Polymer with Competing Depolymerization Pathways: Chain Unzipping versus Chain Scission
Polymer with Competing Depolymerization Pathways: Chain Unzipping versus Chain Scission
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DOI：
10.1021/acsmacrolett.0c00250
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发表时间：
2020-06-16
影响因子：
7.015
通讯作者：
Thayumanavan, S.
中科院分区：
文献类型：
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作者：
Addy, Partha Sarathi;Shivrayan, Manisha;Thayumanavan, S.
受可持续塑料、自修复材料、控释和感官放大需求的推动，对触发解聚的兴趣正在增长。对于许多触发的解聚反应，限速步骤不直接涉及刺激，因此，解聚动力学表现出的浓度和反应性的刺激只有弱或没有相关性。然而，对于许多应用，需要刺激和解聚动力学之间的直接关系。在这里，我们设计，合成，并研究了一种聚合物，其中nudeophile诱导断链（NICS）机制与链解链途径竞争。我们发现，选择的链端功能和亲核试剂的性质决定了这些是主要的途径。NICS途径被认为是依赖于刺激浓度，相反的链解链机制。我们证明了这些分子尺度的可转移性，纳米材料的结构-性能的关系，通过将聚合物配制成主机纳米粒子。
Interest in triggered depolymerization is growing, driven by needs in sustainable plastics, self-healing materials, controlled release, and sensory amplification. For many triggered depolymerization reactions, the rate-limiting step does not directly involve the stimulus, and therefore, depolymerization kinetics exhibit only weak or no correlation to the concentration and reactivity of the stimulus. However, for many applications, a direct relationship between the stimulus and the depolymerization kinetics is desired. Here we designed, synthesized, and studied a polymer in which a nudeophile-induced chain scission (NICS) mechanism competes with the chain unzipping pathway. We find that the choice of the chain end functionality and the character of the nucleophile determines which of these is the predominant pathway. The NICS pathway was found to be dependent on the stimulus concentration, in contrast to the chain unzipping mechanism. We demonstrate transferability of these molecular-scale, structure-property relationships to nanoscale materials by formulating the polymers into host nanoparticles.