高分子相转移催化下烯丙基氯与亲核试剂反应动力学的研究

本文是研究在二乙烯基苯交联聚苯乙烯季铵盐型相转移催化剂下,以烯丙基氯的甲苯溶液为有机相和亲核试剂的水溶液为水相的亲核取代反应动力学。通过气相色谱法定量地研究了搅拌速度、温度和不同亲核试剂对反应的影响。实验表明:反应速率随搅拌速度增大而加快,当搅拌速度达到某个定值后,反应速率不再变化;反应速率随着温度升高而加快,并得到了硫氰酸钾与烯丙基氯反应的表观活化能和活化熵;本文还定量地指出了负离子的反应活性次序为SCN~->I~-。

Polymeric Phase-Transfer Catalysis. Kinetics of Nucleo-philic Displacement Reactions on Allyl Chloride

The kinetics of the polymeric phase-transfer catalyzed displacement reactions of nucleophilic reagents (aqueous phase) on allyl chloride (organic phase), employing cross-linked polystyrene resins (solid phase) bearing quaternary ammonium group, has been investigated. The rate of displacement exhibited a pseudo-first-order dependency on the allyl chloride concentration. The rate of reaction has been studied as a function of stirring speed, temperature and a variety of nucleophilic reagents by means of gas chroma-tography. Reaction rates increased with the increase of stirring speeds up to about 800rpm, and then remained constant beyoud this value. Comparison of the order of activity for anions indicates SCN->I-. Reaction rates increase as temperature increased. In the reaction of allyl chloride in toluene with aqueous potassium thiocya-.nate apparent activation energy is 71.69KJmol-1 at 30 -40℃ and entropies of activation are-86.72 JK-1mol-1 at 30℃ and-86,99 JK-1 mol-1 at 40℃ respectively.