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Polyhedral oligomeric silsesquioxane-capped poly(N-vinyl pyrrolidone) amphiphiles: synthesis, self-assembly, and use as porogen of nanoporous poly(vinylidene fluoride)

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Abstract

In this contribution, we reported the synthesis of polyhedral oligomeric silsesquioxane (POSS)-capped poly(N-vinyl pyrrolidone) (PVPy) via reversible addition-fragmentation chain transfer/macromolecular design via interchange of xanthate (RAFT/MADIX) polymerization. First, a POSS macromer bearing xanthate moiety was synthesized and was then used as the chain transfer agent to mediate the radical polymerization of N-vinylpyrrolidone (NVP). By controlling the mass ratios of the POSS-CTA to NVP, a series of the POSS-capped PVPy amphiphiles were successfully synthesized with various molecular weights. It was found that in bulks, the POSS-capped PVPy was microphase-separated and the POSS end groups were self-organized into the spherical microdomains with the size of 10~100 nm in diameter. In the solvent selective for PVPy (e.g., water), the POSS-capped PVPy was capable of self-assembling into the spherical micelles with an average diameter of 20~50 nm as evidenced by dynamic laser scattering (DLS) and transmission electron microscopy (TEM). Owing to the amphiphilicity, POSS-capped PVPy also displayed the self-assembly behavior in poly(vinylidene fluoride) (PVDF), in which the POSS cages were aggregated into 10~30 nm microdomains. In the nanocomposites of PVDF with POSS-capped PVPy, the spherical POSS microdomains were readily etched by using hydrofluoric acid, leaving the nanopores in the materials.

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Acknowledgments

The financial supports from Natural Science Foundation of China (No. 21774078, 51133003 and 21274091) and Anhui Province Key Laboratory of Environment-friendly Polymer Materials were gratefully acknowledged.

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Authors and Affiliations

  1. College of Chemistry and Chemical Engineering, Anhui University, Hefei, 230601, People’s Republic of China

    Yanhao Zhang & Kangming Nie

  2. School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, People’s Republic of China

    Yanhao Zhang, Bingjie Zhao, Lei Li & Sixun Zheng

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  1. Yanhao Zhang
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  2. Bingjie Zhao
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Zhang, Y., Zhao, B., Li, L. et al. Polyhedral oligomeric silsesquioxane-capped poly(N-vinyl pyrrolidone) amphiphiles: synthesis, self-assembly, and use as porogen of nanoporous poly(vinylidene fluoride). Colloid Polym Sci 297, 141–153 (2019). https://doi.org/10.1007/s00396-018-4440-6

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