Transforming
how plastics are made, unmade, and remade through
innovative research and diverse partnerships that together foster
environmental stewardship is critically important to a sustainable
future. Designing, preparing, and implementing polymers derived from
renewable resources for a wide range of advanced applications that
promote future economic development, energy efficiency, and environmental
sustainability are all central to these efforts. In this Chemical
Reviews contribution, we take a comprehensive, integrated
approach to summarize important and impactful contributions to this
broad research arena. The Review highlights signature accomplishments
across a broad research portfolio and is organized into four wide-ranging
research themes that address the topic in a comprehensive manner:
Feedstocks, Polymerization Processes and Techniques, Intended Use,
and End of Use. We emphasize those successes that benefitted from
collaborative engagements across disciplinary lines.
Converting biomass-based feedstocks into polymers not only reduces our reliance on fossil fuels, but also furnishes multiple opportunities to design biorenewable polymers with targeted properties and functionalities. Here we report a series of high glass transition temperature (Tg up to 184 °C) polyesters derived from sugar-based furan derivatives as well as a joint experimental and theoretical study of substituent effects on their thermal properties. Surprisingly, we find that polymers with moderate steric hindrance exhibit the highest Tg values. Through a detailed Ramachandran-type analysis of the rotational flexibility of the polymer backbone, we find that additional steric hindrance does not necessarily increase chain stiffness in these polyesters. We attribute this interesting structure-property relationship to a complex interplay between methyl-induced steric strain and the concerted rotations along the polymer backbone. We believe that our findings provide key insight into the relationship between structure and thermal properties across a range of synthetic polymers.
Unfavorable thermodynamics often render furans reluctant to engage in high-yielding Diels-Alder (DA) cycloaddition reactions. Here we report the highly efficient conversion of the bio-sourced reactants itaconic anhydride (IA) and furfuryl alcohol (FA) to a single DA adduct. The free energy advantages provided by anhydride ring-opening and crystal lattice energy of the product overcome the loss of aromaticity of the furanoid diene. Detailed 1H NMR studies provided valuable insights about relevant kinetic and thermodynamic features.
Stereo-defects present in stereo-regular polymers often diminish thermal and mechanical properties, and hence suppressing or eliminating them is a major aspirational goal for achieving polymers with optimal or enhanced properties. Here, we accomplish the opposite by introducing controlled stereo-defects to semicrystalline biodegradable poly(3-hydroxybutyrate) (P3HB), which offers an attractive biodegradable alternative to semicrystalline isotactic polypropylene but is brittle and opaque. We enhance the specific properties and mechanical performance of P3HB by drastically toughening it and also rendering it with the desired optical clarity while maintaining its biodegradability and crystallinity. This toughening strategy of stereo-microstructural engineering without changing the chemical compositions also departs from the conventional approach of toughening P3HB through copolymerization that increases chemical complexity, suppresses crystallization in the resulting copolymers, and is thus undesirable in the context of polymer recycling and performance. More specifically, syndio-rich P3HB (sr-P3HB), readily synthesized from the eight-membered mesodimethyl diolide, has a unique set of stereo-microstructures comprising enriched syndiotactic [rr] and no isotactic [mm] triads but abundant stereo-defects randomly distributed along the chain. This sr-P3HB material is characterized by high toughness (U T = 96 MJ/m 3 ) as a result of its high elongation at break (>400%) and tensile strength (34 MPa), crystallinity (T m = 114 °C), optical clarity (due to its submicron spherulites), and good barrier properties, while it still biodegrades in freshwater and soil.
The cover picture shows the scheme of the electrochemical sensor for the detection of Cu2+ based on gold nanoflowers‐modifed electrode and DNAzyme functionalized Au@MIL‐101 (Fe). DNAzyme substrate strand was cleaved into two parts due to the presence of Cu2+, the oligonucleotide fragment linked to MIL‐101(Fe) was able to hybridize with DNA1 adsorbed onto the surface of AuNFs/ITO, so as to generate electrochemical signals' change. The electrochemical biosensor showed a sensitive detection range and a high selectivity. More Details can be found in the Full Paper by Shengpan Xu, Benlin Dai, Jiming Xu, Ling Jiang, and He Huang (DOI: 10.1002/elan.201900343).
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