ISSN:
0887-624X
Keywords:
radical efficiency calculation
;
photoinitiated polymerization
;
Taft correlation
;
structure-reactivity relationships
;
quantum semiempirical calculations
;
Ab initio calculations
;
molecular orbitals
;
Chemistry
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Relative reactivities of radicals derived from several 1-(N,N-dimethylamino)ethylene-2-derivatives towards the polymerization of butyl acrylate have been calculated. It has been observed that the reactivity of the radicals increases as the electron withdrawing character of the groups attached in the β position to the N atom increases. The experimental efficiency factor (f) has been found to be proportional to the σF value defined in the Taft equation. The dependence of the reactivities with the nature of the radicals has also been explained through their frontier orbital characteristics. The presence of heteroatoms next to the radical center could modify, in some cases, the accuracy of these calculations, although the inclusion of more sophisticated quantum-mechanical methods does solve this drawback. Moreover, the enthalpy calculation of the possible radicals formed from a certain molecule gives a good approach to realize about the existence of anomalous behaviors. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2889-2899, 1997
Additional Material:
7 Ill.
Type of Medium:
Electronic Resource
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