Pure and Applied Chemistry

Abstract: A new concept for photodegradable cross-linked polymers utilizing characteristics of rotaxane cross-links and aromatic disulfides is proposed. The cross-linked polymer is obtained by the radical polymerization of a vinyl monomer in the presence of a [3]rotaxane-type cross-linker having two radically polymerizable groups. The [3]rotaxane-type cross-linker was prepared in 93 % yield by the typical rotaxane-forming reaction using a dumbbell-shaped aromatic disulfide possessing a bis(ammonium salt) moiety and a crown ether wheel tethered by a hydroxymethyl group (96 %) and the subsequent vinyl group-endowment (80 %). The radical polymerization of methyl methacrylate (MMA) in the presence of the cross-linker (0.1 mol %) at 60 °C afforded solvent-insoluble polymer in 90 % yield. When the polymer was swollen to a gel in dimethylformamide (DMF) and a small part of the gel was UV-irradiated, the gel was promptly solubilized, probably via the photochemical scission of the S–S linkage of the interlocked aromatic disulfide, causing the efficient decomposition of the rotaxane cross-links. The recovered poly(methyl methacrylate) bearing a small amount of crown ether moiety has a molecular weight of M_n 170 kg/mol (M_w/M_n 2.1) that indicated the occurrence of the site-selective photodegradation.