Some esters of mono‐, di‐, and tricarboxystearic acid as plasticizers: Preparation and evaluation

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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.

Section: Plasticizersmentioning

confidence: 99%

Catalytic hydroformylation and hydrocarboxylation of unsaturated fatty compounds

Frankel

Pryde

1977

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“…An authentic sample of methyl 9(10)-carboxymethylstearate (MCMS) was required for use in recent studies (1,2) of reactions and uses of methyl 9(10)-formylstearate (MFS). Selective hydroformylation of methyl oleate (3) gives high yields of MFS.…”

Section: Introductionmentioning

confidence: 99%

Conversion of methyl 9(10)‐formylstearate to carboxymethylstearate

Dufek

1978

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Methyl 9(10)-formylstearate was converted to methyl 9(10)-carboxymethylstearate. The reactions to prepare the intermediates methyl 9(10)-hydroxymethyl-, 9(10)-acetoxymethyl-, 9(1 0)-methylene-, and 9(10)-formylmethylstearate are described. Methyl 9(10)-hydroxymethylstearate readily loses methanol and forms a trimeric polymer. The acetate of the primary alcohol when pyrolyzed gives 59% yield of methyl 9(10)-methylenestearate. Hydroformylation of the methylene compound followed by permanganate oxidation gave methyl carboxymethylstearate. Evidence is presented to show that pyrolysis of the acetate ester and hydroformylation of the pyrolysis product produce, respectively, only the methylene and formylmcthylstearates. Rates of esterification-transesterification of methyl 9(10)-carboxymethylstearateshow that the carboxymethyl group is 2-3 times as active as the carboxyl group in methyl 9(10)-carboxystearate and that the terminal carboxyl group is about 10 times more active towards esterification than the branched carboxymethyl group.

“…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.…”

mentioning

confidence: 99%

Polyamides from carboxystearic acid

Kohlhase

Frankel

Pryde

1977

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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.