Divinyl phosphonates

Functionalized polymers are of interest in a variety of applications including but not limited to fire retardants, selective sorption resins, chromatography media, controlled release devices and phase transfer catalysts. This research has been conducted in an effort to functionalize a polymer with a variety of different reactive sites for use in membrane applications. These membranes are to be used for the specific separation and removal of metal ions of interest. A porous support was used to obtain membranes of a specified thickness with the desired mechanical stability. The monomer employed in this study was vinylbenzyl chloride, and it was lightly crosslinked with divinylbenzene in a photopolymerization. Specific ligands incorporated into the membrane film include dimethyl phosphonate esters, isopropyl phosphonate esters, phosphonic acid, and triethyl ammonium chloride groups. Most of the functionalization reactions were conducted with the solid membrane and liquid reactants, however, the vinylbenzyl chloride monomer was transformed to vinylbenzyl triethyl ammonium chloride prior to polymerization in some cases. The reaction conditions and analysis tools for uniformly derivatizing the crosslinked vinylbenzyl chloride / divinyl benzene films are presented in detail. 

Other Studies. - The P NMR chemical shifts of alcohols, carboxylic acids and phenols phosphitylated with 2-chloro-4,4,5,5-tetramethyl-dioxaphospholane have been correlated with substituent effects of phenols. P NMR spectroscopy has also been used to study activation pathways of aryl H-phosphonate ester condensation reactions, the conversion of allenyl and divinyl phosphines to 1- and 2-phosphadienes, the reaction of tetraphosphorus decasulfide with dialkyl disulfides, the reaction of phosphine with cyclic olefins, the chemical shift tensors of powder samples of phosphole derivatives, the reactions of alcohols and mercaptans with tetraphosphorus trichalcogen diiodides, the structure of aminomethanebisphosphonic acids, and reactions of 00-di-(2-ethylhexyl)dithiophosphoric acids. ... 

Divinyl ether itself presents a fairly complex case one detailed study claimed that the decomposition of the ether-phosphorus pentachloride complex with SO2 yields the phosphonic dichlorides 78-80 together with vinyl dichlorophosphate whilst a more recent study demonstrated that treatment of the intermediate complex with SO2 yielded 81, and with Asp3 yielded 82 in each case, a co-product was [2-(l-chloroethoxy)vinyl]phosphon-ic dichloride (78). The action of phosphorus pentachloride on the sulphide 83 presumably proceeds through 84, although in the work-up procedures thus far adopted, dehydrohalo-genation occurs to give 85 (R = Cl) ... 

Covalent cross-linking of PBI membranes is another possibility for improvement of their thermal, dimensional, and chemical stability. For example, the PBI can be cross-linked in the imidazole moiety with a low-molecular compound such as bisphenol A-diepoxide [15], divinyl sul-fone [16], terephthaldehyde [17], a-dibromo-p-xylene [18], or dichloromethyl phosphonic acid... 

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