Abstract

More and more controlled polymerization methodologies have been developed in the last decades. However, great challenges still remain in chemoselective polymerizations for advanced polymer precision synthesis. Traditionally, polymerizations in the presence of multifunctional initiators or monomers with more reactive groups suffer from ill-defined products, low efficiency and tedious synthetic steps. Meanwhile, chemoselective copolymerizations from a mixed monomer feedstock is a long-term goal for synthesis of block and multiblock copolymers. Based on the development of novel catalysis, microflow technology, and switchable strategy in the absence/presence of external-stimuli, significant progress has been achieved in chemoselective polymerizations. In this review, chemoselective homopolymerizations (multifunctional initiators and multifunctional monomers) and copolymerizations (mixed monomers and mixed mechanisms) are highlighted in order. The future challenges and opportunities are proposed with the aim to provide the insight into further development of chemoselective polymerizations and advanced polymer precision synthesis.

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