二环己基氧化锡催化合成二甲氧基碳酸双酚A二酯的研究

Study on bis-methylcarbonate of bisphenol-A synthesis using (C_6 H_(11))_2SnO as catalyst

采取格式试剂法合成了二环己基氧化锡((C6H11)2SnO)、二苯基氧化锡(Ph2SnO)、二苄基氧化锡((PhCH2)2SnO)和二叔丁基苯基氧化锡((tert-BuPh)2SnO),并通过FT-IR、XPS和TG对合成有机氧化锡进行系统表征;利用所合成的有机氧化锡为催化剂,以双酚A(BPA)和碳酸二甲酯(DMC)为原料,利用酯交换法合成二甲氧基碳酸双酚A二酯(BMBPA).研究结果表明:Ph2SnO在180℃时容易引发烷基化反应,空间位阻较高的(tert-BuPh)2SnO不利于目标化合物的合成,(C6H11)2SnO具有较高的酯交换催化效果;酯交换反应和烷基化反应的选择性主要受催化剂空间位阻和锡原子电负性高低影响;以(C6H11)2SnO为催化剂,BMBPA的优化合成工艺条件为反应温度180℃、时间10 h、DMC/BPA摩尔比15∶1、催化剂用量0.5 g,此条件下BPA的转化率为71.0%,BMBPA的选择性为26.5%,副反应烷基化比例为2.4%.

（C6Hll）zSnO, PhzSnO, （PhCH2）2SnO and （tert-BuPh）2SnO are synthesized by Grignard reagents, and the synthesized compounds are characterized by FT-IR, XPS and TG. Bis-methylcarbonate of bisphenol-A synthesis from DMC and BPA via organotin oxide is studied, and the eharaeterized results indieate that Ph2SnO results in methylation of BPA with DMC in 180 ~C. And （tort-BuPh）2SnO deteriorated target compound synthesis, however, （C6H）zSnO exhibits the good catalytic activity and high BMBPA selectivity. The product distribution is mainly dependent on the positive Sn cation and steric hindrance of catalyst. The BMBPA synthesis is carried out on （C6HII）zSnO, and the optimized reactions are obtained, that is 180℃, 10 h, DMC/BPA molar ratio 15 ： 1, 0.5 g catalyst. The best BPA conversion and highest BMBPA selectivity achieve 71.0% and 26.5%, but methylation product selectivity only reaches 2.4%.