Reaction rate of crosslinkings by using metallated polymer. I. Grafting and intramolecular crosslinkings at the first stage

Lithium-metallated styrene–p-benzylstyrene copolymer was reacted with chlorine-terminated polystyrene as a crosslinker polymer in tetrahydrofuran (THF) at 25°C. The rate constant was estimated from the changes in the concentration of metallated polymer by using photometrical measurements. The various reaction conditions were chosen and it became clear that the rate constants of grafting (k₁) and intramolecular crosslinkings (k_2intra) were gotten separately at the first stage. As a result, k_2intra showed larger values than k₁ and decreased with increasing degree of polymerization of crosslinker polymers.