The manipulation of a polymer’s properties without altering its chemical composition is a major challenge in polymer chemistry, materials science and engineering. Although variables such as chemical structure, branching, molecular weight and dispersity are routinely used to control the architecture and physical properties of polymers, little attention is given to the often profound effect of the breadth and shape of the molecular-weight distribution (MWD) on the properties of polymers. Synthetic strategies now make it possible to explore the importance of parameters such as skew and the higher moments of the MWD function beyond the average and standard deviation. In this Review, we describe early accounts of the effect of MWD shape on polymer properties; discuss synthetic strategies for controlling MWD shape; describe current endeavours to understand the influence of MWD shape on rheological and mechanical properties and phase behaviour; and provide insight into the future of using MWDs in the design of polymeric materials.

在不改变其化学组成的情况下操纵聚合物的性质是聚合物化学，材料科学和工程学中的主要挑战。尽管通常使用诸如化学结构，支化，分子量和分散性等变量来控制聚合物的结构和物理性质，但很少关注分子量分布（MWD）的宽度和形状对聚合物的经常深刻影响。聚合物的性能。现在，合成策略使探索诸如偏斜和MWD函数超出平均和标准偏差的较高矩的参数的重要性成为可能。在这篇综述中，我们描述了MWD形状对聚合物性能的早期影响。讨论控制随钻测井形状的综合策略；描述当前为了解MWD形状对流变力学性能和相行为的影响所做的努力；并提供有关在聚合物材料设计中使用MWD的未来的见解。