Influence of structure on polymerization rates and Ca-binding of phosphorus-containing 1,6-dienes

Photo- and thermal-polymerizations of 4-diethoxyphosphoryl-2,4,6-tris(ethoxycarbonyl)-l, 6-heptadiene, 4,4-bis(diethoxyphosphoryl)-2,6-bis(t-butoxycarbonyl)-1,6-heptadiene and 4-diethoxyphosphoryl-4-ethoxycarbonyl-2,6-bis(t-butoxycarbonyl)-1,6-heptadiene monomers and their phosphonic and carboxylic acid derivatives were investigated to understand the effect of the cyclic monomer structure on their polymerization reactivity. A strong effect of the substituents at positions 2,4 and 6 of the monomers on polymerization rate was observed. The polymerizability of the monomers was successfully correlated with the (CNMR)-C-13 chemical shifts of the vinyl carbons. Conversion values were consistent with the T-g being a measure of the flexibility of a monomer. The monomers containing phosphonic acid groups were soluble in water and ethanol. The acidic nature of the aqueous solutions of these monomers is expected to give them etching properties, important for dental applications. The interaction of the acid monomers with hydroxyapatite was investigated using (CNMR)-C-13 technique.