Of vinyl acetate by fatty acids

Acid number, 32, 3 Acidolysis, of ethyl a-chlorophenyl-acetate by acetic add, 36,4 of vinyl acetate by fatty acids, 30, 106... 

Acidolysis of vinyl acetate by fatty adds, 30, 106 Acrolein acetal, 32, 5 Acrolein diethyl acetal, 32, 5 Acrylic acid, frans-/3-( -NiTROpHE. NYL)-a-PHENYL-, 35, 89 Acrylonitrile, 30, 80 Acrylonitrile, triphenyl-, 31, 52 Acylation of ethanolamine with phthalic anhydride, 32, 19... 

Vinyl esters are prepared by the reaction of a fatty acid with either acetjfene in direct condensation or vinyl acetate by acidolysis. 

Transesterification has a number of important commercial uses. Methyl esters of fatty acids are produced from fats and oils. Transesterification is also the basis of recycling technology to break up poly(ethylene terephthalate) [25038-59-9] to monomer for reuse (29) (see Recycling, plastics). Because vinyl alcohol does not exist, poly(vinyl alcohol) [9002-89-5] is produced commercially by base-cataly2ed alcoholysis of poly(vinyl acetate) [9003-20-7] (see Vinyl polymers). An industrial example of acidolysis is the reaction of poly(vinyl acetate) with butyric acid to form poly(vinyl butyrate) [24991-31-9]. 

As the caiboxylate moieties of vinyl esters increase in length, the degree of branching due to chain transfer to both monomer and polymer increases. The relationship between the chain-transfer constant (C.T.) and the number of carbon atoms in the caiboxylate portion of a fatty acid vinyl ester in the presence of vinyl acetate is given by the expression... 

The synthesis of monomers derived from fatty acids incorporating end-functions susceptible to classical poly addition reactions has been revived recently and yielded interesting results. Vinyl oleate (VO) and vinyl linoleate (VL) were synthesised by a transvinylation reaction of the corresponding fatty acids with an excess of vinyl acetate (VAc) in bulk using a safe iridium-based catalyst instead of previously used mercury-based counterparts (which are not acceptable today because of safety concerns) [91]. Scheme 4.21 summarises this synthesis in the case of OA. 

Tetraethylene glycol may be used direcdy as a plasticizer or modified by esterification with fatty acids to produce plasticizers (qv). Tetraethylene glycol is used directly to plasticize separation membranes, such as siHcone mbber, poly(vinyl acetate), and ceUulose triacetate. Ceramic materials utilize tetraethylene glycol as plasticizing agents in resistant refractory plastics and molded ceramics. It is also employed to improve the physical properties of cyanoacrylate and polyacrylonitrile adhesives, and is chemically modified to form polyisocyanate, polymethacrylate, and to contain siHcone compounds used for adhesives. 

Fatty acids of sugars are potentially useful and fully green nonionic surfactants, but the lipase-mediated esterification of carbohydrates is hampered by the low solubility of carbohydrates in reaction media that support lipase catalysis in general. Because the monoacylated product (Figure 10.8) is more soluble in traditional solvents than is the starting compound, the former tends to undergo further acylation into a diester. In contrast, the CaLB-catalyzed esterification of glucose with vinyl acetate in the ionic liquid [EMIm][BF4] was completely selective. The reaction became much faster and somewhat less selective when conducted in... 

Among such oxidations, note that liquid-phase oxidations of solid paraffins in the presence of heterogeneous and colloidal forms of manganese are accompanied by a substantial increase (compared with homogeneous catalysis) in acid yield [3]. The effectiveness of n-paraffin oxidations by Co(III) macrocomplexes is high, but the selectivity is low the ratio between fatty acids, esters, ketones and alcohols is 3 3 3 1. Liquid-phase oxidations of paraffins proceed in the presence of Cu(II) and Mn(II) complexes boimd with copolymers of vinyl ether, P-pinene and maleic anhydride (Amberlite IRS-50) [130]. Oxidations of both linear and cyclic olefins have been studied more intensively. Oxidations of linear olefins proceed by a free-radical mechanism the accumulation of epoxides, ROOH, RCHO, ketones and RCOOH in the course of the reaction testifies to the chain character of these reactions. The main requirement for these processes is selectivity non-catalytic oxidation of propylene (at 423 K) results in the formation of more than 20 products. Acrylic acid is obtained by oxidation of propylene (in water at 338 K) in the presence of catalyst by two steps at first to acrolein, then to the acid with a selectivity up to 91%. Oxidation of ethylene by oxygen at 383 K in acetic acid in... 

The affinity for substrates and the water resistance were improved by blending poly (vinyl acetate) with esters of fatty acids such as triglycerides [10]. The waterproofing action and the favourable interaction between these esters and the substrate surface were proposed to explain the performance of these blends. 

The use of biocompatible systems is proposed by Rajot et al. [76], who produced nonionic hydrophobic drugs such as indomethacin encapsulated in poly(vinyl acetate). In addition, oligocaprolactone macromonomers obtained by anionic coordinated ring-opening polymerization, benzyl benzoate, or triglycerides from fatty acids were used as the hydrophobe in order to obtain biocompatible systems. 

A good example of the effect of additive level on a wide number of properties of a magnesium hydroxide filled ethylene vinyl acetate (EVA) co-polymer can be found in work by Rothon and co-workers [2]. This includes effects on flame retardant properties and on ageing. The latter is particularly interesting, as it was found that excess of the fatty acid led to a significant decrease in ageing resistance. This was most marked when a commercial blend of fatty acid was used, but was still very significant with pure stearic acid. 

VCN copolymerizes with various comonomers such as methyl methacrylate [82], isopropenyl acetate [83], vinyl benzoate [82], styrene [84], substimted styrenes [71], and vinyl esters of fatty acids [85]. All these copolymerizations led to alternating copolymers, and their microstructures were characterized by C NMR spectroscopy. 

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