Host-Guest Interaction Mediated Polymerization-Induced Self-Assembly In Water

Recently,polymerization-induced self-assembly(PISA)has attracted general interests as a promising strategy for the mass production of polymeric nanomaterials.The block copolymer self-assemblies simultaneously in situ the polymerization in a PISA process.Thus,BCP nanoparticles are fabricated in one-step and in concentrated solution.However,the primary requirement of PISA is that the polymerization of soluble monomers produce insoluble polymers in the solvent,which limits the selection of monomer/solvent for the practice of PISA.Especially for water,there are limited monomers suitable for aqueous dispersion polymerization and PISA.In this thesis,we developed the aqueous PISA for hydrophobic monomers,based on host-guest interaction.By host-guest complexation with randomly methylated-b-cyclodextrin(CD),waterimmiscible monomers are dispersed in water for PISA,including styrene(St),methacrylates,and acrylates.Length tunable polymer nanotubes are acquired by the aqueous dispersion polymerization of CD/St in one-step.And this aqueous PISA mediated by host-guest interaction could readily introduce functional hydrophobic group(e.g.azobenezene group)into aqueous nanomaterials,using functional hydrophobic monomers.The main contents of this thesis are as follows:(1)The host-guest interaction mediated aqueous PISA has been demonstrated using styrene as the hydrophobic monomer and CD as the host.We systemcatically investigated the host-guest complexation,the solubility,and the polymerization of CD/St,and the regulation of CD over self-assembly.Kinetically trapped lamellae and nanotubes are accessed.(2)By the kinetic regulation over self-assembly,we precisely programmed the structure and the size of nanoparticles.Monodispersed,length tunable nanotubes are acquired by tuning the rate of polymerization.We find that the kinetic of polymerization determines the fusion and reorganization of assemblies.The effects of initiator,temperature,and rate of polymerization is studied for tuning the number of aggregation of assemblies,and controlling the size of nanoparticles.(2)The host-guest interaction mediated aqueous dispersion polymerizations of azocontaining monomer,fluoro-containing monomer,acrylates and methacrylates are studied.The aqueous PISA of 11-[4-(4-Butylphenylazo)phenoxy]undecyl Methacrylate produces cubic particles.This strategy can be used for the synthesisof functional nanomaterials in aquesous dispersion by incorporating functional hydrophobic acrylates and methacrylates during the PISA process.