Article Cite This: Macromolecules XXXX, XXX, XXX−XXX
pubs.acs.org/Macromolecules
Room Temperature Synthesis of Self-Assembled AB/B and ABC/BC Blends by Photoinitiated Polymerization-Induced Self-Assembly (Photo-PISA) in Water Jianbo Tan,*,†,‡ Qin Xu,† Yuxuan Zhang,† Chundong Huang,† Xueliang Li,† Jun He,† and Li Zhang*,†,‡ †
Department of Polymeric Materials and Engineering, School of Materials and Energy, and ‡Guangdong Provincial Key Laboratory of Functional Soft Condensed Matter, Guangdong University of Technology, Guangzhou 510006, China
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S Supporting Information *
ABSTRACT: A series of self-assembled monomethoxypoly(ethylene glycol)-b-poly(2-hydroxypropyl methacrylate)/poly(2hydroxypropyl methacrylate) (mPEG113 -PHPMA/PHPMA) blends are prepared by aqueous photoinitiated polymerizationinduced self-assembly (photo-PISA) of HPMA at room temperature mediated by a binary mixture of mPEG113-CEPA and CEPA (CEPA = 4-cyano-4-(ethylthiocarbonothioylthio)pentanoic acid). High rates of polymerization are observed in all cases, and quantitative monomer conversions can be achieved within 15 min of 405 nm visible light irradiation. Gel permeation chromatography (GPC) measurement confirms good control is maintained under aqueous photo-PISA conditions at different [mPEG113CEPA]/[CEPA] ratios. A morphological phase diagram is constructed for the first time by changing the degree of polymerization (DP) of PHPMA and [mPEG113-CEPA]/[CEPA] ratio. The introduction of homopolymer promotes the formation of higher order morphologies and larger spherical micelles. The obtained AB/B assemblies can be used as seeds for preparing ABC/BC assemblies by seeded polymerization of hydrophilic or hydrophobic monomers. This method provides a facile platform for in situ preparation of various AB/B and ABC/BC assemblies in water at room temperature.
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INTRODUCTION Assemblies of amphiphilic block copolymers have attracted extensive attention due to their broad applications in many research areas, including catalysis, imaging, drug delivery, nanoreactors, and Pickering emulsion.1−6 Typically, block copolymer assemblies are prepared by a two-step cosolvent self-assembly method.7,8 In this method, the block copolymers are first dissolved in a good solvent, and then a poor solvent for one block is added to induce the self-assembly. A variety of morphologies including spheres, worms, vesicles, cubesomes, large compound vesicles, and sunflowers have been prepared by the cosolvent self-assembly method. However, this method can only conduct in diluted solutions (
