Reactivity of individual stereoisomers based on 4-(3-buten-1-ynyl)-1,2,5-trimethyl-4-piperidinol in radical polymerization

The radical polymerization of individual stereoisomers of 4-(3-buten-1-ynyl)-1,2,5-trimethyl-4-piperidinol (1) was investigated. The reaction order with respect to the monomer and the initiator, and also the kinetic and energetic parameters of the polymerization reaction were determined. The values of constants of polymerization of the stereoisomers were found with the help of the “rotating sector” method. It was established that the spatial orientation of the reactive centres with respect to the six-membered heterocycle influences the reactivity of the monomers and leads to a change of the polymerization rate of the stereoisomers by a factor of about 1,5 to 3. To ascertain the influence of the spatial structure on the reactivity of the stereoisomers, quantum chemical calculations for model structures were performed. By means of IR and Raman spectroscopy it was established that the polymerization of 1 occurs via the double bond of the 3-buten-1-ynyl groups.