Methyl ester propoxylates

2-Ethylhexyl laurate, as an exemplary longerchain aliphatic ester, was subjected to direct ethoxylation. The synthesis was described and the obtained products were analyzed qualitatively by means of the mass spectrometry and chromatographic methods. Solubility of the obtained ethoxylates was studied by determination of their cloud points in selected model solutions. It was shown that longer-chain aliphatic esters are feasible as raw materials for ethoxylation in the presence of an appropriate catalyst. They undergo effective and selective reaction with ethylene oxide without formation of excessive amounts of by-products. The obtained products exhibit typical properties of ethoxylate-type nonionic surfactants. Their solubility in water and butyldiglycol solution was relatively lower compared to their methyl ester equivalents.Paper no. S1226 in JSD 4, 167-173 (April 2001).KEY WORDS: Aliphatic esters, ethoxylation, 2-ethylhexyl laurate.The common definition of ethoxylation requires the presence of a labile hydrogen group in the substrate subjected to the reaction, according to Equation (1):where R denotes hydrocarbon chain and X means an intermediate group, such as -O-, -N-, or -S-. However, it was found recently that the reaction can also be performed efficiently with fatty acid methyl ester as the substrate (2,3). Since then several catalysts that allow efficient performance of the reaction have been reported (4-6). Ethoxylation of fatty methyl esters was also carried out using the conventional alkaline catalysts (7), although the rate of ethylene oxide (EO) addition was slow and the product distribution obtained was broad. It was proven that during ethoxylation of fatty methyl ester, EO was inserted selectively between the carbonyl carbon and the methoxy group (8).RCOOCH 3 + nCH 2 CH 2 O → RCO(OCH 2 CH 2 ) n OCH 3[2] Substrate Adduct Ethoxylation product Propoxylation of fatty acid methyl esters was also reported in the literature (9). Earlier studies described the impact of methyl ester chain length, degree of unsaturation, and EO content on the physical properties and performance of methyl ester ethoxylates (7,10,11). However, in considering the more recently described effective ethoxylation of the ester bond, a wide spectrum of additional raw materials appears to be relevant for the manufacture of nonionic surfactants. Some of them are already available commercially. They include longer aliphatic esters applied as ecological organic solvents, lubricants, modern bio-fuel additives, or other auxiliary agents. The aim of this work was to present the results from direct ethoxylation of 2-ethylhexyl laurate as an exemplary longer-chain aliphatic ester subjected to the reaction and to study the solubility of the products obtained in water and in 2-(2-butoxyethoxy)ethanol (butyldiglycol: BDG) solution. EXPERIMENTAL PROCEDURESThe following materials were used: oxirane (Mazovian Petrochemical Works, P / lock, Poland); 2-ethylhexyl laurate, marked as Polcet L (CHEMCO Production and Trade Company, Sobowidz, Poland); and ...

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confidence: 99%

Direct ethoxylation of a longer‐chain aliphatic ester

Hreczuch

Trathnigg

Dziwiński

et al. 2001

“…Immediately thereafter, Lion Corporation (Tokyo, Japan) demonstrated that a magnesium/aluminum oxide-based catalyst also worked well (4). Since then, the development and use of ester alkoxylates have become an active area of research (5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21)(22).…”

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confidence: 99%

Partially saponified triglyceride ethoxylates

Cox

Weerassoriya

2000

Self Cite

Various triglycerides (coconut oil, palm kernel oil, tallow) were ethoxylated with a proprietary catalyst (calcium/aluminum alkoxide complex partially neutralized in an alcohol ethoxylate base) to obtain triglyceride ethoxylates. Triglyceride ethoxylates were then partially saponified with sodium hydroxide to form mixtures of mono-, di-, and triglyceride ethoxylates, fatty acid soap, and glycerol ethoxylate. These mixtures were characterized in terms of physical properties, surface activity, and mildness. Partially saponified triglyceride ethoxylates were found to be unexpectedly mild and capable of imparting mildness to other surfactants.Paper no. S1157 in JSD 3, 213-220 (April 2000).Ethoxylation is the most common method for adding a nonionic hydrophile to an organic hydrophobe. Prior to 1989, substrates suitable for ethoxylation were thought to require a labile hydrogen, most commonly a hydroxyl hydrogen, in order for ethoxylation to occur. In the late 1980s, the concept of ethoxylating esters was introduced by Hoechst and Henkel (1,2). Hoechst demonstrated that ethoxylation of esters was feasible using catalysts based on alkali and alkali earth metals (e.g., sodium hydroxide, sodium methoxide, barium hydroxide, etc.), while Henkel showed that calcined hydrotalcite (aluminum/magnesium oxide complexes) had potential as well. Relatively poor reactivities and conversions, however, prevented these catalysts from being utilized commercially. In the early 1990s, Vista Chemical Company (now CON-DEA Vista Company, Houston, TX) developed a commercially viable process for ethoxylating esters (3). Their process utilized a more complex alkoxylation catalyst (activated calcium and aluminum alkoxides) that efficiently and effectively inserted ethylene oxide between the carbonyl carbon and the ester oxygen. Immediately thereafter, Lion Corporation (Tokyo, Japan) demonstrated that a magnesium/aluminum oxide-based catalyst also worked well (4). Since then, the development and use of ester alkoxylates have become an active area of research (5-22). This paper deals with an extension of ester alkoxylation technology. Previous studies have demonstrated that the CONDEA Vista catalyst (a calcium and aluminum alkoxide complex partially neutralized in an alcohol ethoxylate base) can be used to ethoxylate esters, including triglycerides (5,13-16). It is also known that mono-and diglyceride ethoxylates are mild surfactants (23). The object of this research was first to prepare triglyceride ethoxylates and then partially saponify them to obtain a mild surfactant blend of mono-, di-, and triglyceride ethoxylates and fatty acid soap. It was thought that such a blend would make a lower-cost surfactant for mild personal-wash bars, pastes, and gels. This paper details our initial studies on partially saponified triglyceride ethoxylates (PSTE). It describes the preparation and cursory assessment of PSTE made from three different triglycerides. The impacts of surfactant structure (carbon chain length, unsaturation, degree of ethoxylation, degre...

“…Propoxylations and ethoxylations were performed with KOH and with an alkoxylation catalyst complex (called NOVEL ® II; CONDEA Vista Company, Houston, TX) that consists of a Ca/Al complex partially neutralized in an alcohol ethoxylate base (3). This Ca/Al alkoxide catalyst is an effective ethoxylation catalyst for producing "peaked" or "narrow-range" alcohol ethoxylates, and for the ethoxylation and propoxylation of esters (4)(5)(6)(7)(8)(9).…”

Section: Methodsmentioning

confidence: 99%

Enhanced propoxylation of alcohols and alcohol ethoxylates

Cox¹,

Weerasooriya²

1999

Self Cite

An alkoxylation catalyst consisting of a calcium/ aluminum complex partially neutralized in an alcohol ethoxylate base was found to be substantially more active than a conventional potassium hydroxide catalyst in the propoxylation of alcohols and alcohol ethoxylates. With the Ca/Al alkoxide catalyst, propoxylation was faster, required less catalyst, and proceeded at lower temperatures. The latter is desirable since it could help reduce the formation of allyl alcohol and allyl alcohol propoxylate by-products. The two catalysts produced different oligomer distributions, particularly at higher temperatures, which were found to have a marginal impact on surface chemistry.Paper no. S1085 in JSD 2, 59-68 (January 1999).Alcohol propoxylates and alcohol ethoxylate/propoxylates are used in a variety of applications, most notably as co-monomers in condensation polymerization and as lower-foaming surfactants. Unlike ethylene oxide, propylene oxide adds hydrophobicity and steric bulk because of methyl branching that occurs during oligomerization. The impact of polypropylene oxide on performance properties has been discussed elsewhere (1). Like ethoxylation, propoxylation can be achieved using a conventional catalyst, usually potassium hydroxide (KOH), and conventional alkoxylation equipment. Propylene oxide, however, is less reactive than ethylene oxide. Although the reaction temperature can be increased to compensate for lower reactivity, increasing reaction temperature also increases by-product formation. As shown in Scheme 1, KOH reacts with propylene oxide to form an unsaturated alkoxide (allyl alkoxide) salt (2). After further propoxylation and neutralization, allyl alcohol and allyl alcohol propoxylates are produced. These by-products are undesirable because they reduce the yield of the desired product and, because of unsaturation, they can interfere with polymerization. Consequently, propoxylations are typically performed under mild conditions (around 125°C), require high catalyst levels (thousands of ppm), and take hours instead of minutes to complete. This paper compares the influence of catalyst concentration and reaction rate of two catalysts, KOH and a calcium (Ca)/aluminum (Al) alkoxide complex, on reaction rate, reaction temperature, and oligomer distribution. Because a safe and reliable analytical method is not available at our site for accurately measuring allyl by-product concentrations, we assumed that by-product formation is directly related to temperature and to catalyst level and is independent of catalyst composition.Although this study compares KOH to a Ca/Al alkoxide complex catalyst, other ethoxylation catalysts based on barium, lanthanum, magnesium, and the like may also be effective propoxylation catalysts. EXPERIMENTAL PROCEDURESAlkoxylation catalysts. Propoxylations and ethoxylations were performed with KOH and with an alkoxylation catalyst complex (called NOVEL ® II; CONDEA Vista Company, Houston, TX) that consists of a Ca/Al complex partially neutralized in an alcohol ethoxylate base (3). This ...