Radical ring-opening copolymerization of 2-methylene 1,3-dioxepane and methyl methacrylate: Experiments originally designed to probe the origin of the penultimate unit effect
Ge. Roberts et al., Radical ring-opening copolymerization of 2-methylene 1,3-dioxepane and methyl methacrylate: Experiments originally designed to probe the origin of the penultimate unit effect, MACROMOLEC, 32(5), 1999, pp. 1332-1340
Pulsed-laser polymerization experiments were conducted on the copolymerizat
ion of 2-methylene 1,3-dioxepane (MDO) and methyl methacrylate (MMA) at 40
degrees C. Reactivity ratios, based on the terminal model, were determined
from copolymer compositional analyses as r(MDO) = 0.057 and r(MMA) = 34.12.
The average propagation rate coefficients, [k(p)], were determined for a n
umber of feed compositions ranging from an MDO mole fraction of 0 to 0.916.
It was not possible to obtain a [k(p)] value for the homopolymerization of
MDO as the PLP experiment was compromised by high chain transfer rates to
polymer and monomer. The data mere fitted to a number of copolymerization m
odels, viz, the terminal and the explicit and implicit penultimate unit mod
els and the bootstrap solvent dependence model. It was found that the termi
nal and penultimate unit models for copolymerization could not adequately d
escribe the experimental results. A fit to a bootstrap model was successful
, but the values obtained indicated a very large, unprecedented, partitioni
ng effect.