The molecular weight distribution for living polymerization confined to a surface with little or no monomer diffusion is very different from that in solution. At low [initiator]/[monomer] (I/M), the average number of monomers consumed per initiator (Xn) reaches a limiting value of 72 with polydispersity index = 1.50, because the active chain end is boxed-in intramolecularly by its own growing chain. Large amounts of monomers remain unreacted. At higher I/M, Xn decreases further because the active chain end is boxed-out intermolecularly (from pools of monomers) by other propagating chains. In particular, 1/Xn = 0.0133 + 0.9 I/M, and monomer conversion is Xn = 75 – 2/3 x percent conversion. For nonliving polymerization, Xn is limited to 8 &lt; Xn &lt; 72, for the entire I/M range, regardless of the kinetic parameters.

Box effects in nonliving and living polymerization of slow or non-diffusing monomers confined to a 2D surface

251st National Meeting (2016)

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