GEL CATALYST COMPOSITIONS AND METHOD FOR PREPARING FLEXIBLE POLYURETHANE FOAM

Abstract: Polyurethane foams exhibiting excellent thermal and oxidative stability can be prepared using as the gel catalyst a composition containing at least one organotin compound containing phosphorus and at least one organotin compound wherein a halogen atom is bonded to tin. The properties of foams prepared using the present catalyst compositions are superior to foams prepared using gel catalyst compositions wherein tin, phosphorus and a halogen are present but the phosphorus and halogen are not in the same molecule as the tin atom. The halogen-containing tin compound and the phosphorus-containing tin compound may be the same com­ pound or separate compounds.

Description: "IMPROVEMENTS IN OR RELATING TO ORGANOTIN COMPOUNDS, GEL CATALYST COMPOSITIONS AND METHOD FOR PREPARING FLEXIBLE POLYURETHANE FOAM" This invention relates to the preparation of polyurethane foams. This invention further relates to the use of certain gel catalyst compositions to prepare polyurethane foams exhibiting high levels of oxidative stability relative to products obtained using conventional organotin catalysts or combinations of these organotin catalysts with compounds containing phosphorus and halogen. Certain of these catalyst compositions are novel and constitute¯part of this invention. Flexible polyurethane foams are widely used in the manufacture of furniture, particularly seat cushions, and as packaging material for delicate instruments and other articles that are susceptible to damage during handling and transit. If the foam is incorporated into a piece of furniture or other durable product, the foam must withstand exposure of several years or longer to elevated temperatures, atmospheric oxygen, or both without undergoing significant degradation, resulting in a gradual loss of resiliency and structural strength which may culminate in disintegration of the foam. It is well known to prepare flexible cellular polyurethanes by reacting polyols containing two or more reactive hydrogen atoms, as determined by the Zerewitinoff method, with polyfunctional isocyanates in the presence of a polymerization or gel catalyst and a blowing agent such as water or a relatively low boiling fluorocarbon. A surfactant is often included in the reaction mixture together with a blowing catalyst to obtain the desired uniformly small cell size within the foam when water is used as the blowing agent. Fillers such as bart'tes and various additives such as flame retardants can also be present in the formulation employed to prepare the foam. U. S. Patent 3,620,985 discloses that organotin compounds are effective gel catalysts for cellular poly urethanes. Compounds of the formula RaSnX4-a wherein R is typically butyl or other alkyl radical containing from l to 20 carbon atoms and X is a halogen or other anionic radical are generally less than satisfactory for preparing flexible foams that are exposed to atmospheric oxygen, elevated temperature, i.e. above about 500C, or both over extended periods of time. Under these conditions the foams may lose resiliency and structural integrity, sometimes to the extent that they disintegrate when compressed. This is particularly true of those foams derived from polyethercontaining polyols that are derived at least in part from propylene oxide. These polyols may also contain ester linkages, (-OOCRCOO-), and end groups derived from ethylene oxide to obtain hydroxyl groups bonded to primary rather than secondary carbon atoms. High resiliency polyurethane foams prepared from polyols that contain side chains obtained by the graft polymerization of acrylonitrile, styrene or other vinyl monomer onto a poly(propylene oxide) backbone are usually less susceptible to oxidative and thermal degradation. However, in the presence of conventional organotin gel catalysts even these products undergo a significant decrease in structural strength and become brittle following prolonged exposure to oxygen and/or heat. The resistance of flexible polyurethane foams based on polyether-containing polyols to oxidatively and thermally induced degradation can be improved by employing compounds containing phosphorus and a halogen in combination with the organotin gel catalyst. Catalyst compositions of this type are disclosed in United States Patents 3,067,149; 4,048,100;v4,052,346 and British Patent 1,003,201. This type of catalyst composition may be suitable for certain applications where resiliency is not a requirement, since foams prepared using these catalyst compositions typically recover only a small fraction of their original height within 30 minutes after being compressed to 10% of their original height for 22 hours at a temperature of 70 C, a conventional method for determining resiliency and dry heat stability of flexible polyurethane foams. An objective of this invention is to improve the resiliency and dry heat stability of flexible polyurethane foams prepared from polyether-containing polyols using gel catalyst compositions containing an organotin compound, a phosphorus compound and a halogen compound. Surprisingly it has now been found that if the phosphorus and halogen are both present in a compound containing a tin atom that is in turn, bonded to at least one hydrocarbyl group the resultant foam exhibit improved stability at elevated temperatures relative to a foam prepared using an organotin compound as the gel catalyst in the absence of phosphorus and halogen compounds. In addition, the foam exhibits excellent resiliency following prolonged compression. The phosphorus and halogen can be present in the same organotin compound or in two different organotin compounds. This invention provides a method for preparing a flexible cellular polyurethane exhibiting improved resiliency and resistance to heat-induced degradation by reacting a polyether-containing polyol containing at least two active hydrogen atoms per molecule, as determined by the Zerewitinoff method, with a polyfunctional isocyanate, the reaction being conducted in the presence of a blowing agent and a catalytically effective amount of a gel catalyst composition consisting essentially of at least one organotin compound containing an active halogen and at least one organotin compound containing phosphorus in ehemically combinea orm herein the molar ratio of tin to phosphorus is from 0.045 to 23, the molar ratio of tin to active halogen is from 0.5 to 23, the molar ratio of phosphorus to active halogen is from 0.5 to 22, and wherein the phosphorus-containing organotin compound is an organotin ester of a phosphorus compound selected from the group consisting of ortho-phosphoric, meta-phosphoric, pyrophosphoric, thiophosphoric, phosphorous, phosphinic, phosphinous, phosphonous and phosphonic acids, phosphoryl chloride and oligomeric condensation product of 1) phosphonic acid, 2) mixtures containing phosphoric and phosphonic acids or 3) esters of phosphoric and phosphonic acids and alcohols containing from 1 to 20 carbon atoms. The present gel catalysts are useful for preparing both flexible and rigid polyurethane foams +'rom substantially all of the known polyether-containing polyols, polyfunctional isocyanates and blowing agents. The concentration of the catalyst is usually from 0.005 to 1%, based on the weight of polyol. The present catalysts are organotin esters of monomeric or condensed phosphoric acid, thiophosphoric, phosphorous, phosphonous, phosphinic, phosphinous or phosphonic, acid or phosphoryl chloride. Phosphoryl chloride is, in turn, a derivative of phosphoric acid. The organotin moiety (R2Sn or RSn ) may be the only esterifying group present on the phosphorus-containing acid. Alternatively, the catalyst may be a mixed ester obtained by reacting an organotin halide or an organotin oxide or hydroxide with the desired phosphorus-containing ester derived from an alcohol or phenol. As used herein the term active halogen refers to fluorine, chlorine, bromine and iodine that is bonded directly to a tin or phosphorus atom. All of the present catalyst compositions contain an organotin compound bearing at least one active halogen atom. The active halogen and the phosphorus atom can be present in the same organotin compound, such as dibutylchlorotin diethyl phosphite. Alternatively the catalyst composition may be a mixture of two organotin compounds, one containing phosphorus and the other containing an active halogen atom. Organotin compounds containing both phosphorus and a halogen atom that are useful as gel catalysts in accordance with the present method exhibit the general formula EMI7.1 In the foregoing formulae a is 1 or 2, b is 0, 1 or 2, X represents an active halogen, -OH, -00CR2, -OR2 or -SR3 wherein R2 is hydrocarbyl and R3 is hydrocarbyl, -R4COOR2, 2 or -R OOCR wherein R is alkylene and contains from 2 to 20 carbon atoms, with the proviso that said organotin compound contains at least one active halogen; d is 0, 1 or 2 with the proviso that d can be 0 only when the group represented by Y con- tains phosphorus; f is EMI7.2 wherein V is -OZ or -X and p is 0 or an integer from 1 to 10; Z is EMI7.3 wherein M is -R6, -OR', -(OR6)1OZ or Y, wherein R5 is hydrocarbyl, haloalkyl, halogen or Y, R6 is hydrocarbyl, R7 is hydrocarbyl or hydrogen. R6 is -CH2CH2- or -CH(CH3)CH2-, c is 0 or 1, f is an integer from 1 to 100 m is 0 or an integer from 1 to 10; U is oxygen or sulfur, e si 1 or 2, RÚ is hydrocarbyl or -R3COOR6 wherein R9 is hydrocarbyl and Q is EMI8.1 wherein g is O or an integer from 1 to 6. If b in the foregoing formula is. O and Y does not contain-an active halogen atom, an organotin compound containing at least one tin to halogen bond must be included in the catalyst composition. The term "hydrocarbyl" includes alkyl, cycloalkyl, zryl, aralkyl and alkaryl groups. Any alkyl group contains from 1 to 20 carbon atoms, and the preferred aryl group is phenyl. Several organotin esters of phosphorus-containing acids and organic esters thereof are reported in the chemical literature. Compounds containing a single tin atom are prepared by reacting an organotin oxide or hydroxide with an organic ester of the desired phosphorus-containing acid under conditions conventionally employed for transesterification reactions and in the presence of a liquid hydrocarbon that forms an azeotropic mixture with the alcohol formed as a by-product of the transesterification reaction. Alternatively, the unesterifiedacid can be used or the desired organotin halide can be reacted with the sodium salt Ïf-the phosphorus-containing acid or a partial ester thereof. If the final compound contains a fluorine, chlorine, bromine or iodine atom bonded to tin, the corresponding organohydroxyhalostannane or bis(dlhydrocarbylhalo)distannoxane can be employed as the organotin reactant. An example of the former class of compounds is butylchlorodihydroxystannane C4H9SnCl(OH)2. This class of compounds is disclosed in United States Patent 3,758,536, the pertinent sections of which are hereby incorporated by reference. Compounds containing one or more groups represented by Y In the aforementioned structural formula can be prepared using a reaction product of an organ9tin halide with a diorganotin oxide or organostannoic anhydride when U is oxygen. When U represents sulfur, a diorganotin sulfide or organothiostannoic anhydride is employed. The molar ratio of organotin halide to the oxygen- pr sulfur-containing compound is selected to achieve the desired value of p in the foregoing formula. Organotin compounds containing a plurality of tin atoms joined by sulfur or oxygen are well known in the chemical literature, and a detailed discussion concerning the preparation of these types of compounds in the present specification would be repetitious. The following reactions are typical, wherein Bu represents n-C4Hg-. EMI10.1 Bt:2SnCl2 + xBu2SnO . yClBu2Sn(OSnBu2)xCl ClBu2Sn(OSnBua)xCl + NyOP(OC4H2)2 # ClBuSn(OSnBU2)xOP(OC4H9) Compounds of the general formula ClBu2Sn(OSnBu2)xCl can exist in linear form as shown. Alternatively -these compounds can form cyclic structures wherein the ring contains a plurality of EMI10.2 bonds and from 5 to 10 or more atoms. Cyclic compounds of this type are discussed in chapter 12 of a text entitled "The Chemistry of Organotin Compounds" by R. C. Poller (Academic Press, New York, 1970). The organotin halide canbbe reacted with the phosphorus-containing acid or a partial or complete ester thereof prior to or following reaction of the organotin halide with the organotin compound containing oxygen or sulfur. An example of the former is represented by the reaction EMI11.1 Additional tin atoms can be introduced into the molecule by increasing the molar ratio of the diorganotin sulfide. Alternatively, the corresponding diorganotin oxide can be used in place of the sulfide. The foregoing reaction also demonstrates that the present compounds may contain both monoorganotin and diorganotin groups. During preparation of the present compounds an alkali metal salt of the desired phosphorus-containing acid can be reacted with a bis(organohalotin)oxide using an alcohol as the reaction medium. This reaction proceeds relatively rapidly at a temperature from ambient to about 500C. The advantage of using alcohol is that the reaction product is usually soluble and the sodium halide formed as a by-product precipitates from the reaction mixture. Alternatively, the free phosphorus-containing acid can be reacted with an organotin oxide or an organostannoic anhydride in a liquid hydrocarbon such as toluene that forms an azeotropic mixture with the water formed as a by-product of the reaction. In this instance the reaction is conducted at the boiling point to remove the by-product water as it is formed, thereby providing a driving force for the reaction. In addition to alcohols and liquid hydrocarbons, liquid carboxylic acids can be used as the reaction medium for preparing the organotin compounds employed as gel catalysts in accordance with this invention. It has been found that if the resultant diluted reaction product is employed as a gel catalyst for a flexible polyurethane foam, the thermal stability and resiliency of the foam is superior relative to foams prepared in the absence of the acid. The accompanying examples disclose procedures for preparing the various classes of catalysts that are useful in accordance with the present method. Exemples of specific compounds that are within the scope- of this invention are, represented by the formulae EMI12.1 EMI13.1 EMI13.2 EMI14.1 <tb> <SEP> 0 <tb> <SEP> II <tb> <SEP> C1 <SEP> / <SEP> OP(OH)2 <tb> <SEP> ii <SEP> /i <tb> R2SnOSnR2 <tb> <SEP> C1 <SEP> R1 <SEP> O <SEP> C1 <tb> <SEP> ii <SEP> 1 <SEP> II <SEP> I <tb> R2SnOSnOPOSnR2 <tb> <SEP> I <SEP> 1 <tb> <SEP> R <SEP> OH <tb> <SEP> C1 <tb> {R2l)n12HPO <SEP> and <tb> <SEP> SCH2COOR1 <SEP> 1 <SEP> 0 <SEP> C1 <tb> <SEP> ii <SEP> 1 <SEP> II <SEP> 1 <tb> R2Sn-S-SnCR <SEP> 20POSnR2 <tb> <SEP> OH <tb> wherein R11 is hydrocarbyl. The last of the aforementioned compounds can be prepared by replacing a chlorine atom with a mercaptoester group using equimolar amounts of ester and organotin compound. When the hydrocarbon group bonded to tin in the foregoing formulae is specified it is often shown as butyl. It should be obvious, however, that compounds containing other hydrocarbon groups, e.g. methyl, octyl, phenyl and cyclohexyl, would be equally suitable for use in the present catalyst compositions. Flexible polyurethane foams of improved oxidative stability are prepared by reacting a polyfunctional isocyanate with a polyol containing ether (-C-O-C) or a combination of ether and ester EMI14.2 groups and two or more reactive hydrogen atoms as determined by the Zerewitinoff method. In accordance with the present method, this reaction is catalyzed by one of the organotin compounds of this invention. This reaction is usually exothermic and occurs concurrently with gas evolution, resulting in formation of a cellular structure. The gas-evolving or blowing agent can be water, which reacts with excess polyfunctional isocyanate to yield carbon dioxide. Water can be used in combination with a volatile liquid fluorocarbon such as trichlorofluoromethane Qr dichloromethane. liven water is present as a blowing agent the reaction mixture may also contain a catalyst for the blowing or foaming reaction to coordinate the foaming and polymerization reactions, thereby retaining structural integrity and achieving the desired uniformly small cell size within the foam. Tertiary amines such as bis(N,-dimethylaminoethyl) ether and triethylene diamine are preferred blowing catalysts. One to five tenths of one part by weight of blowing catalyst is usually employed for every one hundred parts of polyol. Silicon compounds, particularly reaction products of silanes wit 1,2-olefin oxides, are often included as cell modifying agents, commonly referred to as surfactants. If one or more amines are employed as blowing catalysts, these will also catalyze the reactions between the polyfunctional isocyanate and polyol. The use of amlnes as gel catalysts is well known in the prior art, however, amines are often less than satisfactory due to their low catalytic activity. In the past it was necessary to employ a prepolymer in order to attain the desired molecular weight while avoiding unduly long rise times. The polyfunctional isocyanates used to prepare poly methanes using the present gel catalysts include both polyisocyanates and polyisothiocyanates. While the invention is described with specific references to the reaction of certain disocyanates, it is generically applicable to the reaction of any compound containing two or more -N=C=G radicals wherein G is oxygen or sulfur. Compounds within this generic definition include polyisocyanates and polyisothiocyanates of the formula R (NCG) x in which x is 2 or more. R can be alkylene, substituted arylene or other divalent hydrocarbon radical that may optionally contain one or more aryl-NCG bonds and one or more alkyl-NCG bonds Although a variety of organic polyisocyanates containing 3 or more isocyanate radicals per molecule can be used in the practice of this invention, diisocyanates are usually preferred in flexible foam formulations. Suitable isocyanates include alkylene diisocyanates such as hexamethylene diisocyanate, and decamethylene diisocyanate, the isomeric toluene diisocyanates and naphthalene diisocyanates, 4,141-diphenylmethane diisocyanate and mixtures of two or more of the foregoing diisocyanates. Triisocyanates obtained by reacting voles of an arylene diisocyanate for each mole of a triol, e.g., products formed from 3 moles of tolylene diisocyanate and 1 mole of hexane triol may also be present in the reaction mixture. A preferrred polyisocyanate is a mixture containing 80S by weight of the 2,14-isomer and 20 percent of the 2,6-isomer of toluene dilsocyanate. Other suitable polyfunctional isocyanatea include hexamethylene diisocyanate, xylylene diisocyanate, l-methyl-2,14-diisocyanates, diphenylmethane-4,4'-diisocyanate, naphthalene-1,5-diisocyanate, triphenylmethane-4,4',4''-triisocyanate and xylene-a,a'-diisothiocyanate. Oligomeric and polymeric isocyanates of the general formulae (R NCG)x and UR (NCG)X]y in which x and y are between 2 and 10, are also useful in the present method as are compounds of the general formula M(NCG)x wherein x is 2 or more and t14 is a difunctional or polyfunctional atom mr gr6up. An example of this type is polymethylene polyphenylisocyanate. Suitable polyether-type polyols include polyalkylene glycols such as polyethylene glycols and polypropylene glycols. "he molecular weight of these compounds is preferably between bout 200 and 5000. As previously disclosed, polyols containing both ether and ester groups within the molecule are suitable for preparing polyurethane foams using the catalysts of this invention. The preparation of polyurethane foams can be accom lishes by forming a prepolymer, i.e. prereacting molar equivalents of a hydroxyl-terminated polyol and isocyanate in he absence of water and thereafter producing a foam by the addition of excess isocyanate, water and optionally other blowing agents and one of the present gel catalysts. Alteractively, foams may be produced by the "one-shot" method in which all of the reactants and catalysts are mixed together and allowec to react in the presence of water or other blowing agent. The polyfunctional isocyanate is typically present in an amount of 5 to 300 percent, preferably from 30 to 50 percent by weight of the polyol. Water may optionally be present as a blowing agent to react with excess isocyanate and generate sufficient carbon dioxide to produce a foam of the desired density. The amount of water is between 1 and 10 percent, preferably between 2 and 5 percent, based upon the weight of the polyol. The amount of isocyanate used can be in excess of the stoichiometric amount required to react with the active hydrogen atoms present in the polyol and any water present, thereby formi ng allophanate EMI19.1 and biuret EMI19.2 linkages in the polymer chains. Depending upon the desired density of the urethane foam and the amount of crosslinking desired, the ratio of equivalent weights of isocyanate groups to moles of active hydrogen atom present in the polyol and any water present should be from 0.8 to 1.2, respectively, preferably between 0.9 and 1.1. The gel catalyst and one or more blowing catalysts are present in an amount corresponding to from 0.01 to 10 parts by weight per 100 parts of polyol. Preferably the gel catalyst is present in an amount corresponding to between 0.005 and 5.0 part by weight per 100 parts of polyol. The formulation employed to prepare polyurethane foams using the gel catalysts of this invention may contain various additives conventionally incorporated into flexible polyurethane foams. These additives include fillers such as bytes and calcium carbonate, flame retarding agents such as antimony oxide and phosphorous compounds such as triphenylphosphine oxide. The following examples demonstrate the oxidative stability and excellent recovery properties that distinguish flexible foams prepared using the present gel catalysts from those obtained using organotin compounds alone or in combination with a halogen compound and a phosphorus compound. All parts and percentages are by weight unless otherwise specified. EXAMPLE 1 Preparation of Dibutylchlorotin Diethyl Phosphite EMI20.1 Sodium diethyl phosphite was prepared by stirring under a nitrogen atmosphere 9.2g (0.4 AU) sodium and 55.2g (0.4 mole) diethyl hydrogen phosphite in 150cc of tetrahydrofuran while maintaining the temperature of the reaction mixture below 1410 C. The resultant product was then added dropwise to a solution containing 122g (0.4 mole) of dibutyltin dichloride and 100cc tetrahydrofuran. The addition was carried out under a nitrogen atmosphere and the temperature of the reaction mixture was first maintained at 400C for 2 hours and then at ambient temperature for 3 hours. The reaction mixture was then filtered and the solvent removed by evaporation under reduced pressure. The residual material wa again filtered and the diethyl hydrogen phosphite removed by heated the filtrate at 800C under reduced pressure until no additional distillate could be collected. The residue weighed 134g and was found to contain 29.08% tin, 9.49% chlorine and 6.89% phosphorus. The calculated values for these elements in the expected product are 29.28%, 8.76% and 7.64X, respectively. EXAMPLE 2 Preparation of Bis(dibutylchlorotin) Phosphate A glass reactor was charged with 91.lg (0.3 mole) dibutyltin dichloride, 200cc n-butanol, 50cc water and 27.3g (0.15 mole) dibasic sodium phosphate dihydrate. The resultant mixture was heated under a nitrogen atmosphere and the water removed by azeotropic distillation until the vapor temperature reached 1170C. The reaction mixture was then filtered and the liquid phase was concentrated under reduced pressure. The liquid residue solidified upon standing and weighed 83 g The product was found to contain 34.60% tin, 11.18% chlorine and 4.42% phosphorus. The calculated values for these elements in the expected product are 37.53% tin, 11.21% chlorine and 4.90% phosphorus. EXAMPLE 3 Preparation od Di[bis(ss-carboethoxyethyl)chlorotin] Phosphate -A, glass reactor was charged with 1) a solution that had been prepared by dissolving 39.2g (0.1 mole) bis(ss-carboethoxyethyl)tin dichloride in 150cc of toluene, and 2) 7.lg (0.05 mole) dibasic sodium phosphate. The resultant mixture was stirred and heated to the boiling point (109 C) for 2 hours, then cooled to 900C and filtered. The filtrate was then concentrated under reduced pressure to yield 35g of a liquid product, di[bis((3-carboethoxy- ethyl)chlorotin3 phosphate, which was found to contain 23.22% tin, 8.96% chlorine and 5.77% phosphorus. EXAMPLE 4 Preparation of Butylchlorotin Cyclic O,O'-monoethyl Phosphate EMI22.1 A glass reactor was charged with 73.6g (O.3 mole) butylchlorotin dihydroxide, 49.9g (0.3 mole) triethyl phosphite and 225cc toluene. The resultant mixture was stirred and heated to 95 C and the by-product ethanol was removed using azeotropic distillation. The reaction mixture was then heated to the boiling point for one hour, after which the mixture was filtered and the filtrate concentrated under reduced pressure. The residue weighed 102g and was found to contain 32.83% tin, 8.50 phosphorus and 8.83 chlorine. The calculated values for the expected product are 33.66% tin, 8.77 phosphorus and 10.06% chlorine. EXAMPLE 5 Preparation of Dibutylchlorotin Dibutyl Phosphite EMI22.2 The aforementioned compound was prepared by the gradual addition, under a nitrogen atmosphere, of 4.8g (0.2 mole) sodium hydride to 38.8g-(0.2 mole) dibutyl hydrogen phosphite which had previously been dissolved in 50cc of tetrahydrofuran. The resultant mixture was heated for 4 hours at 65 C, after which it was cooled to ambient temperature and added dropwise to 60.7 (0.2 mole) dibutyltin chloride which had previously been dissolved in lOOcc of tetrahydrofuran. The resultant mixture was then heated under a nitrogen atmosphere for 3 hours at 65 C, after which it was filtered and the filtrate concentrated under reduced pressure to yield 68g of a clear amber liquid. The liquid was found to contain 27.87 tin, 7.17% chlorine and 4.89 phosphorus. The calculated values for the expected product are 25.73% tin, 7.69 chlorine and 6.72X phosphorus. EXAMPLE 6 Preparation of Bis(ss-carboethoxyethyl)chlorotin Diethyl Phosphite EMI23.1 A glass reactor equipped with a mechanically driven stirrer, condenser and nitrogen inlet was charged with 4.6g sodium. Diethyl hydrogen phosphite, 27.6g (0.2 mole), dissolved in 50cc tetrahydrofuran was added slowly while the temperature was maintained below 30 C. The reaction mixture was stirred at room temperature for 3 hours. The resultant sodium diethyl phosphite was added dropwise to 78.4g (0.2 mole) bis(ss-carboethoxyethyl)ttn dichloride in 150cc tetrahydrofuran. An exothermic reaction occurred. The reaction mixture was stirred at ambient temperature for 3 hours and then filtered. Residual solvent was removed under reduced pressure. The the liquid residue weighed 81g. Calculated By Analysis % Sn 24.06 p 22.84 % P 6.28 5.83 % Cl 7.19 9.06 EXAMPLE 7 Preparation of Bis(ss-carboethoxyethyl)chlorotin Dibutyl Phosphite EMI24.1 Soelum dibutyl phosphite was prepared by the gradual addition room temperature of 19.4g (0.1 mole) dibutyl phosphite to a solution containing 2.4g (0.1 mole) sodium hydride and 50-c tetrahydrofuran. The mixture was stirred at room temperature for 6 hours and 39.2g (0.1 mole) bis(ss-carboethoxyethyltin) dichloride diisolved in 50cc of tetrahydro furan were added. The temperature spontaneously increased to 60 C. Following completion of the addition the reaction mixture was heated at 65 C. for 2 hours.- The mixture was filtered and the filtrate was then concentrated under reduced pressure. 41g of liquid product was obtained. Calculated By Analysis % Sn 21.61 21.00 % Cl 6.46 6.65 % P 5.64 5.55 EXAMPLE 8 Preparation of Butylchlorotin Cyclic -O,O'-chlcro- phosphordate EMI25.1 A glass reactor equipped with a mechanically driven stirred condenser, thermometer, nitrogen inlet and Dean Stark trap was charged with 73.6= (0b3 mole) butylchlorotin dihydroxide, 51.8g (0.3 mole) diethyl chlorophosphate and 200cc toluene. The mixture was heated to 95 C to remove ethanol by azetropic distillation. After all the ethanol was removed, the reaction mixture was concentrated under reduced pressure to yield 98g of a liquid which contained the desired product EXAMPLE 9 Preparation of Dibutyliodotin Dibutyl Phosphate EMI25.2 A glass reactor equipped with a condenser, stirrer and nitrogen Inlet was charged with 43.5g dibutyltin diiodide and 19.5g tibutyl phosphate. The resultant mixture was heated to 125-195 C. When 17.8g of l-iodobutane were collected, heating was discontinued and the reaction mixture was allowed to cool to ambient temperature. 44g of a white solid product was obtained. XAMPThE 10 Preparation of Flexible Polyurethane Foams The compounds described in the preceeding nine examples were employed as gel catalysts for flexible polyurethane foams using the following formulation: Ingredient . Parts (by weight) Polyoll 100 Water 3.5 Poly(oxyethylene oxypropylene) siloxane Blowing catalyst2 0.45 Gel catalyst as specified Toluene diisocyanate3 45.5 1= An ethylene oxide-propylene oxide copolymer available as Niax# 16-56 from the Union Carbide Corporation. 2= A mixture containing 0.15 part of a commercially availble tertiary amine blowing catalyst (Polycat#-77, distributed by Abbott Laboratories) and 0.30 part of triethylene diamine (as a 33% solution in dipropylene glycol). 3= Isocyanate index = 105 The reagents were blended for five seconds using a speed mixer and then poured into a one liter-capacity polyethylene-lined paper cup and allowed to rise. Each of the resultant cylindrical foam samples was cut in half lengthwise and one of the halves was tested for oxidative and thermal stability in accordance with the procedure set forth in the American Society for Testing and Materials (AST.M) Test Method D-1564-71 (suffix A). The sample to be tested was placed in a circulating air oven at a temperature of 1400C for 22 hours, then withdrawn from the oven and allowed to cool for between 10 and 15 minutes. A portion of the flat surface of e2ch sample was depressed to the maximum extent and the pressure released almost immediately. Samples that were sufficiently resilient to recover their original shape without any vIsible damage were considered to have passed the test and all others were considered failures. The procedure employed to determine the 90% compression set value is described in the aforementioned ASTM test method, and consists of compressing a foam sample to 10% of its original height for 22 hours at a temperature of 700C. The height of the foam sample is measured prior to compression and thirty minutes following release of compression. The 90 compression set value is calculated using the formula 90% compression set - (to-t/to-ts) x 1.00. In the foregoing formula to is the height of the foam sample prior to compression, tf Is the height of the sample measured 30 minutes following the release of compression and t5 is the height of the spacer bar employed in the test procedure described in the aforementioned ASTM method. Polyurethane foams employed in seat cushions and mattresses should exhibit 90% compression set values of less than bout 15% All of the present catalysts evaluated produced foams that were within this range. By comparison, foams prepared using several prior art catalyst compositions wherein the tin, phosphorus and halogen are distributed among two or three compounds exhibited 90% compression set values considerably above 15% and as high as 90,. These foams would not be suitable for use in seat cushions or mattresses. The cream time, rise time, dry heat test results (pass or fail),and the 90% compression set values for three of the catalysts disclosed in the preceeding examples are summarized in the following table together with the values obtained using stannous octoate as a control catalyst. Parts of dibutylchlorotin diethyl phosphite 0.13 Part 0.25 Part 0.37 Part Cream time, sec. 10 11 11 Rise time, sec. 82 76 78 Dry heat test Pass - Pass Pass 90% Compression set, floss 8 8 12 Parts of bis (dibutylchlorotin) phosp'nate Cream time, sec. 12 13 Rise time, sec. 79 90 Dry heat test Pass Pass 90Z Compression set, gloss 12 8 Parts of dirbis(B-cprboethoxyethyl) chlorotin] phosphate Cream time, sec. 12 Rise time, sec. 82 Dry heat test Pass 90% Compression set, gloss 8 Parts of Stannous octoate 0.3 Part Cream time, sec. 10 Rise time, sec. 81 Dry heat test Pass 90% Compression set, %loss 9 The combination of dibutyltin dllaurate and tris(2chloroethyl) phosphate is exemplified in United States Patent 3,087,149. The foam properties achieved using this prior art catalyst composition with one formulation identical to the one described in the preceding specification and a second one described in the aforementioned U. S. Patent 3,087,149 are summarized below The polyol disclosed in the aforementioned patent was replaced by the polyol employed in the formulation described in the preceding specification. The resultant foam passed the dry heat stability test, however, the 90% compression set value was 58%. When the same prior art catalyst components: were employed in the formulatIon described In the present specification the foam properties were as follows. Parts of Parts of Cream Rise Dry 90% Compression tris(2-chloroethyl) dibutyltin Time Time Heat Set (after phosphate dilaurate Sec. Sec. Test heating) d 105S 0 0.5 9 75 FaIl not determined 1.5 0.2 10 68 Pass 77 1.5 0.35 9 71 Pass 36 2 0.5 9 80 Pass 80 4 0.5 9 67 82 EXAMPLE 11 This example demonstrates that combinations of a tin compound and a phosphorus compound which does not contain tin do not provIde the desired 90% compression set value of 15 or less. The formulation employed to prepare the foam was identical to that described in the first paragraph of the preceding Example 10. A Tris(2-chloroethyl) phosphate ------- 0.46 part Dibutyltin bis(dsooctyl maleate) ------------- 0.53 part Cream time, sec. --- 12 Rise time, sec. --- 66 Dry heat test --- Pass 90% Compression set,. loss ------------- 91 B Diethylhydrogen phosphite --- 0.20 part Dibutyltin dichloride --- 0.45 part Cream-time, sec. --- 23 Rise time, sec.--- 104 Dry heat test --- Pass 90% Compression set, % oss 78 C Tris(2-chloroethyl)phosphite --- 0.29 part Dibutyltin bis (lauryl mercaptide) --- 0.34 part Cream time, sec. --- 11 Rise time, sec. -- ------------------- - 60 Dry heat test --- Pass 90% Compression set, p loss --- D Tris(2-chloroethyl)phosphite --- 0.135 part Dibutyltin dilaurate --- 0.115 part Cream time, sec. --- 11 Rise time, sec. --- 77 Dry heat test --- Pass 90% Compression set, w loss ------------- 92 E Tris (ncnylphenyl) phosphite --- 0.54 part Dibutyltin dichloride --- 0.24 part Cream time, sec. --- 19 Rise time, sec. --- 1C7 Dry heat test --- Pass 90% Compression set, % loss .------------ 88 F Triisodecyl phosphite --- 0.32 part Dibutyltin chloride --- 0.20 part Cream time, sec. --- 15 Rise time, sec. --- 99 Dry heat test --- Pass 90% Compression set, % loss ------------- 88 EXAMPLE 12 This example demonstrates that f ms prepared using z number of the present catalysts exhibit ceptable levels of dry heat stability and resiliency, the latter having been determined using the value for 25% indent load deflection (ILD) measured using ASTM test method D-1564-71 (suffix A). The catalysts are identified using the number of the example in the preceeding specification that discloses the preparation of the compound. Compound Catalyst 25% of level, Cream Rise Dry heat ILD 2 Example parts time, sec. time, sec. test lb./501n Control 0.3 10 80 Pass 25 1 o,i3 10 82 Pass 2 0.46 13 90 Pass 14 3 o.60 12 -82 Pass 22 4 0.20 13 86 Pass 20 5 O.35 13 76 Pass 25 6 0.20 12 67 Pass 22 7 0.35 10 66 Pass 17 8 0.20 17 124 Pass - Stannous octoate The formulation employed to prepare -the foams as identical to the one described in the first paragraph of the preceding Example 10. EXAMPLE 13 - Dibutylchlorophosphatostannoxane A mixture containing 30.4g (0.1 mol) of dibutyltin dichloride, 49.8g (0.2 mole) of dibutyltin oxide and 250cc of toluene was heated with stirring until a clear solution formed, A'11.5g (0.1 mole) portion of an 85% aqueous solution of ortho-phosphoric acid was then added to the reactor and the resultant mixture was heated at the boiling point for two hours, during which time the water formed as a by-product was removed using a Dean-Stark receiver. The liquid phase of the reaction mixture was evaporated under reduced pressure and the resultant solid was dried in an oven at a temperature of 75OC and under a partial vacuum. The dried solid weighed 77.4g and was found to contain 39.4% tin, 3.15% phosphorus and 7.61% chlorine. The calculated values for the expected product, which can be expresseaiby the empirical formula Sn3C2tH5nCl2POD are 40.4,J tin, 3.52% phosphorus and 8.05% chlorine. This product was dissolved in 2-ethylhexoic acid to form a 33% by weight solution which was subsequently evaluted as a gel catalyst for a polyurethane foam. EXAMPLE 14 This example demonstrates the preparation of a reaction product of bis(dibutylohlorotin)phosphate, dibutyltin sulfide and 2-ethylhexanoic acid. A mixture containing 2.65g (0.01 mole) of dibutyltin sulfide and 6.33g (0.01 mole) of bis(dibutylchlorotin)phosphate prepared as described in the foregoing Example 2 was heated at a temperature of 700C until a clear solution was obtained. A 17.96g (0.12 mole) portion of 2-ethylhexanoic acid was added to this solution and the resultant mixture was heated at 700C for several minutes to obtain a clear liquid. This liquid was then combined with 35.92g of dipropylene glycol and subsequently evaluated as a gel catalyst for a flexible polyurethane foam. EXAMPLE 15 This example demonstrates the preparation of a reaction product of bis(dibutylchlorotin)phosphate, dibutyltin oxide and 2-ethylhexanoic acid. A mixture containing 6.33g (0.05 mole) of bis(dibutylchlorotin)phosphate, 12.45g (0.01 mole) of dibutyltin oxide and 50cc of toluene was heated under a nitrogen atmosphere 'using an oil bath. All of the solid material present dissolved to form a clear solution when the temperature of the oil bath reached 1300C. This solution was then concentrated by evaporation under reduced pressure to yield an amber-colored gel. One possible structure for this gel is EMI34.1 wherein Bu represents n-CXHg-. The gel was combined with 37.56g (0.26 mole) o 2-ethylhexanoic acid and 75.12g of dipropylene glycol. The resultant mixture was heated for 15 minutes at a temperature of 1000C until the gel dissolved. The solution weighed 124g and was subsequently evaluated as a gel catalyst for flexible polyurethane foam. EXAMPLE 16 - Preparation of a reaction product of dibutyltin oxide, dibutyltin dichloride, phosphoric acid and 2-ethvihexanoic acid A reactor was filled with nitrogen and charged with 670g (4.7 moles) of 2-ethylhexanoic acid and 124.4g (0.5 mole) of dibutyltin oxide. This mixture was heated at 50-550C with stirring until a clear solution was obtained. The 8g of water which formed as a by-product of this reaction were removed by heating the reaction mixture to 1000C under a pressure of 25-30mm of mercury. The solution was then allowed to cool to 65-700C, at which time 152g (0.50 moler of dibutyltin dichloride was added and the reaction mixture was heated at a temperature of 600C for 1/2 an hour. A 58g (0.5 mole) portion of phosphoric acid (as an 85% aqueous solution) was gradually added to the reactor. Following completion of the addition the reaction mixture was heated at 600C for one hour. A 5g portion of a filtration aid was added and the reaction mixture was filtered to remove solid materials. The resultant solution was found to contain 11.96, tin, 3.41 phosphorus and 1.55% chlorine. The calculated values for the expected reaction product are 12.5 tin, 3.75% phosphorus and 1.65% chlorine. EXAMPLE 17 - Reaction product of bis(dibutylchlorotin)-:¯ oxide and phenyl phosphonic acid A reactor was charged with 55.3g (0.1 mole) of bis(dibutylchlorotin)oxide, 14.2g (0.09 mole) of phenyl phosphonate and 250cc toluene. This mixture was heated at the boiling point for one hour during which time the 3.500 of water produced as a by-product of the reaction was collected in a Dean-Stark receiver. The resultant clear amber-colored solution was dried using a molecular sieve, after which the solvent and other volatile materials were removed by evaporation under reduced pressure. The resultant solid weighed 63.5g (equivalent to 89% of the theoretical yield) and was found to contain 33.35% tin and 9.71% chlorine. The calculated values for the expected product are 33.49% tin and 10.0% chlorine. EXAMPLE 18 The reaction products prepared using the procedures described in the foregoing Examples 13, 14, 15 and 16 were evaluated as gel catalysts in a flexible polyurethane foam formulation of the following composition: Ingredient Parts by weight Polyol; 200 Water 7.0 Surfact ant2 2.0 Triethylene diamine N-Ethyl morpholine o.. 6 Toluene diisocyanate 90.6 1 An ethylene oxide-propylene oxide copolymer available as Niax#16-56 from the Union Carbide Corporation Poly(oxyethylene oxypropylene)siloxane As a 33% by weight solution in dipropylene glycol 4 Isocyanate Index=105 Plexible polyurethane foams were prepared and evaluated using the procedures described in the preceeding Example 10. Compound of Catalyst Cream Rise Dry Heat 90% Compression Example Level Time Time Test Set 13 0.2 59 113 pass 6.89 14 0.2 65 125 pass 15 0.2 61 117 pass 6.04 16 0.2 65 131 pass 5.79 stannous octoate* 0.3 53 94 pass 5.69 control

Claims: CLAIMS 1. A method for preparing a flexible polyurethane foam exhibiting improved resiliency and resistance to heatinduced degradation by reacting a polyether-containing polyol with a polyfunctional isocyanate in the presence of a blowing agent and a catalytically effective amount bf a gel catalyst composition consisting essentially of at least one organotin compound wherein tin is in the tetravalent state and is bonded to at least one active halogen and at least one'phosphorus-containing organotin compound wherein tin is in the tetravalent state and wherein the molar ratio of tin to phosphorus is from 0.045 to 23, the molar ratio of tin to active halogen is from 0.5 to 23 and the molar ratio of phosphorus to active halogen is form 0.5 to 22 and wherein said phosphorus-containing organotin compound is an organotin ester of a phosphorus compound selected from the group consisting of ortho-phosphoric, meta-phosphoric, pyro-phosphoric, thiophosphoric, phosphorous phosphinic, phosphinous, phosphonous and phosphonic acids, phosphoryl chloride and oligomeric condensation products of 1) phosphonic acid, 2) mixtures containing phosphoric and phosphonic acids or 3) esters of phosphoric and phosphonic acids and alcohols containing from 1 to 20 carbon atoms. 2. A method according to Claim 1 wherein said catalyst composition consists essentially of a single organotin compound exhibiting the general formula EMI38.1 wherein a is 1 or 2, b is 0, 1 or 2 with the proviso that b can be 0 only when the group represented by Y contains an active halogen, X represents an active halogen, -OH -OOCRê, -ORê or -SR wherein Rê is hydrocarbyl and R is hydrocarbyl, -R COOR2, or -R4OOCR2 wherein R4 is alkylene and contains from 2 to 20 carbon atoms, with the proviso that said compound contains at least one halogen atom bonded to tin or phosphorus; d is 0, 1 or 2 with the proviso that d can be 0 only when the group represented by Y contains phosphorus; Y is EMI39.1 wherein V is -OZ or -X and p is O or an integer from 1 to 10; Z is EMI39.2 EMI39.3 wherein M is -R6, -OR7, (OR3)OZ or Y, wherein RB is -CH2CH2- or -CH(CH3)CH2-, f is an Integer from 1 to 100, R is hydrocarbyl, chloroalkyl, halogen or Y, R6 is hydrocarbyl, R7 is hydrocarbyl or hydrogen, c is 0 or 1, m is O or an integer from 1 to 10; U-is oxygen or sulfur, e is 1 or 2, RÚ is hydrocarbyl or R9OOCR8-wherein R9 is hydrocarbyl and 0 is EMI39.4 wherein g is 0 or an integer from 1 to 6. 3. A method according to Claim 2 wherein RÚ, R5, R6 and R7 are alkyl and contain from 1 to 8 carbon atoms. 4. A method according to Claim 1 wherein the active halogen and phosphorus are present in a single organotln compound. 5. A method according. to Claim 4 wherein R' is chioroethyl, e is 2 and m is 0. 6. A method according to Claim 4 wherein said compound is selected from the group consisting of dibutylchlorotin diethyl phosphite bis (dibutylchlorotin) phosphate di[bis(ss-carboethoxyethyl)chlorotin] phosphate butylchlorotin cyclic 0,0'-monoethyl phosphite dibutylchlorotin dibutyl phosphite bis(B-carboethoxyethyl)chlorotin diethyl phosphite bis(ss-carboethoxyethyl)chloroetin dibutyl phophite butylchlorotin cyclic -0,0'-chlorophosphordate dibutyliodotin dibutyl phosphate. 7- A method according to Claim I wherein the reaction mixture contains from 0 to 90%, based on the weight of said polyol, of a mono- or dicarboxylic acid containing from 2 to 20 carbon atoms. 8. A method according to Claim 7 wherein said acid is 2-ethylhexanoic acid. 9. A method according to Claim 1 wherein said gel catalyst composition is the reaction product of at least one organotin compound containing an active halogen bonded to the tin atom and said phosphorus compound. 10. A method according to Claim 1 wherein said gel catalyst composition is the reaction product of at least one monoorganotin or diorganotin compound containing an active halogen bonded to th tin- atom, said phosphorus compound and a mono- or dicarboxylic acid containing from 2 to 20 carbon atoms. 11. A method according to Claim 1 wherein the active halogen and phosphorus are present on different organotin compounds. 12. A flexible cellular polyurethane prepared by reacting a polyether-containing polyol with a polyfunctional isocyanate, said cellular polyurethane exhibiting a level of thermal and oxidative stability at 1400C sufficient to comply with the standards set forth in the American Society of Testing and Materials Test Method -D-1564-71 and a 90% compression set value of between 5 and 15% measured using said Test Method D-1564-71 wherein said cellular polyurethane contains a detectable amount of a gel catalyst composition comprising at least one organotin compound or a thermal decomposition product of said organotin compound, wherein said organotin compound contains tetravalent tin and phosphorus, and at least one organotin compound or a thermal decomposition product thereof, wherein said organotin compound contains tin in the tetravalent state and an active halogen atom, wherein the molar ratio of tin to phosphorus is from 0.045 to 23, the molar ratio of tin to active halogen is from 0.5 to 23 and the molar ratio of phosphorus to active halogen Is from 0.5 to 22, and wherein said compound is an organoin ester of a phosphorus compound selected from the group consisting of ortho-phosphoric, meta-phosphoric, pyrophosphoric, thiophosphoric, phosphorous, phosphinic, phosphinous, phosphonous and phosphonic acids, phosphoryl chloride and oligomeric condensation products of 1) phosphonic acid, 2) mixtures containing phosphoric and pliosphonic acids or 3) esters of phosphoric and phosphonic acids and alcohols containing from 1 to 20 carbon atoms. 13. A cellular polyurethane according to Claim 12 wherein the active halogen and phosphorus are present in a single organotin compound. 14. A cellular polyurethane according to Claim 13 wherein said catalyst composition contains an organotin compound of the general formula EMI42.1 wherein a is 1 or 2, b,is 0, 1 or 2 with the proviso that b can be 0 only when the group represented by Y contains an active halogen, X represents an active halogen, -OH, -00CR2 -OR2 or -SR3 wherein R2 is hydrocarbyl and R3 is hydrocarbyl, -R4COOR2 or -R4OocRZ wherein RB is alkylene and contains from 2 to 20 carbon atoms, with the proviso that said compound contains at least one halogen atom bonded to tin or phosphorus, d is O, 1 or 2 with the proviso that d can be 0 only when the group' represented by Y contains phosphorus; EMI42.2 wherein V is -OZ or -X and P is 0 or an integer from 1 to 10; Z is EMI42.3 wherein M is ¯R6, -OR7, -(OR2)-OZ or Y, wherein Re is -CH2CH2- or -CH(CH3)CH2-, f is an integer from,l to 100, R5 is hydrocarbyl, chloroalkyl, halogen or Y, R6 is hydrocarbyl, R7 is hydrocarbyl or hydrogen, c is 0 or 1, m is 0 or an integer from 1 to io; U is oxygen or sulfur, e is 1 or 2, R1 is hydrocarbyl or 6OOCR8- wherein R9 is hydrocarbyl and EMI43.1 wherein g is 0 or an integer from 1 to 6. 15. A cellular polyurethane according to Claim14 wherein R1, P5, R6 and R7 are alkyl and contain from 1 to 8 carbon atoms. 16. A cellular polyurethane according to Claim 14 wherein P5 is chloroethyl, e is 2 and m is 0. 17. A cellular polyurethane according to Claim 14 wherein said compound is selected from the group consisting of dibutylchlorotin diethyl phosphite bis(dibutylchlorotin) phosphate di[bis(ss-carboethoxyethyl)chlorotin]phosphate butylchlorotin cyclic 0,0'-monoethyl phosphite dibutylchlorotin dibutyl phosphine bis(ss-carboethoxyethyl)chlorotin diethyl phosphite bis(B-carboethoxyethyl)chlorotin dibutyl phosphite butylchlorotin cyclic -0,0'-chlorophosphordate dibutyliodotin dibutyl phosphate. 18. A cellular polyurethane according wherein said catalyst composition is the reaction product -of a monoorganotin or a diorganotin compound containing an active halogen bonded to the tin atom, said phosphorus compound and a mono- or dicarboyxlic acid containing from 2 to 20 carbon atoms. 19. A organotin compound of the general formula EMI44.1 wherein R1 is hydrocarbyl or R9OOCR-, R8 is -CH2CH2- or -CH(CH2)CH2- , R9 is.hydrocarbyl and Q is EMI44.2 wherein g is O or an integer from 1 to 6, M is -R0, -oR7, 4ORS)fOZ or Y, U is oxygen or sulfur, c is O or 1, R6 is hydrocarbyl, R7 is hydrocarbyl or hydrogen, and X is halogen. 20. A gel catalyst composition for preparing-a flexible polyurethane foam, said composition comprising the reaction product of a mono- or diorganotin compound containing an active halogen bonded to tin, a phosphorus compound selected from the group consisting of ortho-phosphoric, metaphosphoric, pyro-phosphoric, thiophosphoric, phosphorous, phosphinic, phosphinous, phosphonous and phosphonic acids, phosphoryl chloride and oligomeric condensation products of 1) phosphonic acid, 2) mixtures containing phosphoric and phosphonic acids or 3) esters of phosphoric and phosphonic acids and alcohols containing from 1 to 20 carbon atoms and a mono- or dicarboyxlic acid containing from 2 to 20 carbon atoms, wherein the molar ratio of tin to phosphorus in said composition is from 0.045 to 23, the molar ratio of tin to active halogen is from 0.5 to 23 and the molar ratio of phosphorus to active halogen is from 0.5 to 22. 21. A method of preparing a flexible polyurethane foam by reacting a polyether-containing polyol with a polyfunctional isocyanate or isothiocyanate in the presence of a blowing agent and a gel catalyst characterized in that the gel catalyst consists essentially of at least one organotin compound wherein tin is in the tetravalent state and is bonded to at least one active halogen and at least one phosphorus-containing organotin compound wherein tin is in the tetravalent state and wherein the molar ratio of tin to phosphorus is from 0.045 to 23, the molar ratio of tin to active halogen is from 0.5 to 23 and the molar ratio of phosphorus to active halogen is from 0.5 to 22,and wherein said phosphorus-containing organotin compound is an organotin ester of a phosphorus compound selected from the group consisting of orthophosphoric, meta-phosphoric, pyro-phosphoric, thiophosphoric, phosphorous, phosphinic, phosphinous, phosphonous and phosphonic acids, phosphoryl chloride and oligomeric condensation products of 1) phosphonic acid, 2) mixtures containing phosphoric and phosphonic acids or 3) esters of phosphoric and phosphonic acids and alcohols containing from 1 to 20 carbon atoms. 22. A method of preparing a flexible polyurethane foam by reacting a prepolymer with a polyfunctional isocyanate or isothiocyanate in the presence of a blowing agent and a gel catalyst, the said prepolymer having been made by reacting a polyether containing polyol with a polyfunctional isocyanate or isothiocyanate characterized in that the gel catalyst consists essentially of at least one organotin compound wherein tin is in the tetravalent state and is bonded to at least one active halogen and at least one phosphoruscontaining organotin compound wherein tin is in the tetravalent state and wherein the molar ratio of tin to phosphorus is from 0.045 to 23, the molar ratio of tin to active halogen is from 0.5 to 23 and the molar ratio of phosphorus to active halogen is from 0.5 to 22 and wherein said phosphorus-containing organotin compound is an organotin ester of a phosphorus compound selected from the group consisting of ortho-phosphoric, metaphosphoric, pyro-phosphoric, thiophosphoric, phosphorous, phosphinic, phosphinous, phosphonous and phosphonic acids, phosphoryl chloride and oligomeric condensation products of 1) phosphonic acid, 2) mixtures containing phosphoric and phosphonic acids or 3) esters of phosphoric and phosphonic acids and alcohols containing from 1 to 20 carbon atoms.

Inventors: BOSSERT, EMILY C., TREADWELL, KENNETH
Applicants: AIR PRODUCTS AND CHEMICALS, INC.
Application year: 1980
Main classification: C08G18
IPC codes: C07F9, C08G18