The Polymerization of Vinyl Alcohol

9634528诺瓦克这笔赠款旨在寻找更直接的方法，从廉价的新单体合成有用的聚合物。具体地说，PI将分别专注于从烯醇和烯胺合成聚乙烯醇(PVOH)、PVOH衍生物和聚乙烯胺(PVAm)衍生物。这项工作的目标之一是将乙醛转化为PVOH，这实际上是由乙烯和氧气合成PVOH。综合方法包括通过从动力学的角度处理难题来绕过固有的热力学限制。从这个角度来看，许多热力学问题可以转化为竞争速率问题，因此可以通过化学(例如催化、条件等)来解决。在这一提议的背景下，烯醇(例如，乙烯醇及其取代的衍生物)将在亚稳定条件下快速生成，并以比它们能互变为热力学上更稳定的醛的速度更快的速度聚合。烯丙醇衍生物在均相Rh(I)、Ir(I)和Ru(II)催化剂上催化异构化为相应的烯醇也将生成替代的烯醇。%从普通且廉价的来源合成重要聚合物，特别是用于从制药到低VOC涂料等应用的水溶性聚合物的合成。***

9634528 Novak This grant is directed torward finding more direct methods of synthesizing useful polymers from inexpensive, new monomers. Specifically, the PI will focus on the synthesis of poly(vinyl alcohol) (PVOH), PVOH derivatives, and poly(vinyl amine) (PVAm) derivatives from enols and enamines, respectively. One goal of this work is the conversion of acetaldehyde to PVOH, which de facto, is the synthesis of PVOH from ethylene and oxygen. The synthetic approach involves circumventing inherent thermodynamic limitations by approaching conundrums from a kinetic perspective. From this vantage point, many thermodynamic problems can be transformed into competitive rate problems, and hence, remedied through chemistry (e.g., catalysis, conditions, etc.). In the context of this proposal, enols (e.g., vinyl alcohol, and its substituted derivatives) will be rapidly generated under meta-stable conditions and polymerized at a rate faster than they can tautomerize to the more thermodynamically stable aldehyde. Alternative enols will also be generated by the catalytic isomerization of allyl alcohol derivatives to the corresponding enols using homogeneous Rh(I), Ir(I), and Ru(II) catalysts. %%% Synthesis of important polymers from common and inexpensive sources, in particular on synthesis of water-soluble polymers used in applications ranging from pharmaceuticals to low VOC paints. ***