Synthesis of star poly(N-isopropylacrylamide) by β-cyclodextrin core initiator via ATRP approach in water

Star poly(N-isopropylacrylamide) (PNIPAAm) based on a β-cyclodextrin (β-CD) core macroinitiator was synthesized by means of atomic transfer radical polymerization (ATRP) in water using copper(I)/2,2bipyridyl complex as a catalytic system at temperature above the lower critical solution temperature (LCST) of the PNIPAAm. The macroinitiator was prepared by the transesterification reaction of the (β-CD) with 2-bromopropionyl bromide. The LCST of the samples upshifts slightly when the absolute molecular mass of the star PNIPAAm increases. Over the phase transition, the solutions became bluish opalescent due to formation of a heterogeneous phase system consisting of collapsed polymer particles in water. Atomic force microscopy and dynamic light scattering analyses indicated two populations of self-assembled polymer structure: a larger population and a smaller population. The smaller size suggests to self-assembly of polymer micelles and the large one corresponds to aggregates of polymer micelles or star polymers coupled. Polydispersity of the star PNIPAAm ranged from 1.60 to 4.04 within 15 h of reaction, which was attributed to the collapse of the PNIPAAm chains at temperature above the LCST that causes a decrease of the polymer reactivity. This was also attributed to the star-star coupling that generates twice the value of the polydispersity for any time before 15 h of polymerization.