DE2055041A1 - Process and molding compound for the manufacture of impact-resistant, fire-resistant, rigid polyurethane moldings - Google Patents

Description

Dk. KURT JACOBSOHN d-so «obkhschi ^ isshbim 9> IOV. 1970

PATENT ADVERTISER FKKISINGEH STRAS8K »9

7Ω ζ50 ^ I MKINZEICHRNl

010-34

0IJTCIJiIATI MILAOROI ΧΙΟ. 4701 Marburg Avenue, Cincinnati, Ohio 45 209, Y.St.A.

Procedure and Poravaese

sur manufacture of impact-resistant, fire-resistant, rigid

Polyurethane forum bodies

for this application the priority is to 13. Horenber 1969 from the USA patent application Serial Ιο. 876 601 to complete

genoaaen.

The invention relates to new Polyurethansohaumatoffe from high degree of deformability, from which rigid Sohaueetoff fore bodies of a pre-existing quality, in particular Bit of a coabination τοη high impact resistance, high Can be produced for extreme returns and high resistance to boiling water. Also look at the Invention to the end products obtained from the rigid polyurethane house yornoasses.

The deformation of polyurethane plastics lu rigid cellular products is known. Tiele of these Erseugnieae consist structurally of a unit and aaohen of Relatively rigid, single-faced polyurethanes τοη relatively high ratio τοη strength to weight öebrauoli. There are already rigid polyurethane foam products such as Trays, doors, tables, bottom drawers, and even chairs, are known.

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TKI.BfON (Olli) 1 »04 ·· · IltlSIlHHll CBlHIITRT ICIU.KIHIUHU ΙΙΛΝ Kl ΒΛ rSB. VJIH Il I NMB A 11 K II D (OHIK KTO. ··· 4 ·· · »OltlOHICKIOKIU, MCnCHXIT

010-34 λ

As useful and two-dimensional as these well-known moldings may be, they often lack fire resistance, especially in combination with the required, similar physical properties, such as high impact strength and high resistance to boiling water. For many purposes, however, there is a combination ▼ on fire resistance with high physical strength and high resistance to the conditions of exercise, such as boiling water, of prime importance. With the well-known rigid foam molding compounds give a certain Auemas8 from Feuerhammvonaögon su, one sets the polyurethane building material molding compounds fire-retardant Additives to .. These fire retardant additives are common halogen- and / or phosphorus-containing compounds, which can optionally be reactive with isocyanates. Those compounds that do not react with isocyanates are referred to as non-reactive fire-resistant materials and are often phosphoric acid or phosphorous acid esters, which may also contain halogen atoms. These non-reactive fire commodities can also contain or contain halogen-containing organic compounds that do not contain any phosphorus atoms (e.g. organic compounds, containing chlorine and / or bromine atoms). The latter type of non-reactive fire retardant include polyvinyl chloride, tetrabromophthalic anhydride, and tetrachlorophthalic anhydride. In addition, a number of inorganic compounds which do not react with isocyanates are known, such as antimony trioxide, dibasic ammonium phosphate and Ammonium polyphosphate, which impart at least some degree of fire retardancy to the polyurethane constituents. The use of non-reactive, organic fire retardants, many of which are known as plasticizers for certain polar polymers, as additives to rigid polyurethane foam molding compounds, however, often affects the

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109822/203 8.

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Sical isohen properties & he start so-foam moldings _? obtained from these molding compounds £ cf. A. Landrock, Polyurethane Foams: !! technology »Properties and Applications, DOD Publication Plastic Report 37 (AD 688132) 37, (1969J7 · Although fire-retardant sheets have already been achieved with the known molded foam articles, these moldings often lack the physical properties and / or the resistance to the environmental conditions required for their use as a commodity when organic, non-reactive fire retardants are used Non-reactive OT2 »niociicn Fe-aerhaacstoffcn to the polyurethane foam poi-masses is a pronounced addition to the Ysi-v / eMung of the balzaniit polyurethane foam molding materials for the production of technical products Rigid polyurethane foam molded articles made from the known molding compositions which contain non-reactive organic fire-retardants cause cracking and significant changes in their dimensions when exposed to boiling water for 30 minutes.

By using reactive fire retardants (i.e. halogen- and / or phosphorus-containing organic compounds with terminal hydroxyl groups) instead of the non-reactive Fire retardants in the previously known polyurethanes ost-off molding compounds often have many disadvantages of the non-reactive fire retardants with regard to the physical properties of the rigid moldings' .nd / or their resistance to environmental conditions eliminated. Fire-retardant moldings with high physical

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Strength and / or resistance to the ambient conditions are therefore often produced with the aid of the known polyurethane foam molding magnets which contain reactive fire retardants as additives. This is not called isocyanate reactive fire-retardant additives (iSeB, httlogenated phosphoric or phosphorous acid esters with terminal hydroxyl groups) are used to replace the polyol component of the Polyurethane foam resin mass or part of this component is used and often affects the deformability the polyurethane foam molding compound. Furthermore, the often offers somewhat limited resistance to hydrolysis of the reactive fire retardants Failure and therefore on the deformation behavior.

In order to produce usable fire-hamming products, it is not only necessary to achieve the required fire retardancy and the required physical properties, but rather the molding compound must also have good deformability. Good formability can be described as the ability of the Sohaumstoff molding composition to give the mold completely filling the form body in a reproducible manner, which are free of Oberfläohenfehlern and internal defects (such as bubbles, voids, cracks, etc. _0). In the case of the polyurethane foam molding compositions known to date, two wide combinations of fire retardancy and deformability or deformability and good physical properties have been achieved; a combination of deformability, high impact resistance, high degree of fire retardancy and high resistance to boiling water has not yet been achieved.

The invention relates in particular to polyurethane foams which are pre-reacted with a polyisocyanate an organic compound reactive with Iaooyanatgruppeη

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bond containing two active hydrogen atoms, and subsequent reaction with a polyol, which e.g. * by reacting an alkylene oxide with a Polyhydroxyverb.verbindungen with at least four hydroxyl groups each Molecule is obtained. This reaction product is produced according to the quaaivorpolymerisatethod, in which catalysts, Surfactants as well as other conventional agents can be added. The Quaeivorpolymerisatverfahren is particularly suitable in Within the scope of the invention, since the deficiencies inherent in the one-step method have been increased when this method is used in Within the scope of the invention is applied * So sioh develops in the one-step process through the exothermic reaction higher temperature, which leads to internal scorching and the development of undesirable surface properties in the finished products »If you combine the fire retardants with all the others Components mixed together in one shot often do not allow the emulsions to mix thoroughly or separate again.

It has now been found that such compositions result in products of improved impact resistance and elasticity and surface smoothness can be denied. if If you also use a preferred shaping process, it is possible to produce products that have a skin obtained, in which the skin is relatively thick, but the core is less thick. According to the invention, become such Special fire retardants added to missable molding compounds, which do not affect the properties of the finished products, but the heat resistance and the finished products Give the ability to resist flame spread, as soon as the point of inflammation is reached.

It has been shown that the addition of many known fire retardants polyurethane foams "non-combustible" in the In the sense of ASTM test standard D-1692, but not in the sense of ASTM test standard E «84. The flame spread is namely at

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109822/2038 ^{r / D} ° ™haben * L

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such products if they pass the tunnel test ASTM test standard E-84 should be underauoht, durohaua not satisfactory. Therefore, the tunnel test was used as a more precise measure chosen for the ßrad achieved fire resistance because it is a more severe test than the test according to ASTM test standard D-1692,

The invention is based on the object of providing rigid polyurethane foam molding compositions which In contrast to the molding compounds known to date, rigid, cellular polyurethane moldings with high impact resistance, 8.B, ball drop sole strength of more than 0.288 mkg, high fire retardancy, e.g. a flame spread value determined by ASTM E-84 of 100 or less, and high Provide resistance to boiling water. A further object of the invention is to provide rigid polyurethane foam molding compounds which have a high degree of deformability and are fire-retardant, impact-resistant, result in rigid foam moldings, which against boiling Resistant to water. The invention also provides fire retardant, sole resistant, rigid, cellular polyurethane products that are resistant to boiling water are.

It has now been found that impact-resistant, fire-retardant, rigid, boiling water-resistant polyurethane foam moldings are obtained if a final reaction product containing isocyanate groups is obtained from a stoichiometric excess of an aromatic polyisocyanate and one bifunctional compound, welohes ansohliessend preferably with a polyether polyol, which is preferably obtained duroh unsetsung of an alkylene oxide or a mixture of alkylene oxides with an alkyl, aryl, aralkyl or heterooyolisohen Polyhydroiyverbindungen with at least four hydroxyl groups per molecule, or with a Gemisoh of polyether polyols, the at least one polyether polyol

^BAD ORIGINAL 109822/2038

O1C-34 * f

contains, differs »» dwoli information about alkylene oxides or a mixture of alkylene oxides !! been obtained with an alkyl, aryl, aralkyl or heterocyclic Poii yhjdroxyverb i näung with at least four hydroxyl groups .je molecule reacted i "t _f in the presence of β ei no catalyst, a Tenoids, one, blowing agent and not with leonyanat reacted organic compounds with a molecular weight of at least 500, which contain halogen and phosphor atoms, of which one of the least one halogen atom is a bromine atom, or of (remnants of organic compounds which do not react with isocyanate and which have an average molecular weight of at least 50,000 and consist of organic compounds containing halogen and / or phosphorus atoms, of which at least one compound of the mixture contains one or more SroaiatoroG.

Polyurethanes are produced by converting a Cluaflivorpolymerisatß having terminal isot ^ yanate groups with an organic compound which has several active water types of fat one. The PoXyino / anat © are compounds (organic molecule β 'with two or more tsoeyanate groups), which are generally used for the production of polyurethane foams, and they can be aliphatic, aromatic, heterooyoXisohö or aryl-AlkjripoXyiaooyaa ^ te in the literature are viale Such components and processes for the production of Polyurothansohauinstoffverbindungen and for mixing the same indicated ^, Representative Pol yi so cyanate, which can be used in the context of the invention, are (1) 2 * 4- odor 2,6-I'oluylendiisoijyanat ode5? Isomeregemi see the same, (2) crude loluylenediisooyanate, ie, an undistilled product which generally consists of 70 95 monomeric and 30 $ of polymeric isocyanates, (3) diphenylmethane-4,4'-diisooyanate, (4-) crude Diphonylmethari-4 _f 4 -αϋ80 ^ αηβΐ, dchc an undistilled product, about! 55% from the '

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010-34 g

4,4 · - and the 2 ₉ 4 '· -ΙβοηβΓ € "η, at 25 $ consists of triisooyanate and bu 20 $> consists of> aue polymeric isocyanates" The polyethy: ien ~ po2yphanyXiaoQyanate vary primarily lilDslohtliob ihree Molecular weights and their molecular weight distribution and therefore in their functionality and in accordance with the general formula

NOO

η «1-2

(5) other aromatic diisocyanates, such as £ .B * p-phenylene diisocyanate, m-phenylene diisocyanate, 1-0hlo: ephenylen ~ 2 _f 4-diisocyanate, 3,3 '~ dimethyl-biephenylene-4,4 ^l -diisocyanate, 3t3 ^f -Dinethoxy-biaphenylene-4 »4 ^t ~ diieooyanat _> 4 ^ '- BIs-'2-methylisooyanatophenyl) methane and 4» 4 ^< -Bie- (2-me * i; hoxyiBooyanatophenyl) -methane, (6) partially or fully hydrogenated analogs of the above-mentioned isocyanates and (7) ara.ikylpolyisooyanate (see e.g. m-xylylone diisocyanate) stoahlometric conditions never θ en established "

The above-mentioned quasi-prepolymer can be converted into the polyisocyanate and diol in a ratio of about 2 equivalents of isoyanate eu 1 total hydroxyl group equivalent Digestion produced according to known processes, so that a prepolymer with a terminal NOO group is obtained. If β.B, in an inert atmosphere, an excess of the polyisocyanate is mixed with a polyether diol, an exothermic reaction takes place, which is controlled in such a way that the temperature riioht rises above about 70 ° 0. Well 1/2 to 2 hours

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the development of heat has ended, and after cooling it persists; the quasi prepolymer from an adduct of 2 equivalents Polyisooyanate and one equivalent of diol, applies in the excess polyisocyanate and can be used without further ado.

The compound that is reacted with the quasi-prepolymer is a bifunctional compound. Although for Production of polyurethane foams in general Hydroxyl-containing organic compounds are used which are also suitable within the scope of the invention, one can also other organic compounds which contain two groups per molecule capable of reacting with laooyanatgruppen, for Use the preparation of adducts with terminal Iaooyanatgruppeη, which is formed by reacting 2 molecules of polyisooyanate with 1 molecule of an organic compound has two isooyanate reactive groups. Solo organic compounds are bifunctional organic compounds of the general formula

R ₁

in which Y is a hydrogen atom, a hydroxyl or amino group, Z is oxygen, sulfur, nitrogen, phosphorus, boron or an carbonyl radical, X is oxygen, nitrogen is sulfur, a divalent hydrocarbon type, sulfur bonded to oxygen or a divalent silicon radical, R ₁ , fi ₂ , H, and R ^ hydrogen, halogen atoms »aliphatic hydrocarbon radicals, aromatic hydrocarbon radicals, halogenated aliphatic or aromatic hydrocarbon radicals} U is a hydrogen atom, a hydroxyl, amide, amino, thiol or carboxyl group, m the value 1 or 2, a has the value 1 or 2 and η has a value from 1 to 500, preferably from 3 to 70, in particular from 6 to 11. These connections will

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with the quasi-prepolymer in the presence of a blowing agent and optionally in the presence of a catalyst3 and / or A surfactant is implemented in a rigid foam.

The above general formula includes monomeric and polymeric compounds in which the terminal groups YZ and XU or U are groups which are reactive with isocyanate, such as hydroxyl, amino, amido, flarboxy, maroapto, sulfonic acid and phoephino groups and the like reference for compounds that fall within the scope of this general formula are poly (oxyalkylene) diols, e.g. poly (oxyethylene) diols, poly (oxypropylene) diols and poly (oxybutylene) diols, polyalkylene diols, e.g. polyethylene diols, polypropylene diols and polybutylene diols, poly (oxyalkylene) diamines, e.g. poly (oxyethylene diamine, poly (oxypropylene) diamine and poly (oxybutylene) diamine {polyalkylene diamines, e.g., polyethylene diamines, polypropylene diamines and polybutylene diamines; o) -Amino-poly (oxyalkylene) alcohols ι ω-amino-polyalkylene alcohols; Poly (oxyalkylene) dioarboxylic acids, for example poly (oxyethylene) dioarboxylic acids, poly (oxypropylene) dioarboxylic acids and poly (oxybutylene) dioarboxylic acids, polyalkylene dioarboxylic acids; co -hydroxy-poly (oxyalkylene) -carboxylic acids | cd -amino-poly (oxyalkylene) carboxylic acids; Poly (oxyalkylene) -dlcarboneäureamidej Polyalkylenedioarbonsäureamlde and the corresponding dithiols, diaulfonic acids, diphosphines, di (sulfonamides, the corresponding bifunctional compounds with mixed functions and the like. Besides diols (compounds with two hydroxyl groups) other compounds which are reactive with ioooyanate can also be used. such as those which contain two amino groups per molecule, one aminogimppe and one hydroxyl group per molecule, two carboxyl groups per molecule, one carboxyl group and one amino group per molecule or one carboxyl group and one hydroxyl group per molecule. The Di Ölβ and isocyanates are selected so that one Quaeivorpolymerisate with suitable for further processing

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n and end products aiii; obtains the desired properties. D: loJLo provide better results and some of the "implementation d ^<i v3 invention suitable diols Bind poly {oxfILrAyleia) - MmIq, Po3y- (oxypropylene) diols _f poly (oxybutylene -cüoXe and CraüKlmüie or · Kißchpol '. .yraerieate same.

Me compounds with several active water atoms can be polyhydroxy compounds, such as friols, tetrols, pentols, hexols, ootols or other polyether polyols; in a less preferred method, aian can also use polyester polyols. The Polyeeterpo3yole are linear polyester having terminal hydroxyl groups and allow easy eioh duroh reacting polyfunctional Carbonaäuren such as adipic acid, with Polyhydroxyvertilndungen such as ethylene glycol _f produced. Polyethers with terminal hydroxyl groups are technically produced by adding alkylene oxides, such as ethylene, propylene or buty: ~ enos: id _f ku poly-hydroxy initiator compounds. The Ziur Ferstellung dor Po are inventions} yätherpolyole used InItiatorverb.1 polyhydroxy alkyl, aryl, aralkyl, or heterocyclic Cyoloallcyl- polyhydroxy compounds, and include triols (for example glycerol, trimethylolpropane, and 1 _f 2,6-HexantrioI) Tetrols (e.g. pentaerythritol and λ-methylglucoside), hexitols (e.g. sorbitol) and ootols (see also sucrose). These and other polyhydroxy compounds can be mixed with one another in various combinations before they are converted into the desired polyether polyols by oxyalkylation, or different polyether polyols can be mixed with one another after they have been prepared. The physical properties of the polyurethane foam are within the scope of the invention control by appropriate selection of poly oils and quasi-prepolymers.

The polyols given above can be carried out using known methods getting produced. The oxyalkylation is carried out e.g. *, by using a stainless steel autoclave

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1 mol pulverulent α-methylgluooside or sucrose together with 10 Ms 25 mol pulverulent alkali (potassium hydroxide) and waeeer charged. The autoclave can then be flushed with nitrogen and heated to 130.degree. C., whereupon the oxyalkylating agent (propylene oxide) is added in portions over the course of about 4 hours, the temperature being slowly increased to 150.degree. When all of the reactants are bugesetzt "to the! Temperature to 150 ° C ₁ keeps up the pressure nioht continues to rise, whereupon after cooling and neutralizing with phosphoric wins the oxyalkylated product.

Polyurethane foams are made by expanding the liquid Synthetic resin produced into a cellular structure with the help of a gas. You can develop gas by adding of water or a compound containing carboxyl groups the liquid, reacting polyurethane resin mixture can be triggered, as a result of which carbon dioxide is generated. But you can also a non-reactive liquid of lower value Add viscosity, which is determined by the groups containing active hydrogen atoms in the reaction of the isooyanate developed heat of reaction evaporated. Bas nascent Gas remains in the closed cells of the finished rigid foam. Trichloromonofluoromethane is usually used for this purpose (Boiling point 23.8 ° C). By adding a mixture of triochloromonofluoromethane and dichlorodifluoromethane (Boiling point -29.8 ° C) to the polyurethane to be foamed one can achieve improved hemorrhage and flow behavior achieve in the shaping of complex shaped products. Although the carbon dioxide generating implementation between water and isocyanate is not essential for the expansion of the foam, small amounts of water can be used (together with the corresponding stoohiometric amount of Isooyanat) be advantageous for the overall reaction if they are a propellant consisting of a halogenated hydrocarbon

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medium can be added. Other volatile Plüesigkeiten that ale blowing agents may be used Bind hexane, Methylahloroform symmetrical Setraohlordifluoräthan and Triohlortrifluoräthan »The replacement of the Trichlormonofluormethans duroh CBrP ₂ CBrF ₂ (boiling point 47 ° C) or CBr ₂ J ₂ (boiling point 25 ° C) has a favorable Effect on the flammability of the polyurethane foam _c Surfactants are used in the production of rigid polyurethane foams to support the dispersing or emulsification of the reaction participants in one another, and as an aid for the nucleation, growth and stabilization of cells in the critical stages of polymerization. It has been shown that various commercially available high surfactants, predominantly of the type of polydimethyleiloxane-oxyalkylene copolymers, are effective within the scope of the invention.

Catalysts which are usually used for the production of polyurethanes are tertiary amines, such as tri-ethylendlamine, N-alkylmorpholines, N, N, N ¹ , N'-tetramethylethylenediaain, N, N, N ', N ^f -Ietramethyl-1 , 3-butanediamine, N, N '-substituted piperazines, 1,4-diaza - ^ / ?. 2,2 _Ji 7-bioycloootane and dialkylalkanolamines, metal salts »eg» tin (II) oaprylate, dibutyltin dilaurate, lead arylate or »naphthenate, iron (III) aetylacetonate. Under certain circumstances mixtures of tin compounds and tertiary amines are very effective and sohei- nen a synergistisohe impact exercise. It was also found that the combination of N, H, N ', Ν'-tetramethyl-1,3-butanedlamine alt the diaoetate of a tertiary amine (ie »H, N, H', H» -tetramethyl-1,3 -butanediamine or Ν, Ν, Ν ', Η'-Τβ ^ β-methyläthylendiaain) the buoyancy and deformability of the polyurethane is regulated, while at the same time a Sohaun with the desired physical properties is created.

The preferred catalyst is N, N, N *, N '- (tetramethyl) butane diamine. This compound is used either in the free state or as a delayed action catalyst (DAC).

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DAC is produced by mixing a tertiary diamond with 2 mol of glacial acetic acid with stirring and under nitrogen at air temperature below 150 ° C. A bo \ chsr catalyst can be produced 2 "to 3 hours before molding and by injection into a given component can be added with the help of an injection needle.

Since polyurethane foams are organic compounds, they are easily flammable »if no measures are taken» to make them flame-retardant. The flammability of polyurethane foams is therefore a factor that limits their use to the greatest possible extent. It has 8ion various methods served to improve the flame retardant properties ron polyurethanes, such as ₀ by incorporating organic and / or inorganic reactant or nioht-reactive additives containing phosphorus, nitrogen "and / or halogens, or duroh coat of flammable foam with a fluff inhibiting agent.

The mechanism by which the various flame retardants improve flame retardancy, Is not fully understood. However, it is believed that phosphorus compounds favor charring, and that halogen compounds are used as chain terminators in the Free-radical chain reactions take place when the polymer decomposes to form flammable oases.

Non-reactive (no active hydrogens naoh Zerewitinoff containing) flame retardant mushrooms, the sioh Suitable for the purposes of the invention are (1) compounds n with a molecular weight equal to or greater than 500 » those phosphoric and phosphorous acid esters, halogenated Phosphoric and phosphorous acid esters and halogenated organic compounds belong to »where at least one of the halogen atoms is a bromine atom, (2) mixture« of compounds » which give an average molecular weight equal to or greater than, to which mixtures of halogenated organic compounds containing bromine and optionally chlorine »and

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010-34 Ις *

Phosphoric acid or phosphorous acid esters or halogenated phosphoric acid or phosphorous acid esters !!; Mixtures of halogen i .e:. * Th organic twists which contain chlorine and bromiorteii Hu-ephoric acid · and / or phosphorous acid esters; Gem'sohö from phosphoric acid or phosphorous acid esters and bromine :? he *, he; Phosphoric acid or phosphorous acid esters; Mixtures of chlorinated phosphoric or phosphorous acid esters and "bromo, it acid- th phosphorus or Phosphorigüäureest" rn belonging Tm scope of the invention one uses the non-reactive, flame retardant additives in minor amounts, preferably in amounts of from 2 "to 30 weight percent, in particular in amounts of 5 to 18 percent by weight of the total geroiechoe. These compounds can be added either to the polyol or to the polyisocyanate educt, or to each; a part of these connections can be added to these two Beatand parts,

Examples of compounds according to the invention either for ß; <■>}! used alone or in special combinations v / erdo «germinate, are Tris« i2,5-dibronpropyl) «phosphate» a Chloretliylester of phosphorous acid mi'ü the general

5! p

o-OH

O CH

also ₀ ch "ci}"

-Jn where: i has a value from 0 to 5,

Tris-i-bromo-3-chloroisopropyl) phosphate and Hexabromoyclododeoaiic The inorganic substances which have also been found to be useful according to the invention include two basic elements Ammonium phosphate and ammonium polyphosphate.

When using a mixture of feuerhi-nmendiin means siittlore the molecular weight is 500 _t vrelches übar- '

BATH ORIGINAL

1 09822/2038

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must increase, determined from the following equation

100 with ti. ^ - _EI

L τ

or

iOO

MG.

mitti · γ egg

Li Ί ~

Mean therein

S = quotient from the percentage by weight of a Component in the overall fire retardant mixture and the molecular weight of the component concerned

Sum of the individual Ε values in the mixture.

Pure a mixture of equal parts of two fire retardant Agents A and B, of which agent A has a molecular weight of 1000 and agent B has a molecular weight of 200, you get"

100

MG.

»» It ti.

mitti. »Average

50/1000 + 50/200

100 0.05 + 0.25

100

The ball drop floor strengths will be at a smooth Polyurethane moldings with an outer skin of 1.27 x 10 χ 25.4 om size and a total density of 0.35 g / om "best imrat. The moldings are divided into two halves of 1.27 χ 10

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χ 12.7 To determine the Kugalfall sole strength, one of the 1.27 x 10 χ 12.7 large pieces is centered on a steel ring of 10 in diameter and clipped on two opposite sides around the Sample to be held in place. The device is constructed in such a way that a steel ball with a diameter of 3.8 cm (225 g) can be dropped onto the center of the test object from progressively greater heights, the height of fall increasing by 10 oa each time. After each case, the specimen is examined for cracks on both sides and if a crack is found it is pardoned as a failure. Then the other 1.27 χ 10 χ 12.7 cm sample is placed on the ring and clamped, and the experiment is continued, starting with the height reached in the previous sample, with further height differences of 10 cm each, until another Jumping of the sample is observed. Pia falling ball impact strength is then the total height of fall in meters, multiplied by 0.225 kg. The mean value from these two measurements is given as the value for the ball-drop floor resistance.

The flame spreading rate is carried out according to the AS! FK ~ test standard E-84 (3teiner-5unnel) on a smooth outer skin exhibiting porous bodies with a density of 0.35 g / osr and a discharge of 1.27 50.8 χ 127 om durohgefuhr- ft. In order to provide the required '7.6 m test area ' , one needs seoh's plates. with tus & soil piles from the HoIs of the Roteiohe (Quercua bürealia) after a certain pretreatment has been obtained. Is;. Not mending polyurethane foams orgo ^ -oi ·; ^r lr .-. ^ ena eohwindlgkeiten 500 to 700.

In dens ± 30 minute test n sindent> w water wild a 2.54 χ 5 _f 1 ζ 5f1 om big a ** ^ glat, .lueeenhe'ii "aafweieen the Pcljurethaneohium ~? Ormki body id-J. ■; # -.- iv · Sas * ^-ΐ: .- ;. · ..ire νο: · ι

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0.55 g / om ⁵ 1/2 hour casually götauoht the surface of boiling water. The test specimen is held under the liquid surface with the help of a wire mesh of 9 _{t 5 mm wide.} At the end of the test, the sample is removed from the water, dried and examined for dimensional changes, color changes, formation of surface cracks, dents, cracks or complete failure. A test piece passes this test if its surface shows no dents, cracks or cracks, and if the test piece has practically no dimensional changes.

Mixed liquid polyurethane foam components are placed in a previously heated, sealable mold of a certain volume in at least twice the amount that would be required to fill the volume of the mold cavity if the components were allowed to foam freely, and then the ingredients are allowed to foam and subsequently hardened. This gives a molded polyurethane foam body that completely fills the mold and has a total diameter that is at least $ 100> higher than the free expansion hole (this is the diameter that the body would acquire if the body were to be foamed unchecked in an open container) The same foam molding compound, and the molded body has significantly improved properties, such as high structural strength and a thick, hard, smooth skin or soft skin on its outer surfaces. The best results are obtained by lifting one end of the longest dimension of the mold approximately »against the horizontal in order to allow a more complete and faster expansion in the mold cavity.

To determine the amount of polyurethane foam components of known free buoyancy, which must be introduced into a form of "known volume, in order to achieve an Ereeugnia with the desired total diameter of $ 100> the free buoyancy upwards", one can see the following

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*, over b 0 .i 2/2 0 3 8

3 ft

If the forin has, for example, a volume of 28,316 oa 'and a polyurethane foam is used with a free volume of 0.08 g / ounce and a porous body of a Gosan ring density of 0.32 g / onr, mfm brings 9.07 kg of the components required for the production of the foam into the mold, in order to illuminate a density factor of 4 ßu * », vio'.n: 'the diet factor is the characteristic for the achievement of the improved results of this compliance procedure is ₀

The moldable porin of a certain volume into which the mixture of the foam components is introduced is expediently heated to at least about 43 to 66 ° C. ₍ preferably to about 49 to 60 ° C.) before the filling the Vereohäumung and Yorhärtung in oin ^ ir period of 4 minutes to t bic, wherein the shape rk "r Alike-hi-m odor a somewhat lower temperature-v & ty.r befir.iRfc than the nngeeet ^ th foam components. After Beeridl ^ mf! The Vc;. 'T.chfi-amungsrea? I: tion _p dh-, naoh dem AuftreiVen; -: u a sollonförniigon Prr? Product in the closed 5Όιέ ·, wass normalivveifc-. © ι ti σ 4 Takes minutes, the vv.-vachäuinte materin.l is hardened in a closed form, aB duroli maintenance of heat or by supplying heat to the fora, vrobej the duration of this heat treatment depends on the type of heat supplied with induction or High-frequency heating only takes seconds, while be i the conventional infrared, hot air heating or similar heating 10 to 30 minutes may be required. The resulting product has aine smooth, hard, wear-resistant skin of relatively high Diohte on its äusssren surfaces completely einsohlieset the inner, more cellular structure and is integrally formed with it, the Gesamtdiohte of the product by at least 100 wobei- i> higher lat than the free buoyancy (preferably-

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0.24 to 0.64 g / om) »In this way one can produce products of high strength and smoothness that produce have a smooth surface.

Example i

54.97 g of a quasi-prepolymer at a temperature of 38 ° C with a "viscosity of 2305 ° C determined at 21 ° C and a free isocyanate content of 25.5 percent by weight, produced by reacting 500 parts by weight of a polymethylene polyphenyl isooyanate (free isocyanate content 31.6 f>) with 65.19 parts by weight of a poly (oxypropylene) diol (average molecular weight 400; hydroxyl jet 285.8), are thoroughly mixed with 60.63 g of a polyol mixture at a temperature of 21 ° C from 19 »07 parts by weight of Tri & - (2,3-diohlorpropyl) -phosphate, 67.76 parts by weight of a poly (oxypropylated) oc-methylgluooside-glycerol hemisohes with a hydroxyl number of 434, 1t35 parts by weight of a dimethylsilioon-alkylene oxide misOH polymerizate (surfactant), 10.49 parts by weight 0.667 parts by weight of N, K, N ', W — tetramethyl-1,3-butanediamine and 0.667 parts by weight of Ν, Ν, Ν ¹ , N'-tetramethyl-1,3-butanediamine diacetate (hereinafter referred to from BAC and herges tellt duroh reaction of 2 moles of acetic acid mixed with 1 mole of N, N, H ¹ , N'-tetramethyl-1,3-butanediamine). If this geroic is allowed to float freely in a paper sliver that has not been impregnated with wax, a total-cell, rigid polyurethane foam with a density of 0.069 g / cm 'is obtained. If, however, an equal amount of the mixture is placed in an ^{aluminum mold preheated to 57 ° 0, with a capacity of 327.75 om 5} , this is closed and clamped together and then placed in a convection oven at 82 ° C for 20 minutes, a smooth outer skin is obtained. rigid foam molding with the following properties:

₂₀ _

109822/2038

^% ff Qeeamtdensity ·> g / nm mkg 20550A1 Oi0-34 Barool hardness Ball drop resistance, 0 »35 45 0.484

The above-described mixture of the quasi pre-polymerizate and the polyol mixture is used in a correspondingly larger amount (29 ⁵ %) in order to create a smooth outer shell foam moldings with a density of 0.35 g / cm and a size of 1.27 50.8 χ χ $ om 27 to manufacture. These foam bodies show a flame propagation speed of 4TO ₁ when s: Le naoh dem Steiners3hen! Dunneltest are examined according to ASTM E-84 »

The test for falling ball impact strength is carried out as described above, and the Barcol hardness is determined according to ASI ¹ M Proo. Volume 47 (1947), p. 1017 »and" British Plastics "Volume 35 (2), S ₈ 80 (1962).

58.34 g of itiiea on its 2eraperatur of 38 ° 0 located quasivorpolytierisata with a free isocyanate content of 25 * 5 weight sprouts, prepared according to Example 1, are thoroughly mixed with 57.26 g of a polyol mixture located at a temperature of 21 ° C, daa from 20 _s 19 Gewi'ihfesteilon a Phosphorigsäureohloräthylester of the general formula

»
CiOH ₉ CH ₉ -OPO-CH

²² II

GH C

₉ CH ₉

ClCH ₂ GH ₂

ο _f

-P -— 0 CH

0
-P (OCH ₂ CH ₂ Ol) ₂

-Jn

(n «0-5), 28.98 parts by weight of a poly (oxypropylated) α-Methylgluooside-Glycerinemiöoheß with a hydroxyl number of 434, 36.88 parts by weight of a poly (oxypropylated)

- 21 ■■ *

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010-34 JlJ ^

α-Methylgluoosid-Glycuringemisohes »n with a hydroxyl number of 555, 0.605 parts by weight N, S, N ', N ¹ -Tatramethy3-1 _f 3-butandiamln, 0.807 Gewichbabeilen DAC, 1.43 parts by weight of the surfactants described in Example 1 and 1t, 10 Gyv / 10 parts monofluorotrichloromethane. The mixture, if allowed to freeze freely, gives a rigid foam with a density of 0.067 g / cm. A molded body produced in accordance with Example I has the following properties:

Total thickness, g / cm 0.35

Barcol hardness 52

Ball drop bottom strength, mkg 0.484

If a smooth outer skin having molded body of 0.35 g / onr density and 1.27 50.8 χ 127 µm size according to the ASIM test standard E-84 are examined, they show a flame burnout speed from 460.

Example 3

56.84 g of a quasi-prepolymer at 38 ° C with a free isocyanate content of 25.5 percent by weight, prepared according to Example 1, are mixed with 58.76 g of a polyol mixture at 21 ° C, which consists of 9 , 84 parts by weight of trlo (2,3- ^d ibrüiapropyl) -; yliuGpL £; t, w 9.84 parts by weight of tri- (fluoroethyl) phosphate, 46.71 parts by weight of a poly (oxy per pyli or ton) K -.KGtfcyr.gluöosid-Glyceringemisches with a hydroxyl number of 434, 20.02 parts by weight of a poly (oacypropylated) α-methyigluooside-Glyceringemisches with a hydroxyl number of 555, 0.59 parts by weight N, N, N ¹ , N'-tetramethyl- I, 3-butanediamine, 0.787 parts by weight DAC, 1.39 parts by weight of the surfactants mentioned in Example 1 and 10.821 parts by weight of monofluorotriochloromethane. If you let this Gemisoh foam freely, you get a foam with a density of 0.07 g / cm ³ . Am made according to Example 1 from the mixture

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Shaped body has the following properties;

Total Thickness, g / am 0.55

Bareo? Hardness 27

Kugelfali impact strength, mkg 0.415

A molded body having a smooth outer skin with a density of ^{0.5 g / m 5} density τωΑ 1.27 ι 50.8 s 127 on Grösee, produced from the same mixture, results in a flame propagation speed of when tested according to ASTM test standard E-84 60

Example 4

The following example explains one of the preferred embodiments of the invention, in which both the polyoxyanate component and the stock formulation containing the polyol component each contain a flame retardant. 61.97 g of a quasi-prepolymer mixture at 38 ° C with a viscosity of 2305 cP, determined at -1 ° 0, consisting of 60.67 C4ewi pitted quaeivorpo3yiDerisat with a free isocyanate content. 25.5 i> (Hergeatollt räch Example 1) and 9.33 parts by weight of the Hiosphorigsäurechioräthyleeter described in Example 2 , are thoroughly mixed with 53.63 g of a 21 ° C polyol mixture with a viscosity of 3540 cP determined at 21 ° C, which consists of 10.78 parts by weight of tris (2,3-dibromopropyl) phosphate, 50.37 parts by weight of a poly (oxypropylated) α-methylglueoside glycerol mixture with a hydroxyl number of 437, 21.59 parts by weight of a poly (oxypropylated) a -Methylglucosid-Glycerinemlsrihes with a hydroxyl number of 555, 0.65 parts by weight Ν, Ν, Ν ·, N ¹ -! Petramethyl-1,3-butanediamine, 0.862 parts by weight DACj 1.53 parts by weight of the surfactants described in Example 1, 12, 80 parts by weight of monofluorotrichloromethane and 1.42 parts by weight of dichlovdifluoromethane are * -

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010-34 ^

stands. If nan allows this mixture to foam freely, nan obtains a rigid foam with a density of 0.067 g / onr *. A molded body produced from the mixture of neon example 1 has the following properties:

Overall density, g / cm 0.35 Barool hardness 45 Ball drop impact strength, mkg 0.472 mkg

Moldings made from the same mixture and exhibiting a smooth Aue-Benhaut and having a density of 0.35 g / cm 2 1.27 x 50.8 χ 127 cn size result after investigation according to According to the ASTM test standard Ε-Θ4, a clamp propagation velocity of tone 40.

Example 5

This example illustrates a modification of the procedure described in Example 4. 68.60 g of a Quaeivorpolymerieetaneatzes located at 38 ° C, consisting of 83.2 parts by weight of quasi prepolymer with a free isocyanate content of 25.5 1 » (prepared according to Example 1), 8.4 parts by weight of the phosphorous acid described in Example 2 and 8.4 parts Parts by weight of tris (2,3-dibromopro-pyl) phosphate are thoroughly mixed with 47.00 g of a polyol mixture located at 21 ° C., which consists of 40.99 parts by weight of a poly (oxypropylated) «-Methylgluoosid-Glyoeringemisohes with a Hydroxyl number of 437, 26.02 parts by weight of a poly (oxypropylated) oc-methylgluooside-glycerol mixture with a hydroxyl number of 555, 8.0 parts by weight of a poly (oxypropylated) glycerine with a hydroxyl number of 647, 0.98 parts by weight Ν, Ν, Ν ·, N'-tetramethyl-1,3-butandlaniin, 0.98 parts by weight of DAC, 1.74 parts by weight of the surfactants described in Example 1 and 16.23 parts by weight of monofluorotriohlomethane. If the mixture is left to foam freely, a rigid foam is obtained

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010-34 fS

with a density of 0.067 g / om. I'm after example 1 from the. Mixture of molded bodies shows practically the same Properties like the molded body according to Example 4.

Example 6

This example illustrates a modification of the procedure described in Example 4. 58.44 g of one located at 38 ° G Quasi prepolymer with a free isocyanate content of 26.35 percent by weight «prepared by reacting 500 parts by weight of a polymethylene polyphenyl isooyanate with a free isocyanate content of # 31.6 with 54.98 parts by weight of a foly (ozypropylene) diol with a middle Molecular weight of 400 and a hydrocyl number of 288, are thoroughly combined with 57.16 grams of one located at 21 ° G Folyolgemisches mixed, which consists of 10.1 parts by weight of tris (2,3-dibromopropyl) ~ phosphate, 10.1 parts by weight of the in Example 2 described phosphorous acid chloroethyl ester, 28.61 parts by weight of a poly (oxypropylated) α-methylgluooside-glycerol mixture with a hydroxyl number of 428, 36.41 parts by weight of a poly (oxypropylated) oc-methylgluooside-glycerol mixture with a hydroxyl number of 555, 0.81 parts by weight Ν, Ν, Ν ', N'-tetramethyl-1,3-butanediamine, 0.81 parts by weight of DAO, 2.02 parts by weight of the surfactants mentioned in Example 1 and 11.12 parts by weight of monofluorotriohlomethane consists. This mixture provides a free 7-bohemian letting Solid foam with a density of 0.067 g / cm. A prepared according to Example 1 from the mixture Shaped body shows practically the same properties as the shaped body according to Example 4.

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010-34 % l

Example 7

60.82 g of a quasi-prepolymer at 58 ° C with a free isocyanate content of 25.6 percent by weight, prepared by reacting a mixture of 460.4 parts by weight of a polymethylene polyphenyl isocyanate (free isocyanate content of 31.6 #) and 89 »6 parts by weight of toluene diisocyanate ( 80 i "2,4- and 2,6-20 # Isomeree; free Isooyanatgehalt 48.07 1>) with 95" 7 parts by weight of poly (oxypropylene) diol (average molecular weight 400; hydroxyl value 271), are grUndIioh with 54 » 78 g of a Polyol- ^ geaisohes located at 2i ° C mixed, which consists of 21.10 parts by weight of Tris- (2,3-dibromopropyl) phosphate, 45.06 parts by weight of a poly (oxypropylated) Saooharose glycerol mixture with a Hydroxyl number of 564.3 »19.31 parts by weight of a poly (oxypropylated) a-Mothylgluoosid-Glycerinemisohes with a Hydroxyl number of 555, 0.58 parts by weight of N, N, N ', N »-tetramethyl-i, 3-butanediamine, 0.84 parts by weight of DAC, 1.49 parts by weight of the surfactants described in Example 1 and 11.61 parts by weight of monofluorotriohlomethane. if if this mixture is allowed to foam freely, a rigid Sohaurn with a density of 0.07 g / cm ^ is obtained. A molded body produced from the mixture according to Example 1 has the following properties:

P %

Total density, g / om 0.35 Barool hardness 46 Ball drop sole strength, mkg 0.334

An article prepared from the same mixture, a continuous smooth outer skin having shaped article of 0 * 35 g / om Diohte and 1.27 ζ 50.8 χ 127 cm results in the study according to the ASTH test standard Έ-84 a Plamnenausbreitungegeeohwindigkeit of 70th

ORIGINAL BATHROOM - 26 -

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20550A1

010-34 95l

Example 8

64.26 g of a quasi-prepolymer at 38 ° C. with a free isocyanate content of 25.3 percent by weight, prepared by reacting 550 parts by weight of a polymethylene polyphenyl isocyanate (free isocyanate content 32.2 #) with 62.99 parts by weight of a poly (oxypropylene) diol (average molecular weight 400; hydroxyl number 271), are thoroughly mixed with 51.34 g of a polyol mixture at 21 ° C, which is composed of 22.51 parts by weight of tria- (2,3-dibromopropyl) phosphate, 61.83 parts by weight of poly ( oxypropylated) sorbitol with a hydroxyl number of 653, 0.56 parts by weight N, N, N ¹ , N'-tetramethyl-1,3-butanediamine, 0.90 parts by weight DAC, 1.80 parts by weight of the surfactants described in Example 1, 11, 15 parts by weight of monofluorotriochloromethane and 1.24 parts by weight of dichlorodifluoromethane. If the mixture is left to foam freely, a foam with a density of 0.069 g / cm * is obtained from this mixture.

Example 9

58.67 g of a quasi-prepolymer at 38 ° 0 with a free isocyanate content of 25.5 percent by weight, prepared according to Example 1, are thoroughly mixed with 56.93 g of a polyol mixture at 21 ° C, which consists of 20.30 parts by weight Tri- (2,3-dibrümpropyl) phosphate, 26.29 ff-awichtstoil-m poly (oxypropylated) sucrose with a hydroacyl number of 438.9, 39.43 parts by weight of a poly (oxypropylated) oc-methylglucoside-glycerol mixture with a hydroxyl number of 555, 0.56 parts by weight N, N, N ¹ "N '-' üetramethyl-i, 3-butanediamine, 0.81 parts

- 27 10 9 8 2 2/2038 _{oe | G | NAU}

010-34 W.

by weight of DAC, 1.44 parts by weight of the surfactants described in Example 1 and 11.17 parts by weight of monofluorotriohlorethane. Nan is given free foaming from this mixture a foam with a density of 0.066 g / om. A molded article produced from the Genisoh has essentially the same properties as the molded article 7.

Example 10

56.97 g of a quasi-prepolymer located at 38 ° C. with a free leooyanate content of 25.4 percent by weight, prepared according to Example 1, are thoroughly welded with 58.63 g of a polyolene isoht at 21 ° C., which is composed of 19 * 71 Parts by weight of sris (1-bron-3-chloroisopropyl) phosphate, 46.66 parts by weight of a poly (oxypropylated) α-methylgluooeide glycerine having a hydroyl number of 434, 20.00 parts by weight of a poly (ozypropylated) «-Methylgluooeid- Glyoeringenisohes with a Hydrozylsahl of 555, 0.59 parts by weight H, N, N ¹ , H'-tetranethyl-1,3-butanedianine, 0.79 parts by weight BAO, 1.40 parts by weight of the surfactant described in Example 1 and 10.84 parts by weight Monofluorotriohlornethane consists of a foam made from this genius by using free Yerso skin fibers and has a density of 0.07 g / cm ⁵ . A molded article produced from Genisch according to Example 1 has the following properties

Antidiohte, g / om 0.35 Barool hardness 35 Ball drop floor strength, mkg 0.472

The FlannenaufelungsgeBeschurz von naoh Example 1 produced samples is below 100.

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Example 11

In addition to the moldings described in Example 1, which were used to determine the Barool hardness, the falling ball strength and the flaram propagation speed according to ASTM E-84, further moldings are produced from the mixtures described in the above examples using the method described in Example 1 . All moldings have a smooth outer skin and have a volume of 66 µm ⁵ (size 2.54 x 5.1 x5 »1 µm) and a total diameter of 0.35 g / µm ⁵ . These fora bodies with a skin content of 66 om- * are examined for their resistance to the action of boiling water for 30 minutes using the test method described above. The results can be found in the following overview:

at
game Hölekulargow.lolit dee
fire retardant additive
zes or middle
Molecular weight of the
Additional mixed things Flames
speed
age Behavior at
30 minutes long
Dive into
boiling
water 1 431 470 fails 2 611 460 Well 3 404 (mean) 60 bad 4th 650 (mlttl,) 40 Well 5 # Well 6th * Well 7th 697 70 Well 8th * Well 9 * Well 10 568 Well

* see examples

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EAD ORIGINAL

Claims (1)

ΟΐΟ-34 Claims 1. Rigid polyurethane foam molding compound for manufacture of sohlagfeaten, fire-retardant »rigid polyurethane foam molded bodies of high resistance to boiling water, characterized in that they are made from a mixture of (1) a through reaction of an aromatic polyisocyanate with a functional organic compound obtained adduct with terminal Iaοcyanatgruppen, (2) a polyether polyol with a functionality of at least 4t produced by reacting one or more alkylene oxides with an alkyl, aryl, aralkyl and / or heterocyclic polyhydroxy compound, or a mixture of polyether polyols which contains at least one polyether polyol, which has been prepared by reacting one or more alkylene oxides with an alkyl, aryl, aralkyl and / or heterocyclic polyhydroxy compound which contains at least four hydroxyl groups, (3) at least one organic Compound with a molecular weight of at least 500, which contains no active hydrogen atoms naoh Zerewitinoff, but halogen and / or phosphorus atoms, with at least one the halogen atom is a bromine atom, or a mixture of halogen- and / or phosphorus-containing organic compounds, which has an average molecular weight of at least 500 and no active hydrogen atoms naoh Zerewitinoff, but contains at least one bromine-containing organic compound, (4) one or more propellants and optionally - 30 - BATH ORIGINAL 109822/2038 ' 010-34 §λ (5) one or more catalysts and (6) one or more consists of several surfactants. 2. More rigid, fire-retardant, more rigid, against boiling Water-resistant polyurethane foam standard body, daduroh characterized in that it consists of the product of the reaction (1) by reacting an aromatic polyisocyanate obtained with a bifunctional organic compound Adducts of terminal isocyanate groups, (2) of a polyether polyol with a functionality of at least 4, produced by reacting one or more alkylene oxides ait an alkyl, aryl, aralkyl and / or heterocyclic organic polyhydroxy compound, or one. Mixture from Polyether polyols, prepared by reacting one or more alkylene oxides with alkyl, aryl, aralkyl and / or heterocyclic organic polyhydroxy compounds, which is at least one by reacting one or more alkylene oxides with an alkyl, aryl, aralkyl and / or heterocyclic organic polyhydroxy compound with at least four Polyether polyol obtained by hydroxyl groups contains, in the presence of (3) at least one organic compound with a Holekulargewioht of at least 300, which contains no active Wasseretoffatoee according to Zerewitinoff, but halogen and / or Phosphoratoae, with at least one of the halogen atoms is a bromine atom, or a mixture of halogen- and / or phosphorus-containing organic compounds, which has an average molecular weight of at least 500 and none active hydrogen atoms according to Zerewitinoff, but contains at least one bromine-containing organic compound, (4) one or several propellants and optionally (5) one or more catalysts and (6) one or more envy. 3. Process for the production of eohlagfeeten, fire-retardant, rigid, boiling water-resistant polyurethane ~ 31 -109822/2038 010-34 34 foam moldings, characterized in that one (1) a duroh reaction of an aromatic polyisocyanate with a bifunctional organic bond obtained adduct with terminal isocyanate groups with (2) a polyether polyol with a functionality of at least 4 »produced by reacting one or more alkylene oxides with an alkyl, aryl, aralkyl and / or heterooyolisohen polyhydroxy compound, or a mixture of polyether polyols, prepared by reacting one or more alkylene oxides with alkyl, aryl, aralkyl and / or heterooyolisohen organisohen Polyhydroxy compounds, which contain at least one duroh reaction of one or more alkylene oxides with an alkyl, Aryl, aralkyl and / or heterocyclic organic polyhydroxy compound contains polyether polyol obtained with at least animal hydroxyl groups, in the presence of (3) at least an organic compound with a molecular weight of at least 300 which does not contain any active hydrogen atoms Zerewitinoff, but contains halogen and / or phosphorus atoms, where at least one of the halogen atoms is a bromine atom, or a mixture of halogen and / or phosphorus-containing organic Compounds which have an average molecular weight of at least 500 and no active hydrogen atoms according to Zerewitinoff, but contains at least one bromine-containing organic compound, (4) »one or more Propellants and optionally (5) one or more catalysts and (6) one or more Teneids. 4. The method according to Anspruoh 3, characterized in that a brominated phosphoric acid ester is used as the organic compound with a molecular weight of at least 500. 5. The method according to Claim 3, characterized in that a brominated phosphorous acid ester is used as the organic compound with a molecular weight of at least 500, - 32 - 109822/2038 010-34 33 6. The method according to claim 3, characterized in that tris (2,3-bronipropyl) ph08phate is used as the organic compound with a molecular weight of at least 500 7. The method according to claim 3, characterized in that the organic compound with a molecular weight of at least 500 tri- (1-bromo-3-chloroisopropyl) -phoephate used. 8. The method according to claim 3 »daduroh characterized in that as a mixture of halogen- and / or phosphorus-containing organisohen compounds, which have an average molecular weight of at least 500, a mixture of erie- (2,3-dibromopropyl) phosphate and a mixture of Phosphorigeäureöhloralkylestern of the general formula -0 — I — 0- ( ClOH ₂ CH ₂ -OP-O-CH ClCH ₂ CH ₂ CH, J-O- CH-: CH- I ³ ₂ CH ₂ C1 J- (0-CH ₂ CH ₂ Cl) ₂ η wherein η has a value from 0 to 5 is used 9 «Molding compound according to claim 1, characterized in that the bifunctional organic compound is a polyether diol. 10, molded body naon claim 2, characterized in that the bifunctional organic compound is a polyether diol » 11. The method according to claim 3, characterized in that the adduct of terminal isocyanate groups has been obtained by reacting an aromatic polyisocyanate with a polyether diol. - 33 -109822/2038