Engineering Polymer Architecture Through Reaction Rates

The properties of macromolecules are intrinsically linked to their chemical composition, molecular weight distribution, and architecture. Variation of these features enables the creation of a vast chemical space capable of accommodating diverse material properties and applications. This review focuses on synthetic methodologies that exploit reaction rates to engineer the architecture of polymers. More specifically, three complementary synthetic strategies were identified: the first strategy is varying the reactivity of the monomers; the second strategy is implementing two simultaneous reactions (orthogonal or competitive); and, the third strategy is implementing reactor engineering principles, where controlling reactor parameters such as monomer concentration, residence time, and flow rate results in different architectures. Finally, this perspective is concluded with a short discussion about the challenges in a posteriori characterizing the architecture of polymers and the benefit of kinetic models to a priori predict the architecture of a polymer.