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

Abstract

Hydroxymethylstearates were made by hydroformylation or oxo reaction of mono-and polyunsaturated fats and esters with either rhodium-triphenylphosphine or cobalt carbonyl catalysts. Rhodium-oxo products were hydrogenated with nickel catalyst, whereas, cobalt-oxo products were heated directly under hydrogen pressure. Hydroxymethyl fatty alcohols also were prepared by a two-step copper-chromite hydrogenation of hydroformylated linseed fatty esters. Of these hydroxymethyl compounds, 39 were converted to their acetates and other acyloxy derivatives and then evaluated as primary plasticizers for polyvinylchloride. For compounds with good compatibility, methyl 9(10)-acetoxymet hylstearate and 9(10)-acetoxymethyloctadecyl acetate gave the lowest flex temperature (-47 C). An unusual combination of good compatibility and low flex temperature was obtained with 2-methoxyethyl 9(10)-acetoxymethylstearate. Addition of more than one acetoxymethyl group in the fatty acid molecule, made possible by rhodium hydroformylation, imparted good compatibility and outstanding permanence (low migration and volatility) but raised flex temperature. Butyl diacetoxymethylstearate, methyl triacetoxymethylstearate, and polyacetoxymethyloctadecyl acetate from linseed esters displayed good compatibility, strength, and volatility characteristics. As glycerides, acetoxymethytated safflower and linseed oils produced good compatibility and outstanding permanence, better than esters commonly used as commercial plasticizers. Z > © ~q > Z r~ o0 < © L~ t,~

Hydroformylation of vegetable oils: More than 50 years of technical innovation, successful research, and development

“…The latter were subsequently converted into acetals whose plasticizer properties proved to be comparable to those of two PVC plasticizers, namely dioctyl phthalate and dioctyl sebacate . Acyl esters derived from oxo‐derived hydroxymethylstearates proved to be effective as plasticizers as well . More intricate mixtures were also hydroformylated using the above Rh/CaCO 3 /PPh 3 catalyst .…”

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

“…Several investigations have been performed on the hydroformylation of unsaturated fatty materials, such as oleic acid and methyl oleate (MO). Properties of the hydroformylation products vary, depending on the catalyst system and substrates used, and many areas of application for these oxoproducts are known; e.g., lubricants (2), plasticizers (3)(4)(5), urethane foams (6)(7)(8), and coatings (9,10). Subsequent oxidation of the product aldehydes results in fatty diacid derivatives, which are important intermediates in the production of cosmetics.…”

Functionalization of soy fatty acid alkyl esters as bioplasticizers

“…It is well known that epoxidized alkyl esters, such as epoxy soybean oil, serve as secondary plasticizers because they stabilize PVC during and after processing by scavenging chlorine liberated from PVC. Epoxide ring opening with different nucleophiles, such as alcohols and acids, is well demonstrated in the literature [17,[24][25][26]. Equal molar ratios of epoxide/nucleophile (1:1) in the presence of acid would produce complete opening of epoxide in good yield (see Scheme 1).…”