Patent GB-1122404-A (GB)
Title: Polyfluoroalkyl derivatives of phosphorous acids
IPC: D06M13/487
Filed: 1965-07-30
Abstract: A lubricating or hydraulic oil composition comprises a compound of the formula <FORM:1122404/C4-C5/1> and <FORM:1122404/C4-C5/2> wherein Rf is a perfluoroalkyl radical of more than 5 carbon atoms, which may have a chlorine or hydrogen atom replacing a fluorine atom in the o -position, X is hydrogen or an alkyl radical, Y is alkoxy, aralkoxy, aryloxy, epoxyalkoxy, an amine radical, halogen, -SH or -OH, n is 2-7 and Q is oxygen or sulphur. Certain of the compounds may themselves be used as lubricants, e.g. for metal surfaces.ALSO:Polyfluoroalkyl phosphorus compounds of the formulae <FORM:1122404/C2/1> <FORM:1122404/C2/2> wherein Rf is a perfluoroalkyl radical of more than 5 carbon atoms which may have a chlorine or hydrogen atom replacing a fluorine atom in the o -position, X is hydrogen or an alkyl radical, Y is alkoxy, aralkoxy, aryloxy, epoxyalkoxy, an amine radical, halogen -SH or -OH, n is 2 to 7 and Q is oxygen or sulphur, may be prepared by (a) reacting a trialkyl phosphite with a fluorohaloalkane which has no fluorine in the a - and b -positions to the reactive halogen, (b) reacting ionically or by a radical mechanism an alkyl phosphonic, thiophosphonic, phosphinic or thiophosphinic acid with a fluoro-olefin or fluorohalo-olefin which has no fluorine on the double bond, or (c) reacting thermally or by a radical mechanism a chlorofluoroiodoalkane or fluoroiodoalkane with an unsaturated alkyl phosphonic, thiophosphonic, phosphinic or thiophosphinic acid or a derivative thereof and deiodinating the resulting product.  Process (a) is suitably effected by mixing the components in molar proportions and heating to 120-170 DEG  C. under a nitrogen atmosphere.  Reaction (b) is suitably effected by initiating the reaction with ultraviolet irradiation, azoisobutyronitrile at 60-70 DEG  C. or with peroxide initiators; sodium alcoholate may also be employed to catalyze the reaction and in the case of alkyl thiophosphonic and thiophosphinic acids being used as starting materials, heating of the reaction mixture is sufficient. Reaction (c) may be effected by heating the reactants at a temperature greater than 150 DEG  C. or with radical-forming irradiation or a radicalforming catalyst; the resulting compounds are subsequently de-iodinated, e.g. by treatment with zinc turnings in HCl.  The acids may be converted to glycidyl esters by treatment with epichlorhydrin and subsequent elimination of HCl in the presence of an HCl acceptor. Ethyleneimine diamides may be prepared by reacting the fluoralkyl phosphinic acid dichlorides with a stoichiometric amount of ethyleneimine in pyridine-ether solution.ALSO:Substrates, e.g. varnished layers, metals, plastics and wood may be treated with a composition comprising a compound of the formula:- <FORM:1122404/B1-B2/1> and <FORM:1122404/B1-B2/2> wherein R1 is a perfluoroalkyl radical of more than 5 carbon atoms which may have a chlorine or hydrogen atom replacing a fluorine atom in the o -position, x is hydrogen or an alkyl radical, Y is alkoxy, aralkoxy, aryloxy, epoxyalkoxy, an amine radical, halogen, -SH or -OH, n is 2-7 and Q is oxygen or sulphur.  The composition applied may be cured by heating for a short period at 120 DEG C.  Preferred compounds for use are those which carry polymerisable ester and amide groups, e.g. compounds of the above formula where the group Y is an ethyleneimine or epoxyalkoxy group.  In specific examples a glycidyl ester precondensate mixture of one of the above compounds is (a) added to a varnish preparation into which two degreased iron plates are dipped and subsequently dried at 25 DEG C for 30 hours and at 150 DEG C for 10 minutes respectively, and (b) dissolved in trichloroethylene mixed with diethylenetriamine and sprayed onto an epoxide resin varnish layer which is subsequently allowed to harden; this same solution is also used to treat a Cellophane (Trade Mark) film, a polyethylene film and a polyester textile fabric.ALSO:Textiles, paper and leather are impregnated with a compound of the formula:- <FORM:1122404/D1-D2/1> and <FORM:1122404/D1-D2/2> wherein Rf is a perfluoroalkyl radical of more than 5 carbon atoms which may have a chlorine or hydrogen atom replacing a fluorine atom in the o -position, x is hydrogen or an alkyl radical, Y is alkoxy, aralkoxy, aryloxy, epoxyalkoxy, an amine radical, halogen, -SH or -OH, n is 2 to 7 and Q is oxygen or sulphur.  The impregnating agent on the substrate may be cured by heating for a short period at 120 DEG C. Preferred compounds are those which carry polymerisable ester and amide groups, e.g. compounds of the above formula where the group Y is an ethyleneimine or an epoxyalkoxy group, and such derivatives are suitably applied in the form of very dilute aqueous solutions or emulsions in trichloroethylene.  In specific examples, suede, cotton cloth a polyester textile fabric and filter paper are treated.