Kinetics Study and Modeling of ATRP emulsion Polymerization Systems

该研究计划的目标是在分散介质中生产用于工程和生物材料应用的聚合物材料。研究计划是研究聚合动力学，开发过程模型和过程控制方案，以更好地设计、操作和优化聚合物反应器。 可控自由基聚合(CRP)技术是取代传统聚合技术的一个快速发展的研究领域。目前学术界和工业界对原子转移自由基聚合(ATRP)重要的CRP变体的关注都得到了实验证据的支持，证明ATRP有能力生产定制的聚合物。但是，大多数ATRP研究都是在散体和溶液介质中进行的。然而，开放文献强调，出于实际和环境原因，有必要研究分散介质中的这一过程。 内部研究实验室配备了用于基础聚合物反应的安瓶实验装置和用于中试乳液聚合和工艺开发的2L反应器容器。反应器容器可以处理分散介质中的聚合体系，其中反应配方由要分散在水相中的化学试剂组成。 在短期内，研究活动将集中在对分散介质中少量单体单独或组合的ATRP体系的基础动力学研究。收集的数据将用于阐明最终产品的化学动力学性质并验证过程模型。将使用特殊仪器进行样品分析，以确定反应程度、分子量分布(MWD)、颗粒大小分布(PSD)并检测聚合物结构，包括链支化。 其次，乳液非均相聚合体系具有较低的粘度、良好的传热性能和较低的环境影响。毋庸置疑，需要可靠的力学模型来进一步阐明目前对ATRP物理化学现象的理解，并检查分散介质中搅拌下的聚合物反应器行为。力学动力学模型源于物理守恒定律。因此，这项研究需要开发数学模型来模拟和优化反应器处理ATRP乳液聚合的过程。此外，动态模型被用来设计带有优化器的基于模型的控制方案，该优化器可以考虑过程约束，并解决无法在线测量过程变量(如聚合物分子量)的问题。 预计这项研究提案的结果将为设计成功的ATRP工艺提供可靠的指导，以制造用于工程和生物材料应用的新型结构聚合物。总体而言，该研究计划旨在进一步促进瑞尔森的聚合物反应研究，并为加拿大学术界和工业界培养高素质的人才。

The goal of the research proposal is to produce polymer materials in dispersed media for engineering and biomaterial applications. The research plan is to investigate polymerization kinetics, develop process models and process control schemes for better design, operation and optimization of polymer reactors. Controlled Radical Polymerization (CRP) technique is a rapidly growing research area taking over conventional polymerizations. The current intensives in both academia and industry for Atom Transfer Radical Polymerization (ATRP) important CRP variant- has been buoyed by experimental evidence proving the ATRP capability to produce tailor-made polymers. But, most ATRP studies have been done in bulk and solution media. However, open literature stresses the need to examine the process in dispersed media for practical and environment reasons. The in-house research lab is equipped with an ampule experimental setup for basic polymer reactions and a 2L reactor vessel for pilot-plant emulsion polymerizations and process development. The reactor vessel can handle polymerization systems in dispersed media for which the reaction recipe consists of chemical reagents to be dispersed in aqueous phase. In the short-term, the research activity will focus on conducting fundamental kinetics study of ATRP systems of few monomers, taken separately or combined, in dispersed medium. The collected data will be explored to elucidate chemical kinetics properties of the end-product and to validate process models. Sample analysis using special instruments will be done to determine the reaction extent, molecular weight distribution (MWD), particle size distribution (PSD) and detect polymer structure including chain branching. Secondly, emulsion heterogeneous polymerization systems are known for having comparatively low viscosity, good heat transfer and low environmental impact. Indisputably, there is a need for reliable mechanistic models to elucidate further the current understanding of the ATRP physico-chemical phenomena and examine the polymer reactor behavior under stirring in dispersed media. Mechanistic kinetic models arise from the conservation laws of Physics. Hence, the study requires the development of mathematical models for process simulation and optimization of the reactor vessel handling ATRP emulsion polymerization. Besides, dynamic models are utilized to design model-based control schemes with an optimiser that can account for process constraints and to address the issue of unavailable online measurements of process variables such as polymer molecular weights. It is expected that the outcome of this research proposal will provide sound guidelines to design successful ATRP processes for making new types of structured polymers for engineering and biomaterial applications. In overall, the research program is to promote, even further, the polymer reaction research at Ryerson and train highly qualified personnel for Canadian academia and industry.