Living Radical Polymerization With Halogen Existent

The thesis consists of two parts: 1.Atom transfer radical polymerization (ATRP) of MMA and St initiated by AIBN/I2/DMF in situ system; 2.polyvinyl acetate terminated with iodine (PVAc-I) and iodo-terminated polymethyl methacrylate (PMMA-I) were as macro-transfer agents and macro-initiator, which were synthesized by degenerative transfer (DT) method in the presence of AIBN, then to prepare copolymers of PVAc-b-MMA and PMMA-b-VAc by DT and ATRP methods.1. The product of AIBN/Br2/DMF in situ system was as the initiator of the atom transfer radical polymerization to initiate methyl MMA and St. Three complexes: CuCl/PMDETA,FeCl2/MA5—DETA and FeCl2/PPh3 were as catalyst respectively. When the moles of AIBN and Br2 were same, remnant bromine existed in initiator system. So there was an induced period before polymerization. After induced period polymerization started. In all three catalyst system, the linear proportionality of the molecular weights to the conversions and straight lines observed in ln (M0/Mt) (where M0 and Mt are the symbols for monomer contents at the beginning and at any time, respectively) versus time plots indicated typical controlled living polymerization characteristics. The polydispersities of the polymer were narrow (MWDs were around 1.19-1.44). The results of analysis for terminate group of obtained polymer by 1H-NMR.2. DT method was applied to prepare iodo-terminated polymethyl methacrylate and polyvinyl acetate. Then they were used as macro-transfer agents and macro-initiate to synthesize copolymers in DT and ATRP methods. We found when PVAc-I was as macro-transfer agents, the polydispersities of the block copolymers were narrow and the molecular weight of copolymers was according with theory ones. On other hand, when PMMA-I was as macro-transfer agents, the resulted copolymers also had a narrow polydispersities but initiator efficiency was low. This is reasonable because...