Synthesis of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine with diphenyl-sulfide modified Pd/C catalysts

被引：0

作者：

Su C. ^{[1
]}

Zhang Q.-F. ^{[1
]}

Feng F. ^{[1
]}

Ma L. ^{[1
]}

Lu C.-S. ^{[1
]}

Li X.-N. ^{[1
]}

机构：

[1] State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology, Institute of Industrial Catalysis, Zhejiang University of Technology, Hangzhou

来源：

Li, Xiao-Nian (xnli@zjut.edu.cn) | 2016年 / Zhejiang University卷 / 30期

关键词：

DBPPD; Diphenyl-sulfide modified Pd/C catalyst; One-step; Reductive alkylation; Two-step;

D O I：

10.3969/j.issn.1003-9015.2016.06.011

中图分类号：

学科分类号：

摘要：

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-Ph2Sx/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 H2O 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-Ph2Sx/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. © 2016, Editorial Board of “Journal of Chemical Engineering of Chinese Universities”. All right reserved.

引用

页码：1313 / 1319

页数：6

共 22 条

[1] Nam S.H., Park S.S., A study of 6PPD (N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine) used as an antidegradant in rubber with GC, American Laboratory, 30, 18, pp. 25-26, (1998)
[2] Chu Z., Zhou L.-F., Preparation of reductive alkylation catalyst and its application
[3] Li L., Li J., Jiang D.-H., Et al., Selective hydrogenation of alkenone to the corresponding saturated ketone over carbon supported palladium catalysts, Journal of Chemical Engineering of Chinese Universities, 27, 1, pp. 71-75, (2013)
[4] Yasumasa T., Takahiro K., Hiroyuki Y., Et al., Selective synthesis of N-aryl hydroxylamines by the hydrogenation of nitroaromatics using supported platinum catalysts, Green Chemistry, 11, 9, pp. 1385-1390, (2009)
[5] Carl D.K., Summit, Daniel L.B., Et al., Method of preparing a sulfided platinum on carbon catalyst
[6] Frederick S.D., Naugatuck, Harold G., Et al., Hydrogenation with platinum metal sulfide catalyst
[7] Dovell F.S., Greenfield H., Platinum metal sulfides as heterogeneous hydrogenation catalyst, Journal of the American Chemical Society, 87, 12, pp. 2767-2768, (1965)
[8] Xu W., Zhang Q.-F., Li X.-N., Aqueous phase synthesis of activated carbon supported palladium sulfides and their catalytic performance, Journal of Chemical Engineering of Chinese Universities, 28, 6, pp. 1269-1274, (2014)
[9] Zhang Q.F., Jiang D.H., Cen J., Et al., Catalytic hydrogenation of sulfur-containing nitrobenzene over Pd/C catalyst: In situ sulfidation of Pd/C for the preparation of PdxSy catalysts, Applied Catalysis A: General, 497, pp. 17-21, (2015)
[10] Takahashi Y., Hara T., Kaneda K., Highly efficient Pd/SiO2-dimethyl sulfoxide catalyst system for selective semihydrogenation of alkynes, Chemistry Letters, 40, 4, pp. 405-407, (2011)

← 1 2 3 →