- Thermodynamic and kinetic study of Diels–Alder reaction between furfuryl alcohol and N-hydroxymaleimides — An assessment for materials application
-
The study of Diels–Alder reactions in materials science is of increasing interest. The main reason for that is the potential thermoreversibility of the reaction. Aiming to predict the behavior of a material modified with maleimido and furyl moieties, 1H NMR and UV-Vis solution studies of the Diels–Alder reaction between furfuryl alcohol and two N-hydroxymaleimides are explored in the present study. Rate constants, activation energy, entropy, and enthalpy of formation were determined from each technique for both reacting systems. Endo and exo isomers were distinguished in 1H NMR, and the transition from a kinetic, controlled Diels–Alder reaction to a thermodynamic one could be observed in the temperature range studied. A discussion on the effect of that on the application in a material was performed. The approach selected considers a simplified equilibrium of the Diels–Alder reaction as the kinetic model, allowing materials scientists to evaluate the suitability of using the reacting molecules for the creation of thermoresponsive materials. The proposed approach determines the kinetic constants without the direct influence of the equilibrium constant value, thereby allowing a more objective data analysis. The effects of the selection of kinetic model, analytical method, and data treatment are discussed.
- Laborie, Marie-Pierre,Roucoules, Vincent,de Oliveira, Jamerson Carneiro
-
-
- Monomer having electron-withdrawing group and process for preparing the same
-
A monomer containing an electron-withdrawing group of the present invention is represented by following Formula (a), (b) or (c): wherein A1, A2, and A3 are each a ring; Ra, Rb, Rc, and Ru are the same or different and are each a hydrogen atom or organic group; at least one of Rs, Rw and Rv, at least one of Rt and Rw1, and at least one of the two Rw2s are each an electron-withdrawing group, and the others are each a hydrogen atom or organic group; W1 is a single bond or linkage group; and n denotes an integer of 2 to 25, where at least two of Ra, Rb, Rc, Rs, Rt, Ru, Rv, Rw, Rw1, Rw2, W1, and carbon atoms constituting ring A1, carbon atoms constituting ring A2, and carbon atoms constituting ring A3 may be combined to form a ring, respectively. The electron-withdrawing groups in Rs, Rt, Rv, Rw, Rw1, and Rw2 are, for example, groups each containing a fluorine atom. The monomer is useful as a raw material for photoresist polymeric compounds.
- -
-
-
- Synthesis of N-Hydroxymaleimide and N-Hydroxyitaconimide and their Related Derivatives
-
Thermolysis of alkyl and aryl carbonates of N-hydroxy-3,6-epoxy-1,2,3,6-tetrahydrophthalimide yielded the corresponding alkyl or aryl N-maleimidyl carbonates.The benzyl or phenyl carbonate afforded N-hydroxymaleimide, either by treatment with trifluoroacetic acid or by refluxing in methanol.N-hydroxyitaconimide was obtained by dehydration of N-hydroxyitaconamic acid with dicyclohexylcarbodi-imide (DCC).The DCC dehydration of N-acetoxy- and N-benzyloxy-itaconamic acids produced iminofuranones, which could be rearranged to imides.Deacylation of N-acetoxymaleimide was unsuccessful, whereas aminolysis of N-acetoxyitaconimide yielded the N-hydroxyimide.
- Akiyama, Masayasu,Shimizu, Kazuyuki,Aiba, Seiichi,Banba, Fumio
-
p. 2122 - 2125
(2007/10/02)
-
