By Anionic Polymerization And Atom Transfer Radical Polymerization Combining The Preparation Of New Comb Polymers

As a kind of polymer with unique chain architectures, comb-like polymers have been used as thermoplastic elastomers, separated membrane, hydrogel, compatibilizer, and drug delivery carriers etc. In addition, they can also be used to prepare nanomaterials. Therefore, the design of chain architecture of comb-like polymers has attracted more and more interest.Well-defined comb-like polymers are usually synthesized by living polymerizations. Among all the living polymerization methods, anionic polymerization has been extensively studied, and is the best method to design chain architectures. However, anionic polymerization can only polymerize a limited range of monomers. Atom transfer radical polymerization (ATRP) has been developed late, but its reaction condition is gentle. More importantly, it can polymerize a wide range of monomers.In this thesis, we described the synthesis and characterization of three comb-like polymers with novel chain architectures by combination of living anionic polymerization and ATRP, including highly branched comb-like polymers, comb-like ionomers, and centipede-like copolymers. The brief contents and results are as follows:1. ATRP of 4-vinylbenzyloxy benzophenone followed by Wittig reaction led to polystyrene backbone with 1, 1-diphenylethene (DPE) pendent groups. In addition, the polystyrene backbone with epoxy pendant groups was also prepared by the similar method. These backbone polymers were characterized by ~1H nuclear magnetic resonance (~1H NMR) spectroscopy, Fourier-transform infrared (IR) spectroscopy, and gel permeation chromatography (GPC) respectively in detail. The results showed that backbone polymers with DPE and epoxy pendant groups, having controlled molecular weight and narrow distribution, were obtained successfully.2. The novel highly branched comb-like polystyrenes with one side chain per repeating unit were synthesized by coupling reaction of living polystyrene carbanions (PSLi) with DPE pendant groups of polystyrene backbone. The resulting polymers were characterized by ~1H NMR, IR, GPC, and SLS in detail. The effects of [PSLi] and...