Journal of Polymer Science Part A: Polymer Chemistry

A series of three polymerizable oligo phenylene ethynylenes on the basis of substituted methacrylates was synthesized and subsequently polymerized. The optical behavior of all three monomer units was tuned by the choice of the substituents on the conjugated side chains. The donor and acceptor group containing polymers showed resonant energy transfer from the donor to the acceptor groups.

Experimental results of the novel imine base/isocyanate mediated (IBI) radical polymerization are reported. Several factors influence IBI radical polymerization of vinyl monomers. Thus, the effects of the initiator combination choice and the reaction temperature on the whole polymerization process are discussed. Thereby, brutto polymerization rate constants and the corresponding activation energies of various IBI polymerizations have been evaluated whereas a classification was possible. By means of ESI MS and MALDI TOF MS spectra, presumptions on the radical formation process were made.

The N-(trimethylsilyl)bis(trifluoromethanesulfonyl)imide-catalyzed (Me₃SiNTf₂-catalyzed) group transfer polymerization (GTP) has been studied for living and stereospecific polymerization of methyl methacrylate (MMA). On the basis of livingness of the Me₃SiNTf₂-catalyzed GTP of MMA, the well-defined syndiotactic-rich and stereoblock 3-, 4-, and 6-armed star-shaped poly(methyl methacrylate)s (PMMA) were successfully synthesized by just controlling the polymerization temperature via the Me₃SiNTf₂-catalyzed GTP of MMA.