Patent GB-796838-A (GB)
Title: Salts of phosphonic acids and compositions containing the same
IPC: C07F9/38
Filed: 1956-06-13
Abstract: The invention comprises salts of vinylphosphonates having the general formula [CH2=CH-P(O)(OR)-O-]nM in which R is an alkyl group having 1 to 6 carbon atoms or a b -chloroalkyl group having 2 to 6 carbon atoms, M is a metal having a valence of at least 2 and n is the valency of the metal M.  Specified metals (M) are magnesium, calcium, strontium, barium, zinc, cadmium, copper, aluminium, iron, cobalt and nickel.  The products may be obtained by heating a diester of vinyl phosphonic acid having the general formula CH2=CHP(O)(OR)2 in which R is as defined above with a halide, preferably the chloride of the metal M.  Examples are given for the production of: (1) calcium ethyl vinyl phosphonate; (2) calcium n-butyl vinyl phosphonate; (3) calcium isoamyl vinyl phosphonate; (4) cadmium ethyl vinyl phosphonate; (5) cadmium isopropyl vinyl phosphonate; (6) cadmium n-amyl vinyl phosphonate; (7) zinc ethyl vinyl phosphonate; (8) barium ethyl vinyl phosphonate; (9) to (11) barium, cadmium, and zinc methyl vinyl phosphonates; (12) magnesium ethyl vinyl phosphonate; (13) and (14) zinc and cadmium n-propyl vinyl phosphonates; (15) strontium isopropyl vinyl phosphonate; (16) cadmium n-butyl vinyl phosphonate; (17) and (18) zinc and barium isobutyl vinyl phosphonates; (19) and (20) zinc and magnesium isoamyl vinyl phosphonates; (21) cadmium n-hexyl vinyl phosphonate; and (22) to (29) calcium, zinc, cadmium, magnesium, barium, strontium, cobaltous, and nickelous, b -chloroethyl vinyl phosphonates respectively.  The heating temperatures in the examples vary from 160 DEG  to 225 DEG  C. and the heating is continued until evolution of the alkyl chloride or ethylene dichloride formed ceases.  The products are useful for the stabilization of halogen-containing resins (see Group IV (a)).ALSO:Halogen-containing polymers are stabilized by dispersing therein a metal salt of a vinyl phosphonate of the formula [CH2=CH-P(O)(OR)-O-]nM in which R is an alkyl group having 1 to 6 carbon atoms or a b -chloroalkyl group having two to six carbon atoms, M is a metal having a valency of at least two and n is the valency of the metal M (see Group IV (b)).  The polymers may be derived from vinyl and vinylidene monomers such as vinyl chloride, vinylidene chloride, vinyl chloroacetate, chlorostyrene and chlorobutadienes and these may be polymerized alone or in admixture with each other or with other halogen-containing or halogen-free vinyl or vinylidene monomers, e.g. vinyl esters of carboxylic acids, such as vinyl-acetate, -propionate, -butyrate, and -benzoate; esters of unsaturated acids, e.g. methyl-, ethyl-, propyl-, butyl-, and allyl acrylates and methacrylates; the methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, allyl, methallyl, and phenyl esters of maleic, crotonic, itaconic and fumaric acids and esters of aconitic acid; vinyl aromatic monomers, e.g. styrene, p-ethyl styrene, divinyl benzene, vinyl naphthalene, a -methyl styrene; dienes such as butadiene; unsaturated amides such as acrylic acid amide and acrylic acid anilide; and unsaturated nitriles such as acrylonitrile.  The halogen-containing resin may also be one in which part or all of the halogen has been introduced into a preformed resin, e.g. chlorinated polyvinyl acetate, chlorinated polystyrene, chlorinated polyvinyl chloride, and chlorinated synthetic rubbers.  The vinyl chloride polymers used may be plasticized with phosphate esters such as alkyl diaryl phosphates in which the alkyl group contains 6 to 14 carbon atoms and the aryl groups are phenyl or cresyl.  Other conventional plasticizers may also be present in the halogen-containing resin, e.g. dioctyl phthalate, tricresyl phosphate and butyl phthalyl butyl glycolate. The metal salt of the vinyl phosphonate functions as a light stabilizer and an example is given to show the effect of adding cadmium ethyl vinyl phosphonate and calcium b -chlorethyl vinyl phosphonate respectively, or light stabilizers to polyvinyl chloride plasticized with di-(2-ethylhexyl) phthalate.  Specified metals (M) which may be present in the metal salts of the vinyl phosphonates are magnesium, calcium, strontium, barium, zinc, cadmium, copper, aluminium, iron, cobalt, and nickel.  Other light stabilizers and also heat stabilizers may also be present.ALSO:A metal salt of a vinyl phosphate of the formula: [CH2=CH-P(O)(OR)-O-]nM in which R is an alkyl group having 1 to 6 carbon atoms or a b -chloroalkyl group having 2 to 6 carbon atoms, M is a metal having a valency of at least two, and n is the valency of the metal M (see Group IV(b)) may be used as a light stabilizing agent for chlorinated natural rubber and rubber hydrochloride.  Other light stabilizers as well as conventional additives such as lubricants and colouring materials may be present.  Specified metals (M) are magnesium, calcium, strontium, barium, zinc, cadmium, copper, aluminium, iron, cobalt and nickel.