GOALI: Novel Processes for the Synthesis of Polyisoprene and Polyisoprene-Polyisobutylene Block and Graft Copolymers based on Natural Rubber Biosynthesis

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The main objective of this project is to design a natural living polymerization (NLP) system that may lead to synthetic "Natural Rubber" (NR) or cis-1, 4-polyisoprene (cPIP). In order to investigate the hypothesis that NR biosynthesis is consistent with the mechanism of living/controlled polymerizations, two simultaneous projects were proposed. In Project I, the study of modified in vitro biosynthesis processes utilizing synthetic polyisobutylene-based macro initiator will be examined. A combination of fully synthetic living carbocationic polymerization, yielding the precursor of the macro initiator, with NR biosynthesis, will produce a fundamentally novel block copolymer, polyisobutylene-b-cis-1, 4-polyisoprene (PIB-b-NR). Project II will demonstrate a conceptually new synthetic living polymerization (NLP), similar to NR biosynthesis, to produce polyisoprene.With this award, the Organic and Macromolecular Chemistry Program supports the research of Professor Judit Puskas of the University of Akron who will demonstrate the viability of the proposed new living polymerization that mimics natural rubber biosynthesis, which may open avenues to novel methods for the production of synthetic cis-polyisoprene. Currently Hevea brasiliensis is the only NR producing species for commercial use, with very little genetic variability, leaving rubber plantations at risk of serious pathogenic attacks. Further, repeated exposure to proteins in NR has led to serious allergenic hypersensitivity. Thus there is great interest to find alternate sources for NR, a strategically important material for the rubber industry (annual revenue 10 billion dollars). The project will produce close interaction with the Goodyear Tire & Rubber Co. where students with be exposed to industrial polymer chemistry, new characterization methods, potential scale-up, the U.S. Department of Agriculture (USDA), and will be trained in the methodology of in vitro biopolymerization.