A block copolymer is synthesized by polymerizing a silane-functionalized norbornene monomer in the presence of a catalyst system that includes a Ziegler-Natta catalyst and cocatalyst, followed by sequential addition and polymerization of a matrix-reactive functionalized norbornene monomer. In some embodiments, an enhanced substrate for a PCB is produced by applying the block copolymer to a substrate that includes glass fiber, followed by applying the base polymer to the substrate having the block copolymer applied thereto.