Polymerization Chemistry

Polymerization and modification play central roles in polymer chemistry and are generally implemented in two steps, which suffer from the time-consuming two-step strategy and present considerable challenge for complete modification. By introducing the radical cascade reaction (RCR) into polymer chemistry, a one-step strategy is demonstrated to achieve synchronized polymerization and complete modification in situ. Attributed to the cascade feature of iron-catalyzed three-component alkene carboazidation RCR exhibiting carbon-carbon bond formation and carbon-azide bond formation with extremely high efficiency and selectivity in one step, radical cascade polymerization therefore enables the in situ synchronized polymerization through continuous carbon-carbon bond formation and complete modification through carbon-azide bond formation simultaneously. This results in a series of α, β, and γ poly(amino acid) precursors. This result not only expands the methodology library of polymerization, but also the possibility for polymer science to achieve functional polymers with tailored chemical functionality from in situ polymerization.

Synthetic polymer materials with desired functionalities in the form of plastics, fibers, rubbers, etc., have played significant roles in human life since last century, which rely mainly on the prosperous development of polymerization and modification methodologies. Polymerization and modification are two fundamental aspects of polymer chemistry and have played central roles in the history of polymer chemistry

These broadly applied two-step strategies have many disadvantages including time consumption, waste of resources, and solubility issues. And complete post-polymerization modification is a considerable challenge owing to the reduced reactivity of functional groups on the polymer chain and the embedding as well as the shielding effect of the polymer chain on functional groups. We questioned whether a one-step strategy can be developed to overcome the disadvantages by realizing synchronized polymerization and modification in one step, constructing and modifying a polymer simultaneously. To develop a one-step strategy to implement polymerization and modification will enable step-economy and efficient complete modification and is therefore highly desirable.

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Industrial Chemistry Open Access