TRIETHYL ALKYL AMMONIUM

Idemitsu Process. Idemitsu built a 50 t x 10 per year plant at Chiba, Japan, which was commissioned in Febmary of 1989. In the Idemitsu process, ethylene is oligomerised at 120°C and 3.3 MPa (33 atm) for about one hour in the presence of a large amount of cyclohexane and a three-component catalyst. The cyclohexane comprises about 120% of the product olefin. The catalyst includes sirconium tetrachloride, an aluminum alkyl such as a mixture of ethylalurninumsesquichloride and triethyl aluminum, and a Lewis base such as thiophene or an alcohol such as methanol (qv). This catalyst combination appears to produce more polymer (- 2%) than catalysts used in other a-olefin processes. The catalyst content of the cmde product is about 0.1 wt %. The catalyst is killed by using weak ammonium hydroxide followed by a water wash. Ethylene and cyclohexane are recycled. Idemitsu s basic a-olefin process patent (9) indicates that linear a-olefin levels are as high as 96% at C g and close to 100% at and Cg. This is somewhat higher than those produced by other processes. 

Note Examples are potassium salts of unbranched alkanoic acids, lecithin, certain polyisocyanates, cellulose derivatives with side-chains, such as (2-hydroxypropyl)cellulose, and cyanobiphenyl derivatives of alkyl(triethyl)ammonium bromide. 

Common inorganic anions F, N03-, SO42" oxyhalides and carboxylates, such as acetate and formate Alkali and alkaline earth metal ions Na, K+, Ca2+ ammonium Alkali and alkaline earth metal ions Li, Na, K, Mg2, ammonium ion alkyl amines methyl amine, triethyl amine, and morpholine... 

Effects of added n-alkyl triethyl ammonium bromides upon the mechanical stability of natural rubber latex (9)... 

Some interesting results have recently become available for the effects of a range of n-alkyl triethyl ammonium bromides upon the mechanical stability of natural rubber latex. The number of carbon atoms in the alkyl group varied from 6 to 18. Figure 6 summarises the results. It is usually believed that the addition of cationic surfactants to an anionic latex such as natural rubber latex invariably leads to a reduction in colloid stability, the effect being attributed to adsorption of the cations with consequent partial neutralisation of the particle charge and reduction of the counterion cloud surrounding the particles. 

Whilst the results summarised in Figure 6 show that this expectation is often realised, they also show that small additions of an n-alkyl triethyl ammonium bromide whose alkyl group contains between approximately 8 and 12 carbon atoms can bring about a small increase in mechanical stability. In such cases, the increase in stability cannot possibly be attributed to enhance-... 

Although the combined additive phosphonylation and esterification of an a,j5-unsatu-rated carboxylic acid by a trialkyl phosphite can thus easily, although not necessarily accurately, be envisaged, that of a similarly unsaturated ester, nitrile, or amide is perhaps not so readily apparent. Harvey showed that successful reaction between triethyl phosphite and such a substrate (Scheme 43) occurs in a protic medium. In this respect, the reactions proceed faster in methanol than in ethanol, but reactions are, in general, (including those of structurally analogous unsaturated ketones) much cleaner and faster when carried out in phenol, and also afford much higher yields in this solvent. It has also been shown that ammonium salts will also act as a proton source to allow completion of addition without alkylation. The later Russian workers used acetic acid with successful results ... 

The behaviour of selenium-containing acids might be expected to parallel that of the sulphur acids, but the position is not so clear. e-Alkyl esters are the products of similar alkylations of sodium salts by alkyl halides and are also produced from hydrogenphos-phonates and diselenides according to equation 19. The reaction between the triethyl-ammonium salt of (R)-(+)-0-ethyl ethylphosphonoselenoic acid and McjSiCl affords the laevorotatory O-silyl ester rather than the 5 e-silyl ester as demonstrated by NMR spectroscopy and also by alternative synthesis By contrast, the use of the sodium salt of the acid leads to the 5 -silyl ester. ... 

It is interesting to note that the very widely used Makosza catalyst , benzyl triethyl ammonium chloride, does not show high efficiency in this study. 4) Phosphonium ions are somewhat more effective and thermally stable than the corresponding ammonium catalysts and both are better than arsonium systems. 5) Substitution of the quaternary ion by alkyl rather than aryl groups yields more effective catalysts. 6) Reaction rates are generally greater in orf/io-dichlorobenzene (and presumably in other chlorocarbon media) than in benzene, and botli are better than heptane. In connection with this latter point, Ugelstad and coworkers have studied the reactions of quaternary ammonium phenoxide ions with alkyl halides in a variety of media and concluded that the... 

Triethanolamine hydrochloride - 719 Triethanolamine linear alkylate sulfonate - 215 Triethanol ammonium lauryl sulfate - 215 Triethyl aluminum - 366, 837, 845, 880 Triethylamine 31, 43, 59, 92, 103, 173, 215,... 

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