端羧基二烯聚合物的固化及聚合物负载催化剂的作用

B. Willoughby
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引用次数: 0

摘要

红外光谱和湿化学技术表明,端羧基聚丁二烯的末端酸基团的行为与代表性的低分子量稀溶液体系相同。与先前的预期相反,铬(III)催化的环氧链延伸表现出三阶特征,并且在高转化率下反应的缓慢进展可以从简单的动力学角度来解释,而无需考虑有限的官能团可及性。本体聚合物和经典溶液反应之间的相似之处预测了催化剂也是聚合物的系统的有效性:描述了两种这样的催化剂的合成和评价。虽然聚合物催化固化的凝胶时间不会变慢,但产品性能实际上可能得到改善,因此,当初始催化剂是铬(III)时,液体丁腈橡胶固化的未增强产品可能达到4.5 MPa的抗拉强度,这一改进可以根据聚合物反应性和阶梯生长过程的经典概念进行合理解释。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
The Cure of Carboxy‐terminated Diene Polymers and the Role of a Polymer‐supported Catalyst
Both infrared spectroscopy and wet chemical techniques reveal that the terminal acid groups of carboxyl-terminated polybutadiene behave in the same manner as in representative low molecular weight dilute solution systems. Contrary to previous expectations the chromium(III)-catalysed epoxy chain extension shows third-order character, and the slow progress of reaction at high conversions can be rationalised on simple kinetic grounds and without recourse to considerations of limited functional group accessibility. The parallels between bulk polymer and classical solution reactions anticipate the effectiveness of a system in which the catalyst is also a polymer: the synthesis and evaluation of two such catalysts are described. Whilst gel times are no slower for the polymer-catalysed cures, product properties may be actually improved, thus, the unreinforced product of a liquid nitrile rubber cure may achieve a tensile strength of 4.5 MPa when the initial catalyst is chromium(III) supported on the same polymer, an improvement which can be rationalised in terms of classical concepts of polymer reactivity and step growth processes.
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