Abstract
Nearly all polymers are derived from nonrenewable fossil resources, and their disposal at their end of use presents significant environmental problems. Nonetheless, polymers are ubiquitous, key components in myriad technologies and are simply indispensible for modern society. An important overarching goal in contemporary polymer research is to develop sustainable alternatives to "petro-polymers" that have competitive performance properties and price, are derived from renewable resources, and may be easily and safely recycled or degraded. Aliphatic polyesters are particularly attractive targets that may be prepared in highly controlled fashion by ring-opening polymerization of bioderived lactones. However, property profiles of polyesters derived from single monomers (homopolymers) can limit their applications, thus demanding alternative strategies. One such strategy is to link distinct polymeric segments in an A-B-A fashion, with A and B chosen to be thermodynamically incompatible so that they can self-organize on a nanometer-length scale and adopt morphologies that endow them with tunable properties. For example, such triblock copolymers can be useful as thermoplastic elastomers, in pressure sensitive adhesive formulations, and as toughening modifiers. Inspired by the tremendous utility of petroleum-derived styrenic triblock copolymers, we aimed to develop syntheses and understand the structure-property profiles of sustainable alternatives, focusing on all renewable and all readily degradable aliphatic polyester triblocks as targets. Building upon oxidation chemistry reported more than a century ago, a constituent of the peppermint plant, (-)-menthol, was converted to the ε-caprolactone derivative menthide. Using a diol initiator and controlled catalysis, menthide was polymerized to yield a low glass transition temperature telechelic polymer (PM) that was then further functionalized using the biomass-derived monomer lactide (LA) to yield fully renewable PLA-PM-PLA triblock copolymers. These new materials were microphase-separated and could be fashioned as high-performing thermoplastic elastomers, with properties comparable to commercial styrenic triblock copolymers. Examination of their hydrolytic degradation (pH 7.4, 37 °C) revealed retention of properties over a significant period, indicating potential utility in biomedical devices. In addition, they were shown to be useful in pressure-sensitive adhesives formulations and as nucleating agents for crystallization of commercially relevant PLA. More recently, new triblocks have been prepared through variation of each of the segments. The natural product α-methylene-γ-butyrolactone (MBL) was used to prepare triblocks with poly(α-methylene-γ-butyrolactone) (PMBL) end blocks, PMBL-PM-PMBL. These materials exibited impressive mechanical properties that were largely retained at 100 °C, thus offering application advantages over triblock copolymers comprising poly(styrene) end blocks. In addition, replacements for PM were explored, including the polymer derived from 6-methyl caprolactone (MCL). In sum, success in the synthesis of fully renewable and degradable ABA triblock copolymers with useful properties was realized. This approach has great promise for the development of new, sustainable polymeric materials as viable alternatives to nonrenewable petroleum-derived polymers in numerous applications.