Closer insight into the structure of moderate to densely branched comb polymers by combining modelling and linear rheological measurements
(2017) Soft Matter — Vol. 13, n° 5, p. 1063-1073 (2017)
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- Abstract
- Synthesis of combs with well-entangled backbones and high densities of long branches has always been a challenge. Steric hindrance frequently leads to coupling of chains and structural imperfections that cannot be easily distinguished by traditional characterization methods. Researches have therefore tried to use combination of different methods to have more information on the actual microstructures. In this work, a grafting-from approach is used to synthesize poly(n-butyl acrylate) combs using Atom Transfer Radical Polymerization (ATRP) in three steps including synthesis of backbone, cleavage of protecting groups and growth of side branches. We have compared the theoretical prediction of linear viscoelastic properties made by time marching algorithm (TMA) tube based model with measured rheological behaviour to provide a better insight on the actual microstructure formed during synthesis. For combs with branches smaller than an entanglement, no discernible hierarchical relaxation can be distinguished, while with longer branches, a high frequency plateau made by entangled branches can be separated from backbone’s relaxation. Dilution of backbone, after relaxation of side branches, may accelerate final relaxation, while extra friction can delay it especially for longer branches. Such a comparison provides a better assessment of the microstructure formed in combs.
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Ahmadi, M., Pioge, S., Fustin, C.-A., Gohy, J.-F., & Van Ruymbeke, E. (2017). Closer insight into the structure of moderate to densely branched comb polymers by combining modelling and linear rheological measurements. Soft Matter, 13(5), 1063-1073. https://doi.org/10.1039/C6SM02576E (Original work published 2017)