Patent GB-963882-A (GB)
Title: Process for the manufacture of unsaturated phosphonic acid dichlorides
IPC: C08F30/02
Filed: 1960-06-20
Abstract: Alkene (or aryl substituted alkene) phosphonic acid dichlorides are obtained by splitting off hydrogen halide from a halogen alkane (or aryl-substituted alkane) phosphonic acid dichloride either chemically with the aid of a tertiary amine or thermally, and isolating the alkene (or aryl-substituted alkene) phosphonic acid dichloride. The reaction is preferably carried out in the absence of water and the halogen alkane phosphonic acid dichloride is suitably one having a straight or branched alkyl group of 2 to 8 carbon atoms and preferably of 2 to 4 carbon atoms substituted by a halogen atom which is preferably in beta-position to the phosphonic acid group. The tertiary amine may be a trialkylamine, a dialkyl aniline, tricyclohexylamine or a heterocyclic base, e.g. pyridine, N-methyltetrahydroquinoline or N-ethylmorpholine.  When a tertiary amine is used the reaction can be carried out in the presence of an inert organic solvent or diluent, and is preferably carried out at room temperature although higher or lower temperatures, e.g. from 0 DEG  to 80 DEG C. may be used. The hydrogen halide can also be split off in the presence of phosphorus trichloride and/or phosphorus oxychloride, e.g. the mixture containing beta-chlorethane phosphonic acid dichloride obtained from the reaction of ethylene, phosphorus trichloride and oxygen as in Specification 963,881 may be used directly in the process. Suitable temperatures for the thermal process of splitting off hydrogen halide are from 60 DEG  to 300 DEG C., preferably 120 to 270 DEG C.  The heating process may be carried out under normal pressure or under reduced or elevated pressure and should be continued until the evolution of hydrogen halide is terminated. Care should also be taken to eliminate the hydrogen halide continuously from the reaction space, e.g. by vigorous boiling under reflux, if necessary under reduced pressure, or by passing a dry inert gas, e.g. nitrogen, carbon dioxide, or a rare gas, through the reaction vessel. The thermal process may suitably be carried out in such a manner that the hydrogen halide is removed continuously from the reaction space and the unsaturated dichloride product is separated continuously by distillation as it is formed e.g. by using a suitable column, the hydrogen halide and the unsaturated dichloride being continuously obtained at the head of the column which may be a packed column.  The thermal process can also be carried out a temperature above the boiling point of the saturated dichloride under normal pressure, e.g. by passing the dichloride in the vaporous state through a zone heated to the desired reaction temperature, either alone or together with a dry inert gas which may be preheated to accelerate the process.  The thermal process may also be carried out in an inert solvent, e.g. dimethyl naphthalene or diethyl diphenyl, having a boiling point higher than that of the reaction product and the solvent may be used as an entraining agent for the unsaturated dichloride product.  In another method the saturated dichloride is heated under pressure at a temperature above the boiling point under normal pressure and the hot liquid released by means of a valve whereby the halogen alkane phosphonic acid dichloride is decomposed into hydrogen halide and the unsaturated dichloride. The dichloride products can be converted to the corresponding unsaturated phosphonic acids by hydrolysis with water, aqueous alkalies or acids; esters of the unsaturated phosphonic acids with alcohols or glycols may also be obtained. The unsaturated phosphonic acid dichlorides, the free acids and the esters thereof may be polymerized or co-polymerized with suitable monomers to yield valuable flame-resistant polymers. Examples are given for the production of vinyl- and propenephosphonic acid dichlorides from beta-chloroethane- and chloro-propane phosphonic acid dichlorides respectively.