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Free radical and RAFT polymerization of vinyl esters with different molecular dimensions are conducted in the nanochannels of metal–organic-frameworks (MOFs). The combination of MOFs with the RAFT technique enables the synthesis of highly isotactic poly(vinyl ester)s with a controlled molecular weight and narrow molecular weight distribution, and stereocontrolled isotactic-block-atactic vinyl ester block copolymers.

Graphical abstract: Free radical and RAFT polymerization of vinyl esters in metal–organic-frameworks

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