GOALI: Collaborative Research: On-Demand Continuous-Flow Production of High Performance Acrylic Resins: from Electronic-Level Modeling to Modular Process Intensification

两个学术小组和一个工业合作伙伴Axalta Coating Systems(前身为杜邦高性能涂料)提出的合作研究项目旨在研究分子氧对自由基聚合(FRP)的影响。分子氧的作用在高温下可以是催化的，在低温下可以是抑制的。FRP对分子氧的研究大多集中在其抑制作用上，因此研究不同反应条件下的氧基催化机理具有重要的理论意义。为了将这一发现转化为实际的工业过程，了解分子氧的浓度如何影响反应速度和所产生的聚合物转化率和微结构是至关重要的。该团队建议：(A)利用密度泛函理论(DFT)确定分子氧引发聚合物链引发和氧从活性聚合物链终止之前的最可能的机理；(B)设计和进行间歇聚合实验，以捕获引发和产物物种，并验证理论预测的物种和机理；(C)开发氧引发聚合管式反应器(PTR)的宏观机理模型，以进行基于模型的设计；和(D)开发模块化的PTR设计，强化和模块化丙烯酸树脂工艺。减少或取消传统的热引发剂(通常是树脂中最昂贵的成分)将降低操作成本。消除传统引发剂在最终产品中留下的残留基团(对聚合物性能，如抗紫外线性能产生不利影响)和玻璃钢反应器的优化操作，将提高树脂质量。除了丙烯酸酯，这项研究的结果可能会影响每一个自由基聚合过程。除了培训两名研究生外，该团队还计划创建计算机建模模块和项目，通过Drexel的Co-op计划和宾夕法尼亚大学的Vagelos能源研究综合计划(Viper)为从代表性不足的群体中挑选出来的本科生提供研究培训机会。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

The proposed collaborative research project between two academic groups and an industrial partner, Axalta Coating Systems (formerly DuPont Performance Coatings), aims to investigate the effects of molecular oxygen on free-radical polymerization (FRP). The effects of molecular oxygen can be either catalytic, at high temperatures, or inhibitory, at low temperatures. The majority of FRP studies with molecular oxygen have focused on its inhibitory effects, so it will be of great fundamental interest to discover the mechanisms of oxygen-based catalysis under different reaction conditions. To translate this finding into practical industrial processes, it is vital to understand how the concentration of molecular oxygen influences reaction rates and resulting polymer conversion and microstructure.The team proposes to: (a) Identify the most likely mechanisms for polymer-chain initiation by molecular oxygen and the departure of oxygen from live polymer chains before they are terminated, using Density Functional Theory (DFT); (b) Design and conduct batch polymerization experiments to capture the initiating and product species and to verify the theoretically-predicted species and mechanisms; (c) Develop a macroscopic mechanistic model of an oxygen-initiated polymerization tubular reactor (PTR) to perform model-based design; and (d) Develop a modular PTR design that intensifies and modularizes acrylic resin processes. The reduction or elimination of conventional thermal initiators (normally the most expensive component of a resin) will lower the operating costs. The elimination of residual groups left by conventional initiators in the final product (which adversely affect polymer properties such as UV resistance) and the optimal operation of FRP reactors will improve the resin quality. Beyond acrylates, the outcomes of this research may impact every free-radical polymerization process. In addition to training two graduate students, the team plans to create computer modeling modules and projects to provide research training opportunities to undergraduates selected from underrepresented groups through Drexel's Co-op program and UPenn's Vagelos Integrated Program in Energy Research (VIPER).This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.