화학공학소재연구정보센터
Macromolecules, Vol.52, No.12, 4694-4702, 2019
Influence of Short-Range Scrambling of Monomer Order on the Hydrolysis Behaviors of Sequenced Degradable Polyesters
The extent to which small changes in monomer sequence affect the behaviors of biological macromolecules is studied regularly, yet the dependence of bulk properties on small sequence alterations is underexplored for synthetic copolymers. Investigations of this type are limited by the arduous syntheses required, lack of scalability, and scarcity of examples of polymer systems that are known to exhibit sensitive sequence/property dependencies. Our group has previously explored the hydrolysis behaviors of a library of sequenced poly(lactic-co-glycolic acids and found a strong correlation with the L-G sequence. To investigate the degree to which properties are dominated in this system by relatively short-range sequence changes, we have incorporated precisely sequenced and mildly "scrambled" L-G oligomers into cyclic macromonomers and subjected them to entropy-driven ring-opening metathesis polymerization, a method that we have recently shown produces polymers with molecular weight control and sequence preservation. The resulting polymers, which have identical composition and molecular weight, were hydrolyzed. Molecular weight decrease, mass loss, thermal behaviors, and film/surface characteristics were monitored to reveal stark differences in degradation behaviors despite the confinement of errors within a short segment.