Contact
    Start Publications Bottlebrush-Guided Polymer Crystallization Resulting in ...
    ←  Publication Finder
    KSV NIMA

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

    Year: 2017

    Journal: Macromolecules, Volume 50, nov-14, page 2103–2111

    Authors: Daniel, William F. M.; Xie, Guojun; Varnoosfaclerani, Mohammad Vatankhah; Burdynska, Joanna; Li, Qiaoxi; Nykypanchuk, Dmytro; Gang, Oleg; Matyjaszewski, Krzysztof; Sheiko, Sergei S.

    Organizations: National Science Foundation [DMR 1407645, DMR 1501324, DMR 1436219, DMR 1436201]; Becton DickinsonTechnologies

    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 10(3)-10(4) 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 (n(A). 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.
    View publication