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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References
Chen, W. & Wunderlich, B. Nanophase separation of small and large molecules. Macromol. Chem. Phys. 200, 283–311 ( 1999).
Ringsdorf, H. & Tschirner, P. Synthesis, structure, and phase behaviour of liquid-crystalline rigid-rod polyesters and polyamides with disc-like mesogens in the main chain. Makromol. Chem. 188, 1431–1445 ( 1987).
Chen, W., Pyda, M., Habenschuss, A., Londono, J.D. & Wunderlich, B. Nanophase separation and crystallization in PEIM-12 poly(4,4'-phthaloimidobenzoyl-dodecamethyleneoxycarbonyl). Polym. Adv. Technol. 8, 747–760 ( 1997).
Beiner, M., Schröter, K., Hempel, E., Reissig, S. & Donth, E. Multiple glass transition and nanophase separation in poly(n-alkyl methacrylate) homopolymers. Macromolecules 32, 6278–6282 ( 1999).
Hamley, I.W. The Physics of Block Copolymers (Oxford Univ. Press, Oxford, 1998).
Fredrickson, G.H. & Bates, F.S. Dynamics of block copolymers: Theory and experiment. Annu. Rev. Mater. Sci. 26, 501–550 ( 1996).
Cowie, J.M.G., Haq, Z., McEwen, I.J. & Velickovic, J. Poly(alkyl itaconates): Observation of dual glass transitions and crystallinity in the dialkyl ester series di-heptyl to di-eicosyl. Polymer 22, 327–332 ( 1981).
Floudas, G. & Stepanek, P. Structure and dynamics of poly(n-decyl methacrylate) below and above the glass transition. Macromolecules 31, 6951–6957 ( 1998).
Arrighi, V. et al. Observation of local order in poly(di-n-alkyl itaconate)s. Macromolecules 33, 4989–4991 ( 2000).
McCreight, K.W. et al. Phase structures and transition behaviors in polymers containing rigid rodlike backbones with flexible side chains. J. Polym. Sci. B 37, 1633–1646 ( 1999).
Nurulla, I., Morikita, T., Fukumoto, H. & Yamamoto, T. Preparation and properties of poly[(2-alkylbenzimidazole)-alt-thiophene]s with long alkyl side chains. Macromol. Chem. Phys. 202, 2335–2340 ( 2001).
Turner Jones, A. Crystallinity in isotactic polyolefins with unbranched side chains. Makromol. Chem. 71, 1–32 ( 1964).
Böhmer, R., Ngai, K.L., Angell, C.A. & Plazek, D.J. Nonexponential relaxations in strong and fragile glass formers. J. Chem. Phys. 99, 4201–4209 ( 1993).
Johari, G.P. Glass transition and secondary relaxations in molecular liquids and crystals. Ann. NY Acad. Sci. 279, 117–140 ( 1976).
Beiner, M., Kabisch, O., Reichl, S. & Huth, H. Structural and dynamic heterogeneities in higher poly(n-alkylmethacrylate)s. J. Non-Cryst. Solids 307–310, 658–666 ( 2002).
Arndt, M., Stannarius, R., Groothues, H., Hempel, E. & Kremer, F. Length scale of cooperativity in the dynamic glass transition. Phys. Rev. Lett. 79, 2077–2080 ( 1997).
Huwe, A., Kremer, F., Behrens, P. & Schwieger, W. Molecular dynamics in confining space: From the single molecule to the liquid state. Phys. Rev. Lett. 82, 2338–2341 ( 1999).
Jackson, C.L. & McKenna, G.B. The glass transition of organic liquids confined to small pores. J. Non-Cryst. Solids 131–133, 221–224 ( 1991).
Donth, E. Glasübergang (Akademie, Berlin, 1981).
Adam, G. & Gibbs, J.H. On the temperature dependence of cooperative relaxation properties in glass-forming liquids. J. Chem. Phys. 43, 139–146 ( 1965).
Tracht, U. et al. Length scale of dynamic heterogeneities at the glass transition as determined by multidimensional nmr. Phys. Rev. Lett. 81, 2727–2730 ( 1998).
Russell, E.V., Israeloff, N.E., Walther, L.E. & Alvarez Gomariz, H. Nanometer scale dielectric fluctuations at the glass transition. Phys. Rev. Lett. 81, 1461–1464 ( 1998).
Donth, E. The Glass Transition. Relaxation Dynamics in Liquids and Disordered Materials (Springer, Berlin, 2001).
Huang, D. & McKenna, G.B. New insights into the fragility dilemma in liquids. J. Chem. Phys. 114, 5621–5630 ( 2001).
Gaur, U. & Wunderlich, B. The glass transition temperature of polyethylene. Macromolecules 13, 445–446 ( 1980).
Christenson, H.K. Confinement effects on freezing and melting. J. Phys. Condens. Matter 13, R95–R133 ( 2001).
Loo, Y.L., Register, R.A., Ryan, A.J. & Dee, G.T. Polymer crystallization confined in one, two, or three dimensions. Macromolecules 34, 8968–8977 ( 2001).
Mao, G. et al. Molecular design, synthesis, and characterization of liquid crystal-coil diblock copolymers with azobenzene side groups. Macromolecules 30, 2556–2567 ( 1997).
Thurn-Albrecht, T. et al. Ultrahigh-density nanowire arrays grown in self-assembled diblock copolymer templates. Science 290, 2126–2129 ( 2000).
Pernot, H., Baumert, M., Court, F. & Leibler, H. Design and properties of co-continous nanostructured polymers by reactive blending. Nature Mater. 1, 54–58 ( 2002).
Frauenfelder, H. & McMahon, B. Dynamics and function of proteins: The search for general concepts. Proc. Natl Acad. Sci. USA 95, 4795–4797 ( 1998).
Beyer, F.L. et al. Graft copolymers with regularly spaced, tetrafunctional branch points: Morphology and grain structure. Macromolecules 33, 2039–2048 ( 2000).
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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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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DOI: https://doi.org/10.1038/nmat966
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