多模块撞击-聚并反应器的构建及其可控制备聚合物基纳米复合材料

Improving interfacial interactions as well as spatial distribution between inorganic nanoparticles and polymer matrix is the key to obtain high-performance nanocomposites. By using chemical process intensification and integration technology, the goal of few equipment, easy controlling and high efficiency can be realized. As a result, polymer matrix nanocomposites with controllable morphologies, stable structure and high quality will be developed. Based on mechanisms of miniemulsion coalescence and intensification technology of micro-impinging stream, a multi-module impinging-coalescence reactor (M-MICR) was proposed in this proposal, and it would be applied to prepare polymer matrix nanocomposites. The the fluid dynamics, the formation mechanism of miniemulsion and the droplet breakup-coalescence mechanisms in the M-MICR reactor were investigated by experiments and CFD simulation. Then, the mini-droplet coalescence rate model for the M-MICR reactor was established, and the optimal reactor structures, operating conditions and synergic relationship between modules would be obtained as well. On this basis, interactive principles between inorganic nucleation and monomer polymerization were explored. It was believed that this work would form a continuous, efficient and integrated route, which provided theoretical guidance and technical support for production of polymer matrix nanocomposites with high quality.

改善无机纳米粒子与聚合基相间的相互作用与空间分布是获取高性能纳米复合材料的关键。利用化工过程强化与集成技术，以减少设备数量、增强过程控制、提高生产效率，是发展形貌可控、结构稳定、性能优异的聚合物基纳米复合材料的新思路。本申请基于细乳液聚并理论和微撞击流强化技术，提出构建多模块撞击-聚并反应器（M-MICR），并将其应用于聚合物基纳米复合材料的制备。借助实验与CFD模拟研究M-MICR反应器的流体力学特性、细乳液形成机制以及微撞击流强化液滴聚并规律，建立撞击流场中液滴聚并速率模型，优化反应器结构与操作参数，获得多模块之间协同运作的最佳条件；以此为基础，探索细乳液滴内无机纳米粒子成核与单体聚合间的相互作用规律，形成连续制备高性能纳米复合材料并精确调控组分分布的连续、高效与一体化新工艺，为聚合物基纳米复合材料的可控制备提供理论指导和技术支持。

改善无机粒子与聚合物的相间作用以及空间分布是制备高性能纳米复合材料的关键。化工过程强化与集成技术为高性能有机-无机纳米复合材料的开发提供了新思路。本项目基于细乳液聚并理论和撞击流强化技术，成功构建多模块撞击-聚并反应器（M-MICR），并将其应用于二氧化锰-聚吡咯（MnO2-PPy）纳米复合材料的制备。以环己烷-复配乳化剂-水为研究体系，利用相转变组分法绘制拟三元相图，并通过实验与CFD模拟相结合的方式，探究了M-MICR的流体力学特性及细乳液形成机理，阐明了物性参数与操作条件对乳液制备过程的影响规律，同时建立了模块间协同操作的条件。研究结果表明，水相入口雷诺数Rew、乳液入口雷诺数Reo/w以及物性参数等对乳液平均粒径及其稳定时间有显著影响；通过调控Rew可以有效地改变液滴破裂与聚并速率的相对大小，进而影响液滴粒径。基于上述理论研究，在M-MICR中考察了反应条件与操作参数对MnO2-PPy复合材料电化学性能的影响规律，揭示了MnO2与PPy复合时的相互作用机制；在较适宜工艺条件下制备的MnO2-PPy纳米复合材料具有无定形多孔结构，其比电容值最高可达297 F g-1，且具有良好的倍率性能和循环稳定性；此外，复合材料中MnO2与PPy的空间分布均匀。综上所述，M-MICR在乳化以及有机-无机纳米复合材料合成应用方面具有明显优势，本项目及其相关的拓展研究可为电化学储能材料的连续、可控制备提供理论指导和技术支持。