Patent GB-727213-A (GB)
Title: Dialkyl monoaryl esters of ortho-phosphoric acid
IPC: C07F9/12
Filed: 1951-11-05
Abstract: Phosphate esters having the formula <FORM:0727213/IV (a)/1> in which R1 is an alkyl group terminating in a methylene group, R2 and R3 are alkyl groups and R4 is a substituted or unsubstituted aryl group (see Group IV (b)) are stated to be useful as plasticizers for vinyl halide-containing polymers such as polyvinyl chloride or vinyl chloride copolymerized with unsaturated material copolymerizable therewith, and also as plasticizers for cellulose esters and ethers and cellulose nitrate.  The esters may be used as the sole plasticizer for the vinyl halide-containing polymer or they may be used with one or more known plasticizers such as di-(2-ethylhexyl) phthalate, dibutyl phthalate, tricresyl phosphate, alkyl diaryl phosphates; tri-(2-ethylhexyl) phosphate, dioctyl adipate, dibutyl sebacate and alkyl benzyl phthalates.  Copolymers referred to are those of vinyl chloride with vinylidene chloride; vinyl esters of carboxylic acids, e.g. vinyl acetate, propionate, butyrate or benzoate; esters of unsaturated acids, e.g. alkyl or alkenyl acrylates such as methyl, ethyl, propyl, butyl and allyl acrylates and the corresponding esters of methacrylic acid; vinyl aromatic compounds, e.g. styrene, ortho- and para-chlorostyrene, 2,5-dichlorostyrene, 2,4-dichlorostyrene, para-ethyl styrene, divinyl benzene; alpha-methyl styrene; vinyl naphthenate; dienes such as butadiene and chloroprene, amides such as the amide and anilide of acrylic acid, nitriles such as acrylonitrile; esters of alpha-beta unsaturated carboxylic acids, e.g. the methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, allyl, methallyl, and phenyl esters of maleic, crotonic, itaconic and fumaric acids, and particularly diethyl maleate.  Similar polymers in which the vinyl chloride is replaced wholly or in part by other vinyl halides, e.g. the bromide or fluoride, may also be used.  Examples describe the preparation of plasticized compositions from a mixture of polyvinyl chloride and 2-ethylhexyl capryl phenyl phosphate or 2-ethylhexyl secondary-butyl cresyl phosphate.ALSO:The invention comprises as new compounds dialkyl monoaryl esters of orthophosphoric acid having the formula <FORM:0727213/IV (b)/1> in which R1 is an alkyl group terminating with a methylene group and preferably containing 1 to 18 carbon atoms, R2 and R3 are alkyl groups, preferably alkyl groups which together contain not more than 17 carbon atoms and R4 is a substituted or unsubstituted aryl group.  The esters may be obtained by reacting a monoalkyl phosphoryl chloride having the formula R1OPOCl2 and a secondary alkanol R2R3CHOH to form a dialkyl phosphoryl monochloride and reacting the resulting dialkyl phosphoryl monochloride with an alkali metal salt of a substituted or unsubstituted phenol which is preferably used in the form of an aqueous solution or aqueous slurry.  The reaction to form the ester may be carried out in aqueous solution at -10 DEG  to 50 DEG  C., preferably at 0 DEG  to 25 DEG  C. and is preferably effected by adding the dialkyl phosphoryl monochloride to the alkali metal phenate solution.  The phenol used may be phenol itself or a phenol substituted with one or more inert substituents, e.g. chlorine, bromine, iodine and fluorine, alkyl groups such as ethyl, propyl, isopropyl, butyl and octyl, aryl groups such as phenyl, nitro groups, and alkoxy groups such as methoxy, ethoxy, propoxy and isopropoxy. Naphthols which may be unsubstituted or substituted with one of the above inert substituents may also be used.  Examples describe the preparation of n-butyl sec.-tetradecyl phenyl phosphate, n-hexyl sec.-amyl p-cresyl phosphate, 2-ethylhexyl sec.-butyl phenyl phosphate, 2-ethylhexyl sec.-butyl cresyl phosphate, 2-ethylhexyl sec.-butyl p-chlorophenyl phosphate, 2-ethylhexyl capryl phenyl phosphate, methyl capryl phenyl phosphate, n-hexadecyl isopropyl phenyl phosphate, and n-hexadecyl sec.-tetradecyl phenyl phosphate. The dialkyl phosphoryl mono-chloride used in each case is prepared by the procedure described in Specification 715,336.  The esters are stated to have utility as synthetic lubricants, functional fluids, damping fluids, bases for greases, hydraulic fluids (see Group XXIX), as film-forming addition agents for extreme pressure lubricants (see Group III), as the liquid medium for filters for air conditioning systems, and as plasticizers for cellulose esters and ethers and cellulose nitrate and particularly for vinyl halide-containing polymers (see Group IV (a)).ALSO:Dialkyl monoaryl esters of orthophosphoric acid have the formula: <FORM:0727213/III/1> in which R1 is an alkyl group terminating in a CH2 group, R2 and R3 are alkyl groups, and R4 is a substituted or unsubstituted aryl group (see Group IV (b)), are stated to be useful as film-forming addition agents for extreme pressure lubricants.