Parisi Daniele, Ahn Junyoung, Chang Taihyun, Vlassopoulos Dimitris, Rubinstein Michael
Institute of Electronic Structure & Laser, Foundation for Research and Technology Hellas (FORTH), Heraklion, Crete 70013, Greece.
Department of Materials Science & Technology, University of Crete, Heraklion, Crete 71003, Greece.
Macromolecules. 2020 Mar 10;53(5):1685-1693. doi: 10.1021/acs.macromol.9b02536. Epub 2020 Feb 20.
We combine linear viscoelastic measurements and modelling in order to explore the dynamics of blends of the same-molecular-weight ring and linear polymers in the regime of the low volume fraction (0.3 or lower) of the ring component. The stress relaxation modulus is affected by the constraint release (CR) of both rings and linear components due to the motion of linear chains. We develop a CR-based model of ring-linear blends that predicts the stress relaxation function in the low fraction regime of ring component in excellent agreement with experiments. Rings trapped by their entanglements with linear chains can only relax by linear-chain-induced constraint release, resulting in much slower relaxation of rings than of linear chains. The relative viscosity of the blend with respect to the linear melt viscosity at ring overlap volume fraction increases proportionally to the square root of ring molecular weight . Our experimental results clearly demonstrate that it is possible to enhance the viscosity and simultaneously the structural relaxation time of linear polymer melts by adding a small fraction of ring polymers. These results not only provide fundamental insights into the physics of the CR process but also suggest ways to fine-tune the flow properties of linear polymers by means of adding rings.
我们结合线性粘弹性测量和建模,以探索相同分子量的环状聚合物与线性聚合物在环状组分低体积分数(0.3或更低)区域内共混物的动力学。由于线性链的运动,应力松弛模量受到环状和线性组分的约束释放(CR)的影响。我们开发了一种基于CR的环状-线性共混物模型,该模型预测环状组分低分数区域内的应力松弛函数,与实验结果非常吻合。被与线性链的缠结所捕获的环状聚合物只能通过线性链诱导的约束释放来松弛,导致环状聚合物的松弛比线性链慢得多。在环状聚合物重叠体积分数下,共混物相对于线性熔体粘度的相对粘度与环状聚合物分子量的平方根成正比。我们的实验结果清楚地表明,通过添加少量环状聚合物,可以提高线性聚合物熔体的粘度,同时提高其结构松弛时间。这些结果不仅为CR过程的物理原理提供了基本见解,还提出了通过添加环状聚合物来微调线性聚合物流动性能的方法。