1,1,3,3-四甲基-2-环己基胍的制备及其催化合成二甘醇双烯丙基碳酸酯

以环己胺和四甲基脲为原料,采用三氯氧磷法制备了1,1,3,3-四甲基-2-环己基胍(CyTMG),通过正交实验对制备条件进行了优化,优化的制备条件为:四甲基脲与三氯氧磷的摩尔比为1:1.0,加入三氯氧磷后、加入环己胺前的反应时间为11h,加入环己胺后、加入蒸馏水前的反应时间为36h,加入蒸馏水后的反应时间为15min。在此条件下,CyTMG收率为50.1%。利用红外光谱、核磁共振、电喷雾质谱等方法对CyTMG的结构进行了表征。将CyTMG作为催化剂和缚酸剂用于CO2法合成二甘醇双烯丙基碳酸酯(ADC)的反应,适宜的反应条件为:反应温度80℃、反应初始压力4.0MPa、氯丙烯与二甘醇摩尔比6、CyTMG与二甘醇摩尔比3.4、反应时间12h,在此条件下,ADC收率为63.0%。采用NaOH溶液回收CyTMG,回收率为80.4%。

Preparation of N-Cyclohexyl-N', N', N, N-Tetramethylguanidine and Its Application in Synthesis of Diethylene Glycol Diallyl Dicarbonate

N-cyclohexyl-N',N',N',N'-tetramethylguanidine(CyTMG) was synthesized from tetramethylurea(TMU) and cyclohexylamine with phosphorus oxychloride(POCl3) as catalyst.Preparation condition was optimized by orthogonal design.Under optimal preparation conditions:n(TMU)∶n(POCl3) 1∶1.0,reaction time between addition of POCl3 and addition of cyclohexylamine 11 h,reaction time between addition of cyclohexylamine and addition of water 36 h,reaction time after addition of water 15 min,yield of CyTMG is 50.1%.Structure of CyTMG was characterized by means of IR,1H NMR and ESI-MS.The prepared CyTMG was used as catalyst and an acid-binding agent to synthesize diethylene glycol diallyl dicarbonate(ADC) through carbon dioxide route.Under suitable conditions:reaction temperature 80 ℃,initial reaction pressure 4.0 MPa,mole ratio of allyl chloride to diethylene glycol 6,mole ratio of CyTMG to diethylene glycol 3.4 and reaction time 12 h,yield of ADC is 63.0%.In addition,CyTMG can be recovered by treating the hydrochloride of CyTMG formed during the process with NaOH and the recovery is 80.4%.