Relying solely on mild ultraviolet irradiation of thiocarbonylthio compounds in the presence of vinyl monomers, a new avenue to well-defined ultrahigh molecular weight (UHMW) polymers has been developed. Through the use of aqueous conditions, well-controlled polymers with high molecular weights that are unprecedented for controlled radical polymerizations have been achieved. This photomediated polymerization approach reaches number-average molecular weights in excess of 8.00^10<sup>6</sup> g/mol with degrees of polymerization above 85,000, making these, to our knowledge, the highest molecular weight polymers ever achieved via reversible-deactivation radical polymerization. In many cases, well-defined UHMW polymers can be obtained in minutes. The utility of the technique is further demonstrated through the synthesis of block copolymers, enabling access to a new field of well-defined UHMW materials.

Exploiting light to push the limits of controlled radical polymerization

255th National Meeting (2018)

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