Atom Transfer Radical Polymerization in the Solid‐State

Poly(2‐vinylnaphthalene) was synthesized in the solid‐state by ball milling a mixture of the corresponding monomer, a Cu‐based catalyst, and an activated haloalkane as the polymerization initiator. Various reaction conditions, including milling time, milling frequency and added reductant to accelerate the polymerization were optimized. Monomer conversion and the evolution of polymer molecular weight were monitored over time using (1)H NMR spectroscopy and size exclusion chromatography, respectively, and linear correlations were observed. While the polymer molecular weight was effectively tuned by changing the initial monomer‐to‐initiator ratio, the experimentally measured values were found to be lower than their theoretical values. The difference was attributed to premature mechanical decomposition and modeled to accurately account for the decrement. Random copolymers of two monomers with orthogonal solubilities, sodium styrene sulfonate and 2‐vinylnaphthalene, were also synthesized in the solid‐state. Inspection of the data revealed that the solid‐state polymerization reaction was controlled, followed a mechanism similar to that described for solution‐state atom transfer radical polymerizations, and may be used to prepare polymers that are inaccessible via solution‐state methods.