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The diffusion coefficients of oligomeric radicals in monomer−polymer systems have a major influence on properties such as polymerization rates and molecular weight distributions. The present work reports the results of an extensive set of studies of diffusion coefficients of rubbery ternary systems comprising polymer, diluent, and oligomer, determined by pulsed-field-gradient NMR, at 25 and 40 °C. Oligomers of methyl methacrylate (MMA) and of butyl methacrylate (BMA) were synthesized by using a catalytic cobalt chain transfer agent to produce macromonomers with a terminal double bond. Where necessary, these were fractionated by preparative GPC to obtain samples ranging from dimeric to decameric; typical polydispersities were 1.08. Pulsed-field gradient NMR is facilitated by being able to monitor the proton NMR of the CH2 hydrogens on the double bond. Matrixes used were high molecular weight polyMMA and polyBMA, the weight fraction of polymer (wp) being varied by adding appropriate amounts of diluent (the saturated equivalents of MMA and BMA, viz., methyl isobutyrate and butyl isobutyrate). Above c* (the concentration at which chains start to overlap), all data for diffusion coefficients Di of an oligomer of degree of polymerization i could be fitted with acceptable accuracy by D1(wp)/Di(wp) = i0.664 + 2.02wp, for both BMA and MMA oligomers in both MMA and BMA matrixes; the same relation also fits earlier data on styrene oligomers in polystyrene. If more accurate scaling parameters are obtained experimentally for smaller oligomers, these can be used to predict data for higher oligomers with even better reliability. For MMA monomer in pMMA, where free-volume parameters are available, the predicted dependences of monomer diffusion coefficient on wp and temperature are in accord with experiment.
Griffiths et al. (Wed,) studied this question.