Vegetable oil derivatives

To overcome these difficulties, drilling fluids are treated with a variety of mud lubricants available from various suppHers. They are mostly general-purpose, low toxicity, nonfluorescent types that are blends of several anionic or nonionic surfactants and products such as glycols and glycerols, fatty acid esters, synthetic hydrocarbons, and vegetable oil derivatives. Extreme pressure lubricants containing sulfurized or sulfonated derivatives of natural fatty acid products or petroleum-base hydrocarbons can be quite toxic to marine life and are rarely used for environmental reasons. Diesel and mineral oils were once used as lubricants at levels of 3 to 10 vol % but this practice has been curtailed significantly for environmental reasons. 

Calcitriol must be protected from air and light. The drug substance exhibits good stability when stored at -15°C to -25°C in an argon atmosphere. The material is stable at room temperature when dissolved in a vegetable oil derivative, containing antioxidants, such as is used in calcitriol soft gelatin capsules (19). 

In polymer applications derivatives of oils and fats, such as epoxides, polyols and dimerizations products based on unsaturated fatty acids, are used as plastic additives or components for composites or polymers like polyamides and polyurethanes. In the lubricant sector oleochemically-based fatty acid esters have proved to be powerful alternatives to conventional mineral oil products. For home and personal care applications a wide range of products, such as surfactants, emulsifiers, emollients and waxes, based on vegetable oil derivatives has provided extraordinary performance benefits to the end-customer. Selected products, such as the anionic surfactant fatty alcohol sulfate have been investigated thoroughly with regard to their environmental impact compared with petrochemical based products by life-cycle analysis. Other product examples include carbohydrate-based surfactants as well as oleochemical based emulsifiers, waxes and emollients. 

Dunn, R. O., Shockley, M. W., and Bagby, M. O. 1996. Improving the Low-Temperature Flow Properties of Alterative Diesel Fuels Vegetable Oil-Derived Methyl Esters. J. Am. Oil Chem. Soc., 73,1719-1728. 

Graboski, M. S., and McCormick, R. L. 1998. Combustion of Fat and Vegetable Oil Derived Fuels in Diesel Engines. Prog. Energy Combust. Sci.,24,125-164. 

The growing recognition of the health benefits associated with phytosterol esters leads to the marketing of new products. Several companies have marketed stanol and sterol ester products. In 1995/1996, Raisio Company from Finland introduced the margarine Benecol with 9% of sitostanol ester. Benecol was also launched in the United States in May 1999. In 1999, Unilever launched its product. Take Control , which contained vegetable oil derived sterol esters. In addition to existing products on the market in 2000, Phytrol , unesterified taU oil phytosterols, was announced (Hicks and Moreau, 2001). 

Natural mixed tocopherols (E306), natural D-a tocopherol, natural o-a tocopherol acetate, natural D-a tocopherol succinate from soybean sources Vegetable oil-derived phytosterols and phytosterol esters from soybean sources Plant stanol ester produced from vegetable oil sterols from soybean sources Whey used in distillates for spirits Lactitol... 

Oleochemicals obtained from various vegetable oils have been discussed earlier in this chapter. Some vegetable oil-derived oleochemical esters, alco-... 

Polymers may also be obtained by taking advantage of either the original carbon-carbon double bonds of the vegetable oils, which make possible the cationic polymerisation technique, or of the carbon-carbon double bonds of vegetable oil derivatives using free radical polymerisation or the olefin... 

Specialised polymers, which are mainly used in engineering applications in the automobile, aircraft and machinery industries, are known as engineering polymers. In this group, aliphatic polyamides are the most important and most widely used. A large number of aliphatic polyamides are obtained from vegetable oil-based products. Among these nylon 6,10, nylon 11, nylon 6,9 and poly(amido amine) are very important. One of the most important commercially used polymers, nylon 11, is obtained entirely from castor oU, whereas vegetable oil-derived components are only partly used to prepare other polymers. 

As non-conjugated double bonds of triglyceride are not sufficiently reactive for effective free radical polymerisation, a number of different approaches have been employed to produce vegetable oil derivatives that will more readily undergo free radical polymerisation. As an example, the incorporation of more reactive carbon-carbon double bonds by chemical... 

As mentioned above, most studies that employ metathesis for monomer synthesis from vegetable oil derivatives take advantage of SM and CM mechanisms (Scheme 5.4) rather than RCM and ROM. 

Recently, renewable PU were synthesised from vegetable oil derivatives by the research team of Cramail [46] in a new and very interesting approach to obtain an a,oo-diene urethane monomer by converting 10-undecenoic acid into the corresponding acyl azide, followed by urethanisation with 10-undecenol (Scheme 5.11). 

This section deals with two methods of metathesis polymerisation which, although much less wide-ranging in applications than the methods described above, are interesting tools for the preparation of polymers from vegetable oil derivatives. 

The only study that correlates the ALTMET polymerisation reaction with a vegetable oil derivative is quite recent [68]. It describes the preparation of alternating copolymers with functional phosphate groups. Diene I (Scheme 5.19) was synthesised from 10-undecenol, and its ALTMET polymerisation with the diacrylate II was carried out in sequence. 

The first publication on the thiol-ene reaction of a vegetable-oil derivative dates to 1957, when Koenig and Swern published the free-radical addition of mercaptoacetic acid to oleic acid, methyl oleate, methyl ricinoleate and 10-undecenoic acid. That is, the synthesis of derivatives of a,(0-dicarboxylic oleic acid through thiol-ene addition [6]. 

Gandini and co-workers described a unique double click strategy related to the preparation of monomers based on vegetable-oil derivatives bearing furan heterocycles appended through thiol-ene click chemistry, and their subsequent polymerisation via the Diels-Alder (DA) polycondensation between furan and maleimide complementary moieties (i.e., a second type of click chemistry). Details about the DA reaction, its mechanism, applications and the reason why it is classified as a click reaction can be found in Chapter 7. 

Vegetable oils derived from the processing of oilseeds account for about 70% of the world s edible oils and fat production, the remainder being animal fats (30%), which include fish oils (2%). Out of the total world production of major oils and fats, about 80% is consumed as human food, a further 6% is used for animal feed, leaving 14% for the oleochemical industry (Richter and Knaut, 1984). 

Vegetable oil derived macromonomers were successfully synthesized from castor, lesquerella, and vemonia oils. CAM was effectively incorporated in vinyl-acrylic and all-acrylic latexes and facilitated film formation in the absence of coalescing solvents. Lesquerella and vemonia methacrylate macromonomers were synthesized and formulated into environmentally friendly UV cured coatings. The lesquerella and vemonia modified coatings exhibited good gloss, pencil hardness, and adhesion to steel substrates. 

Of the 1 billion pounds of saturated and unsaturated fatty acids produced in this country, about 35% of the total and 50% of the unsaturated fatty acids portion come from tall oil. Although originally having served as a low-cost substitute for vegetable oil-derived fatty acids, tall oil fatty acids have come into their own as chemical raw materials. Major uses are in intermediate chemicals and protective coatings. 

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