Industrial propene oxide formation

Cobalt carbonyls are the oldest catalysts for hydroformylation and they have been used in industry for many years. They are used either as unmodified carbonyls, or modified with alkylphosphines (Shell process). For propene hydroformylation, they have been replaced by rhodium (Union Carbide, Mitsubishi, Ruhrchemie-Rhone Poulenc). For higher alkenes, cobalt is still the catalyst of choice. Internal alkenes can be used as the substrate as cobalt has a propensity for causing isomerization under a pressure of CO and high preference for the formation of linear aldehydes. Recently a new process was introduced for the hydroformylation of ethene oxide using a cobalt catalyst modified with a diphosphine. In the following we will focus on relevant complexes that have been identified and recently reported reactions of interest. 

Of great industrial interest are the copolymers of ethene and propene with a molar ratio of 1/0.5, up to 1/2. These EP-polymers show elastic properties and, together with 2-5 wt% of dienes as third monomers, they are used as elastomers (EPDM). Since they have no double bonds in the backbone of the polymer, they are less sensitive to oxidation reactions. As dienes, ethylidenenorbomene, 1,4-hexadiene, and dicyclopentadiene are used. In most technical processes for the production of EP and EPDM rubber in the past, soluble or highly disposed vanadium components are used [69]. Similar elastomers can be obtained with metallocene/MAO catalysts by a much higher activity which are less colored [70-72]. The regiospecificity of the metallocene catalysts toward propene leads exclusively to the formation of head-to-tail enchainments. The ethylidenenor-bornene polymerizes via vinyl polymerization of the cyclic double bond and the tendency to branching is low. The molecular weight distribution of about 2 is narrow [73]. 

Rhodium Catalysts. - The hydroformylation of propene with a Rh/triphenyl-phosphine catalyst is now an established industrial process which will consume over a million tonnes per annum of propene when all licensed plants are operational. Most of the product n-butyraldehyde is converted to 2-ethylhexanol for plasticiser applications. The process is also applicable to the hydroformylation of C2, C4, and C5 alkenes. The process is remarkable for the long lifetime of the Rh catalyst but by-products are formed which deactivate the catalyst and have to be removed. The formation of triphenyl-phosphine oxide, benzaldehyde, and propyldiphenylphosphine under hydroformylation conditions has been investigated where benzaldehyde is produced by or /zo-metallation of triphenylphosphine followed by CO insertion and P-C bond cleavage and propyldiphenylphosphine was assumed to result from reaction of propene with the co-ordinated diphenylphosphine group remaining after benzaldehyde formation. The same authors have also studied the kinetics of the formation of heavy by-products which are dependent on... 

The oxidation of higher olefins has also been studied, and these reactions form ketones (Equation 16.102). Thus, the C-0 bond formation between water and the substituted olefin mediated by palladium occurs at flie internal carbon. For example, paUadium-catalyzed oxidation of propene forms acetone, and this reaction provides one industrial route to this material. Oxidations of substituted olefins to form ketones have also become a common method for the conversion of olefins to ketones during complex-molecule synthesis. Examples of the use of palladium-catalyzed oxidation in complex-molecule synthesis are described later in this chapter. 

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