微反应器内水-Lewis酸引发阳离子聚合制备高性能聚异丁烯的应用基础研究

The polymerization of isobutylene is of core process for manufacturing various polymers and additives with excellent performances. The H2O-Lewis acid is an initiating system with important commercial value, but still meets challenges in terms of controllability, cost, efficiency and flexibility in industry. Therefore, using microreactor as tool, the project focuses on the fundamental research on the synthesis of high performance polyisobutylene via cationic polymerization initiated by H2O-Lewis acid in microreactor, as for establishing new method for fast and controlled polymerization process and promoting the development and innovation of related industries and materials. The main contents include exploring the transformation mechanism of active species in the initiating system, revealing the influence factors and regulation rules on the initiation efficiency, chain initiation time and chain propagation rate, proposing kinetics model based on rational assumptions, recognizing various chain termination mechanisms based on the possibility analysis on the competitive chain reactions and modelling the molecular weight distribution, and figuring out the reaction conditions window endowing the polymerization process with low temperature sensitivity and flexible molecular weight adjustment. Besides, the strategies on achieving fast and pseudo-living polymerization of isobutylene and following-up synthesis of block polymers will also be investigated and discussed.

异丁烯聚合过程是多种性能优异的高分子材料与添加剂的核心生产过程，H2O-Lewis酸是具有重要商业价值的引发体系，但生产中也面临着控制难、代价高、效率低、柔性差等诸多挑战。为此，本项目拟开展微反应器内H2O-Lewis酸引发阳离子聚合制备高性能聚异丁烯的应用基础研究，以期发展异丁烯快速可控聚合的新方法，为相关工业技术及功能材料的发展和革新提供支撑。主要研究内容包括：探明引发体系内的物种转化机制，揭示引发效率、链引发时间和链增长速率的影响因素和变化规律，建立单体转化动力学模型，认识不同中止机制下链增长与链中止相对概率的调变规律，建立产物分子量预测和控制模型，构建温度敏感性低的反应体系，发展高分子量聚异丁烯产品在温和条件下的制备技术与灵活的分子量调控方法，提出异丁烯类活性聚合体系的构建策略，实现聚异丁烯长链正离子的可控制备，探索通过快速活性聚合与原位功能化制备多样化、结构化产物的新技术。

本项目针对温和条件下高活聚异丁烯等功能聚合物的定制合成，从质子源和Lewis酸形成的离子对的活性和稳定性及阳离子聚合过程链反应特性的角度，认识离子对种类、亲核试剂种类和当量、溶剂环境、温度等因素的影响规律，建立定量表征、量化分析和模型预测方法，发展基于微反应技术平台的过程与产物调控策略。主要进展包括：（1）揭示了非极性溶剂中引发溶液配制方式对亲核试剂、AlCl3、H2O相互作用及引发性能的影响，将iPr2O抑制异构化与AlCl3/Et2O配合物促进质子消除的作用相结合，实现了绿色溶剂正己烷中HRPIB的制备；（2）提出并实现了基于碳阳离子短时间稳定性的快速活性阳离子聚合方法；揭示了多种亲核试剂共存对阳离子聚合过程的调控机制，发展高效可控的简化体系；针对特定混合单体找到了适合的引发体系，制备了温度灵敏性高的新型活性聚合物，揭示了相应的构效关系。