Property impact of common linker segments in sequence-controlled polyesters

Abstract

Heterogeneous “linkers” are incorporated into polymers for a number of reasons, most commonly to facilitate the coupling of the targeted backbone segments. Due to their inclusion in the backbone, these linkers have the potential to affect the overall properties of the copolymer, even when present in relatively low weight percentages. To characterize the degree of impact of some common linkers, a set of polymers that incorporate both degradable sequenced segments and linkers were synthesized and systematically examined. Seven sequence-controlled olefin containing ester macrocycles were prepared, each with a unique central moiety, including a five-carbon alkyl chain, diethylene glycol, a urea, a thioether, a triazole, a bioaromatic, and an extension of the ester sequence. The macrocycles were polymerized via ED-ROMP to yield seven polymers that vary only in the the linker segment. The properties of all polymers were compared to determine the relative dominance of the different linker types. The properties tested in the study included thermal behavior, mechanical characteristics, hydrolytic degradation and film qualities. The thermal and mechanical properties proved to be dependent primarily on the ability of the linker to promote interchain interactions, as well as the weight fraction of the linker, whereas the hydrolytic degradation was dominated by the relative hydrophobicity of the linker groups. In all cases, the linker identity was a significant contributer to the behavior.