A novel one-component type II polymeric photoinitiator, poly(vinyl alcohol)-thioxanthone (PVA-TX), is synthesized by a simple acetalization process and characterized. PVA-TX enables photopolymerization of methyl methacrylate and acrylamide in both organic and aqueous media. Photopolymerization proceeds even in the absence of a co-initiator since PVA-TX possesses both chromophoric and hydrogen donating sites in the structure.

A novel polymerization mechanism transformation strategy, combining ring-opening metathesis polymerization (ROMP) and visible light induced cationic polymerization, is successfully applied for the synthesis of polyethylene-graf t-poly(cyclohexene oxide) (PE-g-PCHO). First, cis-cyclooctene (COE) was polymerized via ROMP in the presence of a chain transfer agent and quantitatively hydrobrominated to give bromo functional polyethylene (PEBr). Subsequent irradiation of PE-Br in the visible range using dimanganese decacarbonyl (Mn 2 (CO) 10 ) and diphenyl iodonium hexafluorophosphate (Ph 2 I + PF 6 − ) as radical generator and oxidant, respectively, initiated cationic polymerization of cyclohexene oxide (CHO) resulting in the formation of PE-g-PCHO. The effect of irradiation time and Mn 2 (CO) 10 concentration on the grafting density and efficiency was evaluated. Both the precursor polymers and the corresponding graft copolymers were characterized by 1 H NMR and Fourier transform infrared (FT-IR) spectroscopy, gel-permeation chromatography (GPC), and differential scanning calorimetric (DSC) analyses.

Photoinduced Cu(0)‐mediated atom transfer radical polymerization (ATRP) of methyl methacrylate is investigated by using Cu(0)/N,N,N′,N″,N″‐pentamethyldiethylenetriamine as the catalyst, ethyl 2‐bromopropionate as the initiator, and dimethyl sulfoxide as the solvent. The effect of light on the conventional Cu(0)‐mediated ATRP and molecular weight characteristics of the obtained polymers are described. Although the polymerization can be achieved in the absence of light, low initiation efficiency of the process is observed. By introducing UV light and additional Cu(II) deactivator, not only the rate of polymerization is increased, but also well‐controlled polymers with narrow‐molecular‐weight distributions at ambient conditions are obtained. The chain extension study clearly confirms high end‐group fidelity of the polymer that is active in the further polymerization process.