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Nanophase separation and hindered glass transition in side-chain polymers

Nature Materials volume 2, pages 595–599 (2003)Cite this article

Abstract

Nanophase separation on length scales of 1–5 nanometres has been reported previously for small-molecule liquids1, metallic glasses and also for several semicrystalline, liquid-crystalline2,3 and amorphous4 polymers. Here we show that nanophase separation of incompatible main and side-chain parts is a general phenomenon in amorphous side-chain polymers with long alkyl groups. We conclude from X-ray scattering and relaxation spectroscopy data for higher poly(n-alkyl acrylates) (PnAA) and poly(n-alkyl methacrylates) (PnAMA) that alkyl groups of different monomeric units aggregate in the melt and form self-assembled alkyl nanodomains with a typical size of 0.5–2 nm. A comparison with data for other polymer series having alkyl groups reveals that important structural and dynamic aspects are main-chain independent. A polyethylene-like glass transition within the alkyl nanodomains is observed and discussed in the context of a hindered glass transition in self-assembled confinements. This is an interesting link between central questions in glass-transition research and structural aspects in nanophase-separated materials.

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Figure 1: Structural data for polymer series with long alkyl groups in the side chain.
Figure 2: Relaxation dynamics of polymer series with long alkyl groups in the side chain.

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Acknowledgements

The authors thank Otto Kabisch and Sabine Reichl for contributing X-ray scattering measurements and the Deutsche Forschungsgemeinschaft (SFB 418) for financial support.

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  1. Heiko Huth

    Present address: Fachbereich Physik, Universität Rostock, D-18051, Rostock, Germany

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  1. Fachbereich Physik, Universität Halle, Hoher Weg 8, Halle, D-06099, Germany

    Mario Beiner

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Correspondence to Mario Beiner.

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Beiner, M., Huth, H. Nanophase separation and hindered glass transition in side-chain polymers. Nature Mater 2, 595–599 (2003). https://doi.org/10.1038/nmat966

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