超临界流体
异戊二烯
超临界二氧化碳
化学
临界点(数学)
反应速率常数
丙烯酸甲酯
反应速率
高压灭菌器
超临界水氧化
相(物质)
选择性
二氧化碳
超临界流体萃取
热力学
有机化学
聚合物
动力学
催化作用
数学分析
共聚物
物理
数学
量子力学
作者
Bin Lin,Aydin Akgerman
摘要
The Diels−Alder reaction between isoprene and methyl acrylate was carried out in supercritical carbon dioxide in the temperature range 110−140 °C and the pressure range 95.2−176.9 atm in a 300 cm3 autoclave. The high-pressure phase behavior of the reaction mixture in the vicinity of its critical region was determined in a mixed vessel with a sight window to ensure that all the experiments were performed in the supercritical single-phase region. Kinetic data were obtained at different temperatures, pressures, and reaction times. It was observed that in the vicinity of the critical point the reaction rate constant decreases with increasing pressure. It was also determined that the reaction selectivity does not change with operating conditions. Transition-state theory was used to explain the effect of pressure on reaction rate and product selectivity. Additional experiments were conducted at constant temperature but different phase behaviors (two-phase region, liquid phase, supercritical phase) by adjusting the initial composition and pressure. It was shown that the highest reaction rate is in the supercritical region.
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