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二嵌段刷状共聚物溶液的颜色、结构和流变学

Color, structure, and rheology of a diblock bottlebrush copolymer solution.

作者信息

Wade Matthew A, Walsh Dylan, Lee Johnny Ching-Wei, Kelley Elizabeth, Weigandt Katie, Guironnet Damien, Rogers Simon A

机构信息

Chemical and Biomolecular Engineering Department, University of Illinois at Urbana-Champaign, 607 S Mathews Ave, Urbana, Illinois, USA.

出版信息

Soft Matter. 2020 Jun 7;16(21):4919-4931. doi: 10.1039/d0sm00397b. Epub 2020 May 12.

Abstract

A structure-property-process relation is established for a diblock bottlebrush copolymer solution, through a combination of rheo-neutron scattering, imaging, and rheological measurements. Polylactic acid-b-polystyrene diblock bottlebrush copolymers were dispersed in toluene with a concentration of 175 mg ml, where they self-assembled into a lamellar phase. All measurements were carried out at 5 °C. The solution color, as observed in reflection, is shown to be a function of the shear rate. Under equilibrium and near-equilibrium conditions, the solution has a green color. At low shear rates the solution remains green, while at intermediate rates the solution is cyan. At the highest rates applied the solution is indigo. The lamellar spacing is shown to be a decreasing function of shear rate, partially accounting for the color change. The lamellae are oriented 'face-on' with the wall under quiescence and low shear rates, while a switch to 'edge-on' is observed at the highest shear rates, where the reflected color disappears. The intramolecular distance between bottlebrush polymers does not change with shear rate, although at high shear rates, the bottlebrush polymers are preferentially aligned in the vorticity direction within the lamellae. We therefore form a consistent relation between structure and function, spanning a wide range of length scales and shear rates.

摘要

通过流变中子散射、成像和流变测量相结合的方法,建立了二嵌段瓶刷共聚物溶液的结构-性质-过程关系。聚乳酸-b-聚苯乙烯二嵌段瓶刷共聚物以175 mg/ml的浓度分散在甲苯中,在其中自组装成层状相。所有测量均在5℃下进行。从反射中观察到的溶液颜色显示为剪切速率的函数。在平衡和近平衡条件下,溶液呈绿色。在低剪切速率下,溶液保持绿色,而在中等速率下,溶液呈青色。在施加的最高速率下,溶液呈靛蓝色。层间距显示为剪切速率的递减函数,这部分解释了颜色变化。在静止和低剪切速率下,薄片与壁面呈“面朝上”取向,而在最高剪切速率下观察到转变为“边缘朝上”,此时反射颜色消失。瓶刷聚合物之间的分子内距离不随剪切速率变化,尽管在高剪切速率下,瓶刷聚合物在薄片内优先沿涡度方向排列。因此,我们在广泛的长度尺度和剪切速率范围内建立了结构与功能之间的一致关系。

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本文引用的文献

1
Brush-Like Polymers and Entanglements: From Linear Chains to Filaments.刷状聚合物与缠结:从线性链到长丝
ACS Macro Lett. 2019 Oct 15;8(10):1328-1333. doi: 10.1021/acsmacrolett.9b00519. Epub 2019 Sep 26.
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Persistence Length of Dendritic Molecular Brushes.树枝状分子刷的持久长度
ACS Macro Lett. 2012 Oct 16;1(10):1166-1169. doi: 10.1021/mz3003903. Epub 2012 Sep 18.
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Molecular Bottlebrushes: New Opportunities in Nanomaterials Fabrication.分子刷:纳米材料制备中的新机遇。
ACS Macro Lett. 2012 Sep 18;1(9):1146-1149. doi: 10.1021/mz300402x. Epub 2012 Sep 10.
9
Dilute solution structure of bottlebrush polymers.刷型聚合物的稀溶液结构。
Soft Matter. 2019 Apr 3;15(14):2928-2941. doi: 10.1039/c9sm00033j.
10
Macromolecules with programmable shape, size, and chemistry.具有可编程形状、大小和化学性质的高分子。
Proc Natl Acad Sci U S A. 2019 Jan 29;116(5):1538-1542. doi: 10.1073/pnas.1817745116. Epub 2019 Jan 17.

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