Patent GB-1015616-A (GB)
Title: Azophosphenate compounds
IPC: C08F4/04
Filed: 1963-01-28
Abstract: One or more ethylenically unsaturated monomers containing a CH2 = C< group are polymerized under the influence of a free radical initiator which is a compound of the general formula <FORM:1015616/C3/1> wherein R1 represents hydrogen or an alkyl, aryl, alkylaryl or cycloalkyl group containing up to 12 carbon atoms and R2 and R3, when separate groups, each represent an alkyl, cycloalkyl, alkyl cycloalkyl, arylalkyl, arylalkenyl, alkylarylalkyl or aryl group containing up to 12 carbon atoms or a C3-C12 alkenyl group or one or each R2 group is joined to its adjacent R3 group to form an alicyclic ring of 3 to 9 carbon atoms, the R1 radicals being the same or different and the two pairs of R2 and R3 being the same or different. Examples are given relating to the polymerization of styrene, vinyl acetate, methyl methacrylate and isopropyl methacrylate and the co-polymerization of acrylonitrile and acrylamide.ALSO:The invention comprises compounds of the general formula <FORM:1015616/C2/1> wherein R1 represents hydrogen or an alkyl, aryl, alkylaryl or cycloalkyl group containing up to 12 carbon atoms and R2 and R3, when separate groups, each represent an alkyl, cycloalkyl, alkylcycloalkyl, arylalkyl, arylalkenyl, alkylarylalkyl or aryl group containing up to 12 carbon atoms or a C3-C12 alkenyl group or one or each R2 group is joined to its adjacent R3 group to form an alicyclic ring of 3 to 9 carbon atoms, the R1 radicals being the same or different and the two pairs of R2 and R3 being the same or different. The esters of the above general formula may be prepared by reacting an a -aminoorganophosphonate of the general formula <FORM:1015616/C2/2> with a stable hypochlorite and the acids of the first general formula may be obtained by hydrolyzing the corresponding azo ester.  The hypochlorite may be prepared in situ by passing chlorine into an aqueous system of an alkali metal hydroxide or an alkaline earth hydroxide. It is preferred to employ an excess of hypochlorite, to use hypochlorite concentrations of about 3 to 5% by weight and to have an excess of base present in the reaction system.  The reaction may be performed at -30 DEG  to +35 DEG  C. entirely in aqueous solution although C1-C4 alkanols may be employed to increase the solubility of the reactants.  On heating the compounds of the invention decompose with the evolution of nitrogen and the formation of free radicals which may combine to form 1,2-dihydrocarbyloxyphosphinyl-ethanes or, in the presence of ethylenically unsaturated polymerizable monomers, may provide an initiator for polymerization.  O,O1 - Diethyl 1 - amino - 1 - cyclopropylethyl phosphonate is prepared by passing dry ammonia into a stirred mixture of diethyl phosphite and methylcyclopropyl ketone for 1 hour at room temperature and then for 5 hours a 50 DEG  C. O,O1 - Diethyl 1 - amino - cyclohexylphosphonate is prepared by passing dry ammonia into a stirred mixture of diethyl phosphite and cyclohexanone for 2 hours and 28 DEG  to 43 DEG  C. and then at 50 DEG  C. for 4 1/2 hours.  O,O1 - Diethyl 1 - amino - 1 - phenylethylphosphonate is prepared by reacting diethyl phosphite and acetophenone with ammonia gas for 4 1/2 hours at 50 DEG  C. and then 2 3/4 hours at 100 DEG  C.