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SET-LRP synthesis of PMHDO-g-PNIPAM well-defined amphiphilic graft copolymer

Authors

  • Aishun Ding,

    1. Department of Chemistry, Fudan University, 220 Handan Road, Shanghai 200433, People's Republic of China
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    • Aishun Ding and Guolin Lu contributed equally to this work.

  • Guolin Lu,

    1. Key Laboratory of Organofluorine Chemistry and Laboratory of Polymer Materials, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, People's Republic of China
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    • Aishun Ding and Guolin Lu contributed equally to this work.

  • Hao Guo,

    Corresponding author
    1. Department of Chemistry, Fudan University, 220 Handan Road, Shanghai 200433, People's Republic of China
    • Department of Chemistry, Fudan University, 220 Handan Road, Shanghai 200433, People's Republic of China
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  • Xingliang Zheng,

    1. College of Chemistry and Biological Engineering, Changsha University of Science and Technology, Changsha 410114, People's Republic of China
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  • Xiaoyu Huang

    Corresponding author
    1. Key Laboratory of Organofluorine Chemistry and Laboratory of Polymer Materials, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, People's Republic of China
    • Key Laboratory of Organofluorine Chemistry and Laboratory of Polymer Materials, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, People's Republic of China
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Abstract

A well-defined amphiphilic graft copolymer, consisting of hydrophobic polyallene-based backbone and hydrophilic poly(N-isopropylacrylamide) (PNIPAM) side chains, was prepared by the combination of living coordination polymerization, single electron transfer-living radical polymerization (SET-LRP), and the grafting-from strategy. First, the double-bond-containing backbone was prepared by [(η3-allyl)NiOCOCF3]2-initiated living coordination polymerization of 6-methyl-1,2-heptadiene-4-ol (MHDO). Next, the pendant hydroxyls in every repeating unit of poly(6-methyl-1,2-heptadiene-4-ol) (PMHDO) homopolymer were treated with 2-chloropropionyl chloride to give PMHDO-Cl macroinitiator. Finally, PNIPAM side chains were grown from PMHDO backbone via SET-LRP of N-isopropylacrylamide initiated by PMHDO-Cl macroinitiator in N,N-dimethylformamide/2-propanol using copper(I) chloride/tris(2-(dimethylamino)ethyl)amine as catalytic system to afford PMHDO-g-PNIPAM graft copolymers with a narrow molecular weight distribution (Mw/Mn = 1.19). The critical micelle concentration (cmc) in water was determined by fluorescence probe technique and the effects of pH and salinity on the cmc of PMHDO-g-PNIPAM were also investigated. The micellar morphology was found to be spheres using transmission electron microscopy. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013

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