A. N. Wrigley

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.

Kinetics of the aminolysis of hydrogenated tallow by allylamine and other primary amines in methanol

Kinetics of the aminolysis of hydrogenated tallow by allylamine in methanol solution under sodium methoxide catalysis was studied at several temperatures (60 to 90C) and catalyst concentrations. Under the experimental conditions the triglycerides were rapidly converted to the mixed methyl esters, which slowly reacted with the amine to produce the mixed amides. At constant catalyst concentration, disappearance of triglyceride was found to be first order in triglyceride and in amine. Because rate was found to be directly proportional to catalyst concentration, the experimental over-all rate was −d[Triglyceride]/dt=k3[Triglyceride] [Amine] [RO−], and k3 was 2.022 kg2 mole−2 hr−1. A mechanism proposed by Bunnett and Davis for ester aminolysis involving an ester-amine complex formed in a rapid pre-transition-state equilibrium is consistent with thermodynamic terms which reconcile a large negative entropy of activation (−44.17 cal deg−1 equivalent−1) and relatively small energy of activation (11.60 kcal equivalent−1). Relative rate constants at 70C under sodium-methoxide catalysis for the aminolysis of hydrogenated tallow by a variety of structurally different primary amines agreed, in general, with those found by others for the ethylene glycol-catalyzed reaction of methyl acetate with the same amines at 25C. However, monoethanolamine reacted nineteen times faster than predicted, which suggested a mechanism involving initial attack by the alkoxy anion of the ethanolamine in the rate detering step, followed by rapid, base-catalyzed, acyl acyl oxygen-to-nitrogen (O→N) migration. The velocity constants and thermodynamic constants reported enable prediction of the time required for specific yields under a variety of experimental conditions.

Intrinsic viscosity-number average molecular weight relationship for poly (n-Octadecyl acrylate) and poly (N-n-octadecylacrylamide)

AbstractIntrinsic viscosity-number average molecular weight relationships have been measured, at 30C in benzene, for poly (n-octadecyl acrylate) as [η]=2.72×10−4 Mn0.638 and for poly (N-n-octadecylacrylamide) as [η]=0.82×10−4 Mn0.676. Whole polymers of various molecular weights were prepared in benzene solution at 65C with dodecyl mercaptan as primary regulator. By the use of these parameters, the molecular weight of such polymers and their homologs may now be measured by simple solution-viscosity determinations.In the expression {

Side‐chain crystallinity. II. Heats of fusion and melting transitions on selected copolymers incorporating n‐octadecyl acrylate or vinyl stearate

1/\bar {\rm X}_{n{\text{ }}} {\text{ = 1/ }}\bar {\rm X}_{no{\text{ }}} + {\text{ C}}_{{\text{S }}} \left[ S \right]{\text{ / }}\left[ {\rm M} \right]

Side‐chain crystallinity. IV. Mechanical properties and transition temperatures of copolymers of methyl methacrylate with higher n‐alkyl acrylates and N‐n‐alkylacrylamides

} (relating degrees of polymerization {

Viscosity index. III. Thermodynamic parameters for side chain crystallinity in pour point-modified blends containing n-octadecyl acrylate

\bar {\rm X}_{n{\text{ }}}