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Ring-closure and ring-expansion techniques are the two routes for extensive synthesis of cyclic polymers. Here, we report an alternative blocking-cyclization technique referred to as the third route to prepare cyclic polymers with regulated ring size and ring number by ring-opening metathesis polymerization of di- and monofunctional monomers in a one-pot process, where the polymer intermediates bearing two single-stranded blocks are efficiently cyclized by the cyclizing unit of propagated ladderphane to generate corresponding mono-, bis-, and tricyclic polymers, and the well-defined ladderphane structure plays a crucial role in forming the cyclic topology. Monocyclic polymer is further modified via Alder-ene reaction and the cyclic molecular topology is clearly demonstrated. The diversity features of cyclic polymers are comprehensively revealed. This strategy has broken through the limitations of previous two cyclizing routes, and indeed opens a facile and popular way to various cyclic polymers by commercial Grubbs catalyst and conventional metathesis polymerization.

Blocking-cyclization technique for precise synthesis of cyclic polymers with regulated topology