Hydroformylation nonionic surfactants

Homologous w-alkenecarboxylic acid methyl esters were hydroformyl-ated with the water-soluble rhodium/tppts catalyst in an aqueous-organic two-phase system (75). By addition of surfactants a micellar system was created. Cationic surfactants are better than anionic or nonionic surfactants for this hydroformylation. 

Hydrocarboxylation of the Ce-Cs a-olefins with cobaltcarbonyl/pyridine catalysts at 200 °C and 20 MPa gives predominantly the linear carboxylic acids. The acids and their esters are used as additives for lubricants. The Ce-Cio a-olefins are hydroformylated to odd-numbered linear primary alcohols, which are converted to polyvinylchloride (PVC) plasticizers with phthalic anhydride. Oligomerization of (preferably) 1 -decene, applying BF3 catalysts, gives oligomers used as synthetic lubricants known as poly-a-olefins (PAO) or synthetic hydrocarbons (SHC) [11, 12]. The C10-C12 a-olefins can be epoxidized by peracids this opens up a route to bifunctional derivatives or ethoxylates as nonionic surfactants [13]. 

Rhodium complexes generated from the polyethylene glycol)-functionalized phosphine 9 (n = 1, x = 0, R = Me, Bu), which should behave as a nonionic surfactant and be able to induce micelle formation, have been used as catalysts in the hydroformylation of 1-dodecene in an aqueous/organic two-phase system [31]. The conversion of 1-dodecene was 80% and the n/iso ratio 60 40, with no carryover of the rhodium catalyst into the organic phase. The Rh/9 (n = 1, x = 0, R = Me, Bu) catalyst remained active after one recycle step [31],... 

Microemulsions containing the aqueous Rh-catalyst solution dispersed in a large oily phase of the substrate olefin and product aldehydes can also be formed using relatively large amount of surfactants (155). The application of this technique was demonstrated in hydroformylation of 1-dodecene using either an anionic or a nonionic surfactant (Na-dodecylsulfate and Marlipal 01370, respectively) the catalyst was prepared in situ from Rh(I)-precursors and TPPTS. At... 

Higher molecular primary unbranched or low-branched alcohols are used not only for the synthesis of nonionic but also of anionic surfactants, like fatty alcohol sulfates or ether sulfates. These alcohols are produced by catalytic high-pressure hydrogenation of the methyl esters of fatty acids, obtained by a transesterification reaction of fats or fatty oils with methanol or by different procedures, like hydroformylation or the Alfol process, starting from petroleum chemical raw materials. 

The rhodium/TPPTS-catalyzed hydroformylation of 1-octene and other higher olefins in an aqueous biphasic system was studied at pressures from 40 to 90 bar and temperatures of up to 120 °C. Nonionic amphiphiles of the alkoxyethylene type were applied to promote the contact between the reacting species by enlargement of the interfacial area. The highest reaction rates were obtained at a surfactant concentration of about 1 wt% [109]. 

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