Catalytic hydroformylation and hydrocarboxylation of unsaturated fatty compounds

Frankel, E. N.; Pryde, E. H.

doi:10.1007/bf02909059

Cited by 51 publications

(9 citation statements)

References 34 publications

(38 reference statements)

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“…9 21, 48. These include alkylation,49 radical addition,49–52 acylation,53 ene‐reaction,54 hydroformylation–oxo‐synthesis,55–57 co‐oligomerisation,58, 59 hydroaminomethylation60 and acyloxylation (addition of carboxylic acids) 61, 62…”

Section: Improvement Of Native Oils By Chemical Modificationsmentioning

confidence: 99%

Plant‐oil‐based lubricants and hydraulic fluids

2006

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It is estimated that, at present, approximately 50% of all lubricants sold worldwide end up in the environment via total loss applications, volatility, spills or accidents. More than 95% of these materials are currently mineral oil based. In view of their high ecotoxicity and low biodegradability, mineral oil-based lubricants constitute a considerable threat to the environment. In contrast, most lubricants and hydraulic fluids based on plant oils are rapidly and completely biodegradable and are of low ecotoxicity; moreover, lubricants based on plant oils display excellent tribological properties and generally have very high viscosity indices and flashpoints. However, in order to compete with mineral-oil-based products, some of their inherent disadvantages must be corrected, such as their sensitivity to hydrolysis and oxidative attack, and their behaviour at low temperatures. Various methods to improve the undesirable properties of native plant oils will be discussed. In parallel, government regulations that encourage or enforce the use of bio-based fluids, at least in ecologically sensitive areas, will help to increase their market share. Using the numerous possibilities for selective breeding and/or chemical improvement of the double bond systems of natural fatty acids by increased R&D, the major obstacles regarding the use of plant-based raw materials for the production of lubricant base fluids can be overcome and bio-based fluids should expect a future with increasing market shares.

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Section: Improvement Of Native Oils By Chemical Modificationsmentioning

confidence: 99%

Plant‐oil‐based lubricants and hydraulic fluids

2006

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“…Consequently, multiple numbers of hydroxyl groups having varying degrees of reactivity are present, which tend to complicate subsequent reactions and may lead to premature gelation. Hydroformylation offers another method to prepare polyols whereby aldehyde functional vegetable oil that is first obtained is then hydrogenated to alcohols (6,7). Polyurethanes prepared from these polyols had different mechanical properties, depending on the hydroformylation catalyst that was used.…”

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confidence: 99%

Ozone‐mediated polyol synthesis from soybean oil

Tran¹,

Graiver²,

Narayan

2005

J Americ Oil Chem Soc

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Polyols from vegetable oils can replace petroleumbased polyols in the preparation of polyurethanes and polyesters in a wide range of applications. However, previous preparation methods are either too costly, inefficient, or yield secondary alcohols, which are less reactive than the desired primary alcohols. The objectives of this study were to prepare primary soy-based polyols by a new catalytic ozonolysis process and to characterize the composition of the product mixture. In this new process, the polyols were prepared by passing ozone through a solution of soybean oil and ethylene glycol in the presence of an alkaline catalyst. Unlike conventional ozonolysis that yields aldehydes and carboxylic acids by spontaneous decomposition of the ozonide intermediates, the ozonides in our method reacted with the hydroxyl group of the glycol to form an ester linkage with a terminal hydroxy group. Statistical analysis of the product mixture indicates that the resulting polyol mixture is more uniform than the original TG mixture, having (2-hydroxy)nonanoate as the major component of the new hydroxyl functional TG. The chemical structure of the polyols produced was further characterized by iodine number and 13 C NMR and FTIR spectroscopy, which confirmed the cleavage of the double bonds, the presence of hydroxyl groups, and the formation of new ester linkages.Paper no. J10972 in JAOCS 82, 653-659 (September 2005). FIG. 3.Statistical distribution of soy polyols obtained by alkaline catalytic ozonolysis of soybean oil with ethylene glycol. N, nonanoate; P, palmitate; S, stearate.

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“…Subsequent oxidation of the product aldehydes results in fatty diacid derivatives, which are important intermediates in the production of cosmetics. Hydroformylation of unsaturated fatty acid esters has been reported both with cobalt and rhodium catalysts, and several reviews concerning this topic have appeared (11)(12)(13). MO as well as various polyunsaturated fatty esters can be hydroformylated with cobalt carbonyl to mainly isomeric mixtures of mono formyl compounds (11,(13)(14)(15).…”

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A bulky phosphite‐modified rhodium catalyst for the hydroformylation of unsaturated fatty acid esters

Muilwijk

Kamer

Leeuwen

1997

J Americ Oil Chem Soc

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A series of hydroformylation experiments was performed with a high-grade and a technical-grade-derived methyl oleate (MO) and a rhodium catalyst modified by the bulky tris (2-tert-butyl-4-methylphenyl)phosphite. In the hydroformylation of pure methyl oleate, relatively high turnover numbers were obtained (400-500 mol/mol/h) under mild conditions (molar ratio MO/Rh = 910, 80-100°C and 20 bar; CO/H 2 = 1:1, solvent toluene), leading to about 95% conversion in 3 h. Fast isomerization occurs under these conditions to produce the trans oleate. Trans oleate reacts more slowly than cis oleate. At temperatures below 50°C, isomerization does not occur. The use of technical-grade methyl oleate, containing 14% 9,12 diene, methyl linoleate (ML), results in lower reaction rates because dienes form stable π-allylic intermediates, which slowly undergo hydroformylation. More severe conditions were applied to obtain higher rates. The rate varied from 50 to 400 mol/mol/h, depending on conditions (molar ratio MO/Rh = 910, T = 50-120°C, P = 50-80 bar; CO/H 2 = 1:1-1:6, solvent, toluene). Several isomers of ML were formed during the reaction. Subsequent hydroformylation of these isomers results in a complicated mixture of products. The product mixture consists predominantly of methyl formylstearate, methyl formyloleate, methyl diformylstearate, and some yet unidentified side products. A comparison of the classic triphenylphosphine-modified catalyst and the bulky phosphite-modified catalyst has shown that the latter is several times more active. JAOCS 74, 223-228 (1997).

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Catalytic hydroformylation and hydrocarboxylation of unsaturated fatty compounds

Cited by 51 publications

References 34 publications

Plant‐oil‐based lubricants and hydraulic fluids

Plant‐oil‐based lubricants and hydraulic fluids

Ozone‐mediated polyol synthesis from soybean oil

A bulky phosphite‐modified rhodium catalyst for the hydroformylation of unsaturated fatty acid esters

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