A series of well-defined amphiphilic graft copolymers consisting of hydrophilic poly(acrylic acid) backbone and hydrophobic poly(propylene oxide) side chains were synthesized by sequential reversible addition-fragmentation chain transfer (RAFT) polymerization and atom transfer nitroxide radical coupling (ATNRC) chemistry followed by selective hydrolysis of poly(tert-butyl acrylate) backbone. A new Br-containing acrylate monomer, tert-butyl 2-((2-bromopropanoyloxy)methyl) acrylate, was first prepared, and it can be polymerized via RAFT in a controlled way to obtain a well-defined homopolymer with narrow molecular weight distribution (M w /M n =1.06). Grafting-onto strategy was employed to synthesize PtBA-g-PPO well-defined graft copolymers with narrow molecular weight distributions (M w /M n =1.05-1.23) via ATNRC reaction between Br-containing PtBA-based backbone and poly(propylene oxide) with 2,2,6, 6-tetramethylpiperidine-1-oxyl (TEMPO) end group using CuBr/PMDETA or Cu/PMDETA as catalytic system. The final PAA-g-PPO amphiphilic graft copolymers were obtained by the selective acidic hydrolysis of PtBA backbone in acidic environment without affecting the side chains. The critical micelle concentrations in aqueous media were determined by a fluorescence probe technique. Diverse micellar morphologies were formed with varying the content of hydrophobic PPO segment.

A series of well-defined ferrocene-based amphiphilic graft copolymers, consisting of poly(N-isopropylacrylamide)-b-poly(ethyl acrylate) (PNIPAM-b-PEA) backbone and poly(2-acryloyloxyethyl ferrocenecarboxylate) (PAEFC) side chains, were synthesized by the combination of single-electron-transfer living radical polymerization (SET-LRP) and atom transfer radical polymerization (ATRP). A new ferrocene-based monomer, 2-(acryloyloxy)ethyl ferrocenecarboxylate (AEFC), was prepared first and it can be polymerized via ATRP in a controlled way using methyl 2-bromopropionate as initiator and CuBr/PMDETA as catalytic system in DMF at 40 C. PNIPAM-b-PEA backbone was synthesized by sequential SET-LRP of NIPAM and HEA at 25 C using CuCl/Me 6 TREN as catalytic system followed by the transformation into the macroinitiator by treating the pendant hydroxyls with a-bromoisobutyryl bromide. The targeted well-defined graft copolymers with narrow molecular weight distributions (M w /M n \ 1.20) were synthesized via ATRP of AEFC initiated by the macroinitiator. The electro-chemical behaviors of PAEFC homopolymer and PNIPAM-b-(PEA-g-PAEFC) graft copolymer were studied by cyclic voltammetry. Micellar properties of PNIPAM-b-(PEA-g-PAEFC) were investigated by transmission electron microscopy and dynamic light scattering.

A series of well-defined amphiphilic densely grafted copolymers, containing polyacrylate backbone, hydrophobic poly(methoxymethyl methacrylate) and hydrophilic poly(ethylene glycol) side chains, were synthesized by successive atom transfer radical polymerization. Poly[poly(ethylene glycol) methyl ether acrylate] comb copolymer was firstly prepared via the grafting-through strategy. Next, poly[poly(ethylene glycol) methyl ether acrylate]-g-poly(methoxymethyl methacrylate) amphiphilic graft copolymers were synthesized via the grafting-from route. Poly(methoxymethyl methacrylate) side chains were connected to the polyacrylate backbone through stable C-C bonds instead of ester connections. The molecular weights of both the backbone and the side chains were controllable and the molecular weight distributions were in the range 1.38-1.42. Poly(methoxymethyl methacrylate) side chains were selectively hydrolyzed under mild conditions without affecting the polyacrylate backbone to obtain the final product, poly[poly(ethylene glycol) methyl ether acrylate]-g-poly(methacrylic acid) densely grafted double hydrophilic copolymer. Finally, these double hydrophilic copolymers were used as templates to prepare superparamagnetic Fe 3 O 4 /polymer nano-composites with narrow size distributions via an in situ co-precipitation process, which were characterized by FT-IR, TGA, DLS and X-ray diffraction in detail. The size of the nano-composites can be controlled in a certain range by adjusting the length of the poly(methacrylic acid) side chains and the weight ratio of copolymer to Fe 3 O 4 nano-particle used.