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Effect of block length on the self-assembly of end-capping perfluoroalkyl moieties on the polymer surface

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Abstract

Most research on copolymers with fluorinated monomers has focused on the relationship between fluorinated monomer content and the corresponding surface structure. However, the influence of the non-fluorinated block on the surface structure of the copolymer film is unknown. Various molecular weight poly(butyl methacrylates) (PBMA) end-capped with 2-perfluorooctylethyl methacrylate (FMA) units (PBMA-ec-FMA) have been synthesized by atom transfer radical polymerization (ATRP). The effect of the PBMA block length on the surface structure and properties of the polymers both in the solid state and in solution was investigated using various techniques. X-ray photoelectron spectroscopy (XPS), sum frequency generation (SFG) vibrational spectroscopy and X-ray diffraction (XRD) analyses indicated that longer PBMA blocks enhanced both the enrichment of the fluorinated moieties and the order of the packing orientation of the perfluoroalkyl side chains on the surface. This enhancement was attributed mainly to the molecular aggregate structure of the end-capped polymers with long PBMA blocks in the solution and to the interfacial structure at the air/liquid interface, which favors the -(CF2)7CF3 moieties self-assembling on the polymer surface during film formation. This observation suggests that the polyacrylate block structure in fluorinated diblock copolymers, in addition to the fluorinated monomer content, plays an important role in structure formation on the solid surface.

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Authors and Affiliations

  1. Department of Chemistry, Key Laboratory of Advanced Textile Materials and Manufacturing Technology, Ministry of Education, Zhejiang Sci-Tech University, Hangzhou, 310018, China

    JuPing Yang, QiDi Zhao, Bin Zhou, HuaGang Ni & XinPing Wang

  2. Department of Polymer Science and Engineering, Key Laboratory of Macromolecule Synthesis and Functionalization, Ministry of Education, Zhejiang University, Hangzhou, 310027, China

    ZhiQuan Shen

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  1. JuPing Yang
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Correspondence to XinPing Wang.

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Supported by the National Natural Science Foundation of China (Grant Nos. 50573069 & 20704038) and Program for Changjiang Scholars and Innovative Research Team in University (Grant No. IRT 0654)

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Yang, J., Zhao, Q., Zhou, B. et al. Effect of block length on the self-assembly of end-capping perfluoroalkyl moieties on the polymer surface. Sci. China Ser. B-Chem. 52, 2295–2306 (2009). https://doi.org/10.1007/s11426-009-0292-8

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  • DOI: https://doi.org/10.1007/s11426-009-0292-8

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