Abstract: | Solution polymerization of MMA, with pyridine as the solvent and BZ2O2 and AIBN as thermal initiators, was studied kinetically at 60°C. The monomer exponent varied from 0.45 to 0.91 as BZ2O2] was increased from 1 × 10?2 to 30 × 10?2 mole/liter in a concentration range of 8.3-4.6 mole/liter for MMA. For AIBN-initiated polymerization the monomer exponent remained constant at 0.69 as AIBN] varied from 0.4 × 10?2 to 1.0 × 10?2 mole/liter in the same concentration range for MMA. The k2p/kt Value increased in both cases with an increase in pyridine concentration in the system. This was explained in terms of an increase in the kp value, which was due presumably to the increased reactivity of the chain radicals by donor-acceptor interaction between the molecules of solvent pyridine and propagating PMMA radicals and in terms of lowering the kt value for the diffusion-controlled termination reaction due to an increase in the medium viscosity and pyridine content. |