Kinetics of amine‐cyclic anhydride reactions in moderately polar solutions

Abstract

The validity of extrapolating the reactivity of low molar mass compounds in solution to the polymer‐analogous chemistry between polymer‐bound functionality is investigated for the reaction of primary amines with cyclic anhydrides in the moderately polar solvents, anisole and tetraethyleneglycol dimethylether. The kinetics of amic‐acid formation and imidization of polymeric and small molecule mixtures measured by Fourier‐Transform Infrared Spectroscopy at near‐ambient and elevated temperatures are compared. A Significant decrease in both reaction rates is observed upon changing the primary amine from aliphatic to benzylic, benzylic to 1,2‐diphenylethylamine, and 1,2‐diphenylethylamine to polystyrene‐bound 1,2‐diphenylethylamine. Reasons for the influence of polymer‐bound chemical functionality on the reaction rates for these amines are discussed. The imidization step is found to be rate limiting in the reaction of phthalic anhydride with benzylamine at the functional group concentrations reported (0.14M or less). © 1995 John Wiley & Sons, Inc.

FTIR spectroscopic studies of interfacial reactions between amino functionalized silicon surfaces and molten maleic anhydride copolymers

“…In this case, an observation of an intermediate reaction step 18,26) could not be realized. If the amino-functionalized siloxane network was annealed above 170 8C we observed beginning decomposition and/or intramolecular reactions recognizable in manifold changes in the spectra.…”

“…A partial reconversion of this compound is practicable by heating up to 100 8C under vacuum for 1 h. Simultaneously with this reconversion we can observe in the FTIR spectra a further cross-linking reaction between hydrolyzed siloxane groups to form a highly condensed amino siloxane network, schematically shown in Fig. 2 18,19) . The identification of the cross-linking reaction between hydrolyzed siloxane groups during the heating process was possible on a germanium ATR element to monitor the whole spectral range of interest, i. e., 1 000 -1 200 cm -1 .…”

A one‐step preparation of compatibilized polypropylene‐nanocomposites by reactive extrusion processing

“…is unable to form hydrogen bonds by itself, as the grafted MA groups do not possess a H-bond donor, an equimolar amount of a primary alkyl amine was used to open the anhydride rings, thereby forming an amide-acid structure, 45,46 to provide sites for intermolecular H-bonding to cross-link the rubber. Primary aliphatic amines were used because of their fast reaction in solution with anhydride groups at low temperatures, without the need of a catalyst.…”

Effect of chain length on rates of diffusion-limited small molecule-polymer and polymer-polymer reactions: Phosphorescence quenching studies

“…The mechanisms of these reactions and how they depend on polymer concentration, chain length, and reactivity of the functional group are key to understanding bimolecular termination during free radical polymerizati0n,2'-~~ the kinetics of chain coupling at interfaces, 16 and the structure of surfactant micelles31 and colloids.32 The termination reaction is significant in that the TrommsdorP2 or "gel" effect in free radical polymerization is associated with a downturn of the termination rate constant, k,. The Trommsdorff effect, which is manifested in an autoacceleration of conversion during free radical polymerization, can be deleterious due to the production of product with unwanted properties and because the highly exothermic nature of the reaction can create potentially explosive conditions.…”