Trisiloxane surfactants

Fig. 2.8.2. Structure of the trisiloxane surfactants commonly used as agrochemical...

An industrial blend of ethylene oxide (EO) PEMS marketed as a personal care product was examined by positive ion FIA-APCI-MS and LC-APCI-MS-MS (Fig. 2.8.8) [41]. The FIA-APCI-MS spectrum without LC separation (Fig. 2.8.8(a)) is dominated by ions corresponding to unreacted PEG (m/z 520, 564, 608, 652,...), whilst the ions corresponding to the PEMS (m/z 516, 560, 604, 648,...) could only be clearly observed following LC separation (Fig. 2.8.8(b)). Comparison of the TIC chromatograms of PEMS and PEG (Fig. 2.8.8(c) and (h)) demonstrates the dominance of the PEG by-products in the commercial formulation. It is unclear whether the observed relative intensities are representative of the actual amounts or of the different ionisation efficiencies, due to the confidential nature of the product composition. However, the spectra indicate a trisiloxane surfactant structure of that shown in Fig. 2.8.2 (R = Ac) and FIA-MS analysis of another commercial formulation of this product showed good spectra dominated by the silicone surfactants [48], indicating that the PEG by-product composition can vary significantly in commercially available PEMS formulations. 

As shown in Table 5.5.1,15% of the silicone surfactants annually used were disposed of via wastewater treatment plants [6], but no studies have addressed their fate or persistence in this environmental compartment. Due to the hydrolytic instability and tendency for sorption to surfaces, it is generally thought that limited persistence of the parent molecule in aqueous systems should occur. Consequently more attention has been focused on interactions with solid media such as that resulting from direct application as agricultural adjuvants, and in re-use of sludge. Increased water solubility for the degradation products of trisiloxane surfactants has, however, been observed [10,12,15], demonstrating the need to also monitor the... 

The potential sites of cleavage in the hydrolytic degradation of the trisiloxane surfactant, M2D-C3-0-(E0)n-CH3 (1) are illustrated in Fig. 5.5.3. The Si-0 bond (c) is a likely site of cleavage according to the chemistry of silicones and the relative instability of this bond to hydrolysis [23]. 

The ultimate fate of higher alkyl silanols such as those produced in trisiloxane surfactant degradation, for example CH3-Si(OH)2-CH2 CH2CH2OH, has not been described, and is an area requiring further investigation. The mechanisms described above for the degradation of the methyl siloxanes may or may not be applied to higher alkylated versions. The Si-C bond is not susceptible to hydrolysis [7], and as such the abiotic elimination processes are not likely to occur. 

There are numerous studies on the spreading of trisiloxane surfactants on hydrophobic surfaces (for two comprehensive reviews, see [21,22]), but the... 

Churaev NV, Esipova NE, Hill RM, Sobolev VD, Starov VM, Zorin ZM (2001) The superspreading effect of trisiloxane surfactant solutions. Langmuir 17 1338-1348... 

Raney K, Benton W, Miller CA (1987) Optimum detergency conditions with nonionic siufactants II. Effect of hydrophobic additives. J Colloid Interface Sci 119 539-549 Rosen MJ, Wu Y (2001) Superspreading of trisiloxane surfactant mixtures on hydrophobic siufaces 1. Interfacial adsorption of aqueous trisiloxane surfactant -M-alkyl pyrrolidinone mixtures on polyethylene. Langmuir 17 7296-7305 Stevens PJG, Kimberely MO, Mimphy DS, Policello GA (1993) Adhesion of spray droplets to foliage - the role of dynamic surface tension and advantages of organosil-icone surfactants. Pesticide Sci 38 237-245... 

Stoebe T, Lin Z, Hill RM, Ward MD, Davis HT (1997) Superspreading of aqueous films containing trisiloxane surfactant on mineral oil. Langmuir 13 7282-7286 Stoebe T, Hill RM, Ward MD, Scriven LE, Davis HT (1996) Surfactant-enhanced spreading. Langmuir 12 337-344... 

Svitova T, Hill RM, Smirnova Y, Stuermer A, Yakubov G (1998) Wetting and interfacial transitions in dilute solutions of trisiloxane surfactants. Langmuir 14 5023-5031... 

Svitova TF, Hill RM, Radke CJ (2001) Spreading of aqueous trisiloxane surfactant solutions over liquid hydrophobic substrates. Langmuir 17 335-348... 

Wu Y, Rosen MJ (2002) Superspreading of trisiloxane surfactant mixtures on hydrophobic surfaces 2. Interaction and spreading of aqueous trisiloxane surfactant -n-alkyl pyrrolidinone mixtures in contact with polyethylene. Langmuir 18 2205-2215... 

It is a common misunderstanding that silicones and silicone surfactants are incompatible with hydrocarbon oils this is only partly correct. Small silicone surfactants, such as the trisiloxanes, are very compatible with organic oils. For example, aqueous solutions of the trisiloxane surfactants give very low interfacial tension against alkane oils. The incompatibility between polymeric silicones and some hydrocarbon oils is due more to the polymeric nature of the silicone block rather than to strong phobicity such as that between fluorocarbon and hydrocarbon groups. The compatibility between two species, such as a polymer and a... 

Many small-molecule silicone surfactants have been made and their properties (especially wetting) characterized [7-11]. The best known small-molecule silicone surfactants are the trisiloxane surfactants based on 1,1,1,3,5,5,5-heptamethyltrisiloxane, shown in Figure 6.19. 

The wetting properties of the trisiloxane surfactants will be discussed below. 

Silicone surfactants in aqueous solutions show the same general behavior as conventional hydrocarbon surfactants - the surface tension decreases with increasing concentration until a densely packed film is formed at the surface. Above this concentration, the surface tension becomes constant. The concentration at the transition is called the critical micelle concentration (CMC) or critical aggregation concentration (CAC). The surface and interfacial activity of silicone surfactants was reviewed by Hoffmann and Ulbricht [27]. Useful discussions of the dependence of the surface activity of polymeric silicone surfactants on molecular weight and structure are given by Vick [28] and for the trisiloxane surfactants by Gentle and Snow [29]. 

The efficiency of the nonionic trisiloxane surfactants is comparable to nonionic hydrocarbon surfactants with a linear dodecyl hydrophobe. The surface properties of a homologous series of trisiloxane surfactants M(DE OH)M with n = 4—20 show that the CAC, the surface tension at the CAC and the area per molecule each vary with molecular structure in a way that is consistent with an umbrella model for the shape of the trisiloxane hydrophobe at the air/water interface [29]. The log(CAC) and the surface tension at the CAC both increased linearly with EO chain length. 

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