Promotion Effect of Cationic Gemini Surfactants on 1-Dodecene Hydroformylation in Biphasic Catalytic System

Abstract

Abstract: New cationic gemini surfactants with a rigid spacer group of xylene were synthesized, their compositions and structures were characterized. The cmc and the solubilizations of 1-dodecene in micellar solution were determined by surface tension method and UV-Vis spectrometry respectively. The cmc of new gemini surfactants are lower than CTAB by about an order, but the solubilizations of 1-dodecene in gemini surfactants solution are higher than that in CTAB solution. The promotion effect of cationic gemini surfactants on 1-dodecene hydroformylation in biphasic catalytic system was studied. The results indicated that in the biphasic system containing the catalysts RhCl(CO)(TPPTS)₂ and TPPTS, [TPPTS=tris(sodium-m-sulfonatophenyl) phosphine], the reaction rate of 1-dodecene hydroformylation in the presence of gemini surfactants was faster than that in the presence of conventional surfactant CATB, e.g., the conversion of 1-dodecene is 90% when G(o-xyl) C₂₂ concentration in aqueous solution was 2×10^-3 mol/L, however, the conversion was only 20.4% when the concentration of CTAB was 3×10^-3 mol/L. The greater acceleration of gemini surfactants in 1-dodecene hydroformylation could be attributed to that cationic gemini surfactants had lower cmc and better solubilization for the substrate. The lower cmc and surface tension are favorable for increasing the interfacial area of two phases, breaking phase barrier and promoting the substrate transfer to interface where the substrates coordinate with the active rhodium complex anion species. The regioselectivity for olefin hydroformylation in gemini surfactants.

Key words: Two-phase catalytic system, Gemini surfactant, 1-Dodecene, Hydroformylation, Solubilization

CLC Number:

O643

TrendMD:

XU Bin, LI Min, YANG Min, ZHENG Hong-Jie, HE Yu-E, CHEN Hua, LI Xian-Jun . Promotion Effect of Cationic Gemini Surfactants on 1-Dodecene Hydroformylation in Biphasic Catalytic System[J]. Chem. J. Chinese Universities, 2004, 25(11): 2060.

References

[1] 　Kalck P.,Monteil F..Adv.O rganomet.Chem.[J],1992,34:219_283 [2] 　Cornils B..Angew.Chem.Int.Ed.Eng.l[J],1995,34(15):1575_1577 [3] 　Joo F.,Katho A..J.Mo.lCata.lA:Chem.[J],1997,116(1 2):3_26 [4] 　Herrm ann W.A.,Kohlpain ter C.W..A ngew.Chem.In t.Ed.Engl.[J],1993,32(11):1524_1544 [5] 　Bahrmann H.,Bogdanovic S.;Eds.Cornils B.,Herrmann W.A..A queous-phase Organom etallic Catalysis[M],Weinheim:WileyV CH,1998:306 [6] 　Kohlpain tner C.W.,F ischer R.W.,Co rn ils B..A pp l.Catal.A:General[J],2001,221(1 2):219_225 [7] 　Kuntz E.G..Chem tech.[J],1987,17:570_575 [8] 　WU Xiao-Wei(吴小韦),WANG Yan-Hua(王艳华),CHENG Fang(程)et al..Chem.J.Chinese Universities(高等学校化学学报)[J],2002,23(10):1939_1943 [9] 　Chen H.,Li Y.Z.,Chen J.R.et al..J.M o l.Catal.A:Chem.[J],1999,149(1 2):1_6 [10] 　VanV yve F.,R enken A..Cata.lToday[J],1999,48(1 4):237_243 [11] 　R iisager A.,H an son B.E..J.Mol.Catal.A:Chem.[J],2002,189(2):195_202 [12] 　L iM.,L i Y.Z.,Chen H.et al..J.Mo .lCata.lA:Chem.[J],2003,194(1 2):13_17 [13] 　W ang L.B.,Chen H.,He Y.E.et al..Appl.Cata.lA:General[J],2003,242:85_88 [14] 　Zana R.,In M.,Lévy H..L angm uir[J],1997,13(21):5552_5557 [15] 　Hatto ri N.,H irata H.,O kabayash i H.et al..Co llo id Po lym.Sci.[J],1999,277(4):361_371 [16] 　Menger F.M.,L ittau C.A..J.Am.Chem.Soc.[J],1993,115(22):10083_10090 [17] 　Menger F.M.,Keiper J.S..A ngew.Chem.In t.Ed.[J],2000,39:1906_1920 [18] 　ZHENG Ou(郑欧),ZHAO Jian-Xi(赵剑曦),YOU Yi(游毅).Chem.J.Chinese Universities(高等学校化学学报)[J],2002,23(7):1352_1355 [19] 　Cerichelli G.,L uchetti L.,M ancin i G.et al..L angm uir[J],1999,15:2631_2634 [20] 　LIM in(李敏),XU Bin(徐斌),CHEN Hua(陈华)et al..Chem.J.Chinese Universities(高等学校化学学报)[J],2004,25(4):717_720 [21] 　CHEN Hua(陈华),LIU Hai-Chao(刘海超),LI Yao-Zhong(黎耀忠)et al..J.Mo .lCata.l(分子催化)[J],1994,8(2):124_129 [22] 　Wettig S.D.,Verrall R.E..J.Colloid and Interface Sci.[J],2001,235:310_316 [23] 　SUI Wei-Ping(隋卫平),LIANG Wei(梁伟).Chem.Research and App.l(化学研究与应用)[J],1998,10(2):128_132 [24] 　Chio T.S.,Shimizu Y.,Shirai H.et al..D yes and Pigments[J],2000,45:145_152 [25] 　ZHAO Guo-Xi(赵国玺).Physical Chemistry of Surfactants(表面活性剂物理化学)[M],Bejing:Peking University Press,1991:184 [26] 　ZHU Bu2Yao(朱瑶),ZHAO Guo-Xi(赵国玺).Chemistry(化学通报)[J],1981,(6):21_26 [27] 　Danino D.,T almon Y.,Zana R..Langmuir[J],1995,11:1448_1456