Kinetics Study and Modeling of ATRP emulsion Polymerization Systems

ATRP 乳液聚合系统的动力学研究和建模

• 批准号: RGPIN-2020-07221
• 负责人: Dhib, Ramdhane
• 金额: $ 2.04万
• 依托单位: Ryerson University
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2022
• 资助国家: 加拿大
• 起止时间: 2022-01-01 至 2023-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=747122
• 关键词: Kinetics; Study; Modeling; ATRP; emulsion

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.

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，建立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。控制自由基聚合（CRP）技术是一个迅速发展的研究领域，取代了传统的聚合技术。原子转移自由基聚合（ATRP）是一种重要的CRP变体，目前学术界和工业界对该技术的关注得到了实验证据的支持，证明了ATRP能够生产量身定制的聚合物。但是，大多数ATRP研究都是在散装和溶液介质中进行的。然而，公开的文献强调需要检查分散媒体的实际和环境原因的过程。内部研究实验室配备了用于基本聚合物反应的安瓿实验装置和用于中试工厂乳液聚合和工艺开发的2L反应器容器。该反应器容器可以处理分散介质中的聚合体系，其反应配方由要分散在水相中的化学试剂组成。短期内，研究活动将集中在分散介质中单独或组合的少量单体ATRP体系的基本动力学研究上。收集的数据将用于阐明最终产品的化学动力学性质和验证过程模型。使用专用仪器对样品进行分析，以确定反应程度、分子量分布（MWD）、粒度分布（PSD）和检测聚合物结构，包括链分支。其次，乳液非均相聚合体系具有相对较低的粘度，良好的传热和低环境影响。毫无疑问，需要可靠的机理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聚合物反应器的行为。机械动力学模型源于物理学的守恒定律。因此，该研究需要建立数学模型来模拟和优化处理ATRP乳液聚合的反应器容器。此外，动态模型用于设计基于模型的控制方案，该方案具有优化器，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。预计本研究计划的结果将为设计成功的ATRP工艺提供良好的指导，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大学的聚合物反应研究，并为加拿大学术界和工业界培养高素质的人才。