Abstract:

Methylaluminoxane (MAO) is an important co-catalyst in various olefin polymerization systems, but it remains challenging to produce MAO economically and MAO has low solubility and poor stability in aliphatic hydrocarbon solvents. Therefore, modifying MAO to address the above limitations is of significant importance. The review presents the main techniques for MAO modification, including hydrolytic and non-hydrolytic methods, with a focus on the design and synthesis of modified methylaluminoxane (MMAO) using 3D printing in continuous flow. This flow synthesis platform consists of an isobutylaluminoxane (IBAO) synthesis module, an IBAO and TMA fast complexation module, and anisobutyl-modified product iBu-MMAO synthesis module. Mitigating the risk of solid clogging and a thermal runaway, this approach achieves continuous synthesis of MMAO more safely and stably, with yields up to 80%, and the product has comparable co-catalytic activity to commercial products. On this basis, the analysis and detection methods of MMAO and the application of its series of products in polymerization systems are reviewed, providing theoretical support and technical guidance for the synthesis and application of MMAO.

Key words: methylaluminoxane, flow chemistry, multiphase reactor, hydrolysis, synthesis, olefin polymerization

摘要：

甲基铝氧烷（MAO）是多种烯烃聚合体系的重要助催化剂，但其生产难度大、经济性差，并且在脂肪烃溶剂中溶解度低、稳定性差，因此，通过对MAO改性克服上述问题具有重要研究价值。针对MAO改性的主要技术路线，综述了水解法、非水解法及其他改性策略，并重点介绍基于3D打印技术的改性甲基铝氧烷（MMAO）流动化学反应器设计和合成方法。该MMAO连续流合成平台包括异丁基铝氧烷（IBAO）合成模块、IBAO与三甲基铝（TMA）快速络合模块以及异丁基改性产品iBu-MMAO合成模块，通过有效降低固体堵塞和热失控的风险，实现安全、稳定、连续合成MMAO，收率最高可达80%，且该产品与市售产品的助催化活性相当。在此基础上，综述了MMAO的分析与检测手段，及其系列产品在聚合体系中的应用，为MMAO的合成及应用提供理论支持与技术指导。

关键词: 甲基铝氧烷, 流动化学, 多相反应器, 水解, 合成, 烯烃聚合