The synthesis of sequence-regulated polymers remains a long-standing challenge in the field of polymer chemistry. Using living/controlled catalytic system, sequence-regulated polyester based thermoplastic elastomers (TPEs) and polar conjugated diene monomers based polymers with (AB)n sequence could be synthesized in controlled manner. Without the requirement of specific functionalized groups, TPEs consisting of poly(L-lactide) hard segments and poly(e-caprolactone)-co-p(d-valerolactone) soft segments are successfully synthesized with high stretchability (up to 2100%), strong tensile strength (up to 71.5 MPa), and super-toughness (445 MJ/m3) by simply adjusting microstructures of polymers. Systematic investigation reveals that the block-like, gradient microstructure not only improves ductility by providing flexible elastic network, but also enhances tensile strength through strain induced crystallization. In addition, Lewis pairs were applied for 1,4-selective polymerization of (E,E)-methyl sorbate (MS) and (E,E)-ethyl sorbate (ES). High catalytic activity and high initiation efficiency can be achieved, leading to the formation of PMS with 100% 1,4-selectivity, tunable molecular weight (Mw up to 333 kg/mol) and narrow MWD. Furthermore, simple chemical reactions can efficiently convert PMS to different polymers with strict (AB)n sequence structures, such as poly(propylene-alt-methyl acrylate), poly(propylene-alt-acrylic acid), poly(propylene-alt-allyl alcohol) and poly(ethylene-alt-2-butylene). Their material properties including thermal properties, surface properties and adhesion properties were investigated in details.

Controllable synthesis of sequence-regulated functional polymers based on renewable monomers

ACS Spring 2022

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