Polymer Dispersity Control via Organocatalyzed Living Radical Polymerization

Molecular weight distribution of polymer, termed dispersity (Đ), is a fundamental key parameter for determining polymer material properties. This paper reports a novel approach for controlling Đ, exploiting a temperature‐selective radical generation in organocatalyzed living radical polymerization. The polymers with tailored Đ were synthesized in a batch system without the assistance of an external pump. A unique aspect of this approach is that Đ was tuneable from 1.11 to 1.50 in any segments in diblock, triblock, and multi‐block copolymers and any forms of star and brush polymers without segmental or topological restriction. This approach is amenable to various monomers and free from metels, which are attractive for applications. The approach was also able to generate polymer brushes on surfaces with tailored Đ. An interesting finding was that the polymer brushes exhibited unique interaction with external molecules, depending on Đ.

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