Immobilization of the copper catalyst in atom transfer radical polymerization

Immobilization of the catalyst system for atom transfer radical polymerization (ATRP) on various silica and cross-linked polystyrene supports was studied. The catalyst system comprises a copper halide, complexed by Various amines. The effect of size of support particles, the amount of immobilized catalyst, and the addition of Cu(II) species as deactivator in the polymerization were investigated. In all cases, polymerization occurred, but generally the reactions were not as well controlled in terms of molecular weight and polydispersities as homogeneous systems. The molecular weights did not match the predicted values, and polydispersities were high (1.5 < M-w/M-n < 10). However, control was improved by either an increase in catalyst concentration or the addition of deactivator still bound to support to the system. Potential reasons for the reduced control could be the low mobility of the supported catalyst and/or the steric hindrance and incompatibilities between the immobilized catalyst and the polymer chain, thus resulting in a less efficient halogen transfer process compared with homogeneous ATRP.