Patent GB-947924-A (GB)
Title: Organic phosphorus compounds and process of preparing same
IPC: C07F9/146
Filed: 1960-05-17
Abstract: Compositions comprising phosphorus- and chlorine-containing compounds are prepared by mixing a chlorinated olefin polymer having a chlorine content of 0.2 to 20% by weight, e.g. monochlorotriisobutylene, with from 0.2 to 20 equivalents of an aromatic phosphorochloridite and heating the resulting mixture to a temperature which is at least 125 DEG C. but is below the decomposition temperatures of the components of the mixture.  The phosphorochloridite may be prepared in situ by the reaction of phosphorus trichloride with a phenol or thiophenol. In Example (2) the reaction of monochlorotriisobutylene is described. The compositions of the invention may be hydrolysed by blowing with steam, and the hydrolysis products reacted with excess basic metal compound, e.g. calcium or barium oxide or hydroxide, blown with carbon dioxide and filtered to provide lubricating oil additives. The compositions may also be used as insecticides.  Aromatic phosphorochloridites of formulae ArXPCl2 and (ArX)2PCl where Ar is an aromatic group and X is oxygen or sulphur may be prepared by reacting phenols or thiophenols with phosphorus trichloride.  X may be phenyl or naphthyl, or alkyl or halogen substituted phenyl or naphthyl, e.g. butylphenyl, hexylphenyl, octylphenyl, decylphenyl, dodecylphenyl, hexadecylphenyl, eicosylphenyl, chlorophenyl, dichlorophenyl, chloronaphthyl or dichloronaphthyl. In examples (A) heptylphenyl phosphorodichloridite is prepared by adding heptylphenol to heated phosphorus trichloride over a period of 2-5 hours and refluxing and (B) phenyl phosphorodichloridite and diphenyl phosphoromonochloridite are prepared by adding phenol portionwise to phosphorus trichloride, heating the mixture and fractionally distilling the residue.ALSO:Compositions comprising phosphorus- and chlorine-containing compounds are prepared by mixing a chlorinated predominantly aliphatic olefin polymer having a chlorine content of 0.2 to 20% by weight with from 0.2 to 20 equivalents of an aromatic phosphorochloridite and heating the resulting mixture to a temperature which is at least 125 DEG C. but is below the decomposition points of the components of the mixture.  The phosphorochloridite may be formed in situ by reaction of phosphorus trichloride with a phenol or thiophenol.  Specified polymers are homopolymers and copolymers of isobutylene, ethylene, propylene, amylene, isoprene and butadiene.  The copolymers may comprise a minor proportion of aromatic units, e.g. of styrene and substituted styrenes.  The products may be hydrolysed by blowing with steam.  The hydrolysis products may be reacted with excess basic metal compound, e.g. calcium and barium oxides and hydroxides, and the reaction mixture blown with carbon dioxide and filtered. Examples describe the reaction of chlorinated polyisobutylenes with (1) diphenyl phosphoromonochloridite, (3) beta naphthyl phosphorodichloridite, (4 and 6) heptylphenyl phosphorodichloridite, (5) t.-butylphenyl phosphorodichloridite, (11 and 12) phenyl phosphorodichloridite, (13) 2,21-thiobis-(4-methyl-6-t. butyl phenol) and phosphorus trichloride, (14) diisobutyl-phenol-formaldehyde condensate and phosphorus trichloride, (15 and 16) heptylphenol and phosphorus trichloride and (17) thiophenol; and of heptylphenyl phosphorodichloridite with (7) chlorinated isobutylene-styrene copolymer, (8) chlorinated polyethylene, (9) chlorinated isobutylene-isoprene copolymer and (10) chlorinated polypropylene, the products of Examples 13, 14 and 15 being steam hydrolyzed. The metal derivatives may be used as lubricating oil additives, and aqueous emulsions of kerosene solutions of the products may be used as insecticides.ALSO:Lubricating compositions comprise a mineral lubricating oil and compositions prepared by mixing a chlorinated olefin polymer having a chlorine content of 0.2 to 20% by weight with 0.2 to 20 equivalents of an aromatic phosphoro-chloridite of formula ArXPCl2 or (ArX)2PCl where Ar is an aromatic group and X is oxygen or sulphur, or the precursors thereof (phosphorus trichloride and a phenol or thiophenol) heating the mixture to a temperature which is at least 125 DEG  C. but is below the decomposition temperature of the components of the mixture, hydrolysing the product by blowing with steam and reacting the hydrolysis product with a basic metal compound.  Specified polymers are homopolymers and copolymers of isobutylene, ethylene, propylene, amylene, isoprene and butadiene. The copolymers may contain a minor proportion of aromatic units, e.g. styrene and substituted styrenes.  Specified basic metal compounds are the oxides and hydroxides of calcium and barium.  The reaction of the hydrolysis product therewith may be effected in the presence of promoters, e.g. phenols, alcohols, nitro compounds and oximes, and the product blown with carbon dioxide and filtered. In an example, chlorinated polyisobutylene is reacted with phosphorus trichloride and heptyl phenol and the product hydrolysed by blowing with steam. The hydrolysis product is added to a mineral oil together with barium oxide and heptyl phenol and the resulting product blown with carbon dioxide and filtered.ALSO:Insecticidal compositions comprise phosphorus- and chlorine-containing compounds prepared by mixing a chlorinated olefin polymer having a chlorine content of 0.2 to 20% by weight with 0.2 to 20 equivalents of an aromatic phosphorochloridite of formula ArXPCl2 or (ArX)2PCl where Ar is an aromatic group and X is oxygen or sulphur, or the precursors thereof (phosphorus trichloride and a phenol or thiophenol) and heating the resulting mixture to a temperature which is at least 125 DEG  C. but is below the decomposition temperatures of the components of the mixture.  A 10% solution in kerosene of the reaction product of chlorinated polyisobutylene and heptylphenyl phosphorodichloridite is emulsified in water with the aid of a condensate of diamylphenol and propylene oxide to provide an emulsion for spraying vegetation infested with red spider mites.