Metal oxide condensation reactions

Besides the oxidative and transition-metal-catalyzed condensation reactions discussed above, several other syntheses were developed to generate PPP and PPP derivatives. 

As discussed in a previous section, metal oxides represent an important class of materials exhibiting a broad range of properties from insulators to semiconductors and conductors and have found applications as diverse as electronics, cosmetics and catalysts. Metal oxides have been widely used in many valuable heterogeneous catalytic reactions. Typical metal oxide-catalyzed reactions, including alkane oxidation, biodiesel production, methanol adsorption and decomposition, destructive adsorption of chlorocarbons and warfare agents, olefin metathesis and the Claisen-Schmidt condensation will be briefly discussed as examples of metal oxide-catalyzed reactions. 

In the three-step process acetone first undergoes a Uquid-phase alkah-cataly2ed condensation to form diacetone alcohol. Many alkaU metal oxides, metal hydroxides (eg, sodium, barium, potassium, magnesium, and lanthanium), and anion-exchange resins are described in the Uterature as suitable catalysts. The selectivity to diacetone alcohol is typicaUy 90—95 wt % (64). In the second step diacetone alcohol is dehydrated to mesityl oxide over an acid catalyst such as phosphoric or sulfuric acid. The reaction takes place at 95—130°C and selectivity to mesityl oxide is 80—85 wt % (64). A one-step conversion of acetone to mesityl oxide is also possible. 

Acid catalysts, such as metal oxides and sulfonic acids, generally catalyze condensation polymerizations. However, some condensation polymers form under alkaline conditions. For example, the reaction of formaldehyde with phenol under alkaline conditions produces methy-lolphenols, which further condense to a thermosetting polymer. 

Since does not take part in the reaction, the boundary line between M and MO is independent of logPsoj d so given by a straight vertical line at logPo2 = 16, parallel to the -axis (line 1 in Fig. 7.67). It should be noticed that stability areas across the boundary follow the sequence of condensed phases shown in the equation, i.e. on the left-hand side of the boundary pure metal is the stable phase and on the right-hand side the pure metal oxide. 

SCHEME 3.1 Hydrolysis and condensation reactions of metal alkoxide forming metal oxide. 

In 1990, Schroder and Schwarz reported that gas-phase FeO" " directly converts methane to methanol under thermal conditions [21]. The reaction is efficient, occuring at 20% of the collision rate, and is quite selective, producing methanol 40% of the time (FeOH+ + CH3 is the other major product). More recent experiments have shown that NiO and PtO also convert methane to methanol with good efficiency and selectivity [134]. Reactions of gas-phase transition metal oxides with methane thus provide a simple model system for the direct conversion of methane to methanol. These systems capture the essential chemistry, but do not have complicating contributions from solvent molecules, ligands, or multiple metal sites that are present in condensed-phase systems. 

A corrosion inhibitor with excellent film-forming and film-persistency characteristics is produced by first reacting Cig unsaturated fatty acids with maleic anhydride or fumaiic acid to produce the fatty acid Diels-Alder adduct or the fatty acid-ene reaction product [31]. This reaction product is further reacted in a condensation or hydrolyzation reaction with a polyalcohol to form an acid-anhydride ester corrosion inhibitor. The ester may be reacted with amines, metal hydroxides, metal oxides, ammonia, and combinations thereof to neutralize the ester. Surfactants may be added to tailor the inhibitor formulation to meet the specific needs of the user, that is, the corrosion inhibitor may be formulated to produce an oil-soluble, highly water-dispersible corrosion inhibitor or an oil-dispersible, water-soluble corrosion inhibitor. Suitable carrier solvents may be used as needed to disperse the corrosion inhibitor formulation. 

The metallothermic reduction of oxides is essentially a reaction involving only condensed phases. It follows therefore, that the entropy changes in these reactions are small and that the differences in the heats of formation of the pertinent compounds determine the feasibility of a given reaction. Among the metallic reductants, calcium forms the oxide whose heat of formation is the most negative. As a first approximation, calcium may be considered to be the most effective reducing agent for metal oxides. 

Freeder, B. G. et al., J. Loss Prev. Process Ind., 1988, 1, 164-168 Accidental contamination of a 90 kg cylinder of ethylene oxide with a little sodium hydroxide solution led to explosive failure of the cylinder over 8 hours later [1], Based on later studies of the kinetics and heat release of the poly condensation reaction, it was estimated that after 8 hours and 1 min, some 12.7% of the oxide had condensed with an increase in temperature from 20 to 100°C. At this point the heat release rate was calculated to be 2.1 MJ/min, and 100 s later the temperature and heat release rate would be 160° and 1.67 MJ/s respectively, with 28% condensation. Complete reaction would have been attained some 16 s later at a temperature of 700°C [2], Precautions designed to prevent explosive polymerisation of ethylene oxide are discussed, including rigid exclusion of acids covalent halides, such as aluminium chloride, iron(III) chloride, tin(IV) chloride basic materials like alkali hydroxides, ammonia, amines, metallic potassium and catalytically active solids such as aluminium oxide, iron oxide, or rust [1] A comparative study of the runaway exothermic polymerisation of ethylene oxide and of propylene oxide by 10 wt% of solutions of sodium hydroxide of various concentrations has been done using ARC. Results below show onset temperatures/corrected adiabatic exotherm/maximum pressure attained and heat of polymerisation for the least (0.125 M) and most (1 M) concentrated alkali solutions used as catalysts. 

Ternary Reactions among Polymer Substrates, Organohalogens, and Metal Oxides in the Condensed Phase under Pyrolytic Conditions... 

Gas-phase metal oxide cluster cations have become increasingly interesting because of the possibility that a controlled reaction of size selected clusters might shed some light on condensed-phase catalysts. The possibility of producing small clusters in the condensed phase from deposition of gas-phase clusters has also been a driving force in the study of the reactivity of gas-phase ions. 

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