Abstract
Cuprous N,N‐Diethyldithiocarbamate, Cu(S~2~CNEt~2~), was successfully used as a catalyst in p‐toluenesulfonyl chloride initiating atom‐transfer radical polymerization of methyl methacrylate in both bulk and solution in a heterogeneous system with 2,2′‐bipyridine as the ligand. The polymerization was controlled under various concentration ratios of the monomer to initiator, the molecular weight matched the predetermined value, and the molecular weight distribution of resulting polymers was quite low (M~w~/M~n~ < 1.10). Solvents with different polarity had no significant effect on the living nature of this process. Well‐defined poly(methyl methacrylate) with α‐p‐toluenesulfonyl and ω‐diethylthiocarbamoylthiyl group was obtained. That the polymer chain was capped with an ultraviolet light sensitive group was confirmed by chain extension reactions.
Dependence of M~n~ and M~w~/M~n~ on the monomer conversion of bulk polymerization of MMA at 80 °C with p‐TsCl/Cu(S~2~CNEt~2~)/bpy initiation system. Conditions the same as in Figure 5.
magnified imageDependence of M~n~ and M~w~/M~n~ on the monomer conversion of bulk polymerization of MMA at 80 °C with p‐TsCl/Cu(S~2~CNEt~2~)/bpy initiation system. Conditions the same as in Figure 5.