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Association and relaxation of supra-macromolecular polymers

机译：supra-macromolecular协会和放松聚合物

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This paper describes the structures created by assembling functionalised entangled polymers and the effect these have on the rheology of the material. A polybutadiene (PBd) linear polymer precursor of sufficient molecular weight to be entangled is used. This is end functionalised with the self-associating group 2-ureido-4pyrimidinone (UPy). Interestingly, despite the relatively high molecular weight of the precursor diluting the UPy concentration, the effect on the material's properties is significant. To characterise the assembled microstructure we present linear rheology, extensional non-linear rheology and small angle X-ray scattering (SAXS). The linear rheology shows that the functionalised PBd assembles into large macro-structures where the terminal relaxation time is up to seven orders of magnitude larger than the precursor. The non-linear rheology shows strain-hardening over a broad range of strain-rates. We then show by both SAXS and modelling of the extensional data that there must exist clusters of UPy associations and hence assembled polymers with branched architecture. By modelling the supra-molecular structure as an effective linear polymer, we show that this would be insufficient in predicting the strain-hardening behaviour at lower extension-rates. Therefore, in this flow regime the strain-hardening is likely to be caused by branching. This is backed up by SAXS measurements which show that UPy clusters larger than pair-pair groups exist.
机译：本文描述了创建的结构聚合物和组装functionalised纠缠这些对流变性的影响材料。前体足够的分子量纠缠。与self-associating组2-ureido-4pyrimidinone (UPy)。尽管相对较高的分子量的前身稀释UPy浓度,影响材料的属性有很重要的意义。组织我们呈现线性流变学,具体的非线性流变学和小角x射线散射(粉煤灰)。表明functionalised PBd组装大的宏观结构的终端弛豫时间是7的订单大小大于前体。非线性流变学显示应变强化了广泛的应变率。粉煤灰和建模的具体的数据必须存在UPy协会和集群因此组装与支化聚合物体系结构。结构是一种有效的线性聚合物,我们表演这将在预测不足加工硬化行为较低extension-rates。加工硬化是可能造成的分支。这表明UPy集群比pair-pair群体存在。

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