Edmund F. Jordan

Low temperature aminolysis of methyl stearate catalyzed by sodium methoxide

Aminolysis of methyl stearate by both primary and secondary amine catalyzed by sodium methoxide was found to be rapid at 30°C. under anhydrous conditions. With primary amines under optimum conditions (mole ratio to ester: amine, 10; catalyst, 0.12), the minimum reaction times necessary to obtain yields of amide over 90% were:n-butylamine, 30 min.;iso-butyl-, 1 hour; allyl-, 1.8 hr.; benzyl-, 3.2 hr.;sec-butyl-, 16 hr.; ammonia (a heterogenous reaction requiring an optimum triethylamine to ester ratio of 2 ml./g. and a catalyst mole ratio of 0.20) 2 days. Secondary amines reacted rapidly at 30°C. (15 min. to 24 hr. for a 90% yield of amide) when the nitrogen atom was joined into a saturated ring or held at least one methyl group, but very slowly even at 100°C, when the substituent was dialkyl larger than methyl. Uncatalyzed, all reactions were extremely slow.

Wax compositions from N-allylstearamide and N-allyl hydrogenated tallow amides, by reaction with benzoyl peroxide

When either pure N-allylstearamide or mixed allylamides, made by the aminolysis of hydrogenated tallow, were heated at 90C for 3 hr with benzoyl peroxide, the reaction products were medium-hard, high-melting (ca. 70–80C) waxes of light color suitable for use in polish applications. Hardness increased with increase in benzoyl peroxide, reaching an optimum for 3 to 8 g of peroxide per 100 g amide. Qualitative floor-wear tests on films obtained from paste and emulsion compositions showed the allylamide waxes to be inferior to carnauba and a Fisher-Tropsch wax, but superior to several other synthetic waxes including polyethylene. No special property advantage was found using pure allylsteara-mide. Resistance to oxidation at 90C was good and the waxes emulsified readily.In the reaction of allylstearamide with benzoyl peroxide, polymer formation depends strongly on catalyst concentration (d M/dP=2, compared to 14–50 for allyl esters) and some products of substitution and induced decomposition are formed. Wax properties were related to polyallylstearamide content.

Polymer-Leather Composites V. Preparative Methods, Kinetics, Morphology, and Mechanical Properties of Selected Acrylate Polymer-Leather Composite Materials

This paper reviews an extensive study of largely reported work on polymer-leather composite materials (1–4). In this work two methods were utilized, for depositing selected acrylic polymers into the leather matrix by free radical polymerization (1). In one method polymer was introduced by emulsion polymerization into expanded hydrated panels. In the other, polymer was formed by bulk or solution polymerization in unexpanded acetone-dried panels. The widest feasible range of composite compositions was investigated for both methods. The kinetics of the emulsion process (2), together with the morphology (3) and mechanical properties (4) of both types of composites, were also investigated. In the present paper we attempt to combine the more important aspects of these detailed works into a comprehensive whole and to integrate this peripheral area of composite material science into the main body of work in the field.

The kinetics of the heterogeneous hydrolysis of poly(vinyl formate) and of poly(vinyl formate‐co‐stearate)

The rate of hydrolysis of formate and stearate segments from poly(vinyl formate) and from poly(vinyl formate-co-stearate) suspended in dilute aqueous hydrochloric acid was studied. Evidence was presented to show that the hydrolysis follows pseudo-first-order kinetics. The Arrhenius constants and the entropies and free energies of activation for the hydrolysis of formate and stearate groups from copolymers containing 0, 3, 5, and 10 mole-% vinyl stearate were calculated from the partially reduced reaction rate constants at three temperatures. For the hydrolysis of formate segments, ΔS‡ is markedly affected by the stearate content, whereas the variation in ΔF‡ is small. Variations in vinyl formate content have smaller effects on the thermodynamic constants of the activated complex for the hydrolysis of the stearate segments. At approximately 95°C., some anomalous kinetic behavior was observed.