Robust Amidation Transformation of Plant Oils into Fatty Derivatives for Sustainable Monomers and Polymers

Sustainable fuels, chemicals, and materials from renewable resources have recently gained tremendous momentum in a global scale, although there are numerous nontrivial hurdles for making them more competitive with petroleum counterparts. We demonstrate a robust strategy for the transformation of plant oils into polymerizable monomers and thermoplastic polymer materials. Specifically, triglycerides were converted into <i>N</i>-hydroxyalkyl fatty amides with the aid of amino alcohols via a mild base-catalyzed amidation process with nearly quantitative yields without the use of column chromatography and organic solvents. These fatty amides were further converted into a variety of methacrylate monomers, cyclic norbornene monomers and imino ether monomers. Representative polymers from selected monomers exhibit drastic different physical properties with subtle structural variations, highlighting the potential of this particular amidation reaction in the field of biomass transformation

Sustainable thermoplastic elastomers derived from plant oil and their 'click-coupling' via TAD chemistry

We report the preparation of plant oil based triblock copolymers based on soybean oil monomers. The monomers were polymerized via atom transfer radical polymerization with subsequent chain extension, resulting in poly(styrene-b-soybean oil acrylate-b-styrene) (PS-b-PSBA-b-PS) and poly(styrene-b-soybean oil methacrylate-b-styrene) (PS-b- PSBMA-b-PS) triblock copolymers. These polymers, ranging from thermoplastics to thermoplastic elastomers (TPEs), were obtained by tuning molecular structures. We employed a "click coupling" strategy using triazolinedione (TAD) chemistry to create chemical junctions between the soft middle blocks of the triblock copolymers, which behave similar to physical chain entanglements. This method helps to overcome the drawbacks of plant oil based polymers, allowing for increase of tensile strength without sacrificing elongation. Cyclic tensile tests show that the "click coupled" triblock copolymers exhibit excellent elastic recovery characteristics

Biomass approach toward robust, sustainable, multiple-shape-memory materials

We report biomass-derived, shape-memory materials prepared via simple reactions, including "grafting from" ATRP and TAD click chemistry. Although the biomass, including plant oils and cellulose nanocrystals, has heterogeneous chemical structures in nature, these materials exhibit excellent multiple shape-memory properties toward temperature, water, and organic solvents, which are comparable to petroleum counterparts. The work presented herein provides burgeoning opportunities to design the next-generation, low-cost, biomass-prevalent, green materials for niche applications