Unsaturated soaps

W. Narath, G. Omoski, J. Corr, Enhanced processing of synthetic bar compositions comprising amphoterics based on minimal levels of fatty acid soap and minimum ratios of saturated to unsaturated soap, US Patent No. 6 121 216 (2000). 

CH3(CH2)6CH2CH=CHCH2(CH2)6COOM mono-unsaturated soap... 

Mono-unsaturated soap CH3(CH2)nCH2CH=CHCH2(CH2) —COOM Poly-unsaturated soap CH3(CH2CH=CH)xCH2(CH2)y—COOM [M=Na, K, R4N1... 

Unsaturated aldehydes undergo a similar reaction in the presence of strongly acid ion-exchange resins to produce alkenyUdene diacetates. Thus acrolein [107-02-8] or methacrolein [78-85-3] react with equimolar amounts of anhydride at —10°C to give high yields of the -diacetates from acetic anhydride, useful for soap fragrances. 

Petroleum Oils. When satisfactorily stable kerosene—soap—water emulsions were produced in 1874, dormant (winter) oil sprays became widely used to control scale insects and mites (1). The first commercial emulsion or miscible oil was marketed in 1904 and by 1930 highly refined neutral or white oils, free from unsaturated hydrocarbons, acids, and highly volatile elements, were found to be safe when appHed to plant foHage, thus gready enlarging the area of usefulness of oil sprays (see Petroleum). 

Carboxylate soaps are most commonly formed through either direct or indirect reaction of aqueous caustic soda, ie, alkaH earth metal hydroxides such as NaOH, with fats and oils from natural sources, ie, triglycerides. Fats and oils are typically composed of both saturated and unsaturated fatty acid molecules containing between 8 and 20 carbons randomly linked through ester bonds to a glycerol [56-81-5] backbone. Overall, the reaction of caustic with triglyceride yields glycerol (qv) and soap in a reaction known as saponification. The reaction is shown in equation 1. 

Vatty Acids andFattyAcidLsters. Sulfolane exhibits selective solvency for fatty acids and fatty acid esters which depends on the molecular weight and degree of fatty acid unsaturation (40—42). AppHcations for this process are enriching the unsaturation level in animal and vegetable fatty oHs to provide products with better properties for use in paint, synthetic resins, food products, plastics, and soaps. 

Cobalt in Driers for Paints, Inks, and Varnishes. The cobalt soaps, eg, the oleate, naphthenate, resinate, Hnoleate, ethyUiexanoate, synthetic tertiary neodecanoate, and tall oils, are used to accelerate the natural drying process of unsaturated oils such as linseed oil and soybean oil. These oils are esters of unsaturated fatty acids and contain acids such as oleic, linoleic, and eleostearic. On exposure to air for several days a film of the acids convert from Hquid to soHd form by oxidative polymeri2ation. The incorporation of oil-soluble cobalt salts effects this drying process in hours instead of days. Soaps of manganese, lead, cerium, and vanadium are also used as driers, but none are as effective as cobalt (see Drying). 

Properties are furthermore determined by the nature of the organic acid, the type of metal and its concentration, the presence of solvent and additives, and the method of manufacture. Higher melting points are characteristics of soaps made of high molecular-weight, straight-chain, saturated fatty acids. Branched-chain unsaturated fatty acids form soaps with lower melting points. Table 1 Hsts the properties of some soHd metal soaps. 

In modem manufacturing methods the oil is sometimes reacted directly with the glycerol to form a monoglyceride and this is then reacted with the acid to form the alkyd resin. When the resulting surface coating is applied to the substrate the molecules are substantially linear. However, in the presence of certain driers such as lead soaps there is oxidative cross-linking via the unsaturated group in the side chain and the resin hardens. 

The raw materials for the manufacture of soap, the alkali salts of saturated and unsaturated C10-C20 carboxylic acids, are natural fats and fatty oils, especially tallow oil and other animal fats (lard), coconut oil, palm kernel oil, peanut oil, and even olive oil. In addition, the tall oil fatty acids, which are obtained in the kraft pulping process, are used for soap production. A typical formulation of fats for the manufacture of soap contains 80-90% tallow oil and 10-20% coconut oil [2]. For the manufacture of soft soaps, the potassium salts of fatty acids are used, as are linseed oil, soybean oil, and cottonseed oil acids. High-quality soap can only be produced by high-quality fats, independent of the soap being produced by saponification of the natural fat with caustic soda solution or by neutralization of distilled fatty acids, obtained by hydrolysis of fats, with soda or caustic soda solutions. Fatty acids produced by paraffin wax oxidation are of inferior quality due to a high content of unwanted byproducts. Therefore in industrially developed countries these fatty acids are not used for the manufacture of soap. This now seems to be true as well for the developing countries. 

Even today renewable resources play a dominant role as raw materials for surfactants, but only because of the great contribution made by soaps to the production of surfactants. If the soaps are left out of consideration as native surfactants, petrochemistry holds 65-70% of the production of synthetic surfactants [2]. But for the future a further increase of renewable raw materials is expected in surfactant production [3]. The main reason for this development is the superior digestibility in the environment of products produced from natural materials. The future importance of the renewable raw materials becomes evident from the fact that even now new plants are cultivated or plants are modified to obtain an improved yield. A new type of sunflower has been cultivated to obtain a higher proportion of monounsaturated oleic acid compared with doubly unsaturated linoleic acid [4],... 

When a-sulfo fatty acid esters are used as the major active component in detergents they can cause problems because of their foaming properties. In European horizontal drum-type automatic washers they produce too much foam, and in the rinse cycle of the American and Japanese pulsator-type washers the foam cannot be completely rinsed out [38]. The problem of inefficient rinsing can be solved by the addition of soap [63] or sulfonated unsaturated fatty acid esters [64]. For European applications special foam inhibitors are needed. 

Fatty acids, especially unsaturated ones, offer many possibilities for conversion into a range of chemical feedstocks as exemplified in Schemes 6.3 and 6.4. Most of the fatty acids produced are either converted to the alcohol for subsequent conversion into surfactants or else transformed into metal salts for use as soaps . 

Carothers returned to Illinois chemistry department that fall to concentrate for two more years on organic chemistry with minors in physical chemistry and mathematics. His thesis topic was related to Adams signature discovery, a catalyst used to hydrogenate unsaturated fats for the shortening and soap industries. Carothers and 11 other collaborators produced 18 papers about the catalyst with Adams. At the same time, Carothers... 

Anomolous results have been observed in some emulsion polymerizations—inverse dependencies of N, Rp, and Xn on surfactant concentration. Some surfactants act as inhibitors or retarders of polymerization, especially of the more highly reactive radicals from vinyl acetate and vinyl chloride [Okamura and Motoyama, 1962 Stryker et al., 1967]. This is most apparent with surfactants possessing unsaturation (e.g., certain fatty acid soaps). Degradative chain transfer through allyl hydrogens is probably quite extensive. 

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