烷基铝氧烷合成技术研究进展

doi:10.11949/0438-1157.20221002

摘要/Abstract

摘要：

基于传统釜式反应器的烷基铝氧烷生产技术仍存在过程危险、控制难、收率低、经济性差等问题，首先回顾了传统烷基铝水解路线中将水以不同方式引入反应体系的过程，重点介绍了应用3D打印和流动化学技术的烷基铝氧烷合成系统设计，包括甲基铝氧烷（MAO）与异丁基铝氧烷（IBAO）合成、产物在线监测、反应焓测定以及改性甲基铝氧烷（MMAO）合成。流动化学系统将水以单分散微水滴的形式引入反应体系，提高了反应的传热、传质性能，实现了烷基铝氧烷的小型化、连续化、安全化生产，产品收率高，其助催化活性均达到或超过市售产品水平，并可通过微反应器放大技术进一步扩大生产能力。流动化学合成烷基铝氧烷的技术具有广阔应用前景，也为其他快速、强放热、多相反应提供了解决方案。

关键词: 烷基铝氧烷, 流动化学, 3D打印, 多相反应器, 水解, 合成, 茂金属催化剂

Abstract:

The product of methylaluminoxane (MAO) is available commercially, however, central challenges over poor process control, low product yield, and high safety risks, still remain in its synthesis using large-scale reactors. This review presents several conventional hydrolytic routes for MAO synthesis with different techniques to supply water in the reaction system, and primarily focuses upon the development of continuous flow platforms to synthesize MAO, isobutylaluminoxane (IBAO), and modified methylaluminoxane (MMAO) using 3D printed functional devices. In particular, those flow platforms introduce monodisperse microdroplets of water to improve the heat and mass transfer, achieving inherently safe productions of alkylaluminoxanes with high yield and superior co-catalytic activity. The presented flow strategy has a wide array of applications in chemical synthesis, especially when handling fast, highly exothermic, multiphase reactions.

Key words: alkylaluminoxanes, flow chemistry, 3D printing, multiphase reactor, hydrolysis, synthesis, metallocene catalyst

中图分类号:

TQ 31

张梦波, 楼琳瑾, 冯艺荣, 郑雨婷, 张浩淼, 王靖岱, 阳永荣. 烷基铝氧烷合成技术研究进展[J]. 化工学报, 2023, 74(2): 525-534.

Mengbo ZHANG, Linjin LOU, Yirong FENG, Yuting ZHENG, Haomiao ZHANG, Jingdai WANG, Yongrong YANG. Research progress on synthesis of alkylaluminoxanes[J]. CIESC Journal, 2023, 74(2): 525-534.

图/表 4

图1 几种基于“游离水”工艺合成MAO流程图

Fig.1 Schematics of several free-water approaches for the synthesis of MAO

图2 MAO合成的流动化学平台 (a)、毛细管式微液滴生成器(b)、T型微混合器(c)、微型全混釜串联反应器(d)和气/液/固三相分离器(e)示意图[59]

Fig.2 Schematic of the flow platform for MAO synthesis (a), capillary-based microdroplet generator (b), T-micromixer (c), 6 μCSTRs-in-series (d), and gas/liquid/solid three-phase separator (e)[59]

图3 (a) IBAO合成的流动化学反应平台示意图；(b)盘管式微反应器示意图；(c)反应时的两相流型分布；(d)反应时的温度分布[69]

Fig.3 (a) Schematic of the flow platform for IBAO synthesis; (b) Schematic of coiled tubular microreactor; (c) Two-phase flow pattern distribution during the reaction; (d) temperature distribution during the reaction [69]

表1 代表性的市售MMAO产品

Table 1 Representative commercial MMAO products

产品名称	产品型号	分子式	溶剂	CAS号
3A型改性甲基铝氧烷	MMAO-3A	—[(CH₃)_0.7(i-C₄H₉)_0.3AlO] _x —	正庚烷	146905-79-5
7型改性甲基铝氧烷	MMAO-7	—[(CH₃)_0.86(n-C₈H₁₇)_0.14AlO] _x —	Isopar E^TM	206451-54-9
12型改性甲基铝氧烷	MMAO-12	—[(CH₃)_0.95(n-C₈H₁₇)_0.05AlO] _x —	甲苯	206-54-9

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