Atom Transfer Radical Polymerization Of (Meth) Acrylates Under Microwave Irradiation And Conventional Heating Processes

In this thesis, we tried to use microwave irradiation (MI) in atom transfer radical polymerization (ATRP) of methyl methacrylate by the refluxing of solvent to control the polymerization temperatures in our self-improved domestic microwave oven. ATRPs of MMA under different temperatures using p-TsCl/CuBr/bpy, AIBN/CuBr2/bpy/CH3CN and AIBN/CuCl/bpy initiating systems were successfully carried out under MI. In addition. living radical graft polymerization of methyl methacrylate and butyl acrylate onto Poly (vinyl chloride-co-vinyl acetate) (PVCAc) catalyzed by CuSCN/PMDETA and CuCl/bpy in the solvent N. N-dimethylformamide(DMF) was successfully carried out under conventional heating (CH) process. The graft copolymers were hydrolyzed and their swelling capacity was measured.It was found that plots of In ([M]0/[M]) vs. time and molecular weight evolution vs. conversion showed a linear dependence by the kinetic studies of (R)ATRPs of MMA under MI, and that the "living"/controlled nature of the polymerization systems was not changed under PMI or MI by a series of characterizations for polymers obtained (i.e., chain extension, analysis of end-groups and stereochemistry of PMMA). Under identical polymerization conditions, the apparent constant of propagation (kpapp) under PMI or MI were 5-12 times larger than that under CH, indicating a significantly increase of the polymerization rates under MI. Furthermore, the apparent initiator efficiencies under PMI or MI were improved, indicating that the control over molecular weights under Ml was also improved. And for p-TsCl/CuBr/bpy initiating system, the polydispersities of polymer under MI are narrower than that under CH. It was noted that besides increasing polymerization rate, MI could greatly lower the amount of catalyst used.Living radical graft polymerization of MMA and BA onto PVCAc catalyzed by CuSCN/PMDETA or CuCl/bpy, could be carried out in DMF (50%, v/v) under CH. Aftercopolymerization, the graft copolymer was hydrolyzed, we found that HP(PVCAc-g-PBA) not only swell in organic solvents like DMF, but also swell in water. In addition, the hydrolyzed copolymer showed some pH sensitive character.