Predicting the Plateau Modulus from Molecular Parameters of Conjugated Polymers.

Predicting the Plateau Modulus from Molecular Parameters of Conjugated Polymers.
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从共轭聚合物的分子参数预测平台模量。

DOI:
10.1021/acscentsci.1c01396
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发表时间:
2022-02-23
影响因子:
18.2
通讯作者:
Colby RH
Colby RH
中科院分区:
化学1区
文献类型:
--
作者:
Fenton AM;Xie R;Aplan MP;Lee Y;Gill MG;Fair R;Kempe F;Sommer M;Snyder CR;Gomez ED;Colby RH

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库恩长度lk,库恩单体体积v0,和平台模量GN0,最初提出的Graessley和爱德华兹的柔性聚合物,并扩展Everaers之间的关系,在柔性和刚性制度之间的实验数据有很大的差距。该间隙阻止从该区域中的任何聚合物的链结构预测机械性能。由于共轭聚合物具有半柔性主链和侧链结构,是研究这种交叉区域的理想材料。使用小角中子散射,振荡剪切流变学,和自由旋转链模型,我们已经表明,12个聚合物与芳香族主链填充了很大一部分的差距。我们还表明,这些聚合物中的一些表现出双有序,这降低了GN0。当完全各向同性时,这些聚合物遵循lk,v0和GN0之间的关系,提出了一个简单的交叉在纠缠链Ne中的库恩段的数量。利用半柔性共轭聚合物在柔性和刚性缠结聚合物之间架起一座桥梁。
The relationship between Kuhn length lk, Kuhn monomer volume v0, and plateau modulus GN0, initially proposed by Graessley and Edwards for flexible polymers, and extended by Everaers, has a large gap in experimental data between the flexible and stiff regimes. This gap prevents the prediction of mechanical properties from the chain structure for any polymer in this region. Given the chain architecture, including a semiflexible backbone and side chains, conjugated polymers are an ideal class of material to study this crossover region. Using small angle neutron scattering, oscillatory shear rheology, and the freely rotating chain model, we have shown that 12 polymers with aromatic backbones populate a large part of this gap. We also have shown that a few of these polymers exhibit nematic ordering, which lowers GN0. When fully isotropic, these polymers follow a relationship between lk, v0, and GN0, with a simple crossover proposed in terms of the number of Kuhn segments in an entanglement strand Ne. Bridging the previously unpopulated gap between flexible and stiff entangled polymers using semiflexible conjugated polymers.
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