Alkylphenolic detergents

Higher n-olefins of Cs-Ci4 are used as intermediates in the manufacture of several types of surfactant materials. Linear internal olefins are used in the production of linear alkylbenzene alkylphenol detergent alcohols, which in turn is used to produce alcohol sulfates, alcohol ethoxylates, and alcohol ether sulfates and synthetic lubricants. a-Olefins are used in the production of detergent alcohols, linear alkylbenzene, synthetic lubricants, and a-olefin sulfonates (another ionic surfactant). 

In using the alkylphenols, it is possible to obtain three types of detergents the alkylphenols themselves transformed as salts of calcium, the alkylphenol-sulfides conferring antioxidant properties and finally the alkylphenol-sulfides transformed by action of CO2 into alkylsalicylate-sulfides (Figure 9.9). 

Detergents are metal salts of organic acids used primarily in crankcase lubricants. Alkylbenzenesulfonic acids, alkylphenols, sulfur- and methjiene-coupled alkyl phenols, carboxyUc acids, and alkylphosphonic acids are commonly used as their calcium, sodium, and magnesium salts. Calcium sulfonates, overbased with excess calcium hydroxide or calcium carbonate to neutralize acidic combustion and oxidation products, constitute 65% of the total detergent market. These are followed by calcium phenates at 31% (22). 

Ethoxylated andSulfatedAlkylphenols. Because these aLkylphenols degrade less readily than the sulfated alcohol ethoxylates, their anticipated expansion failed to materialize, although by 1965 they were widely used in retail detergent products. Sulfated alkylphenol ethoxylates are used in hospital cleaning products, textile processing, and emulsion polymerization. Sulfated alkyphenol ethoxylates are sold as colorless, odorless aqueous solutions at concentrations of >30%. The presence of ethylene oxide in the molecule increases resistance to hardness ions and reduces skin irritation. Representative commercial sulfated alkylphenol ethoxylates are given in Table 12. 

Nonionic Surface-Active Agents. Approximately 14% of the ethyleae oxide consumed ia the United States is used in the manufacture of nonionic surfactants. These are derived by addition of ethylene oxide to fatty alcohols, alkylphenols (qv), tall oil, alkyl mercaptans, and various polyols such as poly(propylene glycol), sorbitol, mannitol, and cellulose. They are used in household detergent formulations, industrial surfactant appHcations, in emulsion polymeri2ation, textiles, paper manufacturing and recycling, and for many other appHcations (281). 

Alkylphenols, ammonia, asbestos, chlorinated paraffins, 4-chloroaniline, cyanide, detergents, di- -butyl phthalate, polyaromatic hydrocarbons (PAHs e.g. anthracene, benzopyrene, methylcholanthrene, /i-naphthoflavone), nitrate, nitrite, petroleum oil, phenol, pentachlorophenol, 4-nitrophenol, dinitro-o-cresol, polychlorinated biphenyls (PCBs especially coplanar), polychlorinated dioxins, polybrominated naphthalenes, /i-sitosterol, sulfide, thiourea, urea, acid water, coal dust... 

The reaction between ethylene oxide and long-chain fatty alcohols or fatty acids is called ethoxylation. Ethoxylation of C10-C14 linear alcohols and linear alkylphenols produces nonionic detergents. The reaction with alcohols could be represented as ... 

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]. 

Alkylphenol ethoxylates (APEs) are nonionic surfactants that are used in the manufacturing of plastics, agricultural chemicals, cosmetics, herbicides, and industrial detergent formulations. Alkylphenols such as nonylphenol (NP) are the products of... 

Ethoxyethene. See Ethyl vinyl ether Ethoxylated alkylphenols, emulsifiers, detergents, and dispersants,... 

S.S. Talmage, Environmental and Human Safety of Major Surfactants Alcohol Ethoxylates and Alkylphenol Ethoxylates, Soap and Detergent Association, Lewis, Boca Raton, FL, 1994. 

Alkylphenol ethoxylates (APEO) are no longer used in household detergents in the Western world and represent only a minor portion of the whole non-ionic surfactants group. Even if APEO is a group of surfactants of no commercial importance anymore, there is a need for risk assessment since these compounds are still present in the aquatic environment due to the recalcitrant nature of some of their metabolites (see Chapters 6.1, 6.2.1, 6.3.1 and 6.4). More attention should be given in the future to other non-ionic surfactants like alcohol ethoxylates. 

Nonionic surfactants contain (Fig. 23) no ionic functionalities, as their name implies, and include ethylene oxide adducts (EOA) of alkylphenols and fatty alcohols. Production of detergent chain-length fatty alcohols from both natural and petrochemical precursors has now increased with the usage of alkylphenol ethoxylates (APEO) for some applications. This is environmentally less acceptable because of the slower rate of biodegradation and concern regarding the toxicity of phenolic residues [342]. 

Nonylphenol ethoxylates (NPEOs) are extensively used as surfactants in industrial products (see Chap. 1). NPEOs are a mixture of polyethoxylated mono-alkylphenols, predominantly para-substituted, and are used in the manufacturing of paints, detergents, inks, and pesticides [435, 446]. Surfactants are common water pollutants because of their use in aqueous solutions, which are discharged into the environment in the form of wastewater from treatment plants or sludge stored in landfills. Degradation products of alkylphenol polyethoxylates, i. e., nonylphenol (NP), have the potential to be bioaccumulated, thereby becoming toxic to aquatic [447] and soil microorganisms [435,448]. 

Alkylphenols and their derivatives (APEs) are primarily used as non-ionic surfactants in industrial detergents, though also in textile and leather finishing treatments, water based paints and as components of some personal care products. 

Alkylphenol ethoxylate surfactants are widely used in laundry detergents. Chlorination of these compounds results in the formation of halogenated nonylphenolic DBFs, most of them brominated acidic compounds [126],... 

Table 11.2 outlines the uses of phenol. We will consider the details of phenol uses in later chapters. Phenol-formaldehyde polymers (phenolics) have a primary use as the adhesive in plywood formulations. We have already studied the synthesis of bisphenol A from phenol and acetone. Phenol s use in detergent synthesis to make alkylphenols will be discussed later. Caprolactam and aniline are mentioned in the following sections in this chapter. 

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