异佛尔酮二胺的合成及工艺优化  

Synthesis of Isophorone Diamine and its Reaction Condition Optimization

作　　者：刘迎新[1] 周阔[1] 卢蒙[1] 汪梨超[1] 魏作君[2] 

机构地区：[1]浙江工业大学药学院催化加氢研发基地,浙江杭州310032 [2]浙江大学化学工程与生物工程学院,浙江杭州310027

出　　处：《高校化学工程学报》2015年第3期616-620,共5页Journal of Chemical Engineering of Chinese Universities

基　　金：国家自然科学基金(21106134;21276230;21476211)

摘　　要：以异佛尔酮为原料,经氰化、亚胺化和氢化三步反应合成了异佛尔酮二胺,并对反应工艺条件进行了优化。中间产物异佛尔酮腈合成的优化实验条件:NH4Cl为酸化试剂、DMF为反应介质、0.0669 mol异佛尔酮和0.048 mol Na CN与5 m L浓度为6 mol·L-1的NH4Cl水溶液在70℃下反应4 h,得异佛尔酮腈,收率为94.9%。中间产物异佛尔酮亚胺合成的优化实验条件为:以Ca O为催化剂、氨压0.2 MPa、70℃反应4 h,异佛尔酮腈转化率为97.4%,异佛尔酮亚胺收率为87.6%。异佛尔酮二胺合成的优化实验条件为:温度120℃、氢压6 MPa、氨压0.2 MPa、催化剂为2.0 g Raney Co,反应8 h后,异佛尔酮亚胺的转化率为100%,异佛尔酮二胺的收率为95.6%。另外,对中间产物和终产物分别进行了IR、MS、1H-NMR等分析,确认其结构无误。Using isophorone as the initial material, isophoronediamine was synthesized through three steps including cyanidation, imidization and hydrogenation. The reaction conditions of each reaction step were optimized. The optimized reaction conditions for the intermediate product isophoronenitrile are as follows： NHaCl as an acidification reagent, DMF as a reaction medium, 0.0669 mol isophorone, 0.048 mol NaCN, 5 mL NH4Cl （6 mol.L^-1）, 70℃ and 4 h of reaction time. The yield of isophoronenitrile is 94.9%. The optimized reaction conditions for the intermediate product isophoroneimine are as follows： CaO as a catalyst, ammonia pressure 0.2 MPa, 70℃ and 4 h of reaction time. The conversion of isophoronenitrile is 97.4% and the yield of isophoroneimine is 87.6%. The optimized reaction conditions for isophoronediamine are as follows： reaction temperature 120℃, hydrogen pressure 6 MPa, ammonia pressure 0.2 MPa, 2 g Raney Co as catalyst and reaction time 8 h. The conversion of isophoroneimine is 100% and the yield of isophoronediamine is 95.6%. In addition, the structures of the intermediates and the final product were confirmed by IR, MS and ^1H-NMR.

关 键 词：异佛尔酮 异佛尔酮二胺 RaneyCo 氰化 亚胺化 氢化 

分 类 号：TQ437.4[化学工程] O622.6[理学—有机化学]