Herein, a novel methodology for preparing sequence-controlled polymers was illustrated by using a latent monomer, furan protected maleimde (FMI). At high temperature (110 oC or above), the maleimde (MI) was de-protected by thermodynamically-controlled retro Diels-Alder (rDA) reaction, which was immediately involved in the cross polymerization with styrene (St). Atom transfer radical polymerization (ATRP) of St with FMI was found to create different sequence distribution compared to that of St with naked MI due to the slow release of MI via rDA. By implementing programmable fluctuations of temperature during ATRP of St and FMI, i.e., 40 oC (10.0 h)−110 oC (0.25 h)−40 oC (10.0 h)−110 oC (0.5 h), “living” polymers with tailored sequence distribution was created. The temperature of 40 oC could not trigger the rDA reaction, therefore produced homo-poly(styrene) segments. While, at 110 oC, the rDA reaction prevailed and hetro-segments were obtained. By using different tandem temperature modes, several tailor-made sequences were produced. Functional furan protected MI with alkyne group was also used as a latent monomer in reversible addition-fragmentation chain transfer polymerization, further illustrating the desirable placements of alkyne groups along the polymer chain. This proof-of-concept, i.e., sequence control by a latent monomer, opened a novel avenue for fabricating sequence-controlled polymers.

Sequence-controlled polymers by using a latent monomer-based strategy

254th National Meeting (2017)

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