Surfactants Phosphate Esters

Detergent, wetting agent, emulsifier and coupling agent. 

Lowers surface tension. Water soluble, compatible and stable in concentrated electrolyte solutions. Improves detergency, foaming and increases viscosity of liquid cleaners. An exceptional detergent used in powdered and liquid, alkaline cleaners heavy-duty, all-purpose cleaners for metal working steam cleaning dairy cleaners bottle-washing compounds and floor strippers. Soluble in most oxygenated solvents, aromatic solvents, and chlorinated solvents. 

Aromatic, Sodium Salt Clear, Viscous Liquid Activity, % 85 

Detergent, emulsifier, dispersant and solubilizer for use with nonionic surfactants and concentrated electrolyte solutions. 

Detergent, wetting agent, emulsifier and dispersant. Lowers surface tension. Soluble in water, alcohols, hydrocarbon solvents and chlorinated solvents. Exhibits rust-inhibition properties. 

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Tr i ton QS-44 Surfactant Phosphate ester, acid form, anionic (80% active) Union Carb... 

Organophosphorous product Nonionic surfactant Nonionic surfactant Detergent/degreaser Nonionic surfactant Nonionic surfactant Phosphate ester... 

Ethoxylated alcohols Ethoxylated fatty acids Lauryl sulfates Mono and diglycerides Nonionic surfactants Phosphate esters Quaternary surfactants Sorbitan derivatives... 

COSTEC INC. Industrial Surfactants Phosphate Esters Continued) ... 

As seen in Table 2, sodium hypochlorite bleach maintains excellent stability in the presence of the alkyldiphenyl oxide disulfonates, even after 319 days. Only 2-ethylhexylsulfate exhibited similar inertness to sodium hypochlorite. The bleach solution fared moderately weU with a number of surfactants to the 137-day point, but were not tested at 319 days due to the level of precipitate that developed. Two of the surfactants, phosphate esters and alkyl polysaccharide, exhibited very poor stabihty. 

Inspired by the many hydrolytically-active metallo enzymes encountered in nature, extensive studies have been performed on so-called metallo micelles. These investigations usually focus on mixed micelles of a common surfactant together with a special chelating surfactant that exhibits a high affinity for transition-metal ions. These aggregates can have remarkable catalytic effects on the hydrolysis of activated carboxylic acid esters, phosphate esters and amides. In these reactions the exact role of the metal ion is not clear and may vary from one system to another. However, there are strong indications that the major function of the metal ion is the coordination of hydroxide anion in the Stem region of the micelle where it is in the proximity of the micelle-bound substrate. The first report of catalysis of a hydrolysis reaction by me tall omi cell es stems from 1978. In the years that... 

Most of the phosphate esters are used in the production of hydrauHc fluids (qv), plastic and elastomer additives, flame retardants (qv), oil stabilizers, pesticides (qv), and medicinal intermediates (see Surfactants). Some trialkyl phosphates, OP(OR)2, are outstanding solvents for nitrates, especially (UO2) (N02)2, and therefore are important in uranium processing (see Extraction). 

Smaller amounts of the phosphate esters of the polyethylene glycol which is present ia the ethoxylated alcohol and a trace of NaH2P02 are also present. Table 13 gives aUst of commercial phosphate surfactants. 

Cationic, anionic, and amphoteric surfactants derive thek water solubiUty from thek ionic charge, whereas the nonionic hydrophile derives its water solubihty from highly polar terminal hydroxyl groups. Cationic surfactants perform well in polar substrates like styrenics and polyurethane. Examples of cationic surfactants ate quaternary ammonium chlorides, quaternary ammonium methosulfates, and quaternary ammonium nitrates (see QuARTERNARY AMMONIUM compounds). Anionic surfactants work well in PVC and styrenics. Examples of anionic surfactants ate fatty phosphate esters and alkyl sulfonates. 

Ether carboxylates are used not only in powdered detergents but in liquid laundry detergents for their hard water stability, lime soap dispersibility, and electrolyte stability they improve the suspension stability and rheology of the electrolyte builder [130,131]. Formulations based particularly on lauryl ether carboxylate + 4.5 EO combined with fatty acid salt and other anionic surfactants are described [132], sometimes in combination with quaternary compounds as softeners [133,163]. Ether carboxylates show improved cleaning properties as suds-controlling agents in formulations with ethoxylated alkylphenol or fatty alcohol, alkyl phosphate esters or alkoxylate phosphate esters, and water-soluble builders [134]. 

There are many parallels between phosphates and sulfates of aliphatic alcohols. Both types of surfactants contain ester bonds undergoing hydrolysis in acid solutions. In that case the starting materials are received once more. By dry heating of the salts above a temperature of 140°C destruction will occur forming the corresponding alkenes and an inorganic acid salt. In the same way as sulfonic and sulfinic acids are formed by C-S bonds, C-P bonds lead to phosphonic and phosphinic acids. 

Surfactants are also prepared by the reaction of glycerol derivatives RC02 [CH2CH(0H)CH20] H (R = C6 16 alkyl, n = 1-5) with P4O10 at 60-80°C with subsequent neutralization of the resulting phosphate ester acids with aqueous alkali or alkanolamine solution at 50-70°C [10]. 

Colorless phosphate ester surfactants were also prepared by treating P4O,0 with an organic OH-containing compound in the presence of a phosphinic acid color inhibitor, e.g., bis(hydroxymethyl)phosphinic acid color inhibitor. Thus, 558 parts dodecanol containing 2.4 parts of phosphinic acid color inhibitor was treated with 142 parts P4O10 at 100-135°C. The phosphate ester surfactant had a VCS color value of 1, whereas a sample prepared without the color inhibitor had a VCS color value of 5. Twenty-eight similar surfactants were prepared using various alcohols and alcohol-alkylene oxide condensates [22]. 

The development of monoalkyl phosphate as a low-skin-irritating anionic surfactant is accented in a review with 30 references on monoalkyl phosphate salts, including surface-active properties, cutaneous effects, and applications to paste- and liquid-type skin cleansers, and also on phosphorylation reactions from the viewpoint of industrial production [26]. The preparation and industrial applications of phosphate esters as anionic surfactants were discussed [27]. 

A review of the preparation, properties, the uses of surface-active anionic phosphate esters prepared by the reactions of alcohols or ethoxylates with tetra-phosphoric acid or P4O10 is given in Ref. 3. The preparation and industrial applications of phosphate esters as anionic surfactants were also discussed in Ref. 31. 

In order to obtain anionic polyoxyethylene phosphate surfactants, either the terminal hydroxy group of a polyoxyethylated hydrophobic substance is reacted with a phosphorylating agent or a phosphate ester is oxalkylated. Most often aliphatic and aliphatic-aromatic alcohols are first treated with an alkylene oxide and afterward with one of the phosphorylating agents, such as P4OI0, POCl3, phosphoric acid, or polyphosphoric acid [39-48]. 

TABLE 3 Solubility Properties of Polyoxyethylene Phosphate Esters in Aqueous Solutions of Tetrapotassium Pyrophosphate Compared to Solubility Properties of Other Surfactants... 

In the preparation of surfactants by the reaction of alcohols with P4Ol0 with subsequent neutralization of the partial phosphate esters with a base, the quality of the surfactants is improved by using RNEt3OH (R = Et or benzyl) in alcoholic solution as the base, by using C6 10 alcohol mixtures of hydroxyethylated C7 9 alcohols or equimolar mixtures of C6 I0 alcohols with polyethylene glycol (mol wt 200-1500) and by using a reaction temperature of 55-60°C [8]. 

When ethoxylated nonylphenol and polyethylene glycol is treated with a mixture of H2S04 and H3P04 and neutralized with an alkali metal hydroxide or amine, surfactants containing sulfate esters and phosphate esters are obtained which cause little corrosion of metals such as surfaces of laundering equipments and automobiles [55]. 

A great number of nonionic surfactants have been ethoxylated and subsequently reacted with P4O10. The acid phosphate esters from this reaction possess surface properties and detergency similar to the nonionic surface-active agents employed as reactants. Detergency tests and foam heights from the Ross-Miles method have been reported for a series of compounds. Various formulations for all-purpose cleaners are given as well [37,40,41,44,48]. 

Monoamidotriphosphate compounds have been evaluated for their combined detergent-sequestrant action [65,66]. Good surfactant properties are also attributed to organoaminodialkylenephosphonic acids. Typical compounds of this kind are the tetra- and trialkali salts of decyl-, dodecyl-, and tetradecylaminodi (methylphosphonate). Values of surface tension and detergency are given in Refs. 118 and 216-219. Wash test results, foam behavior, wetting performance, and surface tensions of aqueous solutions of phosphate esters have been tabulated [12,17,18,33,37,50,52,56,90,220]. 

Emulsions are frequently used in the formulation of herbicides. Such emulsions have to form stable concentrates. They will be diluted with water before applying on plants. In this form too the surfactants used have to support the formation of fine droplets at the nozzles and provide a sufficient wetting of leaves. Surfactants have to be used which will not interfere with water hardness. Therefore phosphate esters and phosphonic esters are often applied. 

Aqueous, removable, pressure-sensitive adhesive compositions, useful for high-performance applications, comprise a mixture of a copolymer of alkyl (meth)acrylate and N-substituted (poly)amide of (meth)acrylic acid and a copolymer of alkyl (meth)acrylate and ethylenically unsaturated carboxylic acid, where at least one of the copolymers is an emulsion copolymer. Polyoxyalkyl-enes and phosphate esters may be used as surfactants [234]. 

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