We report a simple, rapid, and solvent-free methodology for solid-state polymerizations yielding poly(phenylene vinylenes) (PPVs) promoted by ball-milling. This solid-state Gilch polymerization method produces PPVs in as little as five minutes of milling. Detailed investigations of the parameter space governing the solid-state polymerization, i.e., milling time, base strength, solid-state dilution, milling frequency, and size of milling balls, revealed that polymerization by ball-milling is a rapid process achieving molecular number average weights of up to 40 kDa in up to 70% yield. To explore the scope, a solid-state polymerization via the dithiocarbamate precursor route is explored.
