethanolamine or ethylenediamine are produced. Also sucrose polyethers like her e.g. in DE-Auslegeschriften 1 176 358 and 1 064 938, as well as Polyethers started on formite or formose (DE-Offenlegungsschriften 2 639 08 respectively.

2,737,951) are suitable according to the invention. There are many Polyethers preferred, the predominant (up to 90 wt .-%, based on all existing OH groups in the polyether) have primary OH groups. Also containing OH groups Polybutadienes are suitable according to the invention.

As polyacetals come e.g. those from glycols, such as diethylene glycol, Triethylene glycol, 4,4'-dioxethoxydiphenyldimethyl methane, hexanediol and formaldehyde possible connections in question.

Also by polymerizing cyclic acetals such as trioxane (DE-Offenlegungsschrift 1,694,128), suitable polyacetals can be produced according to the invention.

Polycarbonates containing hydroxyl groups are those of the known type, e.g.

by reacting diols such as propanediol (1,3), butanediol (1,4) and / or Hexanediol (1.6), diethylene glycol, triethylene glycol, tetraethylene glycol with diaryl carbonates, E.g. diphenyl carbonate or phosgene can be produced (DE-Auslegeschriften 1,694,080, 1,915,908 and 2,221,751; DE-Offenlegungsschrift 2 605 024) representative of the named compounds to be used according to the invention are, for example, in high polymers, Vol. XVI, "Polyurethanes, Chemistry and Technology", written by Saunders-Frisch, Interscience Publishers, New York, London, Volume I, 1962, pages 32-42 and pages 44-54 and Volume II, 1964, pages 5-6 and 198-199, as well as in the Kunststoff-Handbuch, Volume VII, Vieweg-Höchtlen, Carl-Hanser-Verlag, Munich, 1966, e.g. on pages 45-71, described. Mixtures of the abovementioned compounds can of course be used with at least two isocyanate-reactive hydrogen atoms with a molecular weight of 400-10,000, e.g. mixtures of polyethers and polyesters, can be used.

Compounds with at least two isocyanate-reactive compounds Hydrogen atoms and a molecular weight of 32 to 400. Also in this case This is preferably understood to mean compounds containing hydroxyl groups, the serve as chain extenders or crosslinking agents. These connections generally have 2 to 8, preferably 2 to 4, isocyanate-reactive Hydrogen atoms.

Examples of such compounds include: ethylene glycol, Propylene glycol (1,2) and - (1,3), butylene glycol (1,4) and - (2,3), pentanediol (1,5), Hexanediol (1,6), octanediol (1,8), neopentyl glycol, 1,4-bishydroxymethyl-cyclohexane, 2-methyl-1,3-propanediol, glycerine, trimethylolpropane, hexanetriol- (1,2,6), trimethylolethane, Pentaerythritol, quinitol, mannitol and sorbitol, castor oil, diethylene glycol, triethylene glycol, Tetraethylene glycol, higher polyethylene glycols with a molecular weight of up to 400, Dipropylene glycol, higher polypropylene glycols with a molecular weight up to 400, Dibutylene glycol, higher polybutylene glycols with a molecular weight of up to 400, 4,4'-dihydroxydiphenylpropane, Di-hydroxymethyl-hydroquinone.

In this case too, mixtures of different compounds can be used with at least two isocyanate-reactive hydrogen atoms with molecular weights from 32 to 400 can be used.

While it is in principle possible, in addition to phosphorus, nitrogen, Polyols containing sulfur or halogen also contain other isocyanates reactive Components (component (6)) are included in the reaction mixture However, such additional connections are not always necessary and may be even lead to disturbances of the intumescence behavior, so that should be checked in each individual case is how far the addition of such additional reaction components makes sense.

In many cases, however, it makes sense to use monofunctional ones as well Zerewitinoff-active compounds as chain terminators, such as carboxylic acids, amines or in particular alcohols such as methanol, ethanol, isopropanol, butanol, chloroethanol, Trichloroethanol, dimethylaminoethanol, etc., e.g. when it comes to demolition the polyaddition reactions using monofunctional reaction components soluble, relatively low molecular weight products, e.g. for painting purposes, gluing or coating purposes, to manufacture.

For painting purposes it is often advisable to use solvents, or to subsequently dilute or dissolve the intumescent materials with them. Such Solvents are e.g. acetone, ethyl acetate, methyl ethyl ketone, glycol monomethyl ether acetate, Toluene-butanol mixtures, butyl acetate, caprolactone, caprolactam, water, methylene chloride, Trichlorethylene, turpentine oil, sangaiol, resp.

Mixtures of these and other common solvents.

Also the use of plasticizers such as esters and polyesters from phthalic acid, phosphoric acid, adipic acid and mono- and polyhydroxyl compounds should be considered, e.g. diphenyl cresyl phosphate, trichloroethyl phosphate, Bischloroethyl phthalate, polyester made from glycerine, ethyl glycol and adipic acid.

The amounts of the auxiliaries mentioned by way of example can be used each desired purpose can be adapted with considerable variation. Of the A- set amounts are based on the mixture of the reaction components 1-5 usually in the following orders of magnitude: chain terminator 0-15% by weight, solvent 25-300% by weight, plasticizer 5-150% by weight.

The use of the last-mentioned components can be considered However, in individual cases it is necessary to weigh up the possible Disadvantages in fire behavior.

It has been found that for the advantageous properties of the new Intumescent masses, be they solid, porous or in the form of a coating, are not the stoichiometric ratios customary for conventional polyurethane chemistry are characteristic. Rather, components 2, 3, 4 and possibly 5 and 6 regardless of the stoichiometry required with regard to the isocyanate chemistry put together and the mixture obtained in this way in simple preliminary tests with different, within a given quantity range according to the invention, quantities of the Polyisocyanate implemented to empirically determine the desired optimal effectiveness.

The guide quantities found in this way for the individual components 2, 3, 4 and optionally 5 in the reaction mixture to be reacted with the polyisocyanate complement each other 100% and amount to: - for at least two Hydroxyl group-containing phosphorus-containing condensation products (2): 10 to 45, preferably 15 to 35% by weight, - for the hydroxyl compounds (3): 20 to 55, preferably 25 to 45%, - for the cyanuric acid derivatives (4).

0 to 60, preferably 20-50% by weight, - for water (5): 0 to 10, preferably 0 to 2 wt., - for other organic compounds with opposite Isocyanate-reactive hydrogen atoms (6): 0 to 25% by weight.

100 parts by weight of this reaction mixture are usually 15 to 55, preferably 25 to 45 parts by weight of the polyisocyanate reacted.

The intumescent materials can be produced in a solvent or take place without a solution. Porous process products (foams) are of interest these can have densities from approx. 40 to 900 kg / m³, preferably between 80 and 600 kg / m³. A particularly balanced combination between The low volume weight sought for reasons of insulating properties and for the foaming effect in the case of flames in the room unit of the necessary mass provide according to the invention Foams with densities of approx. 250 to 600 kg / m³ represent.

The various reaction components can be brought together individually; however, it is expedient to make a premix of the polyisocyanates (Component 1) reactive components 2, 3, 4 and optionally 5 and 6 and thus receives a liquid reaction component after brief heating, if necessary, in which all the necessary ingredients, possibly also color pigments, plasticizers, Fillers, except for the polyisocyanate, are included. In this way you can formulate the intumescent compositions according to the invention as a two-component mixture or manufacture from this. The usual facilities of polyurethane technology are used for this purpose applicable.

It is entirely possible to premix the components if necessary also add other ingredients to the isocyanate, e.g. urea, Urea condensates, formaldehyde condensates, optionally halogenated powders Polymers such as chlorinated rubber, PVC, phenolic resins, phosphates, amine polyphosphates, phosphoric acid esters, e.g. tricresyl phosphate or di- butyl cresyl phosphate, Al oxide hydrates, Glass powder, plaster of paris, chalk, kaolin, talc, mica, wollastonite, vermiculite, massive or hollow glass - or other silicate beads and other fire behavior modifying additives, e.g. senarmontite.

Although it is not necessary to make the inventive optionally foamed intumescent compositions, catalysts for foam formation or other auxiliaries such as are otherwise customary in foam chemistry, for example also additionally gaseous or low-boiling propellants or propellant gas generators to be used, such additional aids, as well as emulsifying, Foam stabilizing, separating, coloring, preserving, hydrolysis protection Mediating, odor-active or other additives, of course, in individual cases as Recipe component should be considered. For example, sharing leads of catalysts giving rise to carbodiimide formation, such as those in the class the phospholine oxides such as 1-methyl-1-oxo-phospholine, are known, to intumescent materials with improved stability against hydrolysis.

Furthermore, consideration should also be given to such additives in terms of the formulation to use in the intumescent compositions according to the invention, the foam formation in the case of flame exposure can help increase.

Such are, for example, aliphatic and especially special aromatic hydroxycarboxylic acids such as salicylic acid or p-hydroxybenzoic acid, PVC, Carbohydrates or, at elevated temperatures, water, nitrogen or CO-releasing substances such as triazoles, azodicarbonamides, sulfohydrazides or urea dicarboxylic acid anhydride.

The intumescent materials according to the invention can be used, for example, by incorporation in or squeegeeing onto textiles made from organic or inorganic fibers Spraying, pressing or molding and gelling, by cutting or melting, Manufacture moldings or coverings that can be used at temperatures between approx.

Foam 200 and 3500C and thus prevent the flame from spreading, which are therefore suitable as sealing elements, safety devices, fire barriers.

You can grout, seal cable openings, wall openings, whereby e.g. also a kind of concrete from the intumescent and stones and / or distended Particles such as expanded clay, expanded glass, vermiculite, perlite, etc. and / or foam beads on e.g.

Polystyrene-based are manufactured and used by Rann.

Likewise of interest is the production of armored or reinforced ones Coatings of almost any thickness on metal, e.g. steel girders and sheets, Wood, e.g. door leaves, roof beams, on masonry, on plastics, be it cable insulation or foam sheets. If you put the coatings on a stable plate or makes a supporting structure, e.g.

in or on a stretched metal plate, a honeycomb plate made of metal, Cardboard, paper, wood, ceramic or plastic, then can be so slightly fire retardant Panels or wall elements are produced.

The intumescent materials are also used for the production of anti-drumming coverings or soundproofing elements of interest, as well as for purposes of energy absorption.

Also the inner coating of fire-retardant doors, which in case of fire foams and has an insulating effect, should be taken into account, as is the manufacture of door or other seals that foam up in the event of fire and the upstream ones Seal the slot. You can also use sealing profiles, e.g. made of elastic material fill or backfill the intumescent compositions according to the invention and thus a fire protection seal achieve. Suitable arrangement can be used in chimneys, ventilation and air conditioning systems, Build up barriers to pipes and inlet / outlet openings in the event of heating to approx.

3000C to 4000C slow down or prevent the further passage of gases. Such arrangements are e.g.

Stack of closely spaced parallel plates with the Screens and perforated diaphragms coated with intumescent masses or with granules of the intumescent masses loosely filled pipe sections, or pipes and inner coating from the inventive Intumescent materials. The optionally foamed intumescent compositions can also can be used as filter elements for gases that arise when the temperature rises too high close.

One can also, for example, molded bodies that are easily made from the intumescent materials can be produced, or granulates of various grain sizes can be produced in one or more stages foam by heating them to temperatures above 200 "C, preferably up Temperatures between 250 to 18009C; especially 300 - 800 "C. The foaming can be made freely or in closed or open forms, these being Shapes should expediently have openings for the escape of steam and air.

This creates fire-resistant foams, so-called carbonization foams.

The heating can be done by radiant heat, by treating with superheated steam or hot air or other hot gases, by microwaves or high frequency or done by conduction in air or liquid baths or metal baths.

The intumescent compositions according to the invention can also be applied to carrier materials apply and foam there, e.g. by coating expanded clay particles, then Shakes in a mold and heated there, taking a block made in carbonizing foam embedded expanded clay is created.

Mention should also be made of the foaming of cavities, e.g. in cable ducts, but also in bricks and other building materials, e.g. by introducing the Reaction mixtures or finished foam intumescent compounds in a suitable quantity in the cavity of the cold or still warm stone succeeds.

The intumescent compositions according to the invention are also available in the form of bandages, Pipe half-shells or full jackets are suitable for insulating pipes or cables.

It is of interest that the isolation can also be done in situ can by placing the pipe or the piece to be insulated with the reaction mixture coated and this causes foaming if necessary.

The production and processing of the leading to the intumescent materials Reaction mixtures can be carried out continuously or batchwise. One can bring the components together individually or as mixtures. Preferably all will Reaction components combined except for the isocyanate, so that a 2-component processing can take place, e.g. in normal hand-held stirring vessels with mechanical stirrers, in stirrer or nozzle or spray mixheads or in static mixers, such as those from polyurethane chemistry are known. The complete reaction can take place without pressure in cooled, cold or heated molds or under pressure.

In the case of the production of the intumescent materials in the solvent it is expedient to introduce components 2, 3, 4 and the isocyanate in the solvent to be added at temperatures of 20-150 "C. Often a subsequent Stabilization of the solution by adding methanol or water or ammonia (chain terminator) advantageous.

The following experiments are intended to exemplify the subject matter of the invention explain, but not restrict. The specified parts are parts by weight and / or Percentages by weight, unless otherwise noted.

The following series of experiments are intended to establish the relationship between recipe and properties of the intumescent materials accessible according to the invention are exemplary explain.

The following are used as starting materials: As polyisocyanate (1) commercially available obtained by phosgenation of aniline-formaldehyde condensates Technical polyisocyanate isomer mixture with a content of approx. 80% two-ring diisocyanates and approx. 20 4 multinuclear polyisocyanates, as a phosphorus-containing condensation product (2) (C2H5O) 2POCH2N (C2HdOH) 2 is used in technical quality. As a cyanuric acid derivative (4) Melamine is used. The following are used as the polyhydroxyl compound (3): 3a: For comparison purposes, an adduct of ethylene oxide with glycerol, OH number 254 3b: A commercially available adduct of ethylene oxide and epichlorohydrin of dibromoneopentyl glycol, OH number approx. 330, Br content approx. 32%, Cl content approx.

6%.

3c: Adduct of ethylene oxide with dibromoneopentyl glycol, OH number 240, Sre number 0.36, Br content approx. 28 90.

3d: adduct of ethylene oxide with glycerol mononitrate sorbitol (7: 3) OH number 280.

3e: adduct of ethylene oxide with thioglycerol, OH number 260.

The chain terminators used were (A) methanol and (B) isopropanol.

The solvents used were: G: glycol monomethyl ether acetate H: trichlorethylene i: acetone K: diphenyl cresyl phosphate / trichloroethyl phosphate (mixture 1: 1) Examples 1 to 15 are listed in a table below. The production was carried out in Examples 1-10, so that the components except for component 1 (Polyisocyanate) were mixed well and then intensively in a stirred vessel for 20 seconds were homogenized with component 1. The stirred vessel was then left to stand at RT and the reaction takes place with hardening or foaming. In all cases were Porous materials with a hard character (pulverizable!) are preserved, only the material according to example 6 was tough and hard.

In the case of Examples 11-14, the reaction was carried out in a stirred vessel at 850.degree and added component 1 in the course of 45 minutes with thorough stirring. To 1 hour of reaction at 85 ° C. or at reflux, the mixture was cooled and the solution formed by applying it several times, if necessary, to a 0.5 mm thick sheet of iron about 2 mm thick film (after drying off the solvent at 75 "C) formed on this.

The test was carried out in such a way that from the samples produced by way of example Cut a 2 mm thick plate measuring 2 x 2 cm and place it on the same large sheet iron (0.5 mm thick) was placed.

Platelets of the same size were produced from those according to Examples 11 to 14 Coating samples produced.

These platelets were placed on an aluminum tray and placed in a Set the heating cabinet preheated to 350 "C. After 40 minutes, the test specimens were taken out of the heating cabinet and estimated the increase in volume, this is a measure for the intumescent properties of the test item. So was the increase in volume Such test specimen with a 3-minute flame exposure from a natural gas burner from the top here determined. In all cases no afterburning occurred when the flame was removed. The intumescent effect or ability was graded as follows: increase in volume over 500% grade 1 300-500 90 grade 2 below 300% grade 3 In the examples 1-15 it is clear that the intumescent compositions according to the invention are solid, as well as a solution and that it is compared to the reference material according to the German patent application 31 Q9 352.3 an even better intumescence capability own.

Example No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Component (Tle) 1 46 46 46 46 46 46 46 46 46 46 156 156 156 14.5 37 2 29 29 29 29 29 29 29 20 20 29 98 98 98 9.5 29 3a 50 3b 40 40 40 40 55 20 135 135 135 13 40 3c 50 3d 48 3e 50 20 4 48 48 48 48 48 60 45 48 40 50 162 162 162 15 48 5 0.7 0.5 0.5 0.5 0.5 A 5 B 38 15 42 4.7 G 344 344 H 44 I 344 K 40 Iron oxide red 8.5 8.0 8.0 8.0 4.0 3 3 3 CaSO4 2 H2O 20 Aloxid X H2O 50 Silicate hollow beads 40 20 (RG 500 g / l) 350 ° C test 3 1 1 2 1 2 2 2 2 1 1 1 1 1 1 Flame exposure 2 1 1 2 2 1 1 1 1 1 1 1 1 1 1 approx. g / l 710 730 290 500 400 390 800 Example 16 The test product from Example 13 is ground in a ball mill to a fine powder, which is a Sieve with an edge length of 0.1 mm of the mesh passed 100%.

This powder is poured into a small cone on an iron sheet and subjected to the 350 "C test and flame test analogous to Examples 1-15. The powder shows very good (1) intumescent properties in both cases r The same applies for a granulate fraction consisting of the same material with mean particle diameters of about 0.5 cm was obtained on the hammer mill.

One with such granules between two sieve trays with a distance of 3 cm Filled iron pipe allows a stream of air to pass well, but if it is a stream of hot air When the granulate particles reach temperatures above 250 "C, they foam up and seal the tube.

The same applies to a foam disk placed between two wire screens 0.3 cm thick, which was cut from the material according to Example 3.

Example 17 The material obtained according to Example 2 becomes strips 3 mm thick and 1.5 cm wide.

Such a strip of 10 cm length is stored in water for one week and then dried at 45 ° C. One strip treated in this way and one not watered Strips are inserted into the slot of a small steel test door between the frame and Door leaf glued in with a polychloroprene adhesive. Then the door slot with applied directly to a Bunsen burner.

Both strips of material immediately inflate and clog the door slot completely so that neither smoke nor heating gases penetrate through the slot. This The experiment also shows the insensitivity of the new intumescent materials to the ingress of air and moisture.

Example 18 The finely ground powder from Example 16 is used as a filler an alkyd resin lacquer diluted to a solids content of 25% with a toluene-butanol mixture added so that a spreadable mixture with a powder content of 55 wt. arises. This preparation is brushed onto degreased 0.5 mm thick steel sheets and dried out for a week in the room climate. Part of the 1.2 mm thick coated The steel sheet is placed in a water bath so that one half of the coating stands in the water. After 7 days the sheet is taken out of the water and rinsed off and dried. The sheet steel now has an intumescent coating on one side has been leached with water. The steel sheet is now in a on 400 ° C preheated heating cabinet. This is where the intumescent coating is foamed, both on the non-watered and on the watered side about the same strength and very good (8.5 mm). So the water storage did not impair the intumescence behavior.

Analogous water-resistant intumescence behavior is also observed when if instead of the diluted acrylic resin varnish one is called "elephant skin" commercially available aqueous clear lacquer based on an acrylic resin dispersion or Polyvinyl acetate dispersion diluted to a solids content of -25% with water and then used this as a binder for the powdered intumescent material.

Example 19 The solvent-containing reaction mixture obtained according to Example 11 is used to soak a commercially available gauze bandage. This will be at 50 "C dry in a circulating air cabinet. A flexible, non-adhesive one with approx. 1.3 is obtained kg / m of solid impregnated cotton fabric. This is used as a fire protection bandage used for wrapping e.g. plastic or metal pipes.

Instead of the cotton fabric, a glass resp.

mineral fiber fabric, possibly well absorbent Paper fleece or an optionally perforated or slotted metal foil, for example made of aluminum be used.

The impregnated cotton fabric is turned into a three-layer wrap of 9 cm in length and 1.1 cm in diameter and drawn up by means of three small wire rings fixed. The mercury container is now placed inside this coil of a laboratory thermometer, the measuring scale protrudes from the coil, the thermometer is inserted up to the middle of the length of the roll. Now the flame is out of light of a natural gas Bunsen burner so brought under the horizontally clamped thermometer, that the tip of the flame just touches the coil in the middle of the length.

During the flame exposure, the following temperature profile is measured: 2 minutes 115 "C 4 minutes 250" C 6 minutes 3100C 8 minutes 360 "C.

Because the three layers of the wrap are about 2 mm thick of the protective layer to represent the mercury ball of the thermometer can have a very good insulating effect to be spoken.

After cutting open the roll it is evident that the innermost layer is facing 8 minutes still undestroyed, only charred as a protective cover around the thermometer has been preserved.

Claims (10)

Claims 1. Optionally foamed intumescent compositions obtained by reacting 1. polyisocyanates with 2. having at least two hydroxyl groups phosphorus-containing condensation products, obtainable by condensation of optionally Primary or secondary aliphatic, cycloaliphatic, aromatic, araliphatic or heterocyclic mono- and / or polyamines, carbonyl compounds and dialkyl phosphites, optionally with subsequent oxyalkylation, and 3. compounds having at least two hydroxyl groups an average OH number from 150 to 500, which contain phosphorus, nitrogen, sulfur or halogen, and 4. optionally cyanuric acid and / or cyanuric acid derivatives, and 5. optionally Water and 6. optionally other organic compounds with isocyanates reactive hydrogen atoms. 2. Intumescent compositions according to claim 1, obtained by reacting 15 to 55 parts by weight of a polyisocyanate (1) with 100 parts by weight of a mixture, consisting of 10 to 45% by weight of at least two hydroxyl groups containing phosphorus Condensation products (2) and 20 to 55% by weight of at least two hydroxyl groups comprising compounds (3) and 0 to 60% by weight of cyanuric acid (derivatives) (4) and 0 to 10% by weight of water (5) and 0 to 25% by weight of other organic compounds with isocyanate-reactive hydrogen atoms (6). 3. intumescent masses according to claim 1 and 2, characterized in that that the polyisocyanates used are those produced by aniline-formaldehyde condensation and subsequent phosgenation can be obtained. 4. intumescent compositions according to claim 1 to 3, characterized in that that condensation products containing at least two hydroxyl groups are those of the formula (RO) 2PO-CH2-N (CHX-CHX-OH) 2 in which R = C1-C8-alkyl or C1-C8-hydroxylalkyl and X = H or methyl can be used. 5. intumescent compositions according to claim 1 to 4, characterized in that that as component (3) at least two hydroxyl groups containing halogen Polyethers with average OH numbers of 150-500 can be used. 6. intumescent compositions according to claim 1 to 5, characterized in that that as component (3) having at least two hydroxyl groups, chlorine and / or Bromine-containing polyethers with halogen contents of 10-55% by weight and with average OH numbers from 150-500 can be used. 7. intumescent masses according to claim 1 to 6, characterized in that that as component (3) addition products of ethylene oxide and / or epichlorohydrin of dibromoneopentyl glycol with halogen contents of 25-45% by weight and average OH numbers from 200-400 can be used. 8. intumescent materials according to claim 1 - 7, characterized in that that melamine is used as the cyanuric acid derivative. 9. Use of the intumescent compositions according to claim 1 to 8 as cavity fillings, Joint seals, coatings, semi-finished products or profile materials with intumescent properties. 10. Use of the intumescent compositions according to claim 1 to 8 obtained by reaction in forms or by subsequent shaping of the fully reacted reaction mixtures, for the production of moldings with intumescent properties.