Precise Acid Copolymers and Ionomers: Morphology, Dynamics and Mechanical Properties

技术概述：精密酸共聚物是一种新型材料，其官能团沿线性聚乙烯均匀分布。例如，磷酸基可以放在每9、15或21个碳上。该项目涉及九种精确的酸共聚物和一种随机的酸共聚物，它们具有羧酸和膦酸基团，具有单取代或双取代。这些材料已经建立了合成路线。Winey对酸共聚物的形态研究将使用x射线散射、HAADF STEM和电子衍射来确定聚乙烯片段的晶体结构和酸基团组合的性质。酸性共聚物将与Li， Na， Cs和Zn中和，形成部分中和和完全中和的离子单体，Winey将在其中探测离子聚集体的大小，形状，空间排列和组成。已知这些酸性共聚物和离聚体的精度在形态上产生显著的均匀性，使数据解释和与模拟的比较更加严格。本文将首次研究三种精确酸性共聚物和一种随机酸性共聚物及其离聚体的动力学和力学性能。性能测量将包括熔体流变学，探索弹性变形的小应变压缩测试，以及研究塑性变形的大应变循环压缩测试。PI的团队在研究这些卓越聚合物的形态、动力学和机械性能方面具有高度专业化的专业知识，包括先前的工作和现有的合作。PI将研究一组特殊的功能聚合物，其最终目标是了解官能团的排列方式，从而了解它们的排列方式如何决定它们的机械性能。这些功能聚合物沿着聚乙烯分子每隔9、15或21个碳原子就有一个酸基。这些分子前所未有的精度将导致在微观和纳米尺度上更好的结构秩序，这反过来又使分子结构和性质之间的相关性得到改善。PI已经与合成化学家、光谱学家和理论家建立了合作关系，以探索这些非凡的材料，在这个跨学科的团队中，更多的学生和研究人员的教学、学习和培训将得到极大的丰富。这些精确的聚合物是基于聚乙烯，它构成了最大的一类商业聚合物。该项目包括首次对这些材料进行动态和机械性能测量，并以此评估其商业潜力。

TECHNICAL SUMMARYPrecise acid copolymers are novel materials having functional groups spaced exactly evenly along a linear polyethylene. For example, a phosphonic acid group can be placed on every 9th, 15th or 21st carbon. The proposed project involves nine precise acid copolymers and one random acid copolymer having carboxylic acid and phosphonic acid groups with mono- or geminal-substitution. These materials have established synthetic routes. Winey's morphological studies of the acid copolymers will use X-ray scattering, HAADF STEM, and electron diffraction to establish the crystalline structure of the polyethylene segments and the nature of the acid group assemblies. The acid copolymers will be neutralized with Li, Na, Cs, and Zn to form partially- and fully-neutralized ionomers in which Winey will probe the size, shape, spatial arrangement, and composition of the ionic aggregates. The precision of these acid copolymers and ionomers is known to yield remarkable uniformity in the morphologies, making data interpretation and comparisons with simulations more rigorous. The dynamics and mechanical properties will be studied for the first time in three precise acid copolymers and one random acid copolymer, along with their ionomers. The property measurements will include melt rheology, small-strain compression testing to explore elastic deformations, and large-strain, cyclic compression testing to study plastic deformation. The PI's group has highly specialized expertise to study the morphology, dynamics, and mechanical properties of these remarkable polymers in terms of both demonstrated prior work and existing collaborations. NON-TECHNICAL SUMMARYThe PI will study an extraordinary set of functional polymers with the ultimate goal of knowing how the functional groups are arranged and thereby how their arrangement dictates their mechanical properties. These functional polymers have an acid group on every 9th, 15th or 21st carbon atom along a polyethylene molecule. The unprecedented precision in these molecules will lead to better structural order at both the micro- and nanoscale, which, in turn, enable improved correlations between molecular structure and properties. The PI has established collaborations with synthetic chemists, spectroscopists, and theorists to explore these remarkable materials, and within this interdisciplinary team the teaching, learning, and training of more students and researchers will be significantly enriched. These precise polymers are based on polyethylene, which constitutes the largest class of commercial polymers. This project involves the first dynamical and mechanical property measurements of these materials and in so doing will evaluate their commercial potential.