Esterquats COR OVERKEMPE Akzo Nobel BV, Deventer, The Netherlands ANNIKA ANNERLING Akzo Nobel Surface Chemistry AB, Stenungsund, Sweden C. G. VAN GINKEL and PAUL CHRISTOPHER THOMAS § Akzo Nobel Chemicals Research, Arnhem, The Netherlands DAGMAR BOLTERSDORF Akzo Nobel Chemicals GmbH, Diiren, Germany JOHANNA SPEELMAN Akzo Nobel BV, Deventer, The Netherlands |. INTRODUCTION The term eséerquat is commonly used to describe a family of cationic surfactant compounds that is heterogeneous in the chemical sense. In this chapter, we define esterquats as a class of surface-active quaternary ammo- nium compounds having the general formula RsN“)X“”, characterized by the fact that the hydrophobic parts of the moieties “R” are linked to the charged head group via ester bonds R-C(O)O- or ROC(O)-, with XO being any anionic counterion. Somewhat arbitrarily, we further propose that any alkyl chain ina moiety R that contains more than four carbon atoms shall be considered as belonging to the hydrophobic part of the molecule. By application of this definition, an ester compound that contains a moiety R directly bonded to a cationic nitrogen, with R containing more than four carbon atoms, is not considered an esterquat. As a consequence of this specific structure, esterquats upon hydrolysis decompose into non-surface-active fragments. They may be referred to as “cleavable surfactants.” As a matter of fact, esterquats usually biodegrade more rapidly than the related alkylquats. The hydrolytic instability, on the other hand, comprises a challenge to the user and formulator. While tradi- tional alkylquats are virtually stable under the conditions of use, esterquatsare stable in aqueous solutions only in a narrow pH window for a certain period of time. Although this limitation seems acceptable to the formulator for specific applications, it remains unclear as to whether esterquats can replace alkylquats in other applications. However, new legislation might be a driving force to replace products with environmental risk with products that are safer to use. Most esterquats are readily biodegradable and show low toxicity, partly caused by their hydrolytic instability. The earliest mention of esterquats in the open literature dates back to the 1930s [1]. Early uses of esterquats were as textile auxiliaries and dye-leveling agents. However, until recently their commercial relevance was limited. This changed dramatically when in the early 1990s, overnight, a market was cre- ated for several thousands of tons when European detergent manufacturers started to reformulate their rinse cycle softener products to esterquats. ‘Today rinse cycle softeners based on esterquats are in broad use in Europe and the United States, and constitute by far the largest commercial use of this class of compounds. Esterquats are also applied in personal care products, and some industrial areas are following slowly. It is expected that the use of esterquats will grow. Existing products will be used for new and existing applications and technologies and formulations will be adapted to deal with the specific use of esterquats. New products with improved per- formance and environmental properties will be developed and applied in existing and new applications. Il. CHEMISTRY A. Raw Materials Esters are generally prepared by reaction of an acid with an alcohol. In the presence of a catalyst the raw materials are heated to temperatures up to 250°C to remove water and to obtain high conversion. Due to the thermal instability of quaternary ammonium compounds, they are not recommended for use with alcohol or acid functions in the esterification. In the case of esteramines, the esterification is usually carried out with tertiary alkanol- amines and fatty acids. The corresponding esteramine is reacted with an alkylating agent like dimethyl sulfate or methyl chloride to obtain the corresponding quaternary ammonium compound. The alkanolamines most frequently used are triethanolamine (TEA), methyldiethanolamine (MDEA), dimethylethanolamine (DMEA), and 3- (dimethylamino)-1,2-propanediol (DMAPD). Other types of esteramines are prepared from aminoethylethanolamine (AEEA) or other ethoxylated amines (Fig. 1). Some physical properties of the alkanolamines are listed in Table 1 [2]. Most alkanolamines are soluble in water.ae OH —C—OH cont HO—c—c— c—C—OH ‘c—C—OH Methyldiethanolamine ‘Triethanolamine bs N—C—C—OH Ns cm H,N—C—C—N—C—cC—OH o C i, fy Dimethylethanolamine tient 25 propanediol Aminoethylethanolamine FIG. 1 Some alkanolamines used for the preparation of esterquats. The hydrophobic building block of the esteramines is usually derived from fatty acid, which is readily available at low prices. Most esterquats are prepared from fatty acids with chain lengths of 8-18 carbon atoms. The fatty acids can be applied in their native form or (partly) hydrogenated. Most commonly used are tallow or (partially) hydrogenated tallow, but other fatty acids like coco, oleic, palmitic, fish oil or beef tallow [3,4], to name a few, are mentioned frequently, For use in personal care products, fatty acids from a vegetable source are preferred. Alternatives to the fatty acids are methyl esters, triglycerides [5], and acid chlorides. Triglycerides are cheap but lead to mixtures of components including glycerol and mono- and diglycerides. Acid chlorides are generally more expensive but can be used when a higher re- activity is required and the higher price is acceptable. The most commonly used acyl building blocks are listed in Fig. 2. The most commonly applied alkylating agents are dimethyl sulfate and methyl chloride, but other alkyl- ating agents can be used as well. TABLE 1 Physical Properties of Some Alkanclamines Freezing point Boiling point Specific gravity Viscosity Alkanolamine MW CC) @C) (20°C, gem’) 20°C, mPas) Dimethylethanolamine 89 9 135 0.888 3.8 Methyldiethanolamine = 119 21 247 1.042 101 Tricthanolamine 149 18 360 1.126 1013, 34{Dimethylamino)- 119 216 217 1.004 1,2-propanedicl Aminoethylethanolamine 104 38 ad 1.0304 141