Basic and Applicative Studies on Controlled Radical Polymerization

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[I] Mechanisms and Kinetics of Controlled Radical PolymerizationsThe mechanisms and kinetics of variants of controlled radical polymerization (CRP) were experimentally and theoretically studied and systematized. Main results include :(1) Two general GPC methods for determining the rate constants of activation in CRPs were established.(2) The GPC methods were applied to various CRP systems, and the activation rate constants and activation mechanism were established. In particular, it was confirmed that the thermal dissociation for the nitroxide system, the exchanging chain transfer for the PS-I and PS-SCSMe systems, and the atom transfer for the bromide/CuBr system are virtually the only mechanism of activation for the respective systems.(3) A general equation describing the polymerization rates of CRP systems was developed and partly confirmed by experiments[II] Precision Synthesis of New Polymer Materials by CRPs(1) Low-polydispersity copolymers (randoms, blocks, polymacromonomers) and homopolymers (glucose residue-carrying styrenics, acrylates and methacrylates, fullerene-terminated polymers) with well-defined structure were synthesized mostly for the first time.(2) Polymer gels, structurally much more homogeneous than conventional ones, were prepared for the first time.(3) Polymer brushes with controlled chain length and chain length distribution, densely grafted on a silicon wafer, were successfully prepared for the first time.