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Unimolecular Nanoparticles via Carbon-Carbon “Click” Chemistry for All-Polymer Nanocomposites

Authors

  • P. Khanjani,

    1. Centro de Física de Materiales (CSIC, UPV/EHU) - Materials Physics Center, Paseo Manuel de Lardizábal 5, 20018 San Sebastián, Spain
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  • I. Perez-Baena,

    1. Centro de Física de Materiales (CSIC, UPV/EHU) - Materials Physics Center, Paseo Manuel de Lardizábal 5, 20018 San Sebastián, Spain
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  • L. Buruaga,

    1. Centro de Física de Materiales (CSIC, UPV/EHU) - Materials Physics Center, Paseo Manuel de Lardizábal 5, 20018 San Sebastián, Spain
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  • J. A. Pomposo

    Corresponding author
    1. Centro de Física de Materiales (CSIC, UPV/EHU) - Materials Physics Center, Paseo Manuel de Lardizábal 5, 20018 San Sebastián, Spain
    2. IKERBASQUE - Basque Foundation for Science, Alameda Urquijo 36, 48011 Bilbao, Spain
    3. Departamento de Física de Materiales, Universidad del País Vasco (UPV/EHU), Apartado 1072, 20800 San Sebastián, Spain
    • Centro de Física de Materiales (CSIC, UPV/EHU) - Materials Physics Center, Paseo Manuel de Lardizábal 5, 20018 San Sebastián, Spain.
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Abstract

Summary: We report for the first time the synthesis of unimolecular polystyrene-based nanoparticles (PS-NPs) under normal air atmosphere by direct carbon-carbon “click” chemistry (i.e., “self-click” chemistry). First, statistical poly(styrene-co-4-vinylbenzyl chloride) copolymers synthesized by RAFT polymerization were decorated in a facile manner with alkyne groups by reaction with potassium propiolate, providing well-defined nanoparticle precursors (PS-Prec). Next, individual PS-Prec chains were collapsed irreversibly to unimolecular nanoparticles of ca. 12 nm in size by intrachain Cu(II)-catalyzed alkyne dimerization under high-dilution conditions, as revealed by SEC, H1-NMR, DLS and TEM measurements. Based on predictions from a recent compressible thermodynamic model, the resulting nanoparticles could be promising materials for the development of homogeneous, miscible PS-NPs / polycarbonate all-polymer nanocomposites.

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