Investigation of cooperative kinetics on reactions of functional groups on polymer chains

Abstract

The kinetics of aminolysis of 1,2;3,4‐meso‐erythritol dicarbonate and 1,2;3,4;5,6‐mannitol, sorbitol, and dulcitol tricarbonates by n‐butylamine in dimethylformamide solution was investigated. The dicarbonate and tricarbonates are considered respectively as models of dyads and triads in the poly(vinylene carbonate) chain. The theoretical kinetic curves for the dimer and the trimers were calculated by solution of kinetic equations and close agreement with experiment was obtained. A version of the Monte‐Carlo method was developed to provide a model for the reaction process by a computer calculation including the neighboring group effect in enhancing reactivity. The theoretical curve for a trimer coincides with the experimental one. These results confirm the accelerating influence of the unreacted neighboring groups. For the polymeric chain the experimental and calculated curves deviate for conversions beyond 10%. This indicates an additional polymer effect, which is as yet unexplained.

Isocyanate-Free Route to Poly(carbohydrate–urethane) Thermosets and 100% Bio-Based Coatings Derived from Glycerol Feedstock

“…17,35 Goldstein et al investigated the kinetics of aminolysis of erythritol dicarbonate as well as of sorbitol, mannitol, and dulicitol tricarbonates with n-butylamine in DMSO. 28 Using the Monte Carlo method to provide the model reaction including the neighboring group effect, they confirmed that adjacent cyclic carbonate groups have an accelerating influence regarding the conversion with primary amines. 28 In order to examine the role of vicinal cyclic carbonates, the amine reaction of STC was compared with that of ethylene carbonate (EC) and styrene carbonate (SC) by monitoring the reaction using FT-IR and 1 H NMR spectroscopy.…”

“…28 Using the Monte Carlo method to provide the model reaction including the neighboring group effect, they confirmed that adjacent cyclic carbonate groups have an accelerating influence regarding the conversion with primary amines. 28 In order to examine the role of vicinal cyclic carbonates, the amine reaction of STC was compared with that of ethylene carbonate (EC) and styrene carbonate (SC) by monitoring the reaction using FT-IR and 1 H NMR spectroscopy. As is apparent from Figure 3 for the bulk reaction of STC with 1-octylamine, the IR band at 1800 cm −1 corresponds to the carbonyl group of the cyclic carbonate rings, whereas the signal at 1700 cm −1 corresponds to the urethane group formed by the ring-opening of cyclic carbonates with 1-octylamine.…”

“…viscous liquids and easy to handle in NIPU synthesis, the pure sorbitol tricarbonate is a crystalline solid, melts at high temperature of 230 °C close to its decomposition, has low solubility in nonpolar media, and is highly immiscible with most NIPU components. 21,28,29 Here, we present synthetic strategies for preparing high purity sorbitol tricarbonate and for tailoring novel poly(carbohydrate− urethane) thermosets derived from glycerol feedstock. As illustrated in Scheme 2, acrolein (1), which is industrially available by the dehydration of glycerol, was dimerized by means of the zinc-catalyzed McMurry coupling reaction to produce divinyl ethylene glycol (DVG, 2).…”

“…Most likely, this is attributed to difficulties encountered in the direct carbonatization of saccharides and its tedious purification . Such synthetic problems are also well-known for the esterification of saccharides such as sorbitol, yielding complex reaction mixtures. − Moreover, unlike saccharide–glycidyl ether-based cyclic carbonates, which are viscous liquids and easy to handle in NIPU synthesis, the pure sorbitol tricarbonate is a crystalline solid, melts at high temperature of 230 °C close to its decomposition, has low solubility in nonpolar media, and is highly immiscible with most NIPU components. ,, …”

Assessment of Plant and Microalgal Oil-Derived Nonisocyanate Polyurethane Products for Potential Commercialization

“…This result is consistent with the observation in Figure 5A where carbonated triglyceride oil was used. The higher reactivity of vicinal cyclic carbonate groups was predicted by Goldstein et al 44 and demonstrated by Schmidt et al 45 Maisonneuve et al have also discussed that the inductive effect of the substituent of the 5-membered cyclic carbonate plays a role in its reactivity. 6,46 Thus, we can tentatively conclude that the polymerization rate is related to the density of carbonated groups on fatty acid acyl chains.…”