Crosslinking during radical polymerization of dodecyl methacrylate

A much more efficient formation of crosslinks was observed in the free‐radical polymerization of dodecyl methacrylate with respect to the amount of decomposed peroxide than it would correspond to the additional peroxide crosslinking of formed poly(dodecyl methacrylate). Polymer crosslinking also proceeds after using 2,2´‐azoisobutyronitrile as initiator of the polymerization of dodecyl methacrylate, although with a substantially lower efficiency compared to the initiation by peroxide under comparable conditions. The efficient formation of crosslinked structures can be explained by branching and copolymerization of monomer with multifunctional dead polymer. Multifunctionality of the formed macromolecules is a result of transfer and addition reactions of the present free radicals with the formed polymer. The difference in the influence of the initiator follows from the higher reactivity of oxy radicals in transfer reactions with monomer dodecyl methacrylate which results in a greater number of polymerizable double bonds built in the polymer chain.