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Issue 18, 2014
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Effects of molecular geometry on the self-assembly of giant polymer–dendron conjugates in condensed state

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Abstract

A series of giant polymer–dendron conjugates with a dendron head and a linear polymer tail were synthesized via “click” chemistry between azide-functionalized polystyrene (PSN, N: degree-of-polymerization) and t-butyl protected, alkyne-functionalized second generation dendron (tD), followed by a deprotection process to generate a dendron termini possessing nine carboxylic acid groups. The molecular structures were confirmed by nuclear magnetic resonance, size-exclusion chromatographic analyses, and matrix-assisted laser desorption ionization time-of-flight mass spectra. These well-defined conjugates can serve as a model system to study the effects of the molecular geometries on the self-assembly behaviour, as compared with their linear analogues. Four phase morphologies found in flexible linear diblock copolymer systems, including lamellae, bicontinuous double gyroids, hexagonal packed cylinders, and body-centred cubic packed spheres, were observed in this series of conjugates based on the results of small angle X-ray scattering and transmission electron microscopy. All of the domain sizes in these phase separated structures were around or less than 10 nm. A ‘half’ phase diagram was constructed based on the experimental results. The geometrical effect was found not only to enhance the immiscibility between the PSN tail and dendron head, but also systematically shift all of the phase boundaries towards higher volume fractions of the PSN tails, resulting in an asymmetrical phase diagram. This study may provide a pathway to the construction of ordered patterns of sub-10 nm feature size using polymer–dendron conjugates.

Graphical abstract: Effects of molecular geometry on the self-assembly of giant polymer–dendron conjugates in condensed state

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Publication details

The article was received on 01 Aug 2013, accepted on 26 Feb 2014 and first published on 27 Feb 2014


Article type: Paper
DOI: 10.1039/C3SM52087K
Soft Matter, 2014,10, 3200-3208

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    Effects of molecular geometry on the self-assembly of giant polymer–dendron conjugates in condensed state

    X. Dong, X. Lu, B. Ni, Z. Chen, K. Yue, Y. Li, L. Rong, T. Koga, B. S. Hsiao, G. R. Newkome, A. Shi, W. Zhang and S. Z. D. Cheng, Soft Matter, 2014, 10, 3200
    DOI: 10.1039/C3SM52087K

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