The Lewis acid catalyzed polymerization of ylides is a novel method for synthesizing simple hydrocarbon polymers. The chemistry uses C1 carbon feedstock and takes advantage of more abundant and/or renewable sources of carbon. The reaction, a living condensative chain polymerization, proceeds by repetitive formation of sp3–sp3 carbon–carbon bonds and provides exceptional control over molecular weight and polydispersity. In addition the reaction makes available polymer architectures not readily realized by conventional olefin polymerization. The reaction has been used for the controlled synthesis of polymethylidene-co-ethylidene hydrocarbon polymers and copolymers, surrogates for polyethylene–co-polypropylene. The reaction can be run in water at room temperature and atmospheric pressure for the synthesis of polymethylene waxes, The ylide monomer, dimethylsulfoxonium methylide, is generated in situ from a stable salt, trimethylsulfoxonium halide. The reaction is initiated/catalyzed by trialkylboranes, readily available Lewis acids that are stable in water. Applications of this chemistry are being developed for simple practical methods for producing long-chain aliphatic AA, BB and AB macromers for polyester and polyamide synthesis. We will also report on a long-standing challenge in polymer synthesis, the precise introduction of a functional monomer in an all carbon backbone polymer.

Controlled synthesis of simple hydrocarbon polymers from C1 carbon sources: Living polymerization of ylides

251st National Meeting (2016)

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