Precision of Architecture-Controlled Bottlebrush Polymer Synthesis: A Monte Carlo Analysis

Bottlebrush polymers are large macromolecules with a high density of brushes grafted onto a central backbone. Recent experimental work has seen the expansion of these polymer architectures beyond cylinders. Herein we develop a Monte Carlo (MC) method to explore the precision with which these noncylindrical materials can be produced and look to generate design rules for the synthesis of these materials. The computational method captures the stochasticity of the polymerization methods and generates large ensembles of bottlebrush polymers using various synthetic parameters like brush dispersity, backbone dispersity, and rate of polymerization. For each of the cases studied, three independent descriptors (two of them describing the geometrical aspect of the macromolecules and one for the variance in brush lengths) were evaluated. The method highlights the varying tolerance of brush conversion as a function of the target bottlebrush architecture and a need for the low brush (<1.2) and narrow backbone dispersity to get the highest precision in architecture control of bottlebrush polymers. Furthermore, the MC method is utilized to draw comparisons between different methodologies for architecture control. The visualization developed using the Monte Carlo method provides a new way to characterize the precision of architecture-controlled bottlebrush polymer synthesis that is complementary to traditional characterization techniques.