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

Pryde

1977

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: Oxidationmentioning

confidence: 99%

“…Methyl di-and tricarboxystearates were prepared by permanganate oxidation of the hydroformylated methyl esters of safflower and linseed oils, respectively (25). Isolation of di-and tri-carboxystearic acids was accomplished by stepwise extraction with aqueous potassium bicarbonate (25) or with sodium hydroxide or bicarbonate (27).…”

Section: Oxidationmentioning

confidence: 99%

Catalytic hydroformylation and hydrocarboxylation of unsaturated fatty compounds

Pryde

1977

“…For plasticizer evaluation, pure alkyl stearates (95+%) with one, two, and three internal carboalkoxy groups were prepared either by a two-step hydroformylation-oxidation reaction (7)(8)(9) or by direct hydrocarboxylation of vegetable oil methyl esters (1 1,12) followed by direct sulfuric acidcatalyzed esterification and/or transesterification procedures previously reported (10,13).…”

Section: Di- Tri- and Tetraestersmentioning

confidence: 99%

“…26-27 times more reactive than the internal or branched carboxyl group. Because of this difference in reactivity, diesters of CSA with two different alkyl groups could be prepared by selective alkaline transesterification (10). For example, Me-Me diester when treated with dimethylpentanol (Dmp-OH) or ethylhexanol (EtHex-OH) gave Dmp-Me and EtHex-Me diesters.…”

Section: Di- Tri- and Tetraestersmentioning

confidence: 99%

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

Dufek

Thomas

et al. 1976

Methyl mono‐, di‐, and tricarboxystearates were prepared by either a two‐step hydroformylation‐oxidation reaction or direct hydrocarboxylation of unsaturated vegetable oil methyl esters. Procedures were developed for preparing alkyl dicarbomethoxy‐, dicarboethoxy‐, and dicarbobutoxystearates. These triesters, along with some di‐ and tetraesters from mono‐ and tricarboxystearic acids, were evaluated as primary plasticizers for polyvinyl chloride (PVC). Except for butyl carbobutoxystearate, the esters were compatible at the 32% level and had properties equal or superior to those of dioctyl phthalate. Methyl and butyl diesters of carboxystearic acid had undesirable migration and volatility properties. The migration and volatility properties of some tri‐ and tetraalkyl esters were equal to or better than the controls. Of the various esters tested, methyl dicarbomethoxystearate containing 13–49% methyl tricarbomethoxystearate was an efficient plasticizer for PVC at the 32% level.

“…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

Pryde

1977

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.