Catalytic carboxylation of fats. Carboxy acids and esters from monounsaturates

Frankel, E. N.; Thomas, Frederick

doi:10.1007/bf02886865

Cited by 39 publications

(49 citation statements)

References 10 publications

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“…Carboxystearic acid (CSA), prepared by the hydrocarboxylation of oleic acid (22), had the following typical analysis: 9(10)-carboxystearic acid, 89.1%; dicarboxystearic acid, 8.3%; stearic acid, 1.7%; and hydroxystearic acids, 0.5%. Methyl carboxystearate (MCS); prepared by the hydroformylation of methyl oleate followed by air oxidation and extraction with NaHCO3 (19,28), had the following typical composition: methyl 9(10)-carboxystearate, 90.8%; methyl dicarboxystearate, 6.9%; methyl oleate and stearate, 1.0%; others, 1.3%.…”

Section: Methodsmentioning

confidence: 99%

“…Two involve hydroformylation of oleic acid or methyl oleate with either rhodium (18,19) or cobalt carbonyl (20) catalysts followed by air oxidation (21), and one involves direct hydrocarboxylation with palladium catalyst (22). Two involve hydroformylation of oleic acid or methyl oleate with either rhodium (18,19) or cobalt carbonyl (20) catalysts followed by air oxidation (21), and one involves direct hydrocarboxylation with palladium catalyst (22).…”

Section: Introductionmentioning

confidence: 99%

“…bTemperature at which visible flow occurs when flask is heated 0.3-0.6 C/rain and tilted about 60 ~ for[20][21][22][23][24][25][26][27][28][29][30] sec. This temperature is 10 to 20 C higher than softening point determined by the ring and ball method.CMeasured with a du Pont Model 940 Thermomechanical Analyzer with a 10 C/rain temperature rise and with a 1 g weight.dA visual estimate of cold plastic flow of the resin particles.…”

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confidence: 99%

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Polyamides from carboxystearic acid

Kohlhase

Frankel

Pryde

1977

J Americ Oil Chem Soc

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AND SUMMARYA series of polyamide and copolyamide resins were prepared from carboxystearic acid or methyl carboxystearate, with ethylenediamine, hexamethylenediamine, adipic acid, or caprolactam as coreactants. None of the product formulations appeared suitable for use in hot melt adhesives. More promising were the liquid, reactive polyamides made from carboxystearic acid and polyamines. These products gave excellent adhesion value in scouting tests when used as one component in 2-component epoxy adhesives and coatings. In other applications, C-19 polyamides had enhanced solubility and low melting characteristics to make them attractive as modifiers.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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confidence: 99%

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Polyamides from carboxystearic acid

Kohlhase

Frankel

Pryde

1977

J Americ Oil Chem Soc

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“…Formation of formyloleate was maximum at low pressures; formylstearate was maximum at high temperatures, and diformylstearate was maximum at high pressure (11,12) (Table I), Cobalt carbonyl cannot introduce more than one formyl group, probably because conjugation and hydrogenation are major competitive reactions with this catalyst.…”

Section: Diformylstearatesmentioning

confidence: 99%

“…Dehydroformylation leads to a mixture of 9,12(10,13)-and 10,12( 11,13)-diformylstearate ( 11 ). Formyl- oleate was identified as a mixture of methyl 9(10)-formy]-12(i 3)-and 12(13)-formyl-9(10)-octadecenoate.…”

Section: Diformylstearatesmentioning

confidence: 99%

Catalytic hydroformylation and hydrocarboxylation of unsaturated fatty compounds

Frankel

Pryde

1977

J Americ Oil Chem Soc

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AND SUMMARYThe two catalyst systems rhodium-triphenylphosphine and palladium chloride-triphenylphosphine were investigated for the respective hydroformylation and hydrocarboxylation of oleic acid or ester to produce C-19 bifunctional compounds. Compared to conventional cobalt carbonyl for making formylstearate, rhodium-triphenylphosphine permits lower pressures (1000-2000 psi vs. 3000-4000 psi), higher conversions (95% vs. 80%), and no loss of functionality (vs. 15% hydrogenation with cobalt). Although palladium chloride-triphenylphosphine for hydrocarboxylation introduces the carboxyl function directly into the fatty acid chain, CO pressures of 3000-4000 psi and corrosion-resistant equipment are necessary. When applied to polyunsaturated fatty acids, both rhodium and palladium catalyst systems have the outstanding advantage of introducing functionality at each double bond position to produce polyformyl-and polycarboxystearates. Selected formyl derivatives were converted in excellent yield to acetals, to acids and their esters, to hydroxymethyl compounds and their esters, and also to aminomethyl compounds that could be condensed to polyamides. Several of the esters and acetals were effective primary plasticizers for poly(vinyl chloride) that had outstanding low volatility characteristics. Other applications for these new and highly versatile derivatives included rigid urethane foams, urethanemodified coatings, ester lubricants, and a shrinkresist treatment for wool.

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Dicarboxylic Acids

Johnson¹,

Pollock²,

Cantrell³

2000

Kirk-Othmer Encyclopedia of Chemical Technology

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Aliphatic, linear dicarboxylic acids of the general formula HOOC(CH 2 );ynCOOH, and branched dicarboxylic acids are the subject of this article. These dibasic acids are referred to by their trivial names, IUPAC system, or by adding the suffix “dicarboxylic acid” to the name of the hydrocarbon skeleton. For example, a 10‐carbon atom dibasic acid is designated sebacic acid, decanedioic, or 1,8‐octane‐dicarboxylic acid. Physical and chemical properties of most of the common dibasic acids are given and discussed. Manufacture, preparation, and processes for glutaric acid, pimelic acid, suberic acid, zelic acid, sebacic acid, dodecanedioic acid, brassylic acid, C‐19, C‐20, C‐21, and C‐22 dicarboxylic acids are given. Also discussed is the preparation of dicarboxylic acids using microorganisms. The diacids are important industrial intermediates for the manufacture of diesters, polyesters, and polyamides. These derivatives find application as plasticizing agents, lubricants, heat‐transfer fluids, dielectric fluids, fibers, copolymers, inks and coatings resins, surfactants, fungicides, insecticides, hot melt coatings, and adhesives. The prices and mode of shipment for the various commercial grades of the diacids are given. The toxicities and environmental effects of the diacids are also discussed.

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Catalytic carboxylation of fats. Carboxy acids and esters from monounsaturates

Abstract: A highly selective catalytic, one-step synthesis converts oleic acid into 9(10)-carboxystearic acid in high yields (85-99%). Hydrocarboxylation with water and carbon monoxide under pressure (3000-4000 psi)

Cited by 39 publications

References 10 publications

Polyamides from carboxystearic acid

Polyamides from carboxystearic acid

Catalytic hydroformylation and hydrocarboxylation of unsaturated fatty compounds

Dicarboxylic Acids

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