With this award, the Macromolecular, Supramolecular and Nanochemistry Program of the Division of Chemistry is supporting Professor Alexandru Asandei of the University of Connecticut to develop new approaches for the synthesis of diene-based polymers. Polymers have many important applications in everyday life. One type of widely used polymer is prepared from monomers that belong to the diene class. Diene-based polymers are important components of synthetic rubbers in tires of automobiles and high-impact plastics. Professor Asandei aims to develop a sustainable alternative to the synthesis of diene-based polymers at lower production cost in an approach that targets the use of biorenewable monomers. This fundamental research project spans a wide variety of techniques and methods, providing a multi-disciplinary environment for the education and research training of graduate students and undergraduate coworkers. Outreach to high school students from a variety of backgrounds is also planned.
Synthetically, while the production of random diene copolymers benefits from emulsion radical polymerizations, the synthesis of corresponding thermoplastic elastomer block copolymers involves expensive, water sensitive anionic/coordination polymerizations. Thus, inexpensive, water tolerant, controlled radical polymerizations (CRPs) would be highly beneficial. In this research, Professor Asandei and coworkers aim to provide quantitative understanding of the atom transfer radical polymerization (ATRP) of dienes, a process that offers the potential advantages of simplicity, low cost, catalytic nature, tunable, and water tolerance. This research project entails detailed kinetic investigations carried out in inexpensive pressurized glass tubes, which enable both photochemistry and a fast, cost efficient optimization. These studies are expected to provide information on the effect of diene structure, ATRP type, temperature, initiator, solvent, catalyst, ligand, additives and reagent ratios on the molecular weight, polydispersity, rate, side reactions and chain end functionality of associated polymerizations. Such knowledge is expected to enable the development of emulsion diene ATRP, and facilitate the synthesis of complex polydiene-copolymer architectures.