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Comparison of Composition and Properties of Ethoxylated Dodecanoic acid obtained in the Presence of Various Catalysts

Vergleich der Zusammensetzung und Eigenschaften von ethoxylierter Dodekansäure in Anwesenheit von verschiedenen Katalysatoren
B. Trathnigg , W. Hreczuch , J. Szymanowski , C. Rappel and R. Hödl

Abstract

Oxyethylation of dodecanoic acid was performed in the presence of a conventional alkaline catalyst, a homogeneous alkaline earth metal catalyst and a heterogeneous rare earth metal catalyst, respectively. As the result, three series of products were obtained in a range of average polyaddition degrees from N = 3 up to N = 9. The content of the obtained products was determined analytically by different chromatographic techniques: Size Exclusion Chromatography (SEC) with dual detection, gradient Liquid Adsorption Chromatography (LAC) with evaporative light scattering detection (ELSD), and Liquid Exclusion Adsorption Chromatography (LEAC), a new technique, which allows quantitatively accurate determination of the oligomer distribution of ethoxylates.

It was found that the applied catalysts significantly influenced the obtained homologue distributions and the content of di-esters and polyethylene glycols as byproducts. Much more selective ethoxylation is observed in the presence of the multivalent metal catalysts. As the result, the equivalent product series exhibit significant differences of physicochemical properties and surface activity. The new capabilities in analytical determination of the complex mixture of ethoxylated acids and the detected substantial differences in their chemical content can give a new input for more detailed investigation of these products.

Kurzfassung

Die Oxyethlylierung von Dodekansäure wurde in Gegenwart eines konventionellen Alkali-Katalysators, sowie eines homogenen Erdalkalimetall-Katalysators und eines heterogenen Metall-Katalysators der Seltenen Erden durchgeführt.

Dabei wurden drei Produktreihen mit einem durchschnittlichen Polyadditionsgrad von n = 3 bis zu n = 9 erhalten. Die Zusammensetzung der erhaltenen Produkte wurde mit verschiedenen chromatographischen Methoden bestimmt: Größenausschlußchromatographie (SEC) mit dualer Detektion, gradienter Flüssigkeitsadsorptionschromatographie (LAC) mit Lichtstreudetektor (ELSD) und Flüssigkeitsausschlußchromatographie (LEAC), einer neuen Technik, die eine exakte quantitative Bestimmung der Oligomerenverteilung von Ethoxylaten erlaubt. Die Analysen ergaben, daß die verwendeten Katalysatoren einen signifikanten Einfluß auf die erhaltene homologe Verteilung und auf den Gehalt an Di-Estern und Polyethylenglykolen als Nebenprodukte haben. Eine größere Selektivität der Ethoxylierung wurde in Gegenwart der multivalenten Metallkatalysatoren beobachtet. Die equivalenten Produktreihen zeigten signifikante Unterschiede der physikalisch-chemischen Eigenschaften und der Oberflächenarbeit. Die neuen Möglichkeiten der analytischen Bestimmung komplexer Gemische von ethoxylierten Säuren und der entdeckten substantiellen Unterschiede der chemischen Zusammensetzung geben neue Anregungen für weitere genauere Untersuchungen dieser Produkte.


Correspondence to Wiesław Hreczuch Ul. Parkowa 28 B/6, 47-220 Kedzierzyn-Kozle, Poland, Tel./Fax.: +48-77-4 83 80 00, E-mail:

Prof. Dr. phil. Bernd Trathnigg studied chemistry at Karl-Franzens-University in Graz from 1965 to 1973, specializing in polymer chemistry. After receiving his PhD “sub auspiciis praesidentis rei publicae” he spent one year at the Austrian Research Center for Atomic Energy in Seibersdorf working as coordinator of a project on electron beam curing of paints. 1974 he went back to the Institute of Chemistry, Karl-Franzens University Graz, where he received the title of an associate professor in 1990. He has developed of a density detector for liquid chromatography. Now he works mainly on characterization of polymers by liquid chromatography with special emphasis on quantitation, hyphenated techniques in analysis of polymers and surfactants, including 2D-HPLC.

Dr. Wieslaw Hreczuch was born in 1960 and obtained his MSc at the Agricultural Academy in Poznan, Poland, in 1985. In 1993, he obtained his Phd at the Technical University in Poznan, Poland. From 1999 to 2002 he was the Head of the Detergent Department of the Blachownia Institute of Organic Synthesis in Kedzierzyn-Kozle. At present he is the manager of the MEXEO company, Kedzierzyn-Kozle, Poland. His professional activities are related to the synthesis, evaluation and application of nonionic surfactants.

Dr. J. Szymanowski was born in 1943 and graduated from Warsaw Technical University in 1966. He obtained his Phd in 1970 and Doctor Habilis in 1974. Since 1982 he has been a full professor at Poznan Technical University. His area scientific interest is physicochemistry, surfactant and extractant technology and physicochemistry.

Mag. rer. nat. Christina Rappel studied chemistry at Karl-Franzens-University in Graz from 1995 to 2002. In 1999 and 2000 she worked at Böhler Edelstahl GmbH & Co, Kapfenberg in the field of Analytical Chemistry focused on ICP – OES. In 2001 she worked on the analysis of film forming micro emulsions for glucose self-monitoring test strips. In her diploma thesis she specialized in the chromatography of amphiphilic polymers, especially in 2D-HPLC of non-ionic surfactants.

Mag. rer. nat. Renate Hödl studied chemistry at Karl-Franzens-University in Graz from 1998 to 2003. In 2001 she worked on the synthesis of film forming micro emulsions for glucose self-monitoring test strips. In her diploma thesis she specialized in the synthesis and characterization of ethoxylates.


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Received: 2003-8-25
Received: 2004-2-10
Published Online: 2013-05-01
Published in Print: 2004-04-01

© 2004, Carl Hanser Publisher, Munich

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