The incorporation of cleavable comonomers as additives into polymers can imbue traditional polymers with controlled deconstructability and expanded end-of-life options. The efficiency with which cleavable comonomer additives (CCAs) can enable deconstruction is sensitive to their local distribution within a copolymer backbone, which is dictated by their copolymerization behavior. While qualitative heuristics exist that describe deconstructability, comprehensive quantitative connections between CCA loadings, reactivity ratios, polymerization mechanisms, and deconstruction reactions on the deconstruction efficiency of copolymers containing CCAs have not been established. Here, we broadly define these relationships using stochastic simulations characterizing various polymerization mechanisms (e.g., coltrolled/living, free-radical, and reversible ring-opening polymerizations), reactivity ratio pairs (spanning 2 orders of magnitude between 0.01 and 100), CCA loadings (2.5% to 20%), and deconstruction reactions (e.g., comonomer sequence-dependent deconstruction behavior). We show general agreement between simulated and experimentally observed deconstruction fragment sizes from the literature, demonstrating the predictive power of the methods used herein. These results will guide the development of more efficient CCAs and inform the formulation of deconstructable materials.

中文翻译：

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定义涉及可裂解共聚单体添加剂的共聚反应的反应性-解构性关系


将可裂解共聚单体作为添加剂掺入聚合物中可以使传统聚合物具有受控的解构性和扩大的报废选择。可裂解共聚单体添加剂 (CCA) 解构的效率对其在共聚物主链内的局部分布很敏感，这由它们的共聚行为决定。虽然存在描述解构性的定性启发法，但 CCA 负载量、反应性比率、聚合机制和解构反应对含 CCA 的共聚物解构效率之间的全面定量联系尚未建立。在这里，我们使用随机模拟来广泛定义这些关系，这些模拟描述了各种聚合机制（例如，受控/活性、自由基和可逆开环聚合）、反应率对（跨越 0.01 和 100 之间的 2 个数量级）、CCA 负载（2.5% 至 20%）和解构反应（例如，共聚单体序列依赖性解构行为）。我们显示了文献中模拟和实验观察到的解构片段大小之间的普遍一致性，证明了本文所用方法的预测能力。这些结果将指导更有效的 CCA 的开发，并为可解构材料的配方提供信息。