Patent GB-991799-A (GB)
Title: The production of polyurethanes from hydroxyl-containing phosphonic acid esters containing nitrogen
Inventor: OERTEL GUENTER
IPC: C08G18/38
Filed: 1962-04-26
Abstract: The invention comprises polyhydroxyl compounds containing phosphonic acid ester groups and nitrogen atoms which are obtainable by condensing a primary or secondary aliphatic, cycloaliphatic, aromatic, araliphatic or heterocyclic mono- and/or polyamine containing at least one hydrogen atom attached to the amino nitrogen atom and also containing at least two hydroxyl groups with an organic carbonyl compound and a dialkyl or dihaloalkyl or dicycloalkyl phosphite. Preferred polyhydroxyl products are those having the general formula <FORM:0991799/C2/1> in which R and R1 are hydrogen atoms or hydrocarbon radicals which may be substituted by halogen atoms, R11 is a C1-C18 alkyl radical haloalkyl or cycloalkyl radical, X, Y and Z are each alkylene, arylene or aralkylene radicals which may be the same or different and may be interrupted by hetero atoms (e.g. by -O-, -S- or -N- atoms) and/or contain free OH groups and m is O or an integer from 1 to 10. Z may be the same radical as X or Y and may conveniently be an alkylene or aralkylene radical containing 2 to 12 carbon atoms or an arylene radical containing one or two benzene rings such as phenylene, naphthylene, diphenylene or tolylene. R and R1 when they are hydrocarbon radicals can be alkyl, alkenyl, cycloalkyl, cyclo-alkyl substituted alkenyl radicals, aralkyl or aralkenyl radicals and several suitable radicals of each type and of halogen-substituted hydrocarbon radicals are specified. The reaction can be effected by simple mixing of the reactants preferably at 20 DEG  to 100 DEG  C. The products can be used directly for reaction with organic polyisocyanates to form polyurethane plastics (see Divisions B2 and C3), or can be modified beforehand by reacting with alkylene oxides, e.g. ethylene-, propylene- or butylene oxide, epichlorhydrin or styrene oxide. The products may have a molecular weight of from 200 to 10,000 and an OH number of 40 to 800. Examples are given for the production of polyhydroxy compounds from (1) and (2) formaldehyde, diethyl (or dimethyl) phosphite and diethanolamine, (3) and (4) formaldehyde, diethyl (or dimethyl) phosphite and N,N,N1 - tris - (beta - hydroxypropyl) - ethylene diamine, (5) formaldehyde, diethyl phosphite and the product obtained by reacting 2,4-diamino toluene in ethanol with ethylene oxide, (6) formaldehyde, dimethyl phosphite and N,N1 - di - (beta - hydroxypropyl) - ethylene diamine, (7) formaldehyde, diethyl phosphite and a product obtained by reacting a mixture of pentaethylene hexamine and a small amount of water with propylene oxide, (8), (9) and (10) crotonaldehyde (acetaldehyde or iso-butyraldehyde), diethyl phosphite and diethanolamine, (11) cyclohexanone, diethyl phosphite and diethanolamine, and (12) formaldehyde, diethanol-amine and dichloroethyl phosphite.ALSO:Polyurethanes are obtained by reacting organic polyisocyanates with polyhydroxyl compounds containing phosphonic acid ester groups and nitrogen atoms and which are obtainable by condensing a primary or secondary aliphatic, cyclo-aliphatic, aromatic, araliphatic or heterocyclic mono- and/or polyamine containing at least one hydrogen atom attached to the amino nitrogen atom and also containing at least two hydroxyl groups with an organic carbonyl compound and a dialkyl or dihaloalkyl or dicycloalkyl phosphite (see Division C2).  Preferred polyhydroxyl products are those having the general formula <FORM:0991799/C3/1> in which R and R1 are hydrogen atoms or hydrocarbon radicals which may be substituted by halogen atoms, R11 is a C1-C18 alkyl radical haloalkyl or cycloalkyl radical, X, Y and Z are each alkylene, arylene or aralkylene radicals which may be the same or different and may be interrupted by hetero atoms (e.g. by -O-, -S- or -N- atoms) and/or contain free OH groups and m is 0 or an integer from 1 to 10. Z may be the same radical as X or Y and may conveniently be an alkylene or aralkylene radical containing 2 to 12 carbon atoms or an arylene radical containing one or two benzene rings such as phenylene, naphthylene, diphenylene or tolylene.  R and R1 when they are hydrocarbon radicals can be alkyl, alkenyl, cycloalkyl, cycloalkyl substituted alkenyl radicals, aralkyl or aralkenyl radicals and several suitable radicals of each type and of halogen-substituted hydrocarbon radicals are specified. The polyhydroxy phosphorus compounds can be modified by reacting with alkylene oxides, e.g. ethylene-, propylene- or butylene oxide, epichlorhydrin or styrene oxide, before reacting with the organic polyisocyanate to form the polyurethanes.  The organic polyisocyanates may be aromatic, aliphatic (including cycloaliphatic) or heterocyclic polyisocyanates and include a phosphorus-containing polyisocyanate and several suitable compounds are specified including di- and poly-isocyanates, e.g. p,p1,p11-triisocyanato phenyl phosphate.  It is preferred to use aromatic polyisocyanates, e.g. a mixture of toluylene diisocyanates; diphenylmethane-4,41 diisocyanate and the crude isocyanates obtained by phosgenation of the reaction product of aniline and formaldehyde or of a mixture of meta- and para-toluylene diamines. The hydroxyl phosphorus compounds may be used in conjunction with a compound containing active hydrogen containing groups, as determined by the Zerewitinoff method, e.g. polyhydric polyalkylene ethers, hydroxy polyesters (e.g. the reaction product of a polycarboxylic acid with a polyhydric alcohol), polyhydric polythioethers, polyacetals, e.g. the reaction product of a polyhydric alcohol with an aldehyde, e.g. formaldehyde, and propoxylated phosphoric acid.  Cellular polyurethanes are obtained by carrying out the reaction in the presence of a blowing agent, e.g. a halohydrocarbon such as dichlorodifluoromethane or trichlorofluoromethane or by using water and sufficient excess of the polyisocyanate to produce carbon dioxide.  Other additives may also be present, e.g. emulsifiers such as sulphonated castor oil, foam stabilizers, e.g. a silicone oil, colouring agents and/or fillers.  A catalyst may also be present, e.g. a tertiary amine, a tin compound, e.g. stannous chloride or a tin salt of a carboxylic acid, or other metal organic compounds. Non-porous polyurethanes may be obtained by reacting an excess of the organic polyisocyanate with the phosphorus compound and an organic cross-linking agent, e.g. a polyhydric alcohol, a polyamine or hydroxyamine under substantially anhydrous conditions.  A coating composition may be obtained by reacting the polyisocyanate and the phosphorus compound in an inert organic solvent, e.g. xylene, toluene, ethyl acetate, diethyl ether of ethylene glycol, or ethylene glycol monoethyl ether monoacetate and such coating compositions may be used for coating wood, paper, sponge rubber, cellular polyurethanes, or foamed polystyrene and such compositions may contain a pigment or dye-stuff, e.g. iron oxide, carbon black, titanium dioxide, zinc oxide, chrome green or lithol red.  Several examples are given for the production of foamed polyurethanes. An example is also given for the production of a non-foamed polyurethane in which example a polyester prepared from adipic acid and ethylene glycol is chain extended with toluylene diisocyanate, dissolved in ethyl acetate and mixed with a phosphorus compound of the formula <FORM:0991799/C3/2> a phosphorus and chlorine-containing polyisocyanate (prepared as below) and a diurethane obtained from 1 mol. of N-methyl diethanolamine and 2 mols. of phenyl isocyanate and the resulting solution is applied several times to each side of a cotton fabric which is then dried at about 80 DEG C. after each coat, the resulting coated fabric being flameproof.  The phosphorus-containing polyisocyanate is obtained by adding phosgene to a residue obtained by distilling off a mixture of cyclohexylisocyanate and hexamethylene diisocyanate from a heated mixture of hexamethylene diisocyanate and cyclohexyl carbodiimide and then reacting with trichloroethyl phosphite at 90-100 DEG C., with elimination of ethylene chloride.  Specifications 769,682, 804,369 and 819,384 are referred to.ALSO:A coating composition is obtained by reacting in an inert organic solvent an organic polyisocyanate with a polyhydroxyl compound containing phosphonic acid ester groups and nitrogen atoms which is obtainable by condensing a primary or secondary aliphatic, cycloaliphatic, aromatic, araliphatic or heterocyclic mono- and/or polyamine containing at least one hydrogen atom attached to the amino nitrogen atom and also containing at least two hydroxyl groups with an organic carbonyl compound and a dialkyl or dihaloalkyl or dicycloalkyl phosphite (see Division C2). Preferred polyhydroxyl products are those having the general formula <FORM:0991799/B1-B2/1> in which R and R1 are hydrogen atoms or hydrocarbon radicals which may be substituted by halogen atoms, R11 is a C1-C18 alkyl radical, haloalkyl or cycloalkyl radical, X, Y and Z are each alkylene, arylene or aralkylene radicals which may be the same or different and may be interrupted by hetero atoms (e.g. by -O-, -S- or -N- atoms) and/or contain free OH groups and m is 0 or an integer from 1 to 10.  Z may be the same radical as X or Y and may conveniently be an alkylene or aralkylene radical containing 2-12 carbon atoms or an arylene radical containing one or two benzene rings such as phenylene, naphthylene, diphenylene or tolulene.  The inert organic solvent may be xylene, toluene, ethylene glycol diethyl ether, ethyl acetate or ethylene glycol monoethyl ether monoacetate. The composition may contain a pigment or dyestuff, e.g. iron oxide, carbon black, titanium dioxide, zinc oxide, chrome green or lithol red, and is suitable for coating wood, paper, rubber, metal, cellular polyurethane plastics and foamed polystyrene.  In an example a polyester prepared from adipic acid and ethylene glycol is chain-extended with toluyle