Enhancer polyalkylation

Addition of one mole of P,P -dipheny1methy1enediphosphinic acid to tetraisopropyl titanate gives a chelated product, the solutions of which can be used as a primer coat for metals to enhance the adhesion of topcoats, eg, alkyds, polyalkyl acylates, and other polymeric surface coating products, and improve the corrosion resistance of the metal to salt water (102). 

Conversely, vesicants have also been thickened with various substances to enhance deployment, increase their persistency, and increase the risk of percutaneous exposure. Thickeners include polyalkyl methacrylates (methyl, ethyl, butyl, isobutyl), poly(vinyl acetate), polystyrene, plexiglas, alloprene, polychlorinated isoprene, nitrocellulose, as well as bleached montan and lignite waxes. Military thickener K125 is a mixture of methyl, ethyl, and butyl polymethacrylates. When thickened, agents become sticky with a consistency similar to honey. Typically, not enough thickener is added to affect either the color or odor of the agent. 

Di- and polyalkylation can occur during alkylation with alkyl halides since the product alkylbenzenes are more reactive, although the reactivity difference with reactive alkylation systems is small. Toluene, for example, reacts only about 2-5 times faster in some benzylations than benzene.118,119 As alkylbenzenes, however, dissolve preferentially in the catalyst containing layer, heterogeneous systems can cause enhanced polysubstitution. The use of appropriate solvents and reaction conditions as well as of an excess of aromatics allow the preparation of monoalkyl-ated products in high yields. 

Nevertheless, sooner or later the alkylation activity of the zeolite will inevitably decline due to the accumulation of carbonaceous deposits on its surface. A thorough understanding of the nature of the carbonaceous deposits formed and the possible deactivation mechanisms is thus crucial for designing zeolite-based alkylation catalysts with enhanced lifetime. In this respect, poisoning of acid sites or pore blockage (or both) caused by the accumulation carbonaceous deposits on the zeolite surface have been proposed as the most likely deactivation mechanisms (143-148). After the initial stable alkylation period, olefins appear in the reaction medium (conversions below 100%) and the rate of olefin addition to an adsorbed carbenium ion to form heavy polyalkylated intermediates increases with respect to that of hydrogen transfer. Such bulky intermediates remain attached to the active site and thus reduce the number of available Bronsted acid sites. Concomitantly, a decrease in the micropore volume does also take place. In the latter stage of the reaction, where deactivation is accelerated, polymers are formed at the outer zeolite surface and may eventually lead to pore mouth... 

Studies by Kiersznicki and co-workers demonstrated that chlorosulfonic acid is an effective catalyst in the alkylation of arenes by reaction with alkenes. Benzene, toluene and ethylbenzene were alkylated by propene, elhene and 2-butene in the presence of chlorosulfonic acid which strongly catalysed the alkylations and inhibited polyalkylation. Increasing the concentration of the catalyst enhanced the proportion of /7-isomers in the products. Fluoro-, chloro-and bromobenzenes were similarly alkylated by reaction with C2-C4 alkenes using chlorosulfonic acid as catalyst. The optimum alkylation conditions were with a halobenzene alkene ratio of 1 0.25, a catalyst concentration of 0.33 mol mol" of fluorobenzene and 0.5 mol mol of the other halobenzenes, a temperature of 70 C and a reaction time of 2 hours. Alkylation with propene gave haloisopropylbenzenes the monoalkyl products were obtained as o-, m- and p- mixtures, the relative amounts depended on the quantity of catalyst used and the by-products were dialkyl derivatives, sulfonic acids and sulfones. In the reaction of benzene with propene, fluorosulfonic acid was a more potent alkylation catalyst than chlorosulfonic acid. ... 

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