DE3643006A1 - FLAME-RETARDANT POLYURETHANE COMPOSITION CONTAINING PHOSPHORUS COMPOUNDS AND THEIR USE - Google Patents

Description

The invention is directed to those containing phosphorus compounds flame retardant, especially flame retardant or flame-retardant polyurethane compositions. It is preferably polyurethane foams, whole particularly preferred around flexible polyurethane foam sheets, so-called semi-finished products.

The use of various phosphorus-containing flame retardant compounds, especially in connection with Halogens is well known. For example, in US Pat 19 36 985 the manufacture of various Phosphoric acid esters and esters of phosphorous acid described that have an oily consistency and halogen can contain. These substances are suitable for flammability of organic substances to which they are added to reduce. It is stated that their viscosity with increasing carbon content increases.

Birum and others describe in US Pat. No. 3,132,169 the production of various phosphate esters contain both chlorine and bromine. It is stated that polyurethanes, for example insulating foams and base resins for curable coatings and adhesives through the addition of phosphate esters flame retardant. The additional amount is 2-25% by weight based on polyurethane. It is still described that the simultaneous softening and the Use of phosphate esters in polyurethane foams (e.g. in rigid foams) increased their flexibility and in some Cases also the mechanical properties of the foams improved.  

Birum and others describe in U.S. Patent 3,344,112 in addition to the teaching of U.S. Patent 31 32 169 that Bis (2-bromethyl) -2-chloroethylphosphate when added Polystyrene this resistance to discoloration when heated mediated. It is also described that the bis (2-bromethyl) - 2-chloroethyl phosphate rigid polyurethane foams also flexible flexible polyurethane foams flame retardant Impart properties when they are present in amounts of 6% by weight, 8% by weight and 10% by weight can be added.

Stanabach et al., In U.S. Patent 4,046,719, disclose that various haloalkyl phosphate esters containing trihaloneopentyl are useful as flame retardants for normally flammable resin compositions. Tribromone neopentylbis (mono- or dichloro-C _2-4 alkyl) phosphates, tribromo neopentyl (mono- or dichloro-C _2-4 alkyl) phenyl phosphates and bis (tribromoneopentyl) (mono- or dichloro-C _2-4 alkyl) are said to be ) - phosphates impart to the foams the properties of not dripping under fire and being flame-retardant. On an experimental scale, flame-retardant flexible polyurethane foams containing these phosphate esters were produced.

Albright describes several in U.S. Patent 4,240,953 hydrogen, chlorine and bromine substituted neopentylbis (dihaloalkyl) phosphates in which halogen is chlorine or bromine is. It is mentioned that various bis (dichloroalkyl) phosphates are light stable and that when the substituted Neopentyl group is 2,2-dimethyl-3-halopropyl, the Phosphates have a relatively low viscosity.

Albright et al., In US Pat. No. 4,083,825, describe that various hydrogen, chlorine or bromine-substituted neopentylbis (chlorine-containing C _2-3 alkyl) phosphates essentially solve the problem of heat discoloration and the scorching of flame-retardant polyurethanes. On a test scale, various flexible polyurethane foams were flame retardant with these phosphates. It is mentioned that these products experience less discoloration when exposed to high heat than polyurethane foams which are coated with bis (bromopropyl) chloroethylphosphate or (3-bromo-2,2-dimethylpropyl) - (1-bromo-2-propyl) - ( 1-chloro-2-propyl) phosphate are added. Tris (chloropropyl) phosphates have been described to reduce foam discoloration. However, laboratory aging tests showed that the flame-retardant effect of the flexible polyurethane foams had been lost.

Mueller-Tamm and coworkers describe in US patent 30 93 599 that suitable compounds for flame retardant Finishing of plastics in addition to these properties are said to be odorless and volatile.

However, manufacturers of industrial-scale polyurethane foams still face numerous problems if they intend to produce a flame-retardant foam that is easy to sell, especially as a semi-finished product in the form of flexible soft foam sheets. These problems can include:
1. the manufacturability and processability,
2. discoloration and scorching,
3. the smell,
4. the flame retardant effect and
5. the cost.

The manufacturability and processability can depend on the number the required flame retardant compounds to be supplied and depend on their physical manifestations. It simple flame retardant compounds are therefore desirable. Liquid flame retardant compounds are common prefers. Liquids with low viscosity are particularly suitable because they are easy in the foam compositions introduced and evenly distributed in the foam can be. Liquid flame retardant compounds with a Brookfield viscosity of 4000 mPas or less are due Particularly easy to process.  

Low viscosity flame retardant compounds are special preferred for the production of flexible polyurethane foam. The flame retardant compounds often result the so-called additional type better processability than Compounds of the so-called reaction type. Scorching is usually yellow or brown Discoloration of the flame-retardant polyurethane foams, especially in the center of the foam sample that is in the is commonly referred to as "bun". Scorch or Scorching can be a sign of foam decomposition be and occurs mainly in highly hydrated compositions on. Increased ambient humidity during the Foaming can also affect scorching (scorching). Scorching and scorching is common a bigger one in flexible polyurethane foams Problem than in rigid polyurethane foam, which is usually called Insulation foam is known. This is particularly evident for foams from large-scale production and in reduced Scope of foams from small experiments in the laboratory. One of the reasons for this is the increased production volume itself, causing difficulties in heat transfer can lead to the exothermic foam reaction, but also the inherently existing insulation properties of the Polyurethane foam. In industrial manufacturing can the core (bun) can reach temperatures of 100 to 180 °, not just for a few minutes, but up to a few Hours. For example, internal temperatures of 140 ° C to 160 ° C for 15 to 30 minutes. Please refer also manual of flexible polyurethane foams, The Dow Chemical Company, USA, Polyurethane Division (1984), pages 19-20.

Well-controlled laboratory tests on a small scale can regarding scorching and scorching with flame retardant equipped flexible polyurethane foams to results lead that do not occur in large-scale production have to. The best proof of a non-braising Foam, remains the large-scale industrial production of the foam itself.  

Odor is a problem of flame retardant Foam, especially in the case of flexible polyurethanes contain certain flame retardant compounds of the additional type. The smell of mold or mold is often difficult to remove, especially the smell of various liquid flame retardant compounds that are considered particularly strong flame retardant be valid.

The flame retardant effect after manufacture can be inadequate be, especially in the case of different large-scale, flame-retardant flexible polyurethane foams that are a volatile flame retardant Supplementary type agents included. This can be from low molecular weight of the flame retardant compounds originate, although these are easy to incorporate. Around Flame retardant compounds can avoid this disadvantage higher molecular weight can be used. Theirs Contributing can be difficult because it is extraordinary difficult an effective and homogeneous distribution of the flame retardant Can be reached in the foam.

The costs are always for the industrial frother Importance. The cost can not only depend on the price of the foam components depend, but also on the amounts of flame retardant compounds that are necessary to the solve previously mentioned and enumerated problems.

What has been missing so far and what is in question Area needed is a phosphorus-containing flame retardant Compound that when used in polyurethane foam, especially in flexible flexible polyurethane foam an easily marketable flame retardant polyurethane foam results that can be produced without difficulty, especially in the form of flexible foam sheets or thick webs. Phosphorus-containing ones are particularly desirable flame retardant compounds that are easy to incorporate, their Presence prevents heat discoloration that are odorless and effectively develop flame retardant effect as well cause low cost.  

This object of the invention is achieved through the use of (β-neocarbyl) (chloroalkyl) (bromoalkyl) phosphorus compounds as flame retardants in polyurethanes. The stake takes place in such an amount that the flammability and Flammability is effectively reduced.

The invention includes both flame retardant Polyurethane compositions, as well as a method for Reduce the flammability of flame retardant Polyurethanes by incorporating the above Phosphorus compounds in the polyurethanes. Polyurethanes are polymeric resinous materials that are used for Coatings and used as foams. These are used as insulation foams in buildings (e.g. Rigid foams) and as resilient foams for upholstery purposes (for example flexible foams or soft foams).

The invention improves the marketability of industrially manufactured flame-retardant polyurethanes considerably. Through the invention, one or several of the problems in the manufacture of flame retardant equipped polyurethanes and their properties improved. This is especially true for foams and whole especially for flexible foam sheets (slapstock foams). In industrial manufacturing, the solution to processing problems and achieving the desired quality properties not only desired, but can be the basis to be competitive for survival.

Generally it is the flame retardant effect generating (β-neocarbyl) (chloroalkyl) (bromoalkyl) phosphorus compounds to haloalkyl esters of phosphorous acid, the Contain β-neocarbyl, chloroalkyl and bromoalkyl groups. The β-neocarbyl group is a saturated, carbon containing group, the central atom with all four Valences has direct carbon-carbon bonds, one of which is a bond to a carbon atom, which is connected to the phosphorus atom via an oxygen atom is like in a phosphate ester. The β-neocarbyl group is  an alkyl or a haloalkyl group, particularly preferred a haloalkyl group. The suitable halogens are chlorine and Bromine. The chloroalkyl group is a saturated, chlorine-substituted one Hydrocarbon group without a carbon atom with 4 carbon-carbon bonds (4 ° carbon). The Chloroalkyl group is also with the phosphorus connectable. The bromoalkyl group is a saturated, bromine-substituted one Hydrocarbon group without a tetravalent Carbon atom with 4 direct C-C bonds. The bromoalkyl group is also with the phosphorus atom connectable.

The (β-neocarbyl) (chloroalkyl) (bromoalkyl) phosphorus compound which has a flame retardant action is preferably a mixed phosphate ester of the general formula in which X is hydrogen, Cl, Br or a C _1-5 alkyl group, each Y is independently hydrogen, Cl, Br, where at least X or Y is chlorine or bromine, and each R is independently a saturated hydrocarbon group of the formula C. _{n is} H _{2 n} , in which n is an integer from 2 to 5.

The phosphorus-containing flame retardant according to the invention Connection is preferably made by way of a phosphorus-bromine-chlorine-oxirane compound by means of a Process, which Birum and coworkers in the U.S. Patent Nos. 31 32 169 and 33 44 112. Especially with regard to this state of the art includes the term "general formula mixed Phosphate esters "also mixtures made according to the Birum's procedures described in the patents.

Mixtures include both isomeric mixtures as well they have been described by Birum in his patents,  as well as reaction products or by-products of bis (chloroalkyl) - and bis (bromoalkyl) phosphorus compounds and not only simple pure mixtures of (bromoalkyl) - (Chloroalkyl) phosphorus compounds with the diol residue, which in the previous description of mixtures of Until (chloroalkyl) were not taken into account. See also for example Brault et al., J. Organometallic Chem., 66, Pages 71-79 (1974).

The route via phosphorus bromochloroxirane compounds differs away from phosphorus bromochloroxetane compounds in that the first way to manufacture (β-neocarbyl) (chloroalkyl) (bromoalkyl) phosphorus compounds no oxetanes are used, while the second route is oxetanes used. However, the second manufacturing route can also be used Case of oxiranes can be used.

A wash of the mixed phosphate ester with dilute acid can be used. Washing with dilute acid is particularly preferred when using phosphorobromochloroxirane compounds, especially when using catalysts such as AlCl ₃ . The ratio of the groups in the mixed phosphate ester is typical and is not changed by washing with dilute acid. In the compounds of the general formula X, chlorine or bromine is preferred, very particularly preferred, because of its lower volatility and the stronger flame-retardant effect, X is bromine. Y in the general formula is preferably chlorine, bromine or hydrogen; hydrogen is very particularly preferred because it gives the compounds low viscosity and low odor. R is preferably a C ₂ H ₄ and / or a C ₃ H ₆ group. RC ₂ H ₄ is very particularly preferred because this increases the halogen content and the phosphorus content of the esters. However, C ₂ H ₄ is also preferred because it leads to better heat stability and increased color resistance and scorch resistance.

Diols are the most preferred compounds for Preparation of the phosphorus-containing ones according to the invention  flame retardant compounds via phosphorus bromochloroxirane compounds. These diols include 2,2-bis (bromomethyl) -1,3-propanediol, 2,2-dimethyl-1,3- propanediol, 2-bromomethyl-2-methyl-1,3-propanediol and 2,2-bis (chloromethyl) -1,3-propanediol. Most notably 2,2-bis (bromomethyl) -1,3-propanediol and 2,2-dimethyl-1,3-propanediol.

Alkylene oxides (alkyloxiranes) such as ethylene oxide, propylene oxide and butylene oxide are the most preferred compounds for the production of the flame retardant according to the invention Phosphate ester. The most preferred epoxies are Ethylene oxide and propylene oxide.

The polyurethane compositions according to the invention contain organic polyisocyanates, polyals and flame retardant amounts of the phosphorus compounds according to the invention. Preferably is the amount of flame retardant phosphorus compounds 2-20 parts by weight des Polyahls, very particularly preferably 8-12 Parts by weight of the polyal.

The term polyal includes any organic compound that has at least two active hydrogens and an average molecular weight of at least 62. For the purposes of the invention, an active hydrogen is understood to mean a group which has a hydrogen atom which, because of its position in the molecule, has a considerable activity for a Zerewitnoff reaction, as described by Kohlc and co-workers in the Journal American Chemical Society 49, 3181- 88 (1927). Examples of such groups with active hydrogen are -COOH, -OH, NH ₂ , = NH, CONH ₂ , SH and -CONH-. Typical polyals include polyols, polyamines, polyamides, polymercaptans, polyacids, and the like, particularly as described by Rosenkranz et al. In U.S. Patent 3,928,299.

Among the polyals described above are the polyols particularly preferred. Examples of suitable polyols are the polyol polyethers, the polyol polyesters, hydroxyl groups containing acrylic polymers containing hydroxyl groups Epoxy resins, multi-terminal polyurethane polymers OH groups, phosphorus compounds containing several hydroxyl groups and alkylene oxide adducts of polyvalent Thioethers and polythioethers, acetals, including Polyacetals, aliphatic and aromatic polyols and Thiols, including polythiols, ammonia and amines, including aromatic, aliphatic and heterocyclic Amines, as well as polyamines and mixtures of these Links. Alkylene oxide adducts of compounds containing two or more different groups in the above Having senses can be used as well as amino alcohols, which is an amino group and a hydroxyl group exhibit. Also suitable are alkylene adducts of compounds which have an -SH group and an -OH group as well as those that have one amino group and one SH group.

Polyols such as triols are very particularly preferred Equivalent weights ranging from 500 to 2500. One Mixture of triplets and diols can also be used especially if the overall functionality of the Mixtures from 2.5 to 3. These connections will be usually for the production of flexible polyurethane foams used.

Any phosphorus compound containing hydroxyl or hydroxyalkyl groups, which are also considered polyahle and / or other polyahlee can be easily implemented in Presence of an organic polyisocyanate to the to achieve the desired polyurethane, the usual conventional reaction conditions and processes of Polyurethane chemistry can be used. The reactions and the Production can optionally be in the presence of chain extenders Agents, catalysts, surfactants Substances, stabilizers, blowing agents, fillers  and / or pigments. The production of foamed Polyurethanes are made using suitable processes such as those of Hoppe and co-workers in U.S. Patent Re 24,514 are. If water is added as a blowing agent, you can appropriate excess amounts of isocyanate are used to react with water and develop carbon dioxide. It it is also possible to manufacture the polyurethanes via the Run away from prepolymers in which an excess an organic polyisocyanate implemented in the first step with the phosphorus compound, the alpha-halohydroxyalkyl groups contains and optionally a polyol, so that a prepolymer is produced, the free isocyanate groups which then react with water in the second step can to form the foam. Alternatively, the However, components can also be implemented in one work step will. This is known as a one-pot Reaction mixture (one-shot technique). Instead of The addition of water can also include low-boiling hydrocarbons such as pentane, hexane, heptane, pentene or heptene used as blowing agents, as well as azo compounds, such as azohexahydrobenzodinitrile, halogenated hydrocarbons such as dichlorodifluoromethane, trichlorofluoromethane, Dichlorodifluoroethane, vinylidene chloride and methylene chloride. The foams can also be produced using freezing technology as described in US Pat. Nos. 37 55 212; 38 21 130; and 38 49 146 are described. The one-pot Mixing is particularly preferred because it involves all reactants at the same time and at the time of foaming be added. This is the way to make most preferred elastic polyurethane foams. The most, but not all, of the modern continuous working flexible foam systems work on this basis. Suitable organic polyisocyanates that are used can be aromatic, aliphatic and cycloaliphatic Polyisocyanates and mixtures thereof. Representative Examples are diisocyanates, such as m-phenylene diisocyanate, Tolylene-2,4-diisocyanate, toluene-2,6-diisocyanate, Hexamethylene-1,6-diisocyanate, tetramethylene-1,4-diisocyanate,  Cyclohexane-1,4-diisocyanate, hexahydrotoluenediisocyanate (and isomers), naphthylene-1,5-diisocyanate, 1-methoxyphenyl 2,4-diisocyanate, diphenylmethane-4,4-diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-diphenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate and 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate and the Triisocyanates such as 4,4 ′, 4′-triphenylmethane triisocyanate, Polymethylene polyphenyl isocyanate and toluene-2,4,6-triisocyanate and the tetraisocyanates such as 4,4'-dimethyldiphenylmethane 2,2 ', 5,5'-tetraisocyanate. Are particularly suitable because of their easy accessibility and special favorable properties tolylene diisocyanate, diphenylmethane 4,4'-di-isocyanate and polymethylene polyphenyl isocyanate. Raw polyisocyanates can also be used for the invention such as crude toluyl diisocyanate obtained by Phosgenation of a mixture of toluene diamines or crude Diphenylmethylene diisocyanate obtained by Phosgenation of crude diphenylmethylene diamine. The preferred ones undistilled or crude isocyanates are from Kaplan in U.S. Patent 3,215,652. Particularly preferred polyisocyanates are a mixture of 80% by weight 2,4-tolylene diisocyanate with 20% by weight 2,6-tolylene diisocyanate (commonly known as TDI 80/20 or T-80) and a mixture of 65% by weight 2,4-tolylene diisocyanate with 35% by weight of 2,6-tolylene diisocyanate (TDI 65/35 or T-65). These connections are commonly used for Soft polyurethane foams used. TDI 80/20 is the most prefers.

The most polyether polyols for the invention preferred are polyalkylene polyether polyols including polymerization products of alkylene oxides and other oxiranes with water or polyhydric alcohols two to eight hydroxyl groups. Exemplary alcohols for Manufacture of polyether polyols include ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,7-heptanediol, glycerin, 1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, hexane-1,2,6-triol,  alpha-methylglucoside, pentatole and hexatole. The Designation polyhydric alcohols includes sugar, such as glucose, sucrose, fructose and maltose both as Compounds derived from phenols, such as 2,2- (4,4'-hydroxyphenyl) propane, commonly known as the name bisphenol A. Examples of oxiranes which are used for suitable for the preparation of the polyether polyols a simple alkylene oxide, such as ethylene oxide, propylene oxide, Butylene oxide and amylene oxide, glycidyl ether such as t-butyl glycidyl ether and phenylglycidyl ether and statistical or Block copolymers of two or more of these oxiranes. The Polyalkylene polyether polyols can be made from other starting materials, such as tetrahydrofuran and alkylene oxide / tetrahydrofuran copolymers epihalohydrins, as well as from aralkylene oxides such as styrene oxide. The Polyalkylene polyether polyols can be primary, secondary or have tertiary hydroxyl groups. Preferably the Polyethers made from alkylene oxides that are two to six Have carbon atoms, such as ethylene oxide, propylene oxide and butylene oxide. The polyalkylene polyether polyols can according to known methods are produced as they for example in Encyclopedia of Chemical Technology, 18, 633-45; 19, 249-50 (1982) Interscience Publishers, Inc. are described or known from US Patent 19 22 459 are. Likewise suitable polyether polyols and processes for Manufacture of these are described by M. J. Shick in Nonionic Surfactants, Marcek Dekker, INc., New York (1967) and by other authors in U.S. Patents 28 71 219; 28 91 073; 30 58 921; and British Patent 8 98 306. The most preferred polyether polyols include Alkylene oxide addition compounds with water, trimethylolpropane, Glycerin, pentaerythrol, sugar, sorbitan, propylene glycol and mixtures thereof which are hydroxyl equivalent have a weight of 250 to 5000. The most particularly preferred polyether polyols are triols with equivalent weights from 500 to 2500 and the triol / diol mixtures with a total functionality of 2.5 to 3. The Polyether polyols can be poly (oxypropyl) triols with oxyethyl blocks  be 5-20% by weight. These will commonly used for flexible polyurethane foams.

Chain extenders can be used to manufacture the polyurethane compositions according to the invention used will. These connections have at least two functional groups with active hydrogen atoms, such as Water, hydrazine, primary and secondary diamines, amino alcohols, Amino acids, hydroxy acids, glycols and mixtures the same. A preferred group of chain extenders Means are water and primary and secondary aromatic Diamines that are lighter with isocyanate than with water react like phenylenediamine, bis (3-chloro-4-aminophenyl) - methane, 2,4-diamino-3,5-diethyltoluene, tri-secondary butanolamine, Isopropanolamine, diisopropanolamine, N- (2-hydroxy- propyl) ethylenediamine, and N, N′-di (2-hydroxypropyl) - ethylenediamine.

The most preferred chain extender is Water because it is commonly used for flexible polyurethane foams is used.

The urethane reaction of polyisocyanates with polyals is preferably carried out in the presence of a urethane catalyst, which is suitable for the implementation of a Hydroxyl group of an alpha-hydroxyalkyl compound with a Catalyze polyisocyanate. Such is preferred Amount of urethane catalyst used, as in the conventional urethane reactions is used. Any suitable urethane catalyst can be used these include tertiary amines, for example triethylenediamine, N-methylmorpholine, N-ethylmorpholine, diethylethanolamine, N-cocomorpholine, 1-methyl-4-dimethylamino ethylpiperazine, 3-methoxy-N-dimethylpropylamine, N, N-dimethyl-N ′, N′-methylisopropylpropylenediamine, N, N-diethyl-3-diethylaminopropylamine, dimethylbenzylamine and the like. Catalysts containing nitrogen are in U.S. Patents 4,101,470; 44 33 170; 44 50 246 and  44 64 488. Other suitable catalysts are for example tin compounds, such as tin chloride, tin salts of carboxylic acids, such as tin octoate, dibutyltin di-2-ethylhexanoate, as well as others, in U.S. Patent No. 2,846,408 described organometallic compounds.

Wetting agents or surface-active substances are in the generally necessary to produce a high quality highly foamed polyurethane foam of the present Invention because the foam collapses in its absence may or has highly uneven cells. Numerous wetting agents have proven to be suitable. Nonionic surfactants and wetting agents are prefers. Of these, the non-ionic are surface-active Medium produced by the gradual addition of Propylene oxide and ethylene oxide to propylene glycol, preferred. Solid or liquid organosilicones have also proven to be proven suitable. Other surfactants are also useful, but not preferred. This includes Polyethylene glycol ether of long chain alcohols, tertiary Amines or alkylolamine salts of long-chain alkyl sulfuric acid esters, Alkylsulfonic acid esters and alkylarylsulfonic acid esters.

The most preferred wetting agents or surfactants Agents are non-hydrolyzable silicones. These usually become more flexible for manufacturing Flexible polyurethane foams are used. The (β-neocarbyl) (chloroalkyl) (bromoalkyl) phosphorus compound, the flame retardant effect is usually conveyed in such amounts that they are flame retardant to the polyurethane Effect communicates. Quantities of 5 Parts by weight up to 20 parts by weight to 100 parts by weight Polyahl, for example polyol.  

Preferred formulations for flexible polyurethane foams with Are phosphorus compounds according to the present invention Compositions as follows:

Reaction partner concentration part by weight Per 100 parts by weight Polyahl Polyol100 TDI index 80-120 Flame retardant 6-18 Water 1.0-5.5 Silicone surfactant 0.2-3 tertiary amine catalyst 0.02-2 Auxiliary propellant 0.5-40 Tin catalyst 0.05-0.5

Foams with densities of 16 kg / m ³ to 64 kg / m ³ are preferably produced.

The processing conditions are preferably selected according to the following criteria:
1. Processability
2. Color fastness (scorch)
3. Smell
4. Effectiveness of flame retardancy and
5. Combinations of the points.

Processability includes better incorporability. A preferred parameter of processability is Brookfield viscosity. The Brookfield viscosity is at 25 ° C with a Brookfield viscometer measured with the Spindle No. 6 at 100 revolutions per minute, the Rotating body is arranged in the center of a sample Vessel whose diameter is at least 125% of the spindle diameter is.

Preferably, the flame retardant compound has the Polyurethane is introduced by reaction, a Brookfield viscosity of 5000 mPas or less 25 ° C. A Brookfield field is very particularly preferred. Viscosity of 2500 mPas or less, most preferred are products with a viscosity of 500 mPa s or fewer. Particularly suitable connections have one  Brookfield viscosity at 25 ° C of 300 mPa s or fewer. The Brookfield viscosity can only be 50 mPa s or less.

Low-viscosity flame-retardant compounds are obtained in particular when R of the general formula is a C _2-3 alkyl group, especially in the case of ethylene. Low viscosity flame retardant compounds are also obtained when Y is independently hydrogen or chlorine, especially when Y is hydrogen. Difficulties in processing higher viscosity flame retardant compounds can be reduced by using diluents such as non-halogenated phosphate ester compounds, but preferably diluents are not used in the processing.

Color stability or scorching or scorch is a manufacturing feature that can be improved, the discoloration or scorching can be significantly reduced or even eliminated. A preferred method to determine the color stability is that of the National Bureau of Standard for determination of Δ E by means of the Gardner colorimeter, where values are to be achieved of 10 or lower, preferably of 6 or lower, even more preferably of 4 or lower. The determination of the Δ E values with the Gardner colorimeter according to the NBS standard is more fully described in US Pat. No. 4,083,825, column 8, lines 58 to column 11, line 23.

The most preferred measurement method for determining the Discoloration is done with the Hunter colorimeter. The determination according to Hunter differs from the method according to Gardner in that both the sample and the reference sample compared to the color of a standard white pattern will. The standard white sample can be pure magnesium oxide contain. If the samples are made by difference Comparison with the standard are the values essentially equivalent to the values determined according to Gardner. The test methods according to  Gardner or Hunter can be executed on samples of all sizes. However, thin patterns are preferred. Little one Samples of polyurethane foam as test samples are based on the Use of 100 g polyol for the production of polyurethane foam, the immediately after foaming in a paper cylinder 15 cm high and 19 cm in diameter at room temperature be filled in. Smaller patterns can also be made larger samples or test methods in industrial Manufacturing. For the determination with Gardner or Hunter colorimeters, larger patterns are preferred, especially those of continuously working Industrial-scale frothing systems.

Soft foams, which are drawn as representative samples in the industrial production of soft foam, are very particularly preferred for the resistance determination according to Gardner or Hunter. The production output in the form of a ribbon (bun) is cut open and cutouts of a minimum size of 26 cm ² , for example 5.1 cm × 5.1 cm, are obtained from the cross section. Each of the Δ E values from the smaller individual samples is added and the sum divided by the number of samples tested. This gives the average of Δ E of the large pattern. If the pattern is 5 cm high, the sample is a 5 cm edge cube.

Very particularly resistant polyurethane compounds with flame retardant effect and low discoloration obtained when R in the general formula is ethylene. Flame retardant polyurethanes are also lower Obtain discoloration when X is bromine or hydrogen and Y Is hydrogen or when X is chlorine and Y is hydrogen.

The thermal stability of the flame-retardant phosphorus compounds used can serve as an indication of the resistance to charring of the polyurethanes produced according to the invention, in particular of flexible polyurethane foam. These compounds preferably have a high thermal stability. This can be determined particularly well by thermogravimetric analysis, in which the samples are continuously checked for their weight loss with increasing temperature in an oven under a nitrogen atmosphere. The rate of temperature increase is 20 ° C per minute from an initial temperature of 20 ° with a sample size between 0.010 g and 0.020 g. Under these test conditions of thermogravimetric analysis, the sample should preferably have a weight loss of 50% at a temperature of 200 ° C. or higher, preferably only at 250 ° or higher, very particularly preferably only at 280 ° or higher. A TGA ₅₀ value of 300 ° C or higher is particularly preferred, a value of 320 ° C or higher is even more preferred and 360 ° C or more is very particularly preferred. 10% weight loss (TGA ₁₀ ) can also be used in thermogravimetric analysis. Preferred TGA ₁₀ values are those of 160 ° C. or more, very particularly preferably 200 ° C. or more. Values of 240 ° C or more are most preferred. Smell is an essential property and this can be significantly reduced or even foreign smell can be completely eliminated. Odor is particularly reduced if large amounts of diols, such as 2,2-bis (bromethyl) 1,3-propanediol, are avoided as a starting material in the preparation via phosphorobromochloroxirane compounds. This also improves the viscosity. The use of a diol such as 2,2-bis (bromomethyl) 1,3-propanediol via the route of phosphorbromochloroxirane compounds usually results in the formation of a by-product such as tetrabromone neopentane in the amount of 1 to 4% by weight which causes a musty odor. If the presence of such a by-product is kept at a level of less than 1% by weight, preferably less than 0.5% by weight, the unpleasant odor of the resulting flame-retardant polyurethane is generally eliminated to a sufficient extent. This applies in particular to soft foam sheets and tapes.

A preferred way to adjust an odorless polyurethane foam especially in the case of an open cell  Flexible foam, consists in the use of a diol mixture, for example from 2,2-dimethyl-1,3-propanediol (Diol-Q) and 1,3-propanediol (Diol-P) as the starting diol and the way over Phosphorobromochloroxirane compounds. The mix of such Diols should preferably have a molar ratio of diol Q: diol P. from 4: 1 to 1: 4, are particularly preferred Molar ratios from 2: 1 to 1: 2. Surprisingly, leads such a mixture to a low viscosity oily (β-Neocarbyl) (chloroalkyl) (bromoalkyl) phosphorus compound with a viscosity of 500 mPa s or less, even 200 mPa s or less, measured according to Brookfield at 25 ° C. The most preferred way to avoid foreign smell is the use of a diol like 2,2-dimethyl 1,3-propanediol as a starting material via the route of Phosphorobromochloro-oxirane compounds.

Another preferred way to produce odorless flame retardant polyurethane foams is to use a (β-neocarbyl) (chloroalkyl) - (bromoalkyl) phosphorus compound made via phosphorus bromochlorooxetane compounds. In the way via phosphorus bromochloroxetane compounds, a diol such as ethylene glycol or propylene glycol or the like is first reacted with a trihalophosphorus compound such as PCl ₃ . The resulting cyclic phosphite is then reacted with halogen, such as bromine. For example, 3,3-bis- (bromomethyl) oxetane is added to the cyclic phosphite / halogen reaction product. Subsequently, an alkylene oxide, such as ethylene oxide, propylene oxide or butylene oxide, is fed in, the reaction of which forms the (β-neocarbyl) (chloroalkyl) (bromoalkyl) phosphorus compound with a flame-retardant property which does not contain any odor-intensive by-products, such as, for example, tetrabromoneopentane.

The flame retardant effect is a property that improves can be. Flame retardancy is understood to mean that the phosphorus compounds incorporated in the polyurethane Sensitivity of the polyurethanes to continue burning Removal of an ignition source such as a Bunsen burner  decreased. The flame retardant effect of flame retardant Phosphorus compounds of the add-on type are when introduced into Polyurethanes usually a function of phosphorus / - Halogen content. Therefore brominated esters are phosphorous Acid preferred. A higher bromine content improves the flame retardant effectiveness due to the stronger presence within the composition.

A particularly preferred method for determining flame retardant Effect is an oxygen index (for example limiting oxygen index) measured after the oxygen demand test from ANSI / ASTM D-2863-77 (ASTM American Standard) at which the minimum concentration of oxygen in a mixture of dry oxygen and dry Nitrogen is detected in an upward flow that is required to burn in a standard test tube just maintain under equilibrium conditions a candlelight. Other conditions of the ANSI / ASTM D-2863-77 oxygen demand test are in the ASTM test conditions of the American National Standard tests described.

For 10 corresponding samples of types A to D (as specified in D-2863-77 standard) of the flame retardant Composition of the mean limit oxygen index (mean LOI) by 10% or more, preferably by 20% or more, most preferably 30% or more, increases the compositions according to the invention. this happens either by measuring the time until the flame goes out or by the distance from the ignition point according to ASTM D-2863-77 im Comparison with 10 other patterns without the flame retardant Additive. The middle is preferred by the invention LOI value of 10 samples corresponding to types A-D by more as 21, more preferably on 25 or more, very special preferably increased to 30 or more.

For testing rigid polyurethane foam, for example Insulating foam, the method in the Steiner tunnel according to ASTM E-84 or equivalent, such as that of the Underwriter's Laboratories 723. The rigid foam should preferably the requirements of the E-84 exam or an equivalent  Class III tests are sufficient or better. Class II or better foams are particularly preferred. According to the invention it is preferred to use the flame retardant Composition such an amount of the flame retardant bring in that the fire resistance of class I is achieved. For the exams, the German DIN regulation DIN-4102-B2 or equivalent Swiss Standard procedures are used.

When testing flexible flexible polyurethane foam on Flame resistance, it is preferred the flame retardant effect the foam composition after the two-part California To determine the test procedure (both are done vertically Burning test and the smoldering test) as in California State of California Department of Technical Bulletin 117 Consumer Affairs Bureau of Home Furnishings specified (North Highlands, California, January 1980). Preferably, the Pattern of flexible flexible polyurethane foam the two-piece Pass California 117 exam. The previously described flame retardant effect is said to be essentially remain even after aging. A preferred one Method of determination is that the flame retardant equipped polyurethanes at elevated temperature (e.g. 104 ° C) in a forced air oven ages 24 hours and then subjected to the fire tests described above, for example a soft foam from the vertical burning test undergoes the California 117 process.

Reduction in discoloration and odor are both but also in a combination of considerable weight. The Reduction of these problems, like better incorporation, Color fastness, low odor and no loss of flame retardant effect, is particularly desirable. The following Table I shows some of the general advantages of some embodiments of the invention.  

Table I

Phosphate ester - flame retardant effect of introduced groups

The following examples describe the invention closer.

Examples 1-6 show the preparation of (β-neocarbyl) - (chloroalkyl) (bromoalkyl) phosphorus compounds via phosphorus bromochlor / Oxirane compounds (Examples 1-5) and above Phosphorobromine chlorine / oxetane compounds (Example 6). Examples 7 and 8 further show the improved ones Manufacturing conditions and product characteristics of flame-retardant polyurethanes with (β-neocarbyl) - (chloroalkyl) (bromoalkyl) phosphorus compounds.  

example 1 Preparation of (3-bromo-2,2-dimethylpropyl) (2-chloroethyl) (2-bromethyl) phosphorus compounds

138 g of PCl ₃ (1.0 mol) and 250 ml of methylene chloride are introduced into a flask. This mixture is stirred and cooled in an ice water bath while 104 g of neopentyl glycol (ie 2,2-dimethyl-1,3-propanediol) are added gradually. After this addition, the mixture is flushed with nitrogen and warmed to room temperature. As soon as the evolution of HCl begins, the mixture is cooled to about 10 ° C. and 152 g of bromine (0.95 mol) are added dropwise. A slight bromine color can be observed after the addition. The mixture is warmed to room temperature and then 1 ml of TiCl _{4 is} added and 90 g of ethylene oxide are then added dropwise to 100 ml of methylene chloride. The exothermic reaction is controlled to 40 ° C using a cold water bath. When the reaction is complete, the mixture is heated to reflux and some low-boiling compounds are distilled off. After cooling, 125 ml of a dilute alkaline solution are added and the mixture is stirred for 15 minutes. The reaction mixture is then filtered through a filter, the product layer is separated and dried over sodium sulfate, filtered, and the solvent is removed under reduced pressure at 80 ° C. to obtain 393 g of an oil. The yield is 94%. The product has a Brookfield viscosity of 100 mPa s at 25 ° C and 100 revolutions with spindle 6. The TGA ₁₀ value is 257 ° C, the TGA ₅₀ value 304 ° C, MW 416.5; 38.4% by weight bromine, 8.5% by weight chlorine and 7.4% by weight phosphorus.

Example 2 Production of (3-bromo-2,2-dimethyl) - (2-chloropropyl) (2-bromopropyl) phosphorus compounds

The procedure of Example 1 is based on the following starting materials repeated:

69 g PCl ₃ (0.5 mol)
200 ml methylene chloride
52 g neopentyl glycol (0.5 mol)
75 g bromine (0.45 mol)
0.5 ml TiCl ₄
75 g propylene oxide in 100 ml methylene chloride

This process gives 202 g of oil with a yield of 91%. The Brookfield viscosity with spindle 6 100 revolutions per minute at 25 ° C is 300 mPa s. TGA ₁₀ : 227 ° C, TGA ₅₀ : 267 ° C, MW: 444.5, 36% by weight bromine, 8% by weight chlorine and 7% by weight phosphorus.

Example 3 Preparation of (3-bromo-2,2-bis (bromomethyl) - propyl) (2-chloroethyl) (bromethyl) phosphorus compounds

131 g of 2,2-bis (bromethyl) 1,3-propanediol (0.5 mole) and 400 ml of carbon tetrachloride are introduced into a reaction flask. 69 g of PCl ₃ (0.5 mole) are introduced dropwise into the stirred mixture. After this addition, the mixture is stirred for two hours and heated to reflux and finally cooled. The mixture is then cooled to 10 ° C in a cold water bath - and 80 g of bromine (0.5 mole) are added dropwise. The mixture is then stirred for one hour during which it warms to room temperature. The mixture is then heated to 40 ° C. and 1 ml of TiCl _{4 is} added. A mixture is then added dropwise to 50 g of ethylene oxide in 100 ml of carbon tetrachloride and an exothermic reaction occurs. After this addition, the mixture is stirred under reflux for four hours.

After cooling, 200 ml of dilute aqueous HCl are added and stirring is continued. The product layer is separated and then shaken again with 200 ml of salt water, separated and shaken again with 200 ml of dilute (1N) sodium hydroxide solution. The product layer is separated and dried over sodium sulfate, filtered and then the solvent is removed under reduced pressure from 1.33 mbar to 2.66 mbar and 80 ° C. 247 g of oil are obtained, ie a yield of 86%. The Brookfield viscosity with spindle No. 6, 100 revolutions per minute at 25 ° C is 2000 mPa s; TGA ₁₀ : 244 ° C; TGA ₅₀ : 312 ° C.

Example 4 Preparation of (3-bromo-2,2-bis (bromomethyl) propyl) (2-chloropropyl) (2-bromopropyl) phosphorus compounds

The procedure of Example 3 is based on the following starting materials executed:

65.5 g 2,2-bis (bromethyl) -1,3-propanediol (0.25 mol)
400 ml carbon tetrachloride
35.0 g PCl ₃ (0.25 mol)
30 g bromine (0.25 mol)
1 ml TiCl ₄
40 g propylene oxide in 100 ml CCl ₄

Working up as in Example 3 gives 143 g of an oil, ie a yield of 93%; the Brookfield viscosity with spindle No. 6, 100 revolutions per minute at 25 ° C. is 3500 mPas; TGA ₁₀ : 249 ° C; TGA ₅₀ : 306 ° C.

Example 5 Semi-industrial production of (3-bromo-2,3-dimethylpropyl) - (2-bromethyl) (2-chloroethyl) phosphorus compounds:

In a 378 liter Pfaudler reactor with glass lining about 163 kg of methylene chloride are introduced. About 108 kg of neopentyl glycol are added and the Mixture at 40-45 ° C stirred until the neopentyl glycol is completely solved. After dissolution, about 163 kg  this mixture in a 189 liter storage tank transferred in the mixture at a temperature of about Is kept 40-45 ° C. Using dry Nitrogen will bring the pressure in the reservoir to about 69 kPa (gauge pressure) increased.

A dry 568 liter Pfaudler reactor with a glass lining is charged with 142 kg of phosphorus trichloride via an inert gas-flushed line. The feed line is then rinsed using 12.7 kg of methylene chloride to rinse the rest of PCl ₃ in the reactor. The PCl ₃ mixture is then stirred at 100 revolutions per minute and the temperature is kept at 15-20 ° C. The removal of hydrogen chloride takes place through a side nozzle in which there is alkali. A lockable reflux condenser is also available and is locked.

The neopentyl glycol / methylene chloride mixture is then from Storage tank in the 568 liter reactor during three Hours convicted. After the first 10 minutes of the flyover the valve of the reflux condenser is opened slowly and the reflux condenser operated. The storage tank will run out the 378 liter reactor with the remaining neopentyl glycol / - Methylene chloride mixture filled up, so that the entire 108 kg of the dissolved neopentyl glycol in the 568 liters containing reactor to be transferred. The small reactor and the storage tank will contain about 32 kg of methylene chloride rinsed and the rinsing liquid transferred to the main reactor.

After the transfer of the neopentyl glycol mixture, the Headspace of the reactor with dry nitrogen for 20 minutes flushed with the gas through a nozzle with Alkali hydroxide is performed. At the same time, the Cooled reaction mixture to about 5 ° C. Subsequent to the rinsing and cooling is applied to the headspace vacuum for about 30 minutes, while continuing to stir to add the HCl still contained in the reaction mixture remove.  

About 155 kg of bromine are then turned into one from a storage tank transferred separate lined tank of 189 liters. The pressure in this tank is set up with dry nitrogen about 348 kpa and then the pressure in the headspace of the 580 liter reactor to about 1.4 kpa (gauge pressure) increased with dry nitrogen when closed Vent valve.

The bromine is then stirred at a rate of about 0.45 kg per minute introduced into the reactor and the reaction temperature is kept below about 40 ° C. To When the reaction is complete, the mixture is stirred for 30 minutes Kept at room temperature. Then the vent valve opened over the nozzle filled with alkali hydroxide and the headspace of the reactor dry for 30 minutes Nitrogen purged.

A sample is taken from the reaction mixture and one Nuclear magnetic resonance spectral analysis performed on the basis 31p isotope (e.g. 31p-nmr), where the 31p nmr spectrum peaks at 6.29 ppm, at -14.1 ppm and at -38.0 ppm shows. In a gas chromatograph, characteristic Peaks observed after 5.30 minutes, 6.86 minutes and 9.15 minutes.

About 675 g of AlCl ₃ methylene chloride slurried are then introduced into the reaction mixture of the 568 liter reactor through a feed tank arranged above while the mixture is being stirred. The pressure in the reactor is then increased to 9.94 x 10 ⁴ Pa absolute (2 psig) with dry nitrogen and the temperature is maintained at about 40 ° C or lower. Then 91.2 g of ethylene oxide are introduced at a rate of about 0.5 kg per minute or slightly less.

A sample is then taken from the reaction mixture. A 31p-nmr sample is taken and the 31p-nmr spectrum shows peaks at -2.19 ppm, at -2.29 ppm and at -2.42 ppm. With a capillary gas chromatograph be characteristic Peaks after 19.6 minutes, 20.03 minutes and 22.08 minutes observed.  

Mix in the reactor with continuous stirring a solution of about 74.8 kg of water and 4.9 liters of 37% by weight aqueous HCl added. The mixture will then stirred at 100 rpm for 15 minutes and then stirring continued for about 20 revolutions per minute. The Phases separate and the organic phase is obtained.

A sample of the organic phase is analyzed and an 31p-nmr spectrum determined and also a gas chromatogram. These correspond to those previously described Reaction product methylene oxide. 568 liters becomes the separated organic layer Reactor with stirring a solution of about 74.8 kg of water and about 16 kg of a 15 wt.% dilute aqueous NaOH solution added. It runs at 100 revolutions per minute stirred and continued to stir until the layers come together separate as with washing with HCl solution. A sample is taken from the organic phase and a 31p nmr spectrum determined, as well as a gas chromatogram. The analysis results correspond to those of the reaction product of ethylene oxide in this example.

After distilling off volatile substances such as Methylene chloride from the organic layer is obtained Product distilled at 60 ° C or lower under vacuum. The yield of the final product is about 93% of Theory.

Of the product obtained are a sample 31p nmr spectrum recorded and a gas chromatogram created. Both analysis results correspond to those of the Reaction product with ethylene oxide.

The Brookfield viscosity of the product with spindle 6, 100 Revolutions per minute was 100 mPa s at 25 ° C.  

Example 6 Production of (3-bromo or chlorine -2,2-bis (bromomethyl) - propyl (2-chloro or bromethyl) (bromethyl) - phosphorus compounds

A. Preparation of 3,3-bis (bromomethyl) oxetane
325 g of 2,2-bis (bromomethyl) -3-bromo-1-propanol (1.0 mol) and 800 ml of ethanol are introduced into a reaction flask. The mixture is stirred and slowly warmed until a solution forms. 56 g of KOH in 400 ml of ethanol are then added dropwise to the solution. After this addition, the mixture is heated under reflux for two hours. The flask is fitted with a short distillation column and 1200 ml of solvent are removed. After cooling, 400 ml of water and 400 ml of chloroform are added with stirring. The water phase is separated off and extracted with a further 200 ml of chloroform. The product layers are combined, dried over sodium sulfate and then filtered. The solvent is removed under reduced pressure and 211 g of a crude oil are obtained. Distillation of the crude oil product gives 68% of the theoretical yield of the desired product, 3,3-bis (bromomethyl) oxetane. The boiling point is 90 ° C to 91 ° C (1.33 mbar). If isopropanol is used as the solvent, the reaction leads to a theoretical yield of 63%.

B. Preparation of the phosphorus compound of oxetane
45 g of PCl ₃ and 400 ml of methylene chloride are introduced into a reaction flask. The mixture is stirred while 16 g of ethylene glycol are added dropwise. After this addition, the reaction space is flushed with nitrogen until the HCl evolution ceases. The mixture is then cooled to its temperature by means of an ice water bath and 40 g of bromine are added dropwise. When the reaction is complete, 400 ml of perchlorethylene are added and the mixture is heated to 110 ° C. to drive off low-boiling components. The mixture is then cooled to 80 ° C. and 1 ml of TiCl _{4 is} added. Then 61 g (0.25 mol) of 3,3-bis (bromomethyl) oxetane are added. The mixture is then refluxed for four hours. A nuclear magnetic resonance analysis indicates the end of the reaction. The mixture is then cooled to 45 ° C. and a solution of 15 g of ethylene oxide in 50 ml of solvent is added dropwise. After this addition, the mixture is heated to 80 ° C. and then slowly cooled. The reaction mixture is worked up in the same manner as in Example 4. 130 g of an oil are obtained, which is 91% theoretical yield. The Brookfield viscosity with spindle 6, 100 revolutions at 25 ° C is 1000 mPa s; TGA ₁₀ : 253 ° C; TGA ₅₀ : 320 ° C.

Example 7

Laboratory tests on flame retardant flexible Foaming including discoloration studies.

This example shows the discoloration properties of flame-retardant flexible flexible polyurethane foam on a sample of a flame-retardant finished product (sample FR), in which the flame-retardant compound has the general formula in which X, Y and Z have the following meanings: (Comparative Example) Pentabromodiphenyl oxide with a Great Lakes Chemical Chemical phosphate ester diluent THERMOLIN * 101Thermolin * 101 is tetrakis (2-chloroethyl) ethylene diphosphate and (Comparative Example) is available from Olin Corporation.

A 110 index foam was produced from the following components and the previously specified samples FR as follows:

Foam production and oven aging

First, the A-side is weighed into a glass bulb and set aside. The components of the B side are in a paper cup in the order given above brought in. The B side is then mixed for 15 seconds with a mixer from above with variable Speed. Then the A-side immediately becomes B side added and mixed in for another 5 seconds. The mixture of A and B side is then turned into a suitable one Paper container transferred.  

By repeating four foams in this way made and all four foam samples in a preheated Introduced a convection oven and left in it for 30 minutes. The samples were then removed from the oven and brought to room temperature cooled down for the subsequent tests.

Cutting and measuring the color

A 5 cm cross-section strip was made at the top of each Foam sample separated. Then a 5 cm wider Intermediate section taken from the center of each sample. The Bottom of this section was for color determination used.

Color was measured on a Macbeth colorimeter using the Hunter color scale. The Hunter color scale compares the color of the sample with a white standard. Three measurements were carried out on each sample and the mean value was formed. The average Δ E value of each sample was then compared to the average Δ E value, which according to the Hunter Color Scale was determined on a foam, which contained no flame retardant. A value Δ E (foam) was calculated according to the following equation.

Δ E (foam) = Δ E (sample) - Δ E (foam without FR)

The following results were obtained.

Discoloration results

The negative Δ E (foam) values indicate that the foam samples have flame retardant less discoloration than the foam sample containing no flame retardant. Conversely, a positive value indicates that foam samples containing flame retardant have a more intense color than foam samples containing no such agent. The Δ E (foam) values obtained with the FR A, B, D and E (and C) samples are comparable to the values obtained with the FR (6) and FR (7) samples.

The patterns FR (6) and (7) are usually called im essential non-discoloring flame retardant products sold.

Patterns A, B, D and E are essentially non-discoloring flame retardant products. The foams are flame retardant and the samples of specimens FR A, B, D and E are sufficient California 117 exam requirements.

Example 8 Industrial manufacturing

When producing a flexible polyurethane foam block with a quality index of 110 according to the Component mixture are about 10 parts by weight per 100 parts by weight Polyurethane from (3-bromo-2,2-dimethylpropyl) (2-bromethyl) - (2-chloroethyl) phosphorus compounds used as described in following the procedure of Example 5. The foam is easy to manufacture and is flame retardant. The foam has a high flame-retardant effect and passes the California Exam 117, is essentially not discoloring and also essentially odorless.

Claims (14)

1. Flame retardant polyurethane composition, characterized in that it contains one or more (β-neocarbyl) (chloroalkyl) (bromoalkyl) phosphorus compounds as a flame retardant. 2. Polyurethane composition according to claim 1, characterized in that the flame retardant compound has the general formula has in which
X is hydrogen, Cl, Br or a C _1-5 alkyl group, each Y is independently hydrogen, Cl, Br, where at least X or Y is chlorine or bromine and each R is independently a saturated hydrocarbon group of the formula C _n H _{2 n} with n , an integer from 2 to 5. 3. Polyurethane composition according to claim 2, characterized in that in the general formula X is bromine, Y is hydrogen and RC ₂ H ₄ - and / or C ₃ H ₆ -. 4. Polyurethane composition according to claims 1-3, characterized, that they are 5-20 parts by weight flame retardant compounds pro 100 parts by weight Contains polyurethane. 5. polyurethane composition according to claims 1-4, characterized, that they are a polyether polyol and at least one (3-bromo-2,2-dimethylpropyl) (2-bromethyl) (2chloroethyl) - contains phosphorus compound. 6. Method of reducing the flammability of flame-retardant polyurethane by incorporation a general (β-neocarbyl) (chloroalkyl) (bromoalkyl) phosphorus compound / compounds as flame retardant in the polyurethanes.   7. The method according to claim 6, characterized in that the flame retardant compound has the general formula in which X is hydrogen, Cl, Br or a C _1-5 alkyl group, each Y is independently hydrogen, Cl, Br, where at least X or Y is chlorine or bromine and each R independently of one another is a saturated hydrocarbon group of the formula C. _{n is} H ₂ with n , an integer from 2-5. 8. The method according to claim 7, characterized in that in the general formula X is bromine, Y is hydrogen and RC ₂ H ₄ - and / or C ₃ H ₆ -. 9. The method according to claims 6, 7 or 8, characterized, that the flame retardant compound from a Phosphorobromochloroxirane compound or oxetane compound is produced and a Brookfield viscosity of less than 5000 mPa s at 25 ° C. 10. The method according to any of the preceding claims 6-9, characterized, that you have a flame retardant compound with a Brookfield viscosity of less than 300 mPa s used. 11. The method according to any one of the preceding claims 6-10, characterized in that a polyurethane with a Δ E heat color value of 4 or less is used on the Hunter scale. 12. The method according to claim 9, characterized, that one to manufacture the flame retardant compound 3,3-bis (bromomethyl) oxetane used. 13. The method according to any of the preceding claims 6-12, characterized, that 5-20 parts by weight flame retardant compound pro 100 parts by weight Polyurethane used. 14. Use of the polyurethane composition according to claims 1-5 for the production of a flexible polyurethane foam with a density of 16 kg / m ³ to 64 kg / m ^{3 which is} essentially non-discoloring by heat.