[Study of "living" radical polymerization by FTIR in situ]

Three types of living radical polymerization processes were monitored by means of FTIR spectrometer with handful diamond detector called as Dicomp in situ. It was found that both styrene and styrene/hydroxylpropyl methyacrylate (HPMA) could polymerize according to stable free radical polymerization (SFRP) mechanism in presence of 4-hydroxyl tetramethypiperidiyl-1-oxy(HTEMPO). For styrene/HPMA system, the styrene and HPMA conversion monitored by FTIR were linear with increase of molecular weight, but it gave longer induction period compared with that for St bulk polymerization. It was related to the hydrogen-transfer reaction between the propagating radicals with the end HPMA unit and HTEMPO. Furthermore, This following method in situ could be introduced into monitoring heterogeneous polymerization of styrene during atom transfer radical polymerization (ATRP). The apparent kinetics was found to be about zero order and not 1.0 order, due to propagating on the complex including radicals, CuX and bpy in heterogeneous interface. The polymerization rate will be not related to the St in bulk St phase.