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

本项目的主要目标是设计一种天然活性聚合（NLP）体系，该体系可能导致合成“天然橡胶”（NR）或顺式1,4 -聚异戊二烯（cPIP）。为了研究NR生物合成符合活性/可控聚合机制的假设，我们同时提出了两个项目。在项目一中，将研究利用合成聚异丁烯基宏观引发剂修饰体外生物合成工艺。将产生宏观引发剂前体的全合成活性碳阳离子聚合与NR生物合成相结合，将产生一种全新的嵌段共聚物聚异丁烯-b-顺式- 1,4 -聚异戊二烯（PIB-b-NR）。项目II将展示一种概念上的新合成活性聚合（NLP），类似于NR生物合成，以生产聚异戊二烯。有了这个奖项，有机和大分子化学项目将支持阿克伦大学的Judit Puskas教授的研究，他将证明拟议的新的模拟天然橡胶生物合成的活性聚合的可行性，这可能为合成顺式聚异戊二烯的新方法开辟道路。目前，巴西橡胶树是唯一用于商业用途的天然橡胶生产物种，其遗传变异很小，这使得橡胶园面临严重致病的风险。此外，反复暴露于NR中的蛋白质会导致严重的过敏性超敏反应。因此，为橡胶工业（年收入100亿美元）的战略重要材料NR寻找替代来源是非常有兴趣的。该项目将与固特异轮胎橡胶公司密切合作，学生将接触到工业聚合物化学，新的表征方法，潜在的规模扩大，美国农业部（USDA），并将接受体外生物聚合方法的培训。

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.