Fatty Acid Based

SYBRON CHEMICALS INC. Textile Specialty Chemicals - Finishing (Continued)  

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Thermoplastic polyamides are used in coatings to modify alkyd resins (qv) in thixotropic systems (238) and to plasticize nitroceUulose lacquers (239). DETA-taH oil fatty acid-based polyamides are suggested for use as corrosion inhibitors in alkyd paints (240). Printing inks for fiexo-gravure appHcation on certain paper, film and foil webs rely on EDA- and PDA-based polyamides for their specific performance (241). 

Acids that are solids can be purified in this way, except that distillation is replaced by repeated crystallisation (preferable from at least two different solvents such as water, alcohol or aqueous alcohol, toluene, toluene/petroleum ether or acetic acid.) Water-insoluble acids can be partially purified by dissolution in N sodium hydroxide solution and precipitation with dilute mineral acid. If the acid is required to be free from sodium ions, then it is better to dissolve the acid in hot N ammonia, heat to ca 80°, adding slightly more than an equal volume of N formic acid and allowing to cool slowly for crystallisation. Any ammonia, formic acid or ammonium formate that adhere to the acid are removed when the acid is dried in a vacuum — they are volatile. The separation and purification of naturally occurring fatty acids, based on distillation, salt solubility and low temperature crystallisation, are described by K.S.Markley (Ed.), Fatty Acids, 2nd Edn, part 3, Chap. 20, Interscience, New York, 1964. 

Figure 13.16.3 The molecular structure of a triglyceride, a fatty acid based on the triester of oleic acid.

The affinity of the PHA polymerase that performs the polymerization reaction differs clearly for the various 3-hydroxy fatty acids. Based on the composition data of PHA synthesized from alkanes or fatty acids it is clear that the 3-hydroxy fatty acids with chain lengths of 8,9, or 10 carbon atoms are preferred. The affinity of the polymerase decreases for 3-hydroxy fatty acids with longer or shorter chains. 

Another class of PSA-fatty acid-based copolymers has been synthesized from the ricinoleic acid and ricinoleic half-esters with maleic and succinic anhydride, poly(sebacic-co-ricinoleic acid maleate), poly(sebacic-co-ricinoleic acid succinate), and poly(sebacic-co-12-hydroxystearic acid succinate) (P(SA-RAM), P(SA-RAS), and P(SA-HSAS)) (Krasko et al., 2003 Teomim et al., 1999). These syntheses result in poly(anhydride-co-esters). 

The fatty-acid-based collectors have been employed for the past 60 years for flotation of oxide copper/cobalt minerals from Congo, a company formerly owned by Union Minera (Belgium). 

A fatty acid based corrosion inhibitor can form a tenacious film on the metal surfaces of a fuel injection pump. The tight tolerances in high-pressure injection pumps require very little fluid film for proper lubrication. 

The separation and purification of naturally occurring fatty acids, based on distillation, salt solubility and low temperature crystallisation, are described by K.S.Markley (ed). Fatty Acids, 2nd edn, part 3, Chap. 20, Interscience, New York. 1964. 

Caliph, S.M., W.N. Charman, and C.J.H. Porter. 2000. Effect of short-, medium-, and long-chain fatty acid-based vehicles on the absolute oral bioavailability and intestinal lymphatic transport of halofantrine and assessment of mass balance in lymph-cannulated and non-cannulated rats. J Pharm Sci 89 1073. 

R Dieckmann, H von Dohren. Structural model of acyl carrier domains in integrated biosynthetic systems forming peptides, polyketides and fatty acids based on analogy to the E. coli acyl carrier protein. In RH Baltz, GD Hegeman, PL Skatrud, eds. Developments in Industrial Microbiology. Fairfax, VA Society for Industrial Microbiology, 1997, pp 79-87. 

The 10-undecenoic acid motif has also been attached to isosorbide in the preparation of a fatty acid-/carbohydrate-based monomer [131]. ADMET polymerization in the presence of C3 and C4 produced fully renewable unsaturated polyesters (Scheme 18). Most importantly, the transesterification of these polyesters with MeOH, and subsequent analysis by GC-MS of the products, allowed for the quantification of double-bond isomerization during ADMET in a very simple manner. This strategy was then extended to fatty acid-based ADMET polyesters synthesized in the presence of indenylidene metathesis catalysts [132]. With these studies, the knowledge on the olefin isomerization in ADMET reactions was widened, and it is now possible to almost completely suppress this undesired side reaction. 

Ferulic acid, a phenolic acid that can be found in rapeseed cake, has been used in the synthesis of monomers for ADMET homo- and copolymerization with fatty acid-based a,co-dienes [139]. Homopolymerizations were performed in the presence of several ruthenium-based olefin metathesis catalysts (1 mol% and 80°C), although only C5, the Zhan catalyst, and catalyst M5i of the company Umicore were able to produce oligomers with Tgs around 7°C. The comonomers were prepared by epoxidation of methyl oleate and erucate followed by simultaneous ring opening and transesterification with allyl alcohol. Best results for the copolymerizations were obtained with the erucic acid-derived monomer, reaching a crystalline polymer (Tm — 24.9°C) with molecular weight over 13 kDa. 

Various fatty acids, bases and acids for pH adjustment Crude or semirefined viscous petroleum oils 39.40... 

Several combinations of monomers used to prepare polyanhydrides are classified as aliphatic, aromatic, aliphatic-aromatic, amine-based, and fatty acid-based polyanhydrides. The structures of these monomers determine... 

Certik, M., Slavikova, L., and Lai, M. H. 2003a. Preparation of bioproducts enriched with polyunsaturated fatty acids based on solid state fermentations. Hanoi Proceedings of the 8th Asean Food Conference (pp. 654-658). 

Figure 2-2 The n-3 Family Polyunsaturated Fatty Acids Based on Linolenic Acid. The heavy arrows show the relationship between the most important n-3 acids through desaturation (vertical arrows) and chain elongation (horizontal arrows)...

Polyanhydrides Polyanhydrides have a hydrophobic backbone with a hydrolytically labile anhydride linkage. These polymers widely vary in chemical composition and include aliphatic, aromatic, and fatty acid-based polyanhydrides. The rate of degradation depends on the chemical composition of the polymer. In general, aliphatic polyanhydrides degrade more rapidly than the aromatic polymer. Hence, copolymer blends with varying ratios of aliphatic-to-aromatic polyanhydrides can be synthesized to suit specific applications. 

Koelsch, C.M., and Labuza, T.P. (1992). Functional physical and morphological properties of methyl cellulose and fatty acids-based edible barriers. Lebensmittel Wissenschqft and Technologic. 25,401-411. 

Chen, Y. (1999). Selective inhibition of ras-transformed cell growth by a novel fatty acid-based chloromethyl ketone designed to target Ras endoprotease. Ann N Y Acad Sci 886 103-108. 

Fatty Acid-Based Biodegradable Polymers Synthesis... 

Fatty acid based biodegradable polymers have many biomedical applications. This short review focuses on controlled drug delivery using two classes of the polymers polyanhydrides and polyesters based on fatty acids as drug carriers. Different polymer types and compositions are summarized showing the potential of these polymers as drug carriers. 

The identification of individual classes of fatty acids has relied on the use of gas chromatography (GC), equipped with a flame ionization detector. Lipids are sapoiufled after extraction and the fatty acids converted to methyl esters. The fatty acid methyl esters (FAME) are separated using GC. The use of standards ahowed for the identification of individual species of fatty acids based on retention time. The method is quite sensitive and permits the quantification of fatty acid species. The mode of detection has been enhanced with the use of mass spectrometry (MS), which allows for the detection and quantification of unknowns, thus increasing the utility of these methods. The Lipid Library section on the gas chromatography of lipids http //www.lipidlibrary.co.uk/GCJipid/01 intro/index. htm) provides a comprehensive description of these methods. 

Although the general scope of direct acylation of olefins under Friedel-Crafts conditions is rather limited, it has been demonstrated that such reactions can be applied to glycals like 162 to produce C-2 acylated glycals 163 in excellent yields and selectivity (O Scheme 54). Moreover, as reagents, the long-chain fatty acid based acylating species have been shown to be as effective as acetyl chloride [255]. 

Wang MY, Yang YY, and Heng PWS. Skin Permeation of Physostigmine from Fatty Acids-Based Formulations Evaluating the Ghoice of Solvent. IntJPharm2005 290 25-36. 

U.S. 6165955 Chen et al. Fatty acid-based Mild, cold pearlizing... 

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