Assembly and Disassembly of Polymer Hybrids Using Green Solvents

这个发现计划将探索一种新的方法，使用绿色溶剂，使组装和有序的聚合物纳米结构的dissssss。目前，需要多步复杂的化学反应来形成纳米颗粒（NP）或碳纤维，稳定它们，然后将它们附着到聚合物或表面以形成3D有序结构。目前在北美，只有不到9%的聚合物被回收利用，而含有碳或纳米颗粒的可伸缩塑料更不可能被再利用。用于制造和处置聚合物的方法通常使用被认为是挥发性有机化合物（VOC）的有机溶剂，其对于工业用途变得越来越受管制。这些VOC溶剂也不提供自组装过程的功能，同时不考虑寿命的终止。需要一种新的范例来制造这些组件，这些组件可以根据需要容易地分解回NP和聚合物链，可以容易地用于聚合物回收。我们对该计划的重点是开发一种新的连贯的方法，利用溶剂工程，可以采用商品聚合物系统，包括链增长，逐步增长和环氧聚合物系统的主要群体。我们将利用聚合物和纳米化学方法的进步，其中聚合物和纳米颗粒都可以组装，然后在产品使用寿命结束时拆卸。聚合物（RAFT和催化）和纳米（金属氧化物，量子点），碳质材料（石墨烯，碳纤维，生物炭）的进展将通过儿茶酚和网状方法使用可逆连接相互连接。由于NP和聚合物之间的键合需要相当强（例如与超分子化学中的H-键合相比），因此将检查溶剂官能度以促进平衡过程和可逆性的热力学条件。按需定制是我们的目标。将检查具有超临界流体或离子液体的绿色生物基溶剂（乳酸盐、碳酸盐），其可以根据溶质尺寸/形状和溶剂结构、压力和温度来控制聚合物/NP可逆性。学生将接受使用我们最先进的高压设备进行聚合物和纳米合成的培训，并在分子建模（DFT和Gromacs）中了解什么类型的溶剂系统最好，以及如何使用两相系统。组装和拆卸的动力学将使用原位FTIR、拉曼和NMR进行实验测量，并对反应步骤进行建模。聚合物和NP的溶解度将在sc-CO2与生物溶剂或生物溶剂/SCF两相系统中进行检查。 动力学建模、溶解动力学和溶解度建模将与工艺工程的实验数据进行比较。该研究计划将提供新的HQP和新数据，以促进广泛的工业采用，帮助加拿大在先进制造业中竞争，同时帮助引领循环经济。

This Discovery program will explore a new methodology using green solvents to enable the assembly and dissssembly of ordered polymer nanostructures. Currently, multistep complex chemistries are required to form nanoparticles (NPs) or carbon fibers, stabilize them, then attach them to polymers or surfaces to form 3D ordered structures. Less than 9% of polymers are currently recycled in North America, with retractable plastics containing carbon or nanoparticles even less likely to be re-utilized. The processes used for making and disposing of polymers often use organic solvents which are considered volatile organic compounds (VOCs), which are becoming increasingly regulated for industrial use. These VOC solvents also provide no functionality for the self-assembly process, while end of lifetime is not considered. A new paradigm is required to make these assemblies that can be disassembled back into the NPs and polymer chains readily upon demand, that can be easily adopted for polymer recycling. Our focus for this program is to develop a new coherent approach utilizing solvent engineering that can be adopted to commodity polymer systems including the major groups of chain-growth, step-growth and epoxy polymer systems. We will harness advances in polymer and nano chemistry methods in which the polymer and nanoparticles can both be assembled and then dissembled at the end of the products useful lifetime. Advances in polymer (RAFT and catalytic) and nano (metal oxides, quantum dots), carbonaceous materials (graphene, carbon fibers, biochar) will be attached to one another using reversible linkages via catechol and reticular methods. As the bonding between the NPs and polymers needs to be rather strong (compared to H-bonding for example in supramolecular chemistry), the solvent functionality will be examined to facilitate the equilibria process and thermodynamic conditions for reversibility. Decoordination on demand is our goal. Green biobased solvents (lactates, carbonates) with supercritical fluids or ionic liquids will be examined that can control the polymer/NP reversibility, depending on solute size/shape and the solvent structure, pressure and temperature. Students will be trained in polymer and nano synthesis using our state of the art high pressure equipment and in molecular modeling (DFT and Gromacs) on what type of solvent system is best, and how biphasic systems can be used. Both the kinetics of assembly and disassembly will be experimentally measured  using insitu FTIR, Raman and NMR with the reaction steps modelled. Polymer and NP solubilities will be examined in sc-CO2 with biosolvents or biosolvent/SCF biphasic systems.  Kinetic modelling, dissolution kinetics and solubility modelling will be compared to experimental data for process engineering. This research program will provide both new HQP and new data to facilitate wide industrial adoption to help Canada compete in advanced manufacturing while helping to lead the circular economy.