A novel strategy for preparation of multiple nanostructural materials, which is the creation of such materials directly from controlled radical dispersion polymerization in one pot, has been developed. In the formation of polymeric nanomaterials, the chain length ratio of the hydrophobic to hydrophilic blocks is altered continuously, which induces two phase transitions, phase separation to form spherical micelles and re-organization of the resulting spheres to yield multiple morphologies including nanorods, nanotubes, vesicles and doughnuts. This is quite different from self-assembly of the block copolymer in a selective solvent, where nature and solubility parameter of the solvents are changed. In the reversible addition-fragmentation chain transfer (RAFT) polymerization of styrene in methanol using poly(4-vinylpyridine) as macro RAFT agent, the resultant polymeric nanomaterials with various morphologies coexisted generally, however, uniform nanowires and vesicles could be prepared by appropriately selecting concentration of monomer and feed ratio, as well as by strict control of reaction conditions. One advantage of this strategy is that the nanomaterials with a concentration as high as 0.5 g mL−1 can be achieved, this provides possibility for studying extensive applications of the various nanomaterials.
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