Hydroformylation ethylene oxide

Propanediol is a colorless liquid that boils at 210-211°C. It is soluble in water, alcohol, and ether. It is an intermediate for polyester production. It could be produced via the hydroformylation of ethylene oxide which yields 3-hydroxypropionaldehyde. Flydrogenation of the product produces 1,3-propanediol. 

Metal-catalysed hydrocarboxylation of olefins (Equation 3) is the poor relative of the more famous hydroformylation. It generally requires forcing reaction conditions and suffers from mediocre activities and selectivities (n/i ratio). Moreover, the same products can be made via hydroformylation and oxidation of the aldehyde product.431 Consequently, there are few industrial applications of hydrocarboxylation e.g. Ni(CO)4-catalysed production of propionic acid by hydrocarboxylation of ethylene.432,433... 

Other Uses of Ethylene Oxide. About 2 percent of ethylene oxide is consumed in miscellaneous applications, such as its use as a raw material in manufacture of choline, ethylene chlorohydrin, hydroxyethyl starch, and hydrox-yethyl cellulose and its direct use as a fumigant/ sterilant. Production of 1,3-propanediol via hydroformylation of ethylene oxide was begun on a commercial scale in 1999. 1,3-Propanediol is a raw material for polytrimethylene terephthalate, which finds uses in fibers, injection molding, and in film. Use of ethylene oxide in making 1,3-propanediol is expected to be as much as 185 million lb by 2004, up from 12 million lb in 1999. 

Shell produces 1,3 PD from ethylene oxide via hydroformylation with synthesis gas (Fig. 8.8 b). The transformation required two separate steps in the past [55], but has been improved [56], which made the large-volume use of 1,3PD in poly(trimethylene terephthalate) economically viable, and the two steps have been telescoped into one [57, 58]. Shell has a capacity to 70 kt a-1 [59]. 

In retrospect, the catalytic reaction following eq. (1) has promoted recognition of organometallic homogeneous catalysis in the bulk-chemicals industry both hydroformylation (Section 2.1.1) and the Wacker ethylene oxidation are key steps in industrial homogeneous catalysis. 

Karakhanov s group has also been exploring poly(ethylene oxide)- and poly(alkene oxide)-copolymer-bound catalysts [99-102]. A notable aspect of this work is the design of polyethers like 39 that contain jS-cyclodextrins and calyx[4]- and calyx[6]arenes. Such polyethers couple the molecular recognition associated with these macrocycles with the catalytic activity of acac, phosphine, dipyridyl, and catechol ligands. Metals complexed to such ligands have been used in reactions like hydroformylation, Wacker oxidations, and arene hy-droxylation. 

Note that, in some studies, poly(ethylene oxide) oligomers, micelle-forming surfactants derived from them, and their complexes were used to perform such reactions in aqueous and alcohol solutions as hydroformylation [31-33], Wacker oxidation [34,35], hydroxylation of aromatic compounds [36-38], carbon dioxide hydrogenation [39], and epoxidation [40]. It was shown that using poly(ethylene oxide)s substantially increases the reaction rate and, in some cases, allows us to separate a metal complex containing oligo(ethylene oxide) [31,40]. 

Water-soluble macromolecular metal complexes based on terminally functionalized ethylene oxides and ethylene oxide-propylene oxide block copolymers have been used as catalysts for hydroformylation, hydrogenation, Wacker oxidation of imsaturated compounds, hydroxylation of aromatic compounds, oxidation of saturated and alkylaromatic hydrocarbons, metathesis, Heck reaction, and some asymmetric reactions. 

Rhodium complexes with oligo- and poly(ethylene oxide)s modified with phosphine groups 1 were proposed as hydroformylation catalysts as far back as... 

The catalysts obtained were highly active in the hydroformylation of higher alkenes and styrene at 80-120 °C, whereas their activity below the cloud point proved to be low (Table 11-1). Note also that the activity of the catalysts substantially exceeded the activity exhibited under similar conditions by a catalytic system involving rhodium complexes with sulfonated phosphines and oligo(ethylene oxide). Using phosphine 20, a turnover frequency (TOP) in dodecene hydroformylation of 1280 h was obtained All the catalysts could be reused. 

A lower but still rather high activity in two-phase hydroformylation was also exhibited by rhodium complexes with ethylene oxide-propylene oxide block copolymers and butyl ether of poly(propylene oxide)-poly(ethylene oxide) block copolymer modified with diphenylphosphines 3-4 [59]. 

Macromolecular metal complexes with modified poly(ethylene oxide)s have also been applied as catalysts for asymmetric reactions epoxidation, dihydroxy-lation, hydrogenation, and hydroformylation. 

Another of the pioneer polyesters was polytrimethylene terephthalate (PTT). This was recognized very early on as a fiber with outstanding resilience. PTT has been known in many ways as an ideal textile fiber for over 60 years. It remained on the shelf until, in the last decade, it became a commercial product owing to two new routes to the crucial intermediate 1,3-propanediol. One route is petrochemically derived (hydroformylation of ethylene oxide), while the other is a fermentation route using corn sugar to make 1,3-propanediol directly using genetically modified bacteria [40]. 

Synthetic C12+ primary alcohols, produced mainly by the hydroformyl-ation of ethylene oligomers (previous section), compete with fatty alcohols derived from natural oils. They may be sulphated (to give an anionic product) or reacted with ethylene oxide to produce alcohol ethoxylates, the major non-ionic detergent components (possibly approaching IMt per annum worldwide) ... 

Hydroformylation of ethylene oxide to 2-hydroxy propanal Co CCO), Powell et al. (1999)... 

Previously, PTT was produced based on 1,3-PD by chemical synthesis. The traditional chemical routes of commercial synthesis for 1,3-PD production are from acrolein by DuPont and from ethylene oxide by Shell. The route of DuPont is that acrolein is converted to 3-hydroxypropionaldehyde (3-HPA) by hydration, followed to produce 1,3-PD by hydrogenation (Lawrence and Sullivan, 1972). Shell followed the method of hydroformylation of ethylene oxide to 3-hydroxypropanal. This is subsequently extracted and hydrogenated for the production of 1,3-PD (Sullivan, 1993). 

Noteworthy, Co2(CO)g gives also promising results in the hydroformylation of ethylene oxide under the conditions where amines, diamines, or amides... 

Scheme 6.105 Hydroformylation of ethylene oxide with phosphine-modified Co catalysts.

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