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Synthesis and Surface Properties of CO2H Type Gemini Surfactant Having Semifluoroalkyl Group as Hydrophobic Group

Synthese und Oberflächeneigenschaften von CO2H-Geminitensiden mit einer Semifluoralkylgruppe als hydrophobe Gruppe
Tokuzo Kawase, Tomoyuki Ankyu and Tatsuo Oida

Abstract

Novel CO2H type gemini surfactants having semifluoroalkyl group (Rf-(CH2)n-: Rf = C4F9, C6F13, C8F17 and n = 2, 3) as hydrophobic group were successfully synthesized and their surface properties were studied. (Perfluoroalkyl)ethylmalonic esters were synthesized by the reaction of malonic ester with Rf(CH2)2I using NaH as base in THF/DMF. (Perfluoroalkyl)propylmalonic esters were synthesized from allylmalonic ester, namely by the radical addition of Rf-I using AIBN as initiator, and reduction with Zn/AcOH. Those fluoroalkylated malonic esters were connected using Br(CH2)sBr (s = 3, 4) to give dimeric tetraesters. Then, tetraesters were hydrolyzed using KOH/EtOH followed by decarboxylation in AcOH to afford CO2H type gemini surfactants. To study their surface properties, both surface tension-concentration and surface pressure-area isotherms were measured. As expected, COOH geminis showed one order of magnitude lower critical micellar concentrations (CMC) than that of conventional 1+1 type surfactant. In the surface pressure-area measurements, as length of fluoroalkyl increased, lift-off area (AL) decreased, monolayers were clearly formed upon compression and the limited areas (A) for C6F13 and C8F17 were smaller than twice of that of C8F17(CH2)2COOH. Especially, COOH geminis having Rf = C8F17 and -(CH2)3- spacer showed the formation of solid phase monolayers, and the planar five membered ring-like structure was proposed.

Kurzfassung

Neuartige CO2H-Geminitenside mit einer Semifluoralkylgruppe (Rf-(CH2)n-: Rf = C4F9, C6F13, C8F17 und n = 2, 3) als hydrophobe Gruppe wurden erfolgreich synthetisiert und ihre Oberflächeneigenschaften wurden untersucht. Perfluoralkylethylmalonsäureester erhielt man durch die Reaktion von Malonsäureester mit Rf(CH2)2I in THF/DMF, wobei NaH als Base benutzte. Die Perfluoralkylpropylmalonsäureester wurden aus Allylmalonsäureester synthetisiert, und zwar über die radikalische Addition von Rf-I mittels AIBN als Initiator und die Reduktion mit Zn/AcOH. Diese Fluoralkylmalonsäureester wurden mittels Br(CH2)sBr (s = 3, 4) zu dimeren Tetraester verbunden. Die Tetraester wurden dann mit KOH/EtOH hydrolysiert, worauf eine Decarboxilierung in AcOH erfolgte, um die CO2H-Geminitenside zu erhalten. Für die Untersuchung ihrer Oberflächeneigenschaften wurden die Oberflächenspannungs-Konzentrationsisotherme und die Oberflächendruck-Flächenisotherme gemessen. Wie erwartet haben die CO2H-Geminitenside eine kritische Mizellbildungskonzentration (CMC), die um eine Größenordnung kleiner ist als die der konventionellen 1+1-Tenside. Die Messungen des Oberflächendrucks in Abhängigkeit von der Fläche zeigten, dass bei zunehmender Länge der Fluoralkylkette die “lift-off”-Fläche (AL) abnimmt, bei Kompression werden deutlich Monoschichten gebildet und die Grenzflächen (A) von C6F13 und C8F17 werden um das Zweifache kleiner als die von C8F17(CH2)2COOH. Speziell die CO2H-Geminitenside mit einem Rf = C8F17 und einem -(CH2)3-Spacer zeigten die Bildung einer fest Monoschicht. Eine ebene, fünfgliedrige, ringähnliche Struktur wurde daher vorgeschlagen.


Tokuzo Kawase, Department of Chemistry and Materials Technology, Kyoto Institute of Technology, Hashigamicho 1, Matsugasaki, Sakyoku, Kyoto 606-8585, Japan, Tel.: (075)724-7515, Fax: (075)724-7515, E-Mail:

Tokuzo Kawase was born in 1951. He is a Professor of chemistry at Kyoto Institute of Technology. He received his D. Engineering from Kyoto University in 1979 and another Ph.D. from Osaka City University in 1995. His current scientific interests are focused on the synthesis of novel surfactants including fluorinated surfactants.

Tomoyuki Ankyu completed his M.Sc. in applied chemistry from Kyoto Institute of Technology. Presently he is working at Murata Manufacturing Co. Ltd.

Tatsuo Oida is an Associate Professor at Kyoto Institute of Technology. His current scientific interests are focused on the synthesis of novel surfactants and their structure-related surfacant properties.


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Received: 2012-06-20
Revised: 2012-08-20
Published Online: 2013-04-05
Published in Print: 2012-11-01

© 2012, Carl Hanser Publisher, Munich