(682e) Scaling and Chemical Kinetic Mechanisms of Two Dimensional Polymers Via Irreversible Solution-Phase Synthesis
AIChE Annual Meeting
Monday, November 15, 2021 - 4:30pm to 4:45pm
Two-dimensional (2D) polymers are extended networks of multi-functional repeating units that are covalently linked together but confined to a single plane. The past decade has witnessed a surge in interest and effort towards producing and utilizing 2D polymers. However, facile synthesis schemes suitable for mass production are yet to be realized. In addition, unifying theories to describe the 2D polymerization process, like those for linear polymers, have not yet been established. Herein, we perform a chemical kinetic simulation to study the recent synthesis of 2D polymers in homogeneous solution with irreversible chemistry. We show that reaction sites for polymerization in 2D always scale unfavourably compared to 3D, growing as molecular weight to the 1/2 power versus 2/3 power for 3D. However, certain mechanisms can effectively suppress out-of-plane defect formation and subsequent 3D growth. We consider two such mechanisms, which we call bond-planarity and templated autocatalysis. In the first, although single bonds can easily rotate out-of-plane to render polymerization in 3D, some double-bond linkages prefer a planar configuration. In the second mechanism, stacked 2D plates may act as van der Waals templates for each other to enhance growth, which leads to an autocatalysis. When linkage reactions possess a 1000:1 selectivity (Î³) for staying in plane versus rotating, solution-synthesized 2D polymers can have comparable size and yield with those synthesized from confined polymerization on a surface. Autocatalysis could achieve similar effects when self-templating accelerates 2D growth by a factor Î² of 106. A combined strategy relaxes the requirement of both mechanisms by over one order of magnitude. We map the dependence of molecular weight and yield for 2D polymer on the reaction parameters, allowing experimental results to be used to estimate Î² and Î³. Our calculations show for the first time from theory, the feasibility of producing two-dimensional polymers from irreversible polymerization in solution.