Solvent effects on free radical polymerization

Heitele, P. Finckh, S. Weeren, F. Pollinger, and M. E. Michel-Beyerle,7. Phys. Chem., 93,325 (1990). 

198 Quantitative Treatments of Solute/Solvent Interactions, P. Pohtzer and J. S. Murray, Eds., Elsevier, Amsterdam, 1994. 

Michelle L. Coote and Thomas P. Davis Centre for Advanced Macromolecular Design, School of Chemical Engineering Industrial Chemistry, The University of New South Wales, 

Free radical polymerization can be conveniently codified according to the classical chain reaction steps of initiation, propagation, transfer and termination. In cases where a significant solvent effect is operative then the effect is normally exerted in all of these steps. However, for the purpose of facilitating discussion this chapter is broken down into these specific reaction steps. 

Solvent effects on the initiation reaction are primarily on the rate of decomposition of initiator molecules into radicals and in the efficiency factor, f, for polymerization. However, in some instances the solvent plays a significant role in the initiation process, for example, in 

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Solvent Effect on Free Radical Polymerization Rate.56... 

The purpose of this review article is to summarize the historical development of the solvent effect on free radical polymerization and to point out possibilities of specific interactions of the propagating radical with solvent. The effect of metal salts on the propagation process will not be described. Emphasis will be laid on the interpretation of experimental results, relating to the influence of aromatic solvents on propagation rate constants, and on the discussion for the molecular interpretation. 

The solvent effect on free radical polymerization is presumed to be due to the following factors ... 

Czerwihski, W. K., Solvent Effects on Free - Radical Polymerization, Makromol. Chem., 1991,192,1285 1 1297. 

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