二苯硫醚修饰Pd/C催化合成N-(1,3-二甲基丁基)-N＇-苯基对苯二胺的研究  

Synthesis of N-(1,3-dimethylbutyl)-N'-Phenyl-p-Phenylenediamine with Diphenyl-Sulfide Modified Pd/C Catalysts

作　　者：苏倡[1] 张群峰[1] 丰枫[1] 马磊[1] 卢春山[1] 李小年[1] 

机构地区：[1]浙江工业大学工业催化研究所,绿色化学合成技术国家重点实验室培养基地,浙江杭州310014

出　　处：《高校化学工程学报》2016年第6期1313-1319,共7页Journal of Chemical Engineering of Chinese Universities

基　　金：浙江省自然科学基金(LY12b03005);浙江省科技厅项目(2011R09020-01)

摘　　要：利用二苯硫醚（Ph2S）修饰Pd/C制备得到Pd-Ph2Sx/C催化剂,以N-苯基对苯二胺（PADPA）和甲基异丁基酮（MIBK）为原料,分别考察了Pd-Ph2Sx/C催化剂在一步法和两步法还原烷基化制备N-（1,3-二甲基丁基）-N＇-苯基对苯二胺（DBPPD）反应中的性能。并采用X-射线衍射（XRD）和X-射线光电子能谱（XPS）对催化剂进行了表征。结果表明,Pd-Ph2Sx/C催化剂在一步法和两步法合成DBPPD反应中均表现出良好的选择性,通过改变Ph2S用量、温度、压力等反应条件可使DBPPD选择性达96.3%。一步法反应工艺过程中PADPA与MIBK缩合生成的水制约着反应的进行,使PADPA在较低温度（413-433 K）下无法完全转化。两步法合成工艺,即先以活性炭为催化剂,使PADPA与MIBK脱水缩合生成亚胺,再在Pd-Ph2Sx/C催化剂的作用下将亚胺还原生成DBPPD,有效地克服了转化率不能达到100%的难题。在413 K,3 MPa反应条件下,PADPA转化率达100%,DBPPD选择性达97.4%。同时对Pd-Ph2Sx/C催化剂的重复使用性能进行考察发现,Pd-Ph2Sx/C催化剂套用3次后没有发现活性明显下降现象,每次反应PADPA转化率都可达100%,DBPPD选择性保持在95%以上。Diphenyl-sulfide （Ph2S） modified Pd/C catalysts （Pd-Ph2Sx/C） were prepared and studied for ＂one-step＂ and ＂two-step＂ reductive alkylation of N-phenyl-p-phenylenediamine （PADPA） and methyl isobutyl ketone （MIBK） to obtain N-（1,3-dimethylbutyl）-N＇-phenyl-p-phenylenediamine （DBPPD）. The structure of the Pd-Ph2Sx/C catalysts was characterized by X-ray powder diffraction （XRD） and X-ray photoelectron spectroscopy （XPS）. The results show that the Pd-Ph2S/C catalysts have remarkable selectivity for DBPPD synthesis in both ＂one-step＂ and ＂two-step＂ methods. DBPPD selectivity can reach up to 96.3% in one-pot process by changing Ph2S content, temperature and pressure. However, PADPA is difficult to be completely transformed due to the formation of H20 from PADPA and MIBK condensation in the ＂one-step＂ route at low temperature （413-433 K）, where the ＂two-step＂ reaction process can overcome this problem. PADPA and MIBK were first dehydrated to form imines on activated carbon catalysts, and then the imines were reduced to prepare DBPPD with the Pd-Ph2Sx/C catalysts. The results show that PADPA conversion of 100% can be obtained at 413 K and H2 pressure of 3 MPa using the ＂two-step＂ method. Meanwhile, DBPPD selectivity over 97.4% can also be obtained. Additionally, the reusability of the Pd-Ph2S/C catalyst was studied. It is found that the Pd-Ph2Sx/C catalyst can be reused for 3 times without distinctly loss of activity, which shows a wide application potential in industry.

关 键 词：二苯硫醚修饰Pd/C催化剂 一步法 两步法 还原烷基化反应 DBPPD 

分 类 号：TQ426.81[化学工程]