Reverse Atom Transfer Radical Polymerization of Methyl Methacrylate using a New Catalyst, Copper(II) N , N′ ‐Butyldithiocarbamate

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   p appvalues 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   app #  = 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.