Amphicatalytic polymerization by diastereospecific ion pairs leads to formation of stereo-sequence-controlled multiblock polymers. In this polymerization, compatible and dually active ion pairs, in which both the cation and the anion can independently catalyze the polymer chain growth in a single polymerization reaction. Furthermore, cations and anions of the ion pair exhibit different stereoselectivity and growing chains at the cationic and anionic sites can undergo infrequent exchanges between the two sites, thereby covalently linking the polymer chains produced at both sites to afford functionalized vinyl polymers with stereomultiblock microstructures. Operating differently, Lewis pair polymerization utilizes either a frustrated Lewis pair or a classical Lewis adduct in which the Lewis acid and Lewis base work cooperatively to activate the monomer substrate and participate in chain initiation as well as chain propagation or termination/transfer events. Such systems are highly active for polymerization of a variety of monomers and completely chemoselective towards polymerization of divinyl acrylic monomers, thus providing a facile, convenient, yet powerful approach to functional polymeric materials.

Regulating polymer stereomicrostructures and polymerization activity and chemoselectivity by ion pairs and Lewis pairs

253rd National Meeting (2017)

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