Supramolecular Elastomers. Particulate β-Sheet Nanocrystal-Reinforced Synthetic Elastic Networks

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• 作者：Joseph J. Scavuzzo ; Xuesong Yan ; Yihong Zhao ; Jacob D. Scherger ; Junyi Chen ; Shuo Zhang ; Hao Liu ; Min Gao ; Tao Li ; Xiuying Zhao ; Gary R. Hamed ; Mark D. Foster ; Li Jia
• 刊名：Macromolecules
• 出版年：2016
• 出版时间：April 12, 2016
• 年：2016
• 卷：49
• 期：7
• 页码：2688-2697
• 全文大小：601K
• 年卷期：0
• ISSN：1520-5835

文摘

β-Sheet crystals in natural silks are particulate and less than 10 nm in size in all three dimensions. In synthetic supramolecular analogues of natural silks, β-sheet crystals have been found to be fibrous with the longest dimension exceeding 100 nm in the hydrogen-bonding direction. This work demonstrates that particulate β-sheet crystals can be achieved without the use of an elaborate amino acid sequence by simply grafting oligo(β-alanine) segments as pendent side groups to a butyl rubber main chain. The size control in the hydrogen-bonding direction is attributable to an entropic force that opposes the driving force for the self-assembly. The nanocrystals, especially those of trimeric β-alanine segments, display a remarkable ability to simultaneously provide stiffness, extensibility, and strength to the synthetic elastic network and do so highly efficiently at a low volume fraction of the material. The herein studied butyl rubber-based thermoplastic elastomers containing no more than 3.6 vol % of β-sheet nanocrystals are stiffer, stronger, and more extensible than vulcanized butyl rubber reinforced by 20 vol % of carbon black and poly(styrene-b-isobutylene-b-styrene) reinforced by >33 vol % of polystyrene domains. The high reinforcing efficacy of the β-sheet crystals is attributable to two phenomena associated with their small sizes: a stick–slip mechanism for energy dissipation and an auxiliary layer of polymer brush that contributes to increasing the modulus.