Control of Radiation/Living Graft Polymerization in the Solid State

Abstract

AbstractA novel approach for the preparation of well‐defined graft polymers is applied to poly(ether ether ketone) (PEEK) substrates, using a combination of radiation‐induced graft polymerization (RIGP) and atom transfer radical polymerization (ATRP). The ATRP of styrene (St) and styrene sulfonic acid ethyl ester (ETSS) has successfully proceeded from the macroinitiators, which are introduced by RIGP of chloromethylstyrene in the solid‐state PEEK substrates at 50 °C under conditions where no thermal polymerization takes place. By optimizing the catalyst concentration, the grafting degree of St and ETSS increases linearly up to ≈112 and 381%, followed by a unique rapid increase at a speed similar to that observed in solution ATRP. The living nature of the propagating radicals at the terminal of grafted polymers is confirmed by successive ATRP of St from the St‐grafted PEEK films, which are isolated after an initial round of ATRP of St.