Patent GB-790663-A (GB)
Title: Improvements relating to compositions for flame-proofing cellulose containing material, their use, and material treated therewith
IPC: D06M15/423
Filed: 1955-11-03
Abstract: Ortho-phosphoric acid derivatives of the general formula <FORM:0790663/IV (b)/1> wherein R = H or alkyl of 1-4 carbon atoms; and X1 and X2 are alkyl of 1-4 carbon atoms or alkoxy or alkylamino with alkyl groups containing 1-4 carbon atoms (used in flameproofing compositions containing a polymethylol melamine (see Groups IV (a) and VIII) are made from alkyl phosphonic acid dichlorides, o-phosphoric acid mono alkyl ester dichlorides, o-phosphoric acid dialkyl ester monochlorides or o-phosphoric acid mono-dialkylamide dichlorides and ammonia or a primary aliphatic amine in an inert solvent, e.g. chlorobenzene, chloroform, carbon tetrachloride or tetrachlorethane.  In Example 1, monomethylamine hydrochloride is reacted with phosphorus oxychloride to yield o-phosphoric acid monomethylamide dichloride (B.P. 122-128 DEG  C.) which is dissolved in chloroform and added dropwise to a chloroform solution of methylamine at a temperature held between -5 DEG  and 5 DEG  C.  The reaction mixture is stirred, heated, cooled and filtered to remove methylamine hydrochloride.  The product has the formula <FORM:0790663/IV (b)/2> In Example 2, o-phosphoric acid di(methyl)-amide-bis-(ethylamide) is similarly prepared from o-phosphoric acid mono-dimethyl-amide dichloride and ethylamine in benzene.  In Example 3 o-phosphoric acid monoethyl ester dichloride is dissolved in chlorbenzene and added to a chlorbenzene solution of methylamine.  o-phosphoric acid monoethyl ester-bis-(methylamide) (B.P. 110-111 DEG  C. at 0.005 mms.) is isolated from the reaction mixture.ALSO:Cellulosic material is rendered flameproof by treatment with an aqueous solution containing 1 mol. of polymethylol melamine which may be etherified and 2/3 -3 mols. of a substance with the general formula <FORM:0790663/IV (a)/1> in which R is H or an alkyl group of 1-4 carbon atoms and X1 and X2 each represent an alkyl radical of 1-4 carbon atoms, an alkoxy radical of 1-4 carbon atoms, or an alkylamino group in which the alkyl groups have 1-4 carbon atoms. Suitable phosphorus compounds are (a) alkyl phosphonic acid amides, e.g. methyl or ethyl phosphonic acid-bis-(mono-methyl or -ethyl amide), or propyl or butyl phosphonic acid-bis-(monomethylamide); (b) o-phosphoric acid dialkyl ester monoamides, e.g. o-phosphoric acid dimethyl or diethyl ester-mono-, monomethyl-or monoethyl-amide; (c) o-phosphoric acid monoalkyl ester diamides, e.g. o-phosphoric acid mono-methyl-, ethyl-, propyl- or butyl-ester-bis-(monomethylamide) or o-phosphoric acid mono-methyl- or ethyl-ester-bis-(monoethylamide); and (d) o-phosphoric acid triamides, e.g. o-phosphoric acid dimethyl- or diethylamide-bis-(monomethyl or monoethyl amide), or o - phosphoric acid - butylamino - bis - (methylamide).  Cellulosic materials are impregnated with the aqueous solutions and heated to over 80 DEG  C., if desired, after drying.  The compositions of the present invention may be used in the aqueous phase of dispersion of polyvinyl compounds which contain metal oxides, e.g. titanium dioxide, antimony trioxide, chromic oxide or iron oxides in suspension.  In examples: (1) the tris-(monomethylamide) of o-phosphoric acid and trimethylol melamine are dissolved in water. Mercerized cotton muslin is impregnated with the solution, dried and heated for 20 minutes at 120 DEG  C.; (2) o-phosphoric acid (dimethylamido-)-bis-(monoethylamide) is used with trimethylol melamine; (3) o-phosphoric acid monoethyl ester-bis-(monomethylamide) is used with trimethylol melamine trimethyl ether.  Various other flame-proofing compositions according to the invention are also listed in this example; (4) methyl, ethyl or butyl phosphonic acid-bis-(methylamide) is used with trimethylol melamine; (5) flame-proofing mixtures contain o-phosphoric acid diethyl ester amide and dimethylol melamine or o-phosphoric dimethyl ester amide and trimethylol melamine; (6) a polyvinyl chloride dispersion is stirred with a dispersion of antimony trioxide, a naphthalene sulphonic acid-formaldehyde condensate and water.  An aqueous solution of o-phosphoric acid monoethylester - bis - (methylamide) and trimethylol melamine is added and the mixture used to flameproof cotton.