Synthesis And Characterization Of Well-defined Soluble Mq_n-Functionalized Polymers Via RAFT Polymerization

In this thesis, three different Alq3-Functionalized polymers were synthesized via RAFT (co)polymerization technique. The optical properties were also investigated.The main work in this thesis is summarized as following:(1) (2-((8-hydroxyquinoline-5-yl) methoxy) ethyl methacrylate, HQHEMA) was successfully synthesized. The copolymerizations of HQHEMA with styrene (St) or methyl methacrylate (MMA) were carried out in the presence of 2-cyanoprop-2-yl dithionaphthalenoate (CPDN), respectively. The polymerization behaviors showed the typical'living'natures by the first-order polymerization kinetics, the linear dependence of molecular weights of the polymers on the monomer conversions with the relatively narrow molecular weight distributions (PDI), and the successful chain extension experiments. The soluble polymers having tris(8-hydroxyquinoline)aluminum (Alq3) and bis(8-hydroxyquinoline) znic(II) (Znq2) units were obtained via complexation reaction between the polymers and aluminium isopropoxide or zinc acetate in the presence of monomeric 8-hydroxyquinoline, respectively, which had strong fluorescent emission at 520 nm. The obtained polymers were characterized by GPC, 1H NMR, UV-vis and fluorescent spectra.(2) Monomer containing azobenzene unit, (6-[4-(4-methoxyphenylazo) phenoxy] hexylmethacrylate (MMAZO), was synthesized and copolymerized with HQHEMA using CPDN as the RAFT agent and AIBN as the initiator. The obtained polymers were coordinated with aluminium isopropoxide in the presence of monomeric 8-hydroxyquinoline and the Alq3-functionalized polymers were obtained. The concentration of the Al3+ was tested by UV-vis standard curve and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The fluorescent intensity of the polymer increased with UV-vis irradiation time.(3) A novel RAFT agent containing 8-hydroxyquinoline unit, O-ethyl S-(8-hydroxyquinolin-5-yl)methyl carbonodithioate (HQ-MADIX), was successfully synthesized and employed to mediate the polymerization of vinyl acetate (VAc). The polymerization behaviors showed the typical'living'natures. The 8-hydroxyquinoline unit was successfully introduced into the end of the polymer chain. The end-capped Alq3-functionalized polymer was synthesized via coordination reaction with aluminium isopropoxide in the presence of monomeric 8-hydroxyquinoline in THF. The UV-vis and fluorescent spectra indicated that the polymer showed the similar optical properties of Alq3 both in the solution and thin film state.