Reactivity from interaction diagrams

Reactivity acidity, 68-69 basicity, 66-68 electrophilicity, 68-69 from interaction diagrams, 66-69 nucleophilicity, 66-68... 

The performance of single-component polymerizations in a twin screw extruder is dependent on several extruder parameters. Each parameter has its specific influence on the conversion of the reaction and the average molar mass of the polymer formed. To understand the influence of the parameters, a theoretical analysis of the reactive extrusion process was developed in the form of a reactive extrusion interaction diagram. The conclusions which can be drawn from the theoretical and the experimental investigations of a single-component reaction (the polymerization of butylmethacrylate) in a twin screw extruder are as follows ... 

From the interaction diagram as given in Fig. 13.3, the gel effect is identified as a possible source of chemical instabilities. Nevertheless, there are two other chemical effects that influence the stability of reactive extrusion The ceiling temperature and the phase separation. The stability of a reactive extrusion process is influenced by these three factors because they have a direct influence on the viscosity and reaction speed and therefore on the hydrodynamic instabilities. 

Figure 4 Orbital interaction diagrams showing the stabilizing interaction between an unpaired electron and (a) a n acceptor substituent, and (b) a lone-pair donor substituent. From Bernard , F. Epiotis, N. D. Cherry, W., etal. J. Am. Chem. Soc. 1976, 98,469-478 Henry, D. J. Partdnson, C. J. Mayer, P. M. Radom, L. J. Phys. Chem. A 2001, 105, 6750-67564 Coote, M. L. Lin, C. Y. Zipse, H. In Carbon-Centered Free Radicals Structure, Dynamics and Reactivity, M. D. E. Forbes, Ed. Wiley, 2010 pp. 83-104 Hioe, J. Zipse, H. Org. Biomol. C/tem. 2010,8,3609-3617 Poutsma, M. L. J. Org. Chem. 2011, 76, 270-276. ...

Various theoretical methods and approaches have been used to model properties and reactivities of metalloporphyrins. They range from the early use of qualitative molecular orbital diagrams (24,25), linear combination of atomic orbitals to yield molecular orbitals (LCAO-MO) calculations (26-30), molecular mechanics (31,32) and semi-empirical methods (33-35), and self-consistent field method (SCF) calculations (36-43) to the methods commonly used nowadays (molecular dynamic simulations (31,44,45), density functional theory (DFT) (35,46-49), Moller-Plesset perturbation theory ( ) (50-53), configuration interaction (Cl) (35,42,54-56), coupled cluster (CC) (57,58), and CASSCF/CASPT2 (59-63)). 

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