Patent GB-1100288-A (GB)
Title: Organo-metallic fluorine compounds
Inventor: CARPENTIER RAYMOND
IPC: D06M13/236
Filed: 1964-11-19
Abstract: Homopolymers and copolymers of perfluorinated organometallic compounds which contain unsaturated radicals of the formula (R.CO2)m-n-x-M-An wherein M is an atom of a metal of valency m selected from those of periods 3, 4, 5 and 6 of Groups II to VIII of the Periodic Table or is silicon; R is a perfluoroalkyl radical containing at least 3 C atoms, the radicals R being the same or different when m - n - x is at least 2; A is one of the radicals-YR1 and -Y-R2-Y1, in which Y and Y1 represent -CO2- or -O-radicals; R1 is either (a) a straight or branched chain alkyl, alkenyl or alkynyl radical, which may be substituted by at least one Cl or Br atom or an alkoxy, carbalkoxy, acyloxy, acyl or OH radical; or (b) a CH3CO or CF3 radical, the radicals R1 being the same or different when n is at least 2; R2 is a straight or branched chain alkenylene, alkylene or alkynylene radical, the carbon chain of which may be interrupted by O atoms, and which may be substituted by at least one Cl, Br or F atom or OH group; m is 2, 3 or 4 when A is-YR1 and is 3 or 4 when A is -Y-R2-Y1-; n is 1, 2 or 3 when A is -YR1 and is 1 when A is -Y-R2-Y1-; X is O when A is -YR1 and is 1 when A is -Y-R2-Y1; and m - n - x is greater than 0.  The perfluorinated organometallic compounds may be polymerized with one another or with other copolymerizable compounds having ethylenic unsaturation, such as vinyl chloride, vinylidene chloride, vinyl acetate, vinyl benzoate, styrene, ethyl acrylate, methyl methacrylate and vinylpyridine. Examples are given for the preparation of the homopolymers and copolymers and of a fluorinated derivative of polyvinyl alcohol.ALSO:The invention comprises fluorinated organometallic compounds of the general formula (R.CO2)mnx-M-An wherein M represents an atom of valency m selected from those of periods 3, 4, 5 and 6 of Groups II to VIII of the Periodic Table or is silicon; R is a perfluoroalkyl radical containing at least three carbon atoms, the radicals R being the same or different when m-n-x is at least equal to 2; A is one of the radicals-YR and-YR2-Y1, in which Y and Y1, which may be the same or different, represent -CO2- or -O- radicals; R1 represents either (a) a straight or branched chain alkyl, alkenyl or alkynyl radical, which may be substituted by at least one Cl or Br atom, or an alkoxy, carbalkoxy, acyloxy, acyl or OH radical; or (b) an acetyl or CF3 radical, the radicals R1 being the same or different when n is at least equal to 2, R2 is a straight or branched chain alkylene, alkenylene or alkynylene radical the carbon chain of which may be interrupted by O atoms and which may be substituted by at least one Cl, Br or F atom or an OH group, m is 2, 3 or 4, when A is -YR1, and is 3 or 4 when A is Y-R2-Y1-, n is 1,2 or 3 when A is - YR1 and 1 when A is-YR2-Y1-; #x is 0 when A is a radical -YR1 and 1 when A is a radical -Y-R2-Y1, and m-n-x is greater than 0. Compounds in which A is -YR1 may be prepared by reacting at least one perfluorocarboxylic acid of the formula RCOOH and at least one compound of the formula R1YH with a metal M or an oxide, carboxylate, halide or alkoxide thereof.  Compounds in which A is -Y-R2-Y1- may be prepared by reacting at least one perfluorocarboxylic acid of the formula R.COOH and a compound of the formula HY-R2-Y1H with a metal M having a valency of at least 3 or an oxide, carboxylate, halide or alkoxide thereof.  Specified metals are Al, Ti, Zr, Sb, Mg, Si, Zn, Sn, Ni, Hg, Cd, Co and Ce.  Preferred perflurocarboxylic acids contain 6 to 12 carbon atoms.  Examples are given for the production of the complexes. They are useful in oil-proofing porous materials (see Division D1).  Also, the compounds which contain unsaturated radicals are capable of forming homopolymers and copolymers (see Division C3).ALSO:Porous materials are treated with an aqueous solution or emulsion or an organic solution of at least one compound of the formula:-(R.CO2)m-n-x-M-An wherein M represents an atom of valency m selected from those of periods 3,4,5 and 6 of groups II to VIII of the Periodic Table or is silicon; R is a perfluoroalkyl radical containing at least three carbon atoms, the radicals R being the same or different when m-n-x is at least equal to 2; A is one of the radicals -YR1 and -YR2-Y1-, in which Y and Y1 which may be the same or different, represent -CO2-or -O- radicals; R1 represents either (a) a straight or branched chain alkyl, alkenyl or alkynyl group, which may be substituted by at least one Cl or Br atom, or an alkoxy, carbalkoxy, acyloxy, acyl or OH radical; or (b) an acetyl or CF3 radical, the radicals R1 being the same or different when n is at least equal to 2, R2 is a straight or branched chain alkylene, alkenylene or alkynylene radical the carbon chain of which may be interrupted by O atoms and which may be substituted by at least one Cl, Br or F atom or an OH group, m is 2, 3 or 4, when A is -YR1, and is 3 or 4 when A is -Y-R2-Y1-, n is 1, 2 or 3 when A is -YR1 and 1 when A is -YR2-Y1-; x is O when A is a radical -YR and 1 when A is a radical -Y-R2-Y1-, and m-n-x is greater than O.  Compositions containing at least one homopolymer of a compound of the above formula which contains an unsaturated radical; and/or at least one copolymer of a compound of the above formula which contains an unsaturated radical with other copolymerisable compounds having ethylenic unsaturation, may also be used. Specified substrates are natural or synthetic textile fibres, paper, wood, brick, asbestos, leather and skins.  Examples are given in which cotton, craft paper and filter paper are treated and tested.