A new well‐defined telechelic macrophotoinitiator of polystyrene was synthesized by combination of ATRP and click chemistry. The ATRP of styrene by means of 2‐oxo‐1,2‐diphenylethyl‐2‐bromopropanoate (PI‐Br) initiator with CuBr/2,2′‐bipyridine yields polystyrene with photoactive benzoin (PI) and bromine (Br) group (PI‐PSt‐Br). Subsequently, PI‐PSt‐Br was converted to PI‐PSt‐N3 by simple nucleophilic substitution reaction. Alkyne functionalized benzoin (PI‐alkyne) was synthesized by using benzoin photoinitiator and propargyl bromide. Then the coupling reaction between PI‐PSt‐N3 and PI‐alkyne was performed by Cu(I) catalysis. The spectroscopic studies revealed that low‐polydispersity polystyrene with desired photoinitiator functionality at both end of the chain, PI‐PSt‐PI, was obtained.
A combination of ATRP and “click” chemistry is employed for efficient preparation of a novel well‐defined mid‐chain functional macrophotoinitiator of polystyrene. Bromo‐terminated polystyrene (PSt‐Br) is prepared by ATRP of styrene using a methyl‐2‐bromopropanoate initiator with CuBr/PMDETA. Subsequently, PSt‐Br is converted to PSt‐N3 by a simple nucleophilic substitution reaction. A dialkyne‐functionalized photoinitiator (alkyne‐PI‐alkyne) is synthesized using a dihydroxy‐functional photoinitiator and propargyl bromide. Then the “click” reaction between PSt‐N3 and alkyne‐PI‐alkyne is performed by Cu(I) catalysis. Spectroscopic studies reveal that low‐polydispersity polystyrene with the desired photoinitiator functionality in the middle of the chain (PSt‐PI‐PSt) is obtained.
In this article, we present the results of a study of the preparation of a cyclohexene oxide (CHO) mid‐chain functional macromonomer via ATRP of styrene (St) and epoxidation on work‐up with 3‐chloroperoxybenzoic acid. The ATRP initiator, Br? CH? Br, was synthesized by the condensation of 3‐cyclohexene‐1,1‐dimethanol with 2‐bromopropanoyl bromide. The ATRP of St with Br? CH? Br and Cu(I)/bpy yielded well‐defined polystyrene with a cyclohexene mid‐chain group (PSt? CH? PSt). Epoxidation of the PSt? CH? PSt was performed using 3‐chloroperoxybenzoic acid. GPC, IR and 1H NMR analyses revealed that a low polydispersity macromonomer of polystyrene with CHO functionality at the mid‐chain (PSt? CHO? PSt) was obtained. The photoinduced cationic polymerization of PSt? CHO? PSt yielded comb‐shaped and graft copolymers.