The properties, applications, and end-of-life considerations of plastics are fundamentally linked to the structure of the polymer backbones at the core of these materials. With that in mind, editing the polymer backbone composition offers exciting opportunities to transform the plastics economy; yet, few examples of such transformations utilize commodity plastics as starting materials. In this work, we describe the development of a tandem C–H oxidation/hydroxyalkyl azide mediated rearrangement strategy that converts polyethylene into “polyethylene-like” materials with iminium ethers, esters, amides, and other pendant chemical functionality. Control over formation of esters or amides is achieved by variation of the hydroxyalkyl azide reagent, as well as processing conditions. By targeting specific functionalities, a variety of thermal and mechanical properties can be accessed. For example, incorporation of iminium ethers decreases the Young's modulus of post-consumer PE from 196 MPa to 69–83 MPa, but conversion of the iminium ethers to esters and amides produces materials with moduli of 212–287 MPa—values higher than the original material. Thus, the demonstration of a modular backbone editing methodology for polyethylene showcases the broader value of this emerging strategy for polymer modification.

中文翻译：

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氧化聚乙烯的主链编辑：通过羟基烷基叠氮化物介导的重排插入氧原子和氮原子


塑料的性能、应用和报废考虑因素从根本上与这些材料核心的聚合物主链的结构有关。考虑到这一点，编辑聚合物主链成分为改变塑料经济提供了令人兴奋的机会;然而，很少有此类转变的例子使用商品塑料作为起始材料。在这项工作中，我们描述了串联 C-H 氧化/羟基烷基叠氮化物介导的重排策略的开发，该策略将聚乙烯转化为具有亚胺醚、酯、酰胺和其他悬垂化学官能团的“类聚乙烯”材料。通过改变羟基烷基叠氮化物试剂以及加工条件来控制酯或酰胺的形成。通过针对特定功能，可以访问各种热性能和机械性能。例如，掺入亚胺醚会将消费后 PE 的杨氏模量从 196 MPa 降低到 69-83 MPa，但将亚胺醚转化为酯和酰胺会产生模量为 212-287 MPa 的材料，该值高于原始材料。因此，聚乙烯模块化骨架编辑方法的演示展示了这种新兴聚合物改性策略的更广泛价值。