Patent GB-694772-A (GB)
Title: Improvements in phosphonic acid esters
IPC: C07F9/32
Filed: 1949-05-20
Abstract: The Specification as open to inspection under Sect. 91 contains the following subject-matter: In a reaction in solution, aqueous media, or bulk, between olefinic and acetylenic compounds and esters of phosphorous or organic phosphinic acids, the unsaturated compounds may polymerize according to the following equation, n reaching as much as 10,000 <FORM:0694772/IV (a)/1> R, R1 and R11 are H or hydrocarbons, R* is hydrocarbon, M is O or S, R0 is R* or MR*, and the reaction is catalyzed by free radicles, of which there are many examples, preferably at 0-200 DEG  C.  Polymerizable olefinic compounds containing more than one ethylene linkage, including conjugated dienes can give products having a plurality of molecules of phosphorus compound.  A long list of substituent groups which may occur in the olefinic, acetylenic or phosphorus compounds is given and a table gives the formul , n being shown as above, of polymerized addition products from numerous such unsaturated compounds with the phosphorus compounds.  This subject-matter does not appear in the Specification as accepted.ALSO:Alkane phosphonic esters are prepared by reaction of an olefine which may be instituted by various groups, with a dialkyl phosphite in presence of ultra-violet light or a peroxidic catalyst, hydrazines azobenzene and metal alkyls, and generally as catalyst, a source of free radicles.  One to three molecules of the olefine may enter into reaction with one of the phosphite. Examples are given of the monomeric product from equal molar proportions of 1-octene, 1-docecene, and allyl dodecyl ether, and diethyl phosphite, and of a mixture of products containing one and 2 mols. of allyl acetate combined with one of diethylphosphite. A table shows the products obtainable from equimolecular proportions of the reactants, or n-proportions of the olefine to one of the phosphite <FORM:0694772/IV (b)/1> where n is 1-3 from the following olefinic compounds: CH2 = CH2, CH2 = CH.CH3, CH2 = C(CH3)2, CH3.CH = CH.CH3, CH2 = CHOCOCH3CH2.CH-C(O).OCH3, CH2 = C(CH3)CONH2, CH2 = CH.CH2.OCO.C6H5, and CH2 = CH(CH2)8.COOCH3.  The dialkyl phosphites include (C4H9O)2PHO and (C8H17O)2PHO.  The Specification as open to inspection under Sect. 91, also refers to the occurrence of polymerization of the olefinic compounds, the products having high molecular weight, and n in the formula being up to 10,000, and includes as olefinic compounds, those readily polymerizable in presence of free radicals, such as styrene, and methyl methylacrylate, those containing more than one ethylenic linkage, such as allyl acrylate, and conjugated dienes, and also acetylenic compounds.  A long list of substituent groups for the olefinic or acetylenic compounds and for the phosphorus esters is given and the phosphorus compounds may contain sulphur in place of oxygen. Equations are given for further types of addition reaction and a table gives the formul  of mono-molecular and polymerized addition products from numerous further olefinic compounds.  This subject-matter does not appear in the Specification as accepted.