Cyclopolymerization of alkyl alpha-(hydroxymethyl)acrylate (RHMA) ether dimers via atom transfer radical polymerization (ATRP)

Abstract

Thermal stability, high glass transition temperatures and limited shrinkage duringpolymerization as compared to non-cyclic linear polymers are considered to beadvantageous properties of the polymers with high degrees of cyclization derived from cyclopolymerization of alkyl a-(hydroxymethyl)acrylate (RHMA) ether dimers. Thesecyclopolymers have been previously synthesized by conventional free radicalpolymerization. The conventional radical polymerization processes often yield polymerswith ill-controlled molecular weights and high polydispersities because of irreversible termination reactions. However, alkyl a-(hydroxymethyl)acrylate (RHMA) ether dimershave never been cyclopolymerized by controlled radical polymerization techniques.The purpose of this investigation is to get highly cyclized living aliphaticpolymers with controlled molecular weights and low polydispersities. In order to attain this goal, ATRP was applied to alkyl a -(hydroxymethyl)acrylate (RHMA) ether dimersas monomer. CuBr/PMDETA catalyst system was employed and polymerizations werecarried out in xylene. The results indicate that the desired cyclopolymers can be obtainedby ATRP technique.