Beyond Dispersity: Deterministic Control of Polymer Molecular Weight Distribution.

The breadth of the molecular weight distributions (MWD) of polymers influences their physical properties; however, no synthetic methods allow precise control of the exact shape and composition of a distribution. We report a modular strategy that enables deterministic control over polymer MWD through temporal regulation of initiation in nitroxide-mediated polymerization reactions. This approach is applicable to any controlled polymerization that uses a discrete initiator, and it allows the use of MWD composition as a parameter to tune material properties.

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