Sustainable Polymer Reaction Engineering

聚合物几乎存在于世界上的每一种制造产品中。毫不奇怪，聚合物行业的经济指标预测，在可预见的未来，全球产量将大幅增长。大多数合成聚合物都来自石油原料，由于供应限制和负面的环境后果，我们对这些原料的依赖已经达到了临界点。我的研究计划的长期目标是开发可持续聚合的新方法，为聚合物行业面临的环境和经济挑战提供变革性的解决方案。在最近的一篇综述论文中，我将“绿色化学的12条原则”应用于当前的聚合物生产技术，以确定最有可能产生重大影响的研究领域。这导致在目前的提案中针对这些原则中的六个：1-危险性较低的化学合成的设计：用更安全的替代品取代危险溶剂，用毒性较低的单体，通常是生物基材料。2-可再生原料的使用：预计生物基单体在世界聚合物总产量中所占的份额将从2011年的1.5%增加到2020年的3%。许多可再生的生物基单体和溶剂已经在我的研究计划中被利用（例如，甘油、脂肪酸甲酯）。3-催化剂的使用：在许多生物基单体中存在烯丙基部分导致阻碍聚合的降解链转移。使用阳离子引发剂和活性自由基聚合方法是有希望的。4-使用更安全的溶剂和反应条件：用水基（乳液）聚合取代溶剂基聚合方法。5-提高能源效率：鉴于聚合反应通常具有高度放热的性质，绝热操作是提高能源效率的明显选择。然而，复杂的温度依赖性动力学可能导致产品质量的严重损害。6-实时分析工艺条件以防止污染：使用反应量热法和在线监测聚合反应是我们继续积极探索的领域。基于上述原则，我将致力于开发可持续的聚合物反应工程技术。我的方法包括使用更安全的溶剂替代品或乳液聚合，将可再生材料纳入聚合物产品和运行反应。我的主要目标是生产环保型压敏胶（PSA）。四个高度创新的项目使用乳液聚合生产PSA将满足我的目标：1。丙烯酸酯化油酸甲酯和其它植物油源与传统单体的共聚合。2.萜烯的掺入（例如，α-蒎烯）加入到共聚物配方中。3.氮氧自由基介导的聚合用于生产PSA的用途。4.用于PSA生产的绝热乳液聚合。这些方法尚未在PSA生产的背景下进行研究，也未被广泛用于生产其他聚合物产品。虽然加拿大拥有丰富的可再生资源，但全球对不可再生化石燃料的依赖日益增加，这给社会、经济和环境留下了不可持续的足迹。显然，我们需要立即采取行动来管理我们的地球，聚合物行业有很大的改进潜力。这项研究将通过培训HQP和最大限度地提高加拿大在新兴环境和经济重要性领域的表现，推动加拿大的生物经济和清洁技术。

Polymers are found in almost every manufactured product in the world. Not surprisingly, economic indicators for the polymer industry predict a significant global increase in production for the foreseeable future. Most synthetic polymers are derived from petroleum feedstock and we have reached a critical point in our dependence on these feedstock due to supply limitations and negative environmental consequences. The long-term objective of my research program is to develop new methods in sustainable polymerization to provide transformative solutions to the environmental and economic challenges confronting the polymer industry. In a recent review paper, I applied the “12 principles of green chemistry” to current polymer production technology in order to identify research areas with the highest probability of significant impact. This led to the targeting of six of these principles in the current proposal: 1- The design of less hazardous chemical syntheses: Replace hazardous solvents with safer alternatives and monomers with less toxic, typically, bio-based materials. 2- The use of renewable feedstock: It is predicted that the share of total world polymer production occupied by bio-based monomers will increase from 1.5% (2011) to 3% in 2020. Many renewable, bio-based monomers and solvents have already been exploited in my research program (e.g., glycerol, fatty acid methyl esters). 3- The use of catalysts: The presence of allylic moieties in many bio-based monomers leads to degradative chain transfer which impedes polymerization. The use of cationic initiators and living radical polymerization approaches are promising. 4- The use of safer solvents and reaction conditions: Replace solvent-based polymerization methods with water-based (emulsion) polymerization. 5- Increase in energy efficiency: Given the often highly exothermic nature of polymerization reactions, adiabatic operation is an obvious choice to improve energy efficiency. However, the complex temperature-dependent kinetics may lead to serious compromises in product quality. 6- The analysis of process conditions in real-time to prevent pollution: The use of reaction calorimetry and in-line monitoring of polymerization reactions is an area that we continue to actively explore. Given the above principles, I will pursue my long-term objective to develop sustainable polymer reaction engineering technologies. My approach involves using safer solvent alternatives or emulsion polymerization, incorporating renewable materials into polymer products and running reactions adiabatically. My principle target is the production of environmentally benign pressure-sensitive adhesives (PSAs). Four highly innovative projects using emulsion polymerization to produce PSAs will address my objectives: 1. Copolymerization of acrylated methyl oleate and other vegetable oil sources with traditional monomers. 2. Incorporation of terpenes (e.g., alpha-pinene) into copolymer formulations. 3. The use of nitroxide-mediated polymerization for the production of PSAs. 4. Adiabatic emulsion polymerization for PSA production. These approaches have not been studied in the context of PSA production, nor have they been exploited widely for the production of other polymer products. Although Canada possesses abundant renewable resources, the increasing global dependence on non-renewable fossil fuels is leaving an unsustainable social, economic and environmental footprint. The need for immediate action on the stewardship of our planet is obvious, and there is great potential for improvement in the polymer industry. This research will advance Canada’s bio-economy and clean technology by training HQP and maximizing Canada’s performance in an area of emerging environmental and economic importance.