Flow Toolkit for Measuring Reaction Enthalpy and Application to Highly Exothermic Synthesis of Alkylaluminoxanes

Flow Toolkit for Measuring Reaction Enthalpy and Application to Highly Exothermic Synthesis of Alkylaluminoxanes
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用于测量反应焓的流量工具包及其在烷基铝氧烷高放热合成中的应用

DOI:
10.1021/acs.oprd.2c00072
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发表时间:
2022-04
期刊:
Organic Process Research & Development
影响因子:
--
通讯作者:
Yongrong Yang
Yongrong Yang
中科院分区:
其他
文献类型:
--
作者:
Mengbo Zhang;Yirong Feng;Linjin Lou;Haomiao Zhang;Jingdai Wang;Yongrong Yang

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我们提出了一个流动的策略来表征反应焓,并展示了应用于烷基铝的快速和放热的水解合成烷基铝氧烷。我们的平台主要包括一个三维打印的微混合器和一个绝热真空箱中的管式反应器,辅以热成像相机记录温度分布。在稳态下的温度增加用于计算释放的热,其进一步解耦以量化反应焓和混合焓。我们验证了硫酸和氢氧化钠之间的经典中和反应的概念,与理论值的偏差小于2%。在应用中,我们确定了三异丁基铝水解的放热反应焓和混合吸热焓分别为−143.13和+7.66 kJ/mol,三甲基铝水解的放热反应焓和混合吸热焓分别为−164.63和+5.03 kJ/mol。所提出的平台,一方面,产生新的见解的微型反应器放大烷基铝氧烷合成,另一方面,可以很容易地用于测量其他反应的反应时间。
We present a flow strategy to characterize reaction enthalpy and showcase the application in synthesis of alkylaluminoxanes from the fast and exothermic alkylaluminum hydrolysis. Our platform mainly encompasses a three-dimensional printed micromixer and a tubular reactor in an adiabatic vacuum box, aided by a thermal imaging camera to record temperature profiles. The temperature increase at steady state is used to calculate the released heat, which is further decoupled to quantify the reaction enthalpy and enthalpy of mixing. We validate the concept with the classic neutralization reaction between sulfuric acid and sodium hydroxide, with less than 2% deviation from theoretical values. In application, we determine the exothermic reaction enthalpy and the endothermic enthalpy of mixing to be −143.13 and +7.66 kJ/mol for triisobutylaluminum hydrolysis and −164.63 and +5.03 kJ/mol for trimethylaluminum hydrolysis, respectively. The presented platform, on the one hand, yields new insights into the microreactor scale-up for alkylaluminoxane synthesis and, on the other hand, can be readily used to measure reaction enthalpies of other reactions.
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