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，以合成“天然橡胶”(NR)或顺式-1，4-聚异戊二烯(CPIP)。为了研究天然橡胶生物合成与活性/可控聚合反应机制相一致的假设，提出了两个同时进行的方案。在项目I中，将研究使用基于合成聚异丁烯的大分子引发剂的改进的体外生物合成过程。将完全合成的活性碳阳离子聚合，产生大分子引发剂的前体，与天然橡胶的生物合成相结合，将产生一种全新的嵌段共聚物，聚异丁烯-b-顺-1，4-聚异戊二烯(PIB-b-NR)。项目二将展示一种概念上的新的合成活性聚合(NLP)，类似于天然橡胶的生物合成，以生产聚异戊二烯。获得这一奖项，有机和高分子化学计划支持阿克伦大学的Judit Puskas教授的研究，他将展示拟议的模拟天然橡胶生物合成的新活性聚合的可行性，这可能为合成顺式聚异戊二烯的新方法开辟道路。目前，巴西橡胶树是唯一一种用于商业用途的天然橡胶生产树种，遗传变异很小，使橡胶种植园面临严重的病原菌攻击风险。此外，反复接触NR中的蛋白质已导致严重的过敏性超敏反应。因此，人们对寻找天然橡胶的替代来源非常感兴趣，天然橡胶是橡胶工业的一种具有战略重要性的材料(年收入100亿美元)。该项目将与固特异轮胎橡胶公司产生密切的互动，在那里，有经验的学生将接触到工业聚合物化学、新的表征方法、潜在的放大能力、美国农业部(USDA)，并将接受体外生物聚合方法学方面的培训。

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.