铁催化的光调控原子转移自由基聚合及产品工程研究

Exploiting tailor-made specialty chemicals based on production functionality is a new trend in chemical engineering field. On the other hand, the concentration of catalyst used in normal atom transfer radical polymerization (ATRP) system is relatively high, and the catalyst is sensitive to oxygen. In this project, a new modified ATRP technique will be developed for preparing functional (self-cleaning) polymeric material with tailor-made chain structure.. A novel iron-based photo-controlled ATRP (photoATRP) with ppm amounts of catalyst will be designed and implemented for the first time. Subsequently, a kinetic model of Fe(III)-based photoATRP will be developed and used to estimate kinetic coefficients based on a series of polymerization kinetic data. Furthermore, we will develop an advanced control technique for the preparation of polymer with tailor-made chain structure through coupling copolymerization kinetic model with rector model. Finally, in accordance with the demand of self-cleaning materials, we aim to achieve a triplet “preparation technology-polymer chain structure-polymer functionality” multiscale study, and guide for manufacturing a useful product with desired function. . In short, this project is put forward based on the shortcomings of conventional ATRP and the new trend of chemical engineering field. It not only realizes the interdisciplinary research, but also enriches the connotation of chemical engineering discipline. In addition, the implementation of this project will be beneficial for developing tailor-made self-cleaning polymeric materials.

面对以产品功能为导向定制化工产品的化工发展趋势,及传统原子转移自由基聚合（ATRP）技术至今仍存在的催化剂浓度高且易失活的问题，本项目提出开展自清洁功能导向的基于新型ATRP技术定制聚合产品的研究。. 首先，设计新型的具有低催化剂浓度的铁催化的光调控ATRP技术，并对该技术进行系统的聚合动力学实验研究；基于完备的动力学数据，建立均聚动力学模型并提出模型中动力学参数估算方法；进一步，通过构建光调控ATRP技术的共聚动力学模型及半连续反应器模型，结合先进的反应器控制技术，建立聚合物链结构的定制平台；最终，根据自清洁功能需求，建立“制备工艺”-“聚合物链结构”-“聚合物的性能”三者之间的关系。. 本项目的提出既针对了传统ATRP技术所面临的现实问题又顺应了化工发展趋势，一定程度上实现了多学科交叉及丰富了化工学科内涵。同时，本项目开展将对新型自清洁化工产品的开发提供有益指导。

该项目基于光控原子转移自由基聚合（photoATRP）装置简单且便于操作的优点，以及铁系催化剂资源丰富、成本低、毒性低且生物相容性好的优势，开展了铁催化photoATRP研究。研究内容包括：新型铁催化可控聚合体系的开发；聚合反应动力学规律的实验与建模研究；以及基于模型可控制备含氟功能聚合物。该项目实施过程中，研究工作开展顺利，成功开发了新型的铁催化photoATRP体系。在实验的基础上，构建了普适的铁催化photoATRP动力学模型，定量分析了动力学特征与规律。并利用该技术成功指导了含氟功能聚合物的可控制备。此外，项目开展过程中进一步拓展了相关研究，包括电调控铁催化ATRP体系和无金属photoATRP体系的实验和模拟研究，以及用于构筑油水分离膜的智能聚合物可控制备研究。该项目所获得的研究结果可为其它新型可控自由基聚合的开发提供动力学实验与建模研究基础，并为以功能为导向的聚合物精确制造提供理论依据。基于上述研究结果，已发表SCI论文10篇，协助培养研究生2名。项目负责人本人受聘上海交通大学化学工程系长聘教轨副教授。