Abstract

A series of fluorine-containing amphiphilic ABC triblock copolymers comprising hydrophilic poly(ethylene glycol) (PEG) and poly(methacrylic acid) (PMAA), and hydrophobic poly(p-(2-(4-biphenyl)perfluorocyclobutoxy)phenyl methacrylate) (PBPFCBPMA) segments were synthesized by successive atom transfer radical polymerization (ATRP). First, PEG-Br macroinitiators bearing one terminal ATRP initiating group were prepared by chain-end modification of monohydroxy-terminated PEG via esterification reaction. PEG-b-PBPFCBPMA-Br diblock copolymers were then synthesized via ATRP of BPFCBPMA monomer initiated by PEG-Br macroinitiator. ATRP polymerization of tert-butyl methacrylate (tBMA) was directly initiated by PEG-b-PBPFCBPMA-Br to provide PEG-b-PBPFCBPMA-b-PtBMA triblock copolymers with relatively narrow molecular weight distributions (Mw/Mn ≤ 1.43). The pendant tert-butyoxycarbonyls were hydrolyzed to carboxyls in acidic environment without affecting other functional groups for affording PEG-b-PBPFCBPMA-b-PMAA amphiphilic triblock copolymers. The critical micelle concentrations (cmc) were determined by fluorescence spectroscopy using N-phenyl-1-naphthylamine as probe and the self-assembly behavior in aqueous media were investigated by transmission electron microscopy. Large compound micelles and bowl-shaped micelles were formed in neutral aqueous solution. Interestingly, large compound micelles formed by triblock copolymers can separately or simultaneously encapsulate hydrophilic Rhodamine 6G and hydrophobic pyrene agents.

Highlights

  • IntroductionOwing to the unique properties[1,2,3,4,5] (high thermostability, high insulating ability, excellent chemical inertness, aging and weather resistances, low refractive index, and low surface energy) originating from low polarizability, strong electronegativity, small van der Waals radius of F atom, and strong C-F bond, fluoropolymers are extensively employed as a class of high performance materials in recent years[6,7,8,9]

  • Owing to the unique properties[1,2,3,4,5] originating from low polarizability, strong electronegativity, small van der Waals radius of F atom, and strong C-F bond, fluoropolymers are extensively employed as a class of high performance materials in recent years[6,7,8,9]

  • We have presented a convenient synthesis of well-defined PFCB-containing poly(ethylene glycol) (PEG)-b-PBPFCBPMA-b-PtBMA amphiphilic ABC triblock copolymers with relatively narrow molecular weight distributions (Mw/Mn ≤ 1.43) via sequential atom transfer radical polymerization (ATRP)

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Summary

Introduction

Owing to the unique properties[1,2,3,4,5] (high thermostability, high insulating ability, excellent chemical inertness, aging and weather resistances, low refractive index, and low surface energy) originating from low polarizability, strong electronegativity, small van der Waals radius of F atom, and strong C-F bond, fluoropolymers are extensively employed as a class of high performance materials in recent years[6,7,8,9]. Along with the high crystallinity and thermal and chemical resistances, most fluoropolymers are difficult to dissolve or melt so that industrial manufacturing would be costly and technically difficult. These issues are not easy to be solved, which hinder the development and application of fluoropolymers. Synthesis of PFCB aryl ether-containing amphiphilic copolymers bearing hydrophilic and lipophobic segments would yield the fluoropolymers with different architectures, but deepen our understanding on the structure-property relationship of PFCB aryl ether-based polymethacrylates

Methods
Results
Conclusion

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