Abstract
Summary: The homogeneous bulk reverse ATRP using AIBN/Cu(SC(S)N(C~4~H~9~)~2~)~2~/bpy as the initiating system has been successfully carried out for methyl methacrylate. Well‐controlled polymerizations with low polydispersities ($\overline M _{\rm w} /\overline M _{\rm n}$ = 1.10–1.30) have been achieved. The revised number‐average molecular weights ($\overline M _{{\rm n}({\rm rev})}$'s) increased linearly with monomer conversion and were close to the $\overline M _{{\rm n}({\rm th})}$ values. The polymerization rate followed the first‐order kinetics in monomer, while it is about 2.0 order in initiator concentration and 1.15 order in Cu(II) concentration. The k values for the homogeneous bulk reverse ATRP of MMA initiated by AIBN/Cu(SC(S)N(C~4~H~9~)~2~)~2~/bpy (1:2:6) at 80, 90, 100 and 110 °C were 0.402 × 10^−4^, 1.021 × 10^−4^, 2.952 × 10^−4^, and 3.687 × 10^−4^ (s^−1^), respectively. On the basis of the Arrhenius plot, the apparent activation energy was calculated to be ΔE = 87.1 kJ/mol. The obtained PMMA was functionalized with an ultraviolet light sensitive ω‐SC(S)N(C~4~H~9~)~2~ group characterized by means of ^1^H NMR spectroscopy, and which was also proved by its chain extension with fresh MMA under UV‐light irradiation at room temperature. A polymerization mechanism for this novel initiation system is proposed.
Dependence of $\overline M _{{\rm n}({\rm rev})}$ and $\overline M _{\rm w} /\overline M _{\rm n}$ on the monomer conversion for the homogeneous bulk reverse ATRP of MMA at different concentration of catalyst.
magnified imageDependence of $\overline M _{{\rm n}({\rm rev})}$ and $\overline M _{\rm w} /\overline M _{\rm n}$ on the monomer conversion for the homogeneous bulk reverse ATRP of MMA at different concentration of catalyst.