DE2220200A1 - Injectable mixtures for polyurethane foams - Google Patents

Description

PATEN ΓΑ NWÄLTc

DR.-ING. BY KREISLER DR.-ING. SCHÖNWALd2220200 DR.-ING. TH. MEYER DR. FUES DIPL-CHEM. ALEK VON KREISlER DIPL-CHEM. CAROLA KELLER DR.-ING. KLÖPSCH D1PL.-INO. SELTING

5 COLOGNE 1, DEICKMANNHAUS

Cologne, April 24, 1972 Ke / Ax

MARLES -KUHLMANN-WYAM30TTE,

25, Boulevard de l'Amiral Bruix, Paris (France).

Injectable mixtures for polyurethane foams

The invention relates to polyurethane spray mixes, the low flame spread of the produced therefrom Foam, have increased stability, shelf life and a useful life of 6 months or more and form foams by injection molding which, when tested by the tunnel test ASTM E-84 or its equivalent, form a Have flame spread of 25 or less.

To find entry into the building and construction industry, need mixtures for the production of polyurethane foams a viscosity at which they can be sprayed and a shelf life or useful life of at least 6 months. The preparation of such mixtures is known, e.g. from U.S. Patent No. 3,091-551. Recently It was decided that the polyurethane foams formed had excellent flame retardancy have to. In detail, it was stipulated that only those injectable mixtures can be approved Form foam that has a flame spread of 25 or less on the ASTM E-84 tunnel test. Different Methods have so far been described in an effort by those skilled in the art

209846/1 1.08

Considered making sprayable mixes with the above properties. For example, were various halogen-containing and / or phosphorus-containing compounds either as a polyol component of the mixture or used as an addition to it. The known compounds did not solve the problems for various reasons'. For example, they lead to excessively viscous and therefore non-sprayable mixtures and shorten the shelf life of the blends and / or seriously affect the physical properties of the rigid polyurethane foams formed .

The invention relates to a polyurethane spray mixture which has a shelf life or useful life of at least 6 months and a viscosity sufficient for spraying with conventional equipment and after foaming forms a rigid polyurethane foam which, when tested according to the ASTM E-84 tunnel test, causes flame spread of 25 or less. The spray mixes according to the invention contain the following ingredients, .related to their total weight:

a) 20 to 40 parts by weight of an ester-containing polyol that by reacting an alkylene oxide condensate of a polyhydric alcohol with 2 to 6 hydroxyl groups with tetrabromophthalic anhydride and a lower alkylene oxide has been formed.

b) 2 to 15 parts by weight of a polyoxyalkylene condensate of ; Sucrose or α-methylglucoside, with the condensate • has a hydroxyl number of 400 to 600,

c) 40 to 60 parts by weight of a polyaryl polyalkylene polyisocyanate with a functionality of 2.2 to 3.5 or a prepolymer containing terminal isocyanate groups, by reacting a stoichiometric excess of the polyaryl polyalkylene polyisocyanate with component (a) or (b) has been formed,

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d) 1.0 to 15 parts by weight of a phosphorus ©)! organic Link, ·

e) 0.2 to 2.0 parts by weight of a catalyst,

f) 0.15 to 3.0 parts by weight of a wetting agent,

g) 5 to 30 parts by weight of a propellant and h) 0 to 1.5 parts by weight of water.

The sprayable mixtures according to the invention can be built up and used by various methods. In a one-step process, all reactants become one mixed together at the same time, e.g. using a nozzle or a spray head with separate Feeding the individual streams and several outlet openings or a spray gun with one outlet opening and internal mixing of the components. In a more common embodiment of the one-shot process with premixing the reactants are divided into two components, with the polyisocyanate being the polyol components is kept separate until actual spraying or mixing. In a pre-polymer process, at least a portion of the polyol with the polyisocyanate in the usual manner to form a liquid prepolymer or Semiprepolyraeren reacted in a mixture with the other components before spraying. The g-possibly used Any remaining polyol is usually added prior to actually mixing or spraying the ingredients with the other components combined, in & general as two separate, intimately mixed streams impinging on the surface to be treated.

Regardless of whether a one-step process, n, the premixing process or prepolymer process' is used, this reaction; - .; participants are injected in such a way that they are as intimate Apply the mixture on a common surface to be treated, causing foaming and foaming practically immediately firm adhesion of the foam on the common upper

2 0 9 8 4 6/1108

surface ". During the rather quickly occurring Mixing the reactants increases the temperature of the reaction mixture as a result of the exothermic heat of reaction and the high activity of the catalyst used above the boiling point of the propellant, which causes the Forming polyurethane foams under the pressure of the enclosed gas and, after solidification, a hard polyurethane foam forms with an exceptionally fine structure. The surface to be treated can be heated from the outside however, this is seldom necessary. It is more useful, if not absolutely necessary, to raise the reactants to about 43 ° before the actual spraying 54 C to compensate for a certain loss of heat due to the atomization of the constituents Spraying process is due. When preheating the Reaction participant is not wanted before spraying, the amount of catalyst used can be increased to increase the rate of the foaming reaction. This can however, have some adverse effect on the properties of the foam and add to its cost. It is evident, however, that for best results the process conditions, e.g. the temperature, the Catalyst content, the boiling point of the propellant, the distance between the spray head and the surface to be treated and the like., must be optimally designed. Based on the present description, this would be apparent to one skilled in the art be easily possible.

As already mentioned, there are several critically important ingredients that make up the spray mixes according to the invention form. Flame-retardant polyurethane foams are only made when the above-mentioned components are used obtained in the above tunnel test a Have flame spread of 25 or less.

An essential component of the sprayable mixtures according to the invention is an ester-containing polyol, which by

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Reaction of a condensate of an alkylene oxide and a polyhydric alcohol having 2 to 6 hydroxyl groups with tetrabromophthalic anhydride and a lower alkylene oxide has been prepared. These polyols are the subject of US patent application 728 814 (May 13, 1968) by the applicant. It has been found that polyurethane foams with the required low flame spread can only be obtained by using these ester-containing polyols. Those esterhaltigen polyols are prepared by the three reactants are heated for 0.5 to 10 hours to temperatures between 50 ° and 15O ⁰ C, preferably between 75 ° and 150 ⁰ C »The temperature must be kept below 150 ⁰ C, the Prevent the reaction of carboxyl groups and hydroxyl groups with the formation of water. The reaction * is generally carried out under a pressure of 0 to 7 atmospheres. It is also possible to give the Alkylenoxydkondensate and tetrabromophthalic anhydride in a reaction vessel and 0 to 10 hours at 50 ^Oe to 150 ⁰ C to 'heat "Subsequently, the alkylene oxide is added to the reaction mixture under pressure added while maintaining the reaction temperature between 75 ° and 15O ⁰ C is held. After the reaction has ended, the reaction mixture can be filtered. It is devolatilized, by heating it from about 0.5 to 3 hours at 80 ° to 11O ⁰ C under a pressure of less than 10 mm Hg. If appropriate, a solvent which is inert in the reaction can be used for the preparation of the polyols used according to the invention.

The for the preparation of the ester-containing polyols according to Amounts of reactants used in the invention can vary. In general, however, this is Molar ratio of the alkylene oxide condensate to the anhydride 1: 0.1 to 1:12, preferably 1: 1 to 1.6. The amount of alkylene oxide is chosen so that the acid number of the reaction mixture of alkylene oxide condensate and anhydride is 5 or less, preferably 1 or less. The hydroxyl number of the

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ester-containing polyol varies considerably. In general, however, the polyols have a hydroxyl number of about 20. to 600, preferably from about 150 to 600.

As already mentioned, three essential reaction parts- ' taker used for the production of the ester-containing polyols according to the invention, namely an alkylene oxide condensate a polyhydric alcohol having 2 to 6 hydroxyl groups, a halogen-containing organic acid anhydride and a Alkylene oxide. Suitable alkylene oxides for the preparation of the ester-containing polyols according to the invention are, for example Ethylene oxide, propylene oxide, the isomeric n-butylene oxide, hexylene oxide, octylene oxide, dodecene oxide, methoxy and other alkoxypropylene oxides, styrene oxide and cyclohexene oxide. Halogenated alkylene oxides are also suitable, e.g. Epichlorohydrin, epiiodohydrin, epibromohydrin, 3,3-dichloro-. propylene oxide, 3-chloro-1,2-epoxypropane, 3-chloro-1,2-epoxybutane, 1-chloro-2,3-epoxybutane, 3,4-dichloro-1,2-epoxybutane, 1,4-dichloro-2,3-epoxybutane, 1-chloro-2,3-epoxybutane and 3,3,3-trichloropropylene oxide. Any mixtures of the pre- • The alkylene oxides mentioned above can also be used.

Pur the production of the ester-containing polyols according to Invention suitable alkylene oxide condensates of polyhydric alcohols with 2 to 6 hydroxyl groups are generally known, e.g. from U.S. Patents 1,922,459O 190,927 and 3,346,557. They are generally produced by the catalytic condensation of an alkylene oxide or a mixture of Alkylene oxides prepared with the polyhydric alcohol either simultaneously or sequentially. Any alkylene oxides, those mentioned above can be used. Examples of suitable polyhydric alcohols are Ethylene glycol, propylene glycol, the isomeric n-butylene oxides, 1,5-pentanediol, 1,6-hexanediol, glycerine, trimethylolpropane, 1,2,6-hexanetriol, sorbitol, sucrose, α-methyl glycoside and Mention pentaerythritol. Any mixtures of the above

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mentioned alcohols can also be used. in the in general, the condensates suitable for the purposes of the invention have a molecular weight between 100 and 10,000, preferably between 300 and 6,000.

Tetrabromophthalic anhydride is used as the third reactant for the production of the ester-containing polyols used. It has been found that only with ester-containing polyols made from tetrabromophthalic anhydride mixtures with the advantages mentioned above can be obtained. Ester-containing polyols derived from related anhydrides, e.g. tetrachlorophthalic anhydride, do not form mixtures with the necessary stability and flame retardancy. Generally 20 to 40 parts by weight of the ester-containing polyols, based on the total weight of the components, in the injectable mixtures used according to the invention.

The second component of the sprayable mixtures according to -der Invention is an alkylene oxide condensate of sucrose or α-methyl glucoside with a hydroxyl number of about 4-00 to 600. These condensates are produced by adding an alkylene oxide or a mixture of alkylene oxideη either simultaneously or is reacted successively with sucrose or α-methylglucoside '. Mixtures of these condensates can also be used. The lower alkylene oxides can be used as alkylene oxides for the production of these condensates 2 to 4 carbon atoms, e.g. ethylene oxide, propylene oxide and butylene oxide, can be used. In general, 2 to 15 parts by weight of the condensate, based on the total weight of all components, in the sprayable mixtures according to Invention used.

Another essential component of the sprayable mixtures according to the invention is a polyaryl polyalkylene polyisocyanate or a prepolymer made therefrom and having terminal isocyanate groups. Any suitable Polyaryl polyalkylene polyisocyanates can be used. 209846/1108

poly
• Polyphenylene polyisocyanates containing both diisocyanates and triisocyanates are preferred. Mixtures of isocyanates are suitable, as described for example in US Pat. No. 2,683,730, British Pat. No. 874 4-30 and Canadian Pat. No. 665,495. It is also possible to use mixtures of polyphenylpolymethylene polyisocyanates which are not in the The frame of these patents lie. Such a mixture is particularly advantageous which has a viscosity of about 150 to 250 cP at 25 ^° C. and an isocyanate content of at least about 31 % , and in which the isocyanate is about 42 to 4-8 % as monomeric diphenylmethane diisocyanate. The polyaryl polyalkylene polyisocyanate is preferably prepared by reacting aninline with formaldehyde in proportions such that an amine product is obtained which consists of about 40 to 60 % diphenylmethane diamine and the remainder of higher polyamines, so that by phosgenation of the resulting mixture of diphenylmethane diamine and higher polyphenylpolymethylene polyamines da.s product about 40 to 60 % diphenylmethane diisocyanate, 20 to 30 % triisocyanate, 8 to 17 % tetraisocyanate and 5 to 30 % penta isocyanate or higher. Contains polyisocyanates. In a preferred process for producing the polyphenylpolymethylene polyisocyanates, the aniline-formaldehyde reaction must therefore be started, in which the aniline and the acid catalyst are first mixed and reacted with one another and then the resulting mixture of acid salt, eg aniline hydrochloride, and aniline is reacted with formaldehyde The mixture of diphenylmethanediamine and high polyamines is formed. The amine product initially obtained is then neutralized with approximately the stoichiometric amount of a base or even with a very small excess of a base, e.g. sodium hydroxide and potassium hydroxide.

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_ 9 -

lized, whereupon the amines to be phosgenated τοη the salt formed by decanting and distillation to remove the water and the salt are separated. This mixture of amines can then be phosgenated to produce a mixture of organic polyisocyanates by any phosgenation reaction, as described, for example, in US Patents 2,683,160, 2,683,730-2,875,226. In order to obtain the desired percentage of Diisoeyanaten, the desired viscosity and the desired isocyanate content, the reaction is preferably in two stages, namely first at a temperature of about -20 ° to 80 ° C and then in a second stage at a temperature of about 90 ° to 200 ⁰ C performed. The polyphenyl polymethylene polyisocyanates are thus preferably produced by reacting phosgene with the above mixture of amines in two stages at a temperature such that the temperature of the exothermic reaction which takes place when these two components are combined initially is not substantially above about 90 ⁰ C , whereby a carbamyl chloride-amine hydrochloride slurry is formed, which is then ^{reacted with phosgene at a temperature above about 90 °} C. but below about 200 ^° C., the above-described mixture of polyphenylpolymethylene polyisocyanates being formed. An inert organic solvent is preferably used in the phosgenation of the amine. For this purpose, both the amine and the phosgene are premixed with the organic solvent and then reacted in a solution in the two stages mentioned above to form the organic polyisocyanate. A high-speed mixer is preferably used for combining the phosgene solution and the amine solution in the production of the product of the first stage, ie the carbamyl chloride-amine hydrochloride

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Slurry used.

Any suitable high-speed mixer, e.g. turbine mixers, colloid mills and pumps, e.g. centrifugal pumps, contain the components that rotate at high speeds and thus an intimate Ensure contact between the amine and the phosgene in a relatively short time, can for the preferred embodiment of the method according to the invention can be used. Intensive mixers are preferred at speeds of about 100 rpm or more. ..

Any suitable solvent which is against the amine, the isocyanate formed and against the Phosgene are inert can be used. Solvents of the formula, for example, are suitable

in which the radicals B, which may be the same or different can, lower alkyl radicals, hydrogen atoms, halogen atoms, Are nitro groups, aryloxy groups and alkoxy groups. Also suitable are hydrocarbons, ethers and Ester. Possible halogen atoms are, for example, chlorine, bromine, iodine and fluorine. Suitable as aryloxy residues are for example phenoxy radicals, cresoxy radicals and ethylphenoxy radicals. The alkoxy radical can, for example be an ethoxy group, methoxy group, propoxy group and butoxy group. Furthermore, hydrocarbon mixtures, e.g. Kerosene, can be used. As specific examples of suitable compounds are benzene, toluene, xylene, Chlorobenzene, o-dichlorobenzene, nitrobenzene, cyclohexane, Durolj, o-, m- and p-cymene, dodecylnaphthalene ethyl acetate and diphenyl.

It also proved advantageous to have a low 209846 / 1VQ8

To use the amount of acid in the condensation of the aniline with formaldehyde in order to obtain a mixture of amines which, after phosgenation, contains the correct amount of diisocyanate and total isocyanate mentioned above and has the viscosity mentioned above. This amount is preferably about 1 to 15 % of the acid required for reaction with all of the amine in the. Reaction mix required

As already mentioned, prepolymers produced from the abovementioned polyisocyanate with terminal Isocyanate groups are also used as the isocyanate component of the sprayable mixtures according to the invention be used. These prepolymers are made by reacting a stoichiometric excess of the Polyisocyanates produced with one of the two above-mentioned poly components. Generally will about 40 to 60 parts by weight of the isocyanate component, based on the total weight of the ingredients, for the Purposes of the invention used.

As mentioned earlier, it is a phosphorus containing organic Compound used in the sprayable mixtures according to the invention. These connections are general known. Suitable phosphorus-containing organic compounds are, for example, OiO-diethyl-η, η-bis (2-hydroxyethyl) aminomethylphosphonate, Tris (ß-chloroethy1) phosphate, Tricresyl phosphate, triphenyl phosphate, Cresyl diphenyl phosphate, tris (2,3-dibromopropyl) phosphate, Tris (trichloropropyl) phosphate and tris (chlorobromopropyl) phosphate. Any organic compounds containing phosphorus that are not decomposed, i.e. not with Isocyanate groups reacting can be used for the purposes of the invention. They lend the products not only the flame retardant properties, but also reduce the brittleness and fragility of the foam. Generally about 1 to 15

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Parts by weight of the phosphorus-containing compound, based on the total weight of the ingredients, used in the mixtures according to the invention.

For the mixtures according to the invention, highly active catalysts are used which essentially Immediate foaming of the reaction mixture when it hits the surface to be treated. It is not uncommon for the foaming reaction to begin as soon as the components of the mixture reach the surface to be treated. Suitable catalysts for the purposes of the invention are triethylenediamine, Dimethylaminoethanol, tetramethylethylenediarain, tetramethylbutanediamine, dibutyltin diacetate, Dibutyltin dilaurate, dibutyltin di-2-ethylhexoate and Mixtures of these compounds. Other catalysts with comparable or higher activity can also be used will. In general, when using mixtures of the abovementioned catalysts, the Quantities can be varied in the entire possible range. Are preferred as catalysts according to the invention dimethylaminoethanol, dibutyltin dilaurate and mixtures of dimethylaminoethanol and dibutyltin dilaurate.

The amount of catalyst used generally depends on the activity of the catalyst and / or the temperature the reactant prior to mixing or spraying. Of course, if you use more reactive ones Catalysts or, if higher temperatures of the reactants are used, lower amounts of catalyst necessary. In general, about 0.2 to 2.0 parts by weight, preferably about 0.3 to 0.6 Parts by weight of catalyst, based on the total weight of all components, are used.

For the production of high quality polyurethane 209846/1108

Foams according to the invention is a wetting agent or surfactant required, as none Use this means to collapse the foams tend to contain very large irregular cells. Numerous wetting agents were found to be suitable. Nonionic surface-active substances are preferred Agents and wetting agents. Of these, the nonionic surface-active ones proved to be particularly advantageous Means, which are produced by the successive addition of propylene oxide and then ethylene oxide Propylene glycol are produced, e.g. those in the trade under the name "Pluronic" available products, and the solid or liquid water-soluble organosilicones, especially those manufactured by the Silicone Division of Union Carbide Corporation will. Further suitable, although not preferred, surface-active agents are the polyethylene glycol ethers of long-chain alcohols, salts of tertiary amines or alkylolamines with long-chain alkyl acid sulfate esters, Alkylsulphonic acid esters and alkylarylsulphonic acids.

The amount of surfactant or wetting agent in the reaction mixture is also important however, it varies somewhat depending on the efficiency of the wetting agent. Are generally suitable about 0.15 to 3.0 parts by weight of surfactant, based on the total weight of the components. When using quantities below the lower limit the foams tend to form large and uneven cells, while amounts greater than about 3 »O share the properties of the foam does not improve and its strength seems to deteriorate somewhat.

The surfactant or wetting agent can be used in in practice either the polyol or the prepolymer

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or the isocyanate component with no noticeable differences are added as a result. When admixing with the prepolymer, however, it can be advantageous to use the Form foam as soon as possible after admixture with prepolymer, especially if possible there is a reaction between the components.

For the injectable mixtures according to the invention, blowing agents must be used which are inert to all reactants, but soluble or dispersible in at least one reactant and insoluble in the final polyurethane foam. The higher the solubility in the reactants or in the reactants, the lower the boiling point of the solvent can be, which in any case at a pressure of 1 atmosphere has a boiling point of not below about -3O ⁰ G and not above about 99 ° C, preferably should not be above about 4-9 ° C so that it is evaporated during the polymerization reaction. In general, the halogenated alkanes, as well as other solvents which are used in addition to or instead of them, should be readily liquefiable and have such a solubility in the reactant or in the reactants that their vapor pressure is considerably reduced, in order to avoid the need to use expensive high-pressure equipment avoid. If the gas is relatively insoluble, it should be such that it is easily dispersible. Foaming takes place when the gas is released by reaching a temperature that is sufficiently above its boiling point. This can of course be largely regulated by removing the exothermic heat or not removing it. In cases where the heat of reaction is insufficient to evaporate the solvent used, external heating is required.

The halogenated alkanes meet all requirements 209846: / 1108- Y

and are particularly suitable as easy-to-use propellants. Fluorotrichloromethane with a boiling point of about 24 ^° C. has proven to be a particularly "advantageous blowing agent and, like many of the halogenated alkanes of the" Freön "or" Genetron "type, has the advantage that it is in the glycol or polyol or prepolymer or in the isocyanate component Representative solvents suitable as blowing agents, including the preferred halogenated alkanes and their boiling points at a pressure of 1 atmosphere, are given in the table below.

formula Freon 12 Freon 21
Freon ΛΛ Molar
weight boiling point CCl ₂ F ₂ 1,1-difluoroethane Freon 1 "14B ₂ 120.9 -29.8 CH ₅ -CHF ₂ C ^ FgCcyclisclOFreon C-518
CClF ₂ -CClF ₂ Freon 114 Freon 115 66.1 -54 CHCl ₂ F Methylene chloride 200
170.9 -6.1
5.6 CBrF ₂ -CBrF ₂ Carbon tetrachloride
material 102.9
157.4 9
25.8 CCl ₂ F-CClF ₂ Isobutane 259.9 47.5 CH ₂ Cl ₂ butane 187.4 47.6 CCl ₄ n-pentane 85 40 Isopentane 155 75.6 Neopentane 58 -10 η-hexane 58 0 2,2-dimethylbutane 72 .56.1 Heptane 72 27.8 72 8.9 86 69 86 49 100 79-98.5

Of course, mixtures of these gases, e.g. mixtures of soluble and relatively insoluble gases, can also be used.

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be used as propellants and solvents. Mixtures of halogenated alkanes with other compatible solvents, or gases such as carbon dioxide, methane, ethane, propane, butanes, pentanes, hexanes, heptanes _t propylene and nitrogen, are also suitable _r if these solvents or gases in the reactants or in the Eeaktionsteilnehmem together with the halogenated Alkane are dissolved or dispersed. The non-halogenated alkane solvents or gases can be present alone, but are preferably used in amounts up to about 75 % of the solvent mixture. In general, and for the best properties of the foams, particularly the insulating properties, they should not constitute more than 25% of the solvent with the remainder being halogenated alkane or halogenated alkanes. In general, from 5 to 30% by weight of propellant, based on the total weight of the ingredients, is used for the purposes of the invention.

As already mentioned, small amounts of water can be used in the sprayable mixtures according to the invention will. In general, the amount of water is 0 to 1.5 parts by weight. For the production of foams with the desired rating in the tunnel test, water is not essential. However, as in In connection with the plasticizer mentioned, it can be added to the sprayable mixture to improve the physical properties To improve the properties of the foam.

The invention is further illustrated by the following examples. All parts are understood to be parts by weight, unless otherwise stated.

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example 1 Production of an ester-containing polyol

In a reaction vessel equipped with a thermometer, stirrer, nitrogen inlet and heat exchanger, 464 parts of tetrabromophthalic anhydride and 400 parts of a condensation product of propylene oxide and pentaerythritol (hydroxyl number 556) 6 ^{e set ) en} The reaction vessel was then flushed with nitrogen 0 atmospheric pressure blown off, sealed and heated to 140 ° C. Period of 5 hours 116 parts of propylene oxide were added to the reaction mixture, then, the temperature of the mixture was maintained at 140 ⁰ C. The pressure after the addition was 0.7 to 1.05 atü.Wach completion of the addition of the Propylenoxyds the reaction mixture was stirred for 3 hours at 140 ⁰ C. The mixture was then devolatilized by being held for 1 hour at 11O ⁰ C and under a pressure of less than 5 mm Hg. The product had the following key figures: hydroxyl number-228, acid number 0.1, bromine content 32.6 %. -

B) Production of a two-component polyurethane injection mixture

A two-component polyurethane injection mix was prepared as follows: Component A was made by mixing of 80 parts of the ester-containing polyol described in section (A) with 15 parts of a condensate of Propylene oxide and sucrose with a hydroxyl number of 570, 5 parts of 0,0-diethyl.-n, n-bis (2-hydroxyethyl) aminomethylphosphonate, 1.5 parts of a surfactant Means based on silicone "DC-193", 4.0 parts of diethylenetriamine, 1.0 part of water and 50 parts of trichlorofluoromethane. Component B was made by mixing of 112 parts of polymethylene polyphenyl isocyanate (functionality 2.8) and 19.7 parts of tris (β-chloroethyl) phosphate

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manufactured.

Mn part of the two-part system described above was set aside for storage stability testing. The shelf life is determined by periodically spraying the mixture and measuring the time up to the point at which the foam is no longer tacky. The remainder was sprayed and foamed at 21-27 ° C using a De Vilbiss Company spray gun. The results of the storage stability test and the physical properties of the foam are given in Table I below. The experiment described above was repeated using, as the ester-containing polyol, a polyol prepared in the manner described in section (A), except that tetrachlorophthalic anhydride was used in place of tetrabromophthalic anhydride. The polyol had a hydroxyl number of 285, an acid number less than 0.1 and a chlorine content of 18.0 %. A spray mix was prepared in the manner described above. However, this mixture had a flame spread of 30.8 in the tunnel test according to ASTM E-84.

Table I. not sticky after Sec. test on shelf life 60 Il time in Weeks 64 Il O . 60 Il 2 65 Il 3 68 Il 4th 70 Il 9 80 13th 26th

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Physical Properties

ASTM E-84 tunnel test 15th O ₁ • 5 Flame spread 330 1, smoke 9, 1, 7 kg / m ⁵ supplied fuel 1, 7 kg / m ⁵ Volume weight: 28, 5 2 kg / cm ^ core 28, all in all 1, 6th 111 Compression hardness at 10 % compression 8th 166 K-factor: 0, 11 at the start 0, / q after 10 days of aging at 6O ⁰ C 209 2 kg / cnr Taber abrasion resistance, cycles / cm 97 74 kg / cm ² Closed cell content 2, 48 kg / cm interlaminar bond strength 2, 24 Tensile strenght - 1, Shear strength 2, Water vapor transmission rate, perm / inch Butler chimney test: 85 remaining weight in %
the original weight B. .9% Flame height ,1 % Moisture aging at 37.8 ⁰ C, 100 %
relative humidity, volume change: .6% 1 day - .9 % 2 days 7 days 14 days .5% 28 days , 3% Moist aging at 70 ° C, 100 %.
relative humidity, volume change: , 3% 1 day - . 2 days 7 days

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14 days 15.1 %

28 days 16.0%

Aging at -29 ° C, volume change

after 1 day -0.5%

Example 2

The experiment described in Example 1 was repeated with the difference that on the first attempt (A) the Water was omitted, in the second experiment (B) neither water nor tris (ß-chloroethyl) phosphate were used and in the third experiment (C) the 0,0-diethyl-n, n-bis (2 ~ hydroxyethyl) aminometh: $ phosphonate was omitted. Bet the storage stability test gave essentially the same results as in Example 1. The physical properties of the foams are given in Table II below.

Table II

attempt A. Tunnel test according to ASTM E-84 25th 124 B. C. Physical own
societies Flame spread 555 smoke Volume weight, kg / m * 51.24 20.5 25.1 core 52.4 545 275 all in all 0.98 ρ
Compression hardness, kg / cm
10 % compression 54.6 26.45 K factor 0.110 54.76 27.59 . at the start after 10 days of aging
at 60 ⁰ C 0.122 1.2 1.2 Taber abrasion resistance,
Cycles / cm 0.120 0.155 0.148 0.195 167 108

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Content of closed

Cells, % 92 90

interlaminar adhesion,

kg / cm ^ 1.49 - 55. . - 2 , 18 Tensile strength, kg / cm 1.49 1, 2 1 , 54 Shear strength, kg / cm 2.59 1, 54 2 , 60 Permeable to water vapor
ability, Permian / inch 1.88 2, Butler chimney test: 87 remaining weight in %
of the original
Weight 84 88 B. * Flame height B. C.

6.2 8.0 0.4 6.9 9.3 0.6 7.1 10.5- 1.7 7.8 11v5 2.8 9.2 9.7 - 5.6

Humidity aging "at 57.8 C, 100% relative humidity, volume change in %

* 1 day

2 days

7 days 14 days 28 days

• Damp aging at 70 ° C, 100% relative humidity, Change in volume in%

1 day

■ -> .. 2 days

^ 7 days

14 days

28 days

Aging at -29 ° C, volume change after 1 day in % -0.2 -0.2 -5.8

Example 3

The experiment described in Example 1 was carried out using the starting materials mentioned below repeated. The composition and physical properties of the foams produced are in Table III given. All mixtures had essentially

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19.8 24.9 7.4 20.8 26.4- 8.6 22.5 28.5 12.5 22.9 29.9 16.0 25.7 32.5 20.9

Lichen the same resistance as the mixture prepared according to Example 1. Furthermore, all of them had foams a flame spread of less than 25 in the ASTM E-8 * tunnel test.

Table III Components A. Physical Properties 53.96 96 B. C. D. Ester-containing poly oil
according to Example 1, parts 80 Volume weight kg / no Compression hardness at 10 _? % Together
compression, kg / cm 1.76 80 80 80 Or-methylgluco sidpo lyo l ^x 15th Content of closed
Cells, % 88 15th 15th 15th O, O-diethy1-n, n-bi s (2-
hydroxyethyl) aminomethyl
phosphonate 5 Butler chimney test: 15.2 5 5 5 surfactant
based on silicone 0.5 remaining weight, % 0.5 0.5 0.5 Tetramethylene ethylenediamine 1.0 Flame height, cm 1.0 1.0 1.0 water - 1.0 - 1.0 Trichlorofluoromethane 29.0 23.0 30.0 24.0 Polymethylene polypbenyl
isocyanate 80.0 98.0 80.0 98.0 Tris (ß-chloroethyl) phosphate - - 8.0 10.0 52.52 55.8 51.4 1.76 1.41 1.05 94 96 95 87 90 89 15.2 15.2 15.2

Moist aging at 70 C,
100 % relative humidity,
Volume change in %

1 day

2 days 7 days

14 days 28 days

209846/1108

6th 4th 4th 5 10 4th 6th 7th 9 4th 9 9 15th 6th 11 19th 8th 14th 25th 11

Heat aging at 93 ⁰ C,
Volume change in %

1 day 2 1 3 1

2 days 2 1 3 1 7 days 4 2 5 2

14 days 5 3 6 2

28 days 7 4 8 3

Aging at -29 ° C, volume change after 1 day, % -1.2 -1.0 -1.0 -0.5

* Polyol produced by converting propylene oxide with ct-methylglucoside; Polyol OH number 525.

Example 4

Various polyurethane spray mixes are prepared in the manner described in Example 1. In In all cases, the spray mixes have improved stability and the foams made from them have an ASTM E-84 tunnel test score of 25 or less. The mixes are in essentially prepared in the manner described in Example 1 with the following exceptions:

A) A polymethylene polyphenylene isocyanate with a functionality of 5 »2 is used instead of that according to the example 1 used polyisocyanates used »

B) An ester-containing polyol made by reaction of 1 mole of a polyol produced by reacting propylene oxide with α-methyl glucoside and having an OH number of 515 with tetrabromophthalic anhydride and Propylene oxide is used instead of that according to Example 1 ester-containing polyol is used.

C) Tricresyl phosphate is used instead of tris (ß-chloroethyl) phosphate used.

D) The experiment described in Example 1 is under

209846/1108

Repeated use of the polyol mentioned under (B), but without water.

209S46 / 1108

Claims (8)

Claims '' 4% sprayable mixtures for the production of polyurethane foams, Contains the following components, each based on their total weight: (a) 20 to 40 parts by weight of an ester-containing polyol, that by reacting an alkylene oxide condensate a polyhydric alcohol having 2 to 6 hydroxyl groups with tetrabromophthalic anhydride and one lower alkylene oxide has been formed, (b) 2 to 15 parts by weight of a polyoxyalkylene condensate of sucrose or a-methylglucoside, where the Condensate has a hydroxyl number of 400 to 600, (c) 40 to 60 parts by weight of a polyaryl polyalkylene polyisocyanate with a functionality of 2.2 to 3 * 5 or a prepolymer containing terminal isocyanate groups, which is produced by reaction of a stoichiometric Excess of the polyaryl polyalkylene polyisocyanate formed with component (a) or (b) has been, (d) 1.0 to 15 parts of a phosphorus-containing organic Link, (e) 0.2 to 2.0 parts of a catalyst, (f) 0.15 to 3.0 parts of a wetting agent, (g) 5 »0 to 30 parts of a propellant and (h) 0 to 1.5 parts of water. 2. Injectable mixtures according to claim 1, characterized in that they contain an ester-containing component (a) Contain polyol obtained by reacting a condensate of propylene oxide and pentaerythritol with tetrabromophthalic anhydride and propylene oxide has been produced. 3. Injectable mixtures according to claim 1, characterized in that 209846/1108 records that it is a polyoxypropylene condensate as component (b) Contained from sucrose. 4. Injectable mixtures according to claim 1, characterized in that that they are a polyoxypropylene condensate as component (b) of a-methylglueoside. 5 · Sprayable mixtures according to claim 1 to 4, characterized characterized in that it is used as component (c) polymethylene polyphenyl isocyanate contain. 6. Sprayable mixtures according to claim 1 to 5, characterized in that they are as component (d) O, O-diethyln, n-bis (2-hydroxyethyl) aminomethylphosphonate contain. 7. Injectable mixtures according to claim 1 to 5, characterized characterized in that they are tris (ßchloräthyl) phosphate as component (d) contain. 8. Injectable mixtures according to claim 1, containing as component (a) an ester-containing polyol which, by reaction of a condensate of propylene oxide and pentaerythritol with tetrabromophthalic anhydride and propylene oxide has been prepared, as component (b), a polyoxypropylene condensate of sucrose, as component (c) a polymethylene polyphenyl isocyanate, as an ingredient (d) 0,0-diethyl-n, n-bis (2-hydroxyethyl) aminoethylphosphonate, as component (e) diethylenetriamine, as component (f) a silicone surfactant and as component (g) trichlorofluoromethane. 209846/1 108