An enhanced prepreg for printed circuit board (PCB) laminates includes a substrate and a resin applied to the substrate. The resin includes a curable polymer and a polymerization initiator polymer having a backbone with a free radical initiator forming segment that breaks apart upon being subjected to heat to generate a plurality of non-volatile initiating species. This resin composition eliminates possible volatile loss of the free radical initiator during all processing steps in the preparation of PCB laminates. The resin may additionally include a cross-linking agent, flame retardant and viscosity modifiers. In one embodiment, a sheet of woven glass fibers is impregnated with the resin and subsequently dried or cured. The glass cloth substrate may include a silane coupling agent to couple the resin to the substrate. In another embodiment, resin coated copper (RCC) is prepared by applying the resin to copper and subsequently curing the resin.