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Well‐defined amphiphilic polymethylene‐b‐poly(acrylic acid) diblock copolymers: New synthetic strategy and their self‐assembly
Authors:Hui‐Chao Lu  Yang Xue  Qiao‐Ling Zhao  Jin Huang  Shen‐Gang Xu  Shao‐Kui Cao  Zhi Ma
Affiliation:1. Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, People's Republic of China;2. School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450002, People's Republic of China
Abstract:Well‐defined amphiphilic polymethylene‐b‐poly (acrylicacid) diblock copolymers have been synthesized via a new strategy combining polyhomologation and atom transfer radical polymerization (ATRP). Hydroxyl‐terminated polymethylenes (PM‐OH) with different molecular weights and narrow molecular weight distribution are obtained through the polyhomologation of dimethylsulfoxonium methylides following quantitative oxidation via trimethylamine‐N‐oxide dihydrate. Subsequently, polymethylene‐based macroinitiators (PM‐MIs Mn = 1,300 g mol?1 [Mw/Mn = 1.11] and Mn = 3,300 g mol?1 [Mw/Mn = 1.04]) are synthesized by transformation of terminal hydroxyl group of PM‐OH to α‐haloester in ~100% conversion. ATRPs of tert‐butyl acrylate (t‐BuA) are then carried out using PM‐MIs as initiator to construct PM‐b‐P(t‐BuA) diblock copolymers with controllable molecular weight (Mn = 8,800–15,800 g mol?1 Mw/Mn = 1.04–1.09) and different weight ratio of PM/P(t‐BuA) segment (1:1.7–1:11.2). The amphiphilic PM‐b‐PAA diblock copolymers are finally prepared by hydrolysis of PM‐b‐P(t‐BuA) copolymers and their self‐assembly behavior in water is preliminarily investigated via the determination of critical micelle concentrations, dynamic light scattering, and transmission electron microscope (TEM). © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012
Keywords:amphiphiles  diblock copolymers  living polymerization  polyolefins  self‐assembly
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