Polymers from fatty acids

Fatty acids and fatty acid methyl esters (FAME) can be used directly or after functionalization as monomers for the synthesis of a variety of polymeric materials. The most important functionalization possibilities of the double bonds and the ester gronps have been extensively reviewed in the literature (Biermann et al., 2001, 2007 Biermann and Metzger 2004). 

Aam BB, Heggset EB, Norberg AL, S0rlie M, Varum KM, Eijsink VGH. 2010. Production of ChitooUgosaccharides and Their Potential Applications in Medicine. Mar Drugs 8 1482-1517. 

Amado FDR, Rodrigues LF, Forte MMC, Ferreira CA. 2006. Properties evaluation of the membranes synthesized with castor oil polyurethane and polyaniline. Polym Eng Sci 46 1485-1489. 

Amgoune A, Thomas CM, Roisnel T, Carpentier JF. 2006. Ring-Opening Polymerization of Lactide with Group 3 Metal Complexes Supported by Dianionic Alkoxy-Amino-Bisphenolate Ligands Combining High Activity, Productivity, and Selectivity. Chem Eur J 12 169-179. 

Anderson KS, Schreck KM, Hillmyer MA. 2008. Toughening Polylactide. Polym Rev 48(1) 85-108. 

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O. Turiing, Efficient Routes to Degradable and non-Degradable Renewable Polymers from Fatty Acids. Ph.D thesis, Fakultat fiir Chemie und Biowissenschaften Karlsruher Institut fiir Technologie, University of Karlsruhe, Germany, 2012. 

Despite being sister reactions , works reporting on use of thiol-yne reactions for the synthesis of monomers and polymers from fatty-acid derivatives are much scarcer than those using the thiol-ene approach. 

Snap. A critical ingredient for emulsion polymerization is the soap, which performs a number of key roles, including production of oil (monomer) m water emulsion, provision of the loci for polymerization (micelle), stabilization of the latex particle, and imputation of characteristics to the finished polymer. Both fatty acid and rosin acid soaps, mamly derived from tall oil, are used in ESBR,... 

Olefin metathesis is also a highly versatile technique for the synthesis of polymers from renewable resources. In this respect, especially ADMET polymerization and ROMP have been used to prepare macromolecules starting from fatty acid precursors due to their inherent double-bond functionality. Nevertheless, also other feedstock and methods have been applied, as will be reviewed within this section. 

Mecking showed an efficient way to produce a,G>diesters from fatty acid esters yielding excellent monomers for semicrystalline polyesters [63], Some part of the diesters was hydrogenated to diols and was transesterified with the diesters from the hydroesterification of methyl oleate into long-chain polyesters (Scheme 24). The properties of this thermomorphic polymer are related to those of polyethylene. 

Polymers Unsaturated fatty-acid chains offer opportunities for polymerisation that can be exploited to develop uses in surface coatings and plastics manufacturing. Polyunsaturated fatty acids can be dimerised to produce feedstocks for polyamide resin (nylon) production. Work is also ongoing to develop polyurethanes from vegetable oils through manipulation of functionality in the fatty-acid chains, to produce both rigid foams and elastomers with applications in seals, adhesives and moulded flexible parts (see Chapter 5 for more information). 

Polyanhydrides prepared from fatty acids are good candidates for the delivery of hydrophilic drugs due to the desired hydrophobicity of the natural fatty acids in the main chain of the polyanhydrides 11). These polyanhydrides have two series of acid monomers one has longer carbon chain, such as dimer erucic or oleic acid another has shorter carbon chain, such as sebacic acid (2). Fatty acids can be incorporated into the polymer chain by one of two ways by... 

An interesting study on the synthesis of polyethylene (PE) mimics derived from fatty-acid derivatives and thiol-ene polymerisation [39] involved preparation of two different diene monomers from a commercially available derivative of undecenoic acid, 11-bromo-l-undecene, and 10-undecenol for the synthesis of a series of non-biodegradable polymers (Scheme 6.13). The authors considered these non-biodegradable polymers to be renewable plant oil-derived substitutes for PE. 

Hojabri L, Kong X, Narine SS (2010a) Novel long chain unsaturated diisocyanate from fatty acid synthesis, characterization, and application in bio-based pol5nirethane. J Polym Sci Pol Chem 48 3302-3310... 

Solomon and Hopwood [24] find that, in the case of alkyd prepared from fatty acid, glycerol, and phthalic anhydride in the molar ratio 1.0 1.26 1.11, the measured hydroxyl values are considerably less than the calculated figures and the difference between these values increases with the molecular weight and the complexity of the polymer molecule. The difficulties encountered in the kinetic analysis of the formation of alkyd resins could be related, at least in part, to the availability of the hydroxyl group. 

Montarnal, D., Cordier, P, Soulie-Ziakovic, C. etal. (2008) Synthesisof self-healing supramolecular rubbers from fatty acid derivatives, diethylene triamine, and urea. Journal of Polymer Science Part A-Polymer Chemistry, 46,7925-7936. 

Definition Syn. polymer made from oxirane (ethylene oxide), fatty acids, and amides derived from fatty acids Uses Emulsifier in cosmetics Manuf./Distrib. Somerset Cosmetic Co. Variati PEG oleamine CAS 26635-93-8 (generic)... 

Additives. Because of their versatility, imparted via chemical modification, the appHcations of ethyleneimine encompass the entire additive sector. The addition of PEI to PVC plastisols increases the adhesion of the coatings by selective adsorption at the substrate surface (410). PEI derivatives are also used as adhesion promoters in paper coating (411). The adducts formed from fatty alcohol epoxides and PEI are used as dispersants and emulsifiers (412). They are able to control the viscosity of dispersions, and thus faciHtate transport in pipe systems (413). Eatty acid derivatives of PEI are even able to control the viscosity of pigment dispersions (414). The high nitrogen content of PEIs has a flame-retardant effect. This property is used, in combination with phosphoms compounds, for providing wood panels (415), ceUulose (416), or polymer blends (417,418) with a flame-retardant finish. 

Three generations of latices as characterized by the type of surfactant used in manufacture have been defined (53). The first generation includes latices made with conventional (/) anionic surfactants like fatty acid soaps, alkyl carboxylates, alkyl sulfates, and alkyl sulfonates (54) (2) nonionic surfactants like poly(ethylene oxide) or poly(vinyl alcohol) used to improve freeze—thaw and shear stabiUty and (J) cationic surfactants like amines, nitriles, and other nitrogen bases, rarely used because of incompatibiUty problems. Portiand cement latex modifiers are one example where cationic surfactants are used. Anionic surfactants yield smaller particles than nonionic surfactants (55). Often a combination of anionic surfactants or anionic and nonionic surfactants are used to provide improved stabiUty. The stabilizing abiUty of anionic fatty acid soaps diminishes at lower pH as the soaps revert to their acids. First-generation latices also suffer from the presence of soap on the polymer particles at the end of the polymerization. Steam and vacuum stripping methods are often used to remove the soap and unreacted monomer from the final product (56). 

The diacids for these polymers are prepared via different processes. A2elaic acid [123-99-9] for nylon-6,9 [28757-63-3] is generally produced from naturally occurring fatty acids via oxidative cleavage of a double bond in the 9-position, eg, from oleic acid [112-80-1] ... 

A/-Chloro fatty acid amides have been synthesized from the direct halogenation of the amide in boiling water (28). They are useful as reactive intermediates for further synthesis. Fluorination has also been reported by treating the fatty amide with fluorine-containing acid reagents at 200 °C to reach a fluorinated amide with less reactivity toward fluorocarbon polymers (29). 

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