Ethylene and dimethyl acetals from hydroformylated linseed, soybean, and safflower methyl esters as plasticizers for polyvinyl chloride

Abstract

Dimethyl and ethylene acetals of polyformylated unsaturated fatty esters were prepared, characterized, and evaluated as polyvinyl chloride plasticizers. Dimethyl acetals were prepared with trimethyl orthoformate as a water scavenger in the acid catalyzed acetalation reaction. With ethylene acetals, water was removed azeotropically. Although the acetals prepared were mixtures, molecular distillation gave diacetal esters of 80–90% purity and triacetal esters of 80–95% purity. The samples were characterized by gas liquid chromatography and by IR and NMR spectra. Compared to di‐2‐ethylhexyl phthalate as a plasticizer for polyvinyl chloride, the triacetal esters (both dimethyl and ethylene acetals) gave less migration and at least equivalent volatility characteristics; the triacetals also gave equivalent compatibility and strength, but somewhat less desirable low temperature and heat stability properties. The diacetal esters also had good compatibility, equivalent strength, somewhat better low temperature, but less desirable migration and volatility properties.

Chemical Routes for the Transformation of Biomass into Chemicals

“…The products find different applications, mainly in the synthesis of polymers (plasticizers) or copolymers (urethanes), as lubricants, and as coatings. In this way, the use of ethylene and dimethyl acetals obtained from hydroformylated linseed, soybean, and safflower methyl esters gives plasticizers for PVC . Plasticizers from carboxystearic acid esters for PVC have also been prepared by hydroformylation and oxidation or direct hydrocarboxylation of vegetable oil methyl esters.…”

“…In this way, the use of ethylene and dimethyl acetals obtained from hydroformylated linseed, soybean, and safflower methyl esters gives plasticizers for PVC. 1168 Plasticizers from carboxystearic acid esters for PVC have also been prepared by hydroformylation and oxidation or direct hydrocarboxylation of vegetable oil methyl esters. Recently, the kinetics and mechanism of the hydroformylation of soybean oil by homogeneous ligand-modified rhodium catalysts at 343-403 K and 4000-11000 kPa have been studied in the presence of triphenylphospine or triphenylphosphite.…”

Catalytic hydroformylation and hydrocarboxylation of unsaturated fatty compounds

“…Although the monoacetal derivatives are useful only as secondary plasticizers, di-and triacetal derivatives are more compatible and can serve as primary plasticizers (Table IV) (39). Compared to bis(2-ethylhexyl) phthalate, triacetal esters gave less migration, at least equivalent volatility characteristics, comparable compatibility numbers and strength, but somewhat less desirable low temperature and heat stability properties.…”

Acyl esters from oxo‐derived hydroxymethylstearates as plasticizers for polyvinyl chloride

“…From these aldehyde products, several new and unusual derivatives of industrial interest have been made. Oxo fatty derivatives made as plasticizers for polyvinylchioride (PVC) include acetal esters (5,6), esters of mono-, di-, and tricarboxystearic acid (E.J. Dufek, unpublished data), and acetoxyglycerol acetal esters (W.E.…”