Morphology of polystyrene-block-poly(styrene-co-acrylonitrile) and polystyrene-block-poly(styrene-co-acrylonitrile-co-5-vinyltetrazole) diblock copolymers prepared by nitroxide-mediated radical polymerization and “click” chemistry |
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Authors: | Daniel Gromadzki,Peter ?ernoch,Olivier Diat,Petr &Scaron těpá nek |
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Affiliation: | a Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Heyrovsky Sq. 2, 162 06 Prague 6, Czech Republic b Structure et Propriétés d’Architectures Moléculaires, UMR 5819 (CEA-CNRS-UJF), DRFMC/SPrAM, CEA-Grenoble, 38054 Grenoble cedex 9, France c Centre de Recherches Paul-Pascal, CNRS, avenue du Docteur-Schweitzer, F-33600 Pessac, France |
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Abstract: | Well-defined polystyrene-block-poly(styrene-co-acrylonitrile) PS-block-P(S-co-AN) and poly(styrene-co-acrylonitrile-co-5-vinyltetrazole) PS-block-P(S-co-AN-co-5VT) block copolymers with various content of acrylonitrile units in the statistical block were synthesized by nitroxide mediated radical polymerization (NMRP) and post-functionalized using efficient “click” chemistry process. In the second step, acrylonitrile units were successfully modified using 1,3-dipolar cycloaddition (“click” chemistry) type polymer analogue reaction. The original pristine diblock copolymers can be molecularly dissolved in THF and dioxane while the “tetrazolated” versions aggregate to clusters as determined by dynamic light scattering (DLS). Small-angle X-ray scattering (SAXS) and Transmission Electron Microscopy (TEM) revealed ordered lamellar morphology with interlamellar spacing d = 60 nm increasing to d = 80 nm for “tetrazolated” diblock copolymers. The morphological features of diblock copolymer thin layers observed by Atomic Force Microscopy (AFM) depend on the tunable content of both acrylonitrile and 5-vinyltetrazole units and on the quality (polarity) of the solvents used. |
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Keywords: | Polystyrene-block-poly(styrene-co-acrylonitrile-co-5-vinyltetrazole) TEMPO &ldquo Click&rdquo chemistry Morphology Membrane |
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