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Mutual macromolecular crowding as the basis for polymer solution non-ideality

机译：相互高分子拥挤作为聚合物溶液非理想性的基础

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摘要

Semidilute polymer solutions differ greatly from dilute solutions in properties such as viscosity, relaxation time, elastic modulus, colloid osmotic pressure, and light scattering. Previously, Matsuoka and Cowman proposed a single semiempirical expression for the nonideality contribution due to the concentration and intrinsic viscosity dependence, which has no other adjustable parameters, but quantitatively fits data for flexible, semiflexible, and rigid polymers in good solvents. In this report, the excluded volume theory as proposed by Ogston and Laurent is generalized to include mutual crowding between identical polymers based on hydrodynamic volumes, and applied to derive the expression for the nonideality contribution to specific viscosity, colloid osmotic pressure, and light scattering. Additionally, consideration of the contribution of mutual macromolecular crowding to the effective solvent viscosity allows prediction of polymer relaxation time and elastic modulus in semidilute solutions. This theoretical approach now allows the prediction of semidilute polymer solution properties based only on concentration and intrinsic viscosity, and conversely allows intrinsic viscosity (and thus average molecular weight) to be calculated from measurements made on semidilute solutions of known concentration. Copyright (c) 2016 John Wiley & Sons, Ltd.
机译：半硫酸盐聚合物溶液在诸如粘度，弛豫时间，弹性模量，胶体渗透压和光散射等性质中的稀释溶液而异。此前，Matsuoka和Cowman提出了由于浓度和特性粘度依赖性而具有其他可调节参数的非前熟贡献的单一效应，但是在良好的溶剂中定量地拟合了柔性，半成品和刚性聚合物的数据。在本报告中，作为ogston和劳伦特提出的排除的体积理论是推广的，以包括基于流体动力学体积的相同聚合物之间的相互拥挤，并施加用于导出对特定粘度，胶体渗透压和光散射的非前近贡献的表达。另外，考虑了相互大分子挤出到有效溶剂粘度的贡献允许预测半iltute溶液中的聚合物弛豫时间和弹性模量。该理论方法现在仅允许仅基于浓度和特性粘度来预测新ildute聚合物溶液性质，并且相反地允许根据对已知浓度的新iltute溶液的测量来计算待计算的特性粘度（并且因此平均分子量）。版权所有（c）2016 John Wiley＆Sons，Ltd。

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