Polyfunctional catalysts

Ammonium acetate and sodium methoxide are effective catalysts for the ammonolysis of soybean oil (49). Polyfunctional amines and amino alcohols such as ethylenediamine, ethanolamine, and diethanolamine react to give useful intermediates. Ethylenediamine can form either a monoamide or a diamide depending on the mole ratio of reactants. With an equimolar ratio of reactants and a temperature of >250° C, a cyclization reaction occurs to give imidazolines with ethylenediamine (48) ... 

Catalytic processes frequently require more than a single chemical function, and these bifunctional or polyfunctional materials innst be prepared in away to assure effective communication among the various constitnents. For example, naphtha reforming requires both an acidic function for isomerization and alkylation and a hydrogenation function for aromati-zation and saturation. The acidic function is often a promoted porous metal oxide (e.g., alumina) with a noble metal (e.g., platinum) deposited on its surface to provide the hydrogenation sites. To avoid separation problems, it is not unusual to attach homogeneous catalysts and even enzymes to solid surfaces for use in flow reactors. Although this technique works well in some environmental catalytic systems, such attachment sometimes modifies the catalytic specifici-... 

The studies mentioned in this brief account did not concern the kinetics of complex reactions taking place on the so-called polyfunctional catalysts, which were treated by Weisz (56) the theory of the use of these catalysts has been further worked out for some consecutive or parallel reactions carried out in the reactors with a varying ratio of catalyst components along the catalyst bed [e.g. (90, 91, 91a) ]. Although the description of these reactions, not coupled in the sense defined in Section III, is beyond the scope of this treatment, we mention here at least an experimental... 

It may be possible to achieve an adequate solution of these problems by developing catalysts with snrface properties that have been tailored deliberately so as to provide a favorable catalytic action on all intermediate steps that need it. Such catalysts should be polyfunctional and exhibit a certain degree of chemical and structural surface microheterogeneity. Electrochemical nanoelectrochemistry (see Chapter 36) may be a possible approach for synthesizing snch snrfaces. For a detailed investigation and control of these catalytic surfaces, the tools available among the experimental physical methods (see Chapter 27) will be nsefnl. 

In the design of a homogeneous catalyst for the plain hydrogenation of thiophenes it is necessary to take into account that, unlike simple alkenes, (102) and (103) are polyfunctional ligands which can bind metal centers in a variety of bonding modes, often in a rapid equilibrium with each other.166-172,192 Among the possible coordination modes, the /-(S) and the 772-(C,C)... 

However, the use of polyfunctional solid catalysts (involving both red-ox and acid properties) could modify, in some cases, the characteristics of some of the actual industrial processes. 

The use of a polyfunctional catalyst could enhance the life of the catalyst. A clear example is the use of H3PWi2O40-SO4 /ZrO2 mixtures for isobutane/ butenes alkylation (Table 13.4-). However, modifications of the t) pe of reactor could also favor extended catalyst longevity." During the last few years, other alternatives have been proposed that favor a better catalyst regeneration and/or lower catalyst deactivation the use of supercritical isobutene regeneration or dense-C02 enhanced the reaction media. ... 

Thermosets cure into nonmelting, insoluble polymers. Frequently, the curing needs heat, pressure, or catalyst to proceed. Often the final cure, which is nothing more than completion of the cross-linking, takes place in the fabrication or molding operations. The chemistry is about the same as you saw in the thermoplastics, but there are more reactive sites per monomer. (They are polyfunctional.) Consequently, more three-dimensional cross-linking takes place. 

Preparation of coatings as free films. The oligomeric esterdlols were mixed with the crosslinkers HMMM or polyfunctional isocyanate. The molar ratio esterdlol/HMMM was 2 1 leading to an OH/OCH3 ratio of 4 6. The OH/NCO ratio was 1 1. Some 1 wt% diethanolamine salt of p-toluene sulphonlc acid, respectively 0.2 wt% Dabco were used as catalyst. The coatings were applied to Bonder 101 plates which had been sprayed with a thin layer (1-2 pm) of teflon. 

The extent of crosslinking in polyurethanes depends on a combination of the amount of polyfunctional monomers present and the extent of biuret, allophanate, and trimerization reactions [Dusek, 1987]. The latter reactions are controlled by the overall stoichiometry and the specific catalyst present. Stannous and other metal carboxylates as well as tertiary amines are catalysts for the various reactions. Proper choice of the specific catalyst result in differences in the relative amounts of each reaction. Temperature also affects the extents... 

More structurally complex epoxides can be ring-opened intramolecularly in a synthetically useful fashion. Thus, in their approach to methyl-substituted trmis-fused tetrahydropyran subunits found in marine natural products, Mori and co-workers <99TL8019> treated the polyfunctional arylsulfonyl epoxide 67 with Lewis acid to induce a (s-endo cyclization onto the epoxide moiety, with concomitant ejection of arylsulfinate, to provide the bicyclic ether 68. This system was found to be highly sensitive to the nature of the Lewis acid catalyst used. 

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