Bottlebrush-Guided Polymer Crystallization Resulting in Supersoft and Reversibly Moldable Physical Networks

William F.M. Daniel, Guojun Xie, Mohammad Vatankhah Varnoosfaderani, Joanna Burdyńska, Qiaoxi Li, Dmytro Nykypanchuk, Oleg Gang, Krzysztof Matyjaszewski, Sergei S. Sheiko

Research output: Contribution to journalArticle

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Abstract

The goal of this study is to use ABA triblock copolymers with central bottlebrush B segments and crystalline linear chain A segments to demonstrate the effect of side chains on the formation and mechanical properties of physical networks cross-linked by crystallites. For this purpose, a series of bottlebrush copolymers was synthesized consisting of central amorphous bottlebrush polymer segments with a varying degree of polymerization (DP) of poly(n-butyl acrylate) (PnBA) side chains and linear tail blocks of crystallizable poly(octadecyl acrylate-stat-docosyl acrylate) (poly(ODA-stat-DA)). The materials were generated by sequential atom transfer radical polymerization (ATRP) steps starting with a series of bifunctional macroinitiators followed by the growth of two ODA-stat-DA linear-chain tails and eventually growing poly(nBA) side chains with increasing DPs. Crystallization of the poly(ODA-stat-DA) tails resulted in a series of reversible physical networks with bottlebrush strands bridging crystalline cross-links. They displayed very low moduli of elasticity of the order of 103-104 Pa. These distinct properties are due to the bottlebrush architecture, wherein densely grafted side chains play a dual role by facilitating disentanglement of the network strands and confining crystallization of the linear-chain tails. This combination leads to physical cross-linking of supersoft networks without percolation of the crystalline phase. The cross-link density was effectively controlled by the DP of the side chains with respect to the DP of the linear tails (nA). Shorter side chains allowed for crystallization of the linear tails of neighboring bottlebrushes, while steric repulsion between longer side chains hindered the phase separation and crystallization process and prevented network formation.

LanguageEnglish (US)
Pages2103-2111
Number of pages9
JournalMacromolecules
Volume50
Issue number5
DOIs
StatePublished - Mar 14 2017

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Crystallization
Polymers
Polymerization
Crystalline materials
Atom transfer radical polymerization
Crystallites
Phase separation
Block copolymers
Copolymers
Elastic moduli
Mechanical properties
acrylic acid
poly(octadecylacrylate)

ASJC Scopus subject areas

  • Organic Chemistry
  • Materials Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry

Cite this

Daniel, W. F. M., Xie, G., Vatankhah Varnoosfaderani, M., Burdyńska, J., Li, Q., Nykypanchuk, D., ... Sheiko, S. S. (2017). Bottlebrush-Guided Polymer Crystallization Resulting in Supersoft and Reversibly Moldable Physical Networks. Macromolecules, 50(5), 2103-2111. DOI: 10.1021/acs.macromol.7b00030

Bottlebrush-Guided Polymer Crystallization Resulting in Supersoft and Reversibly Moldable Physical Networks. / Daniel, William F.M.; Xie, Guojun; Vatankhah Varnoosfaderani, Mohammad; Burdyńska, Joanna; Li, Qiaoxi; Nykypanchuk, Dmytro; Gang, Oleg; Matyjaszewski, Krzysztof; Sheiko, Sergei S.

In: Macromolecules, Vol. 50, No. 5, 14.03.2017, p. 2103-2111.

Research output: Contribution to journalArticle

Daniel, WFM, Xie, G, Vatankhah Varnoosfaderani, M, Burdyńska, J, Li, Q, Nykypanchuk, D, Gang, O, Matyjaszewski, K & Sheiko, SS 2017, 'Bottlebrush-Guided Polymer Crystallization Resulting in Supersoft and Reversibly Moldable Physical Networks' Macromolecules, vol 50, no. 5, pp. 2103-2111. DOI: 10.1021/acs.macromol.7b00030
Daniel WFM, Xie G, Vatankhah Varnoosfaderani M, Burdyńska J, Li Q, Nykypanchuk D et al. Bottlebrush-Guided Polymer Crystallization Resulting in Supersoft and Reversibly Moldable Physical Networks. Macromolecules. 2017 Mar 14;50(5):2103-2111. Available from, DOI: 10.1021/acs.macromol.7b00030
Daniel, William F.M. ; Xie, Guojun ; Vatankhah Varnoosfaderani, Mohammad ; Burdyńska, Joanna ; Li, Qiaoxi ; Nykypanchuk, Dmytro ; Gang, Oleg ; Matyjaszewski, Krzysztof ; Sheiko, Sergei S./ Bottlebrush-Guided Polymer Crystallization Resulting in Supersoft and Reversibly Moldable Physical Networks. In: Macromolecules. 2017 ; Vol. 50, No. 5. pp. 2103-2111
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