Photoinduced Cu(0)‐Mediated Atom Transfer Radical Polymerization

Abstract

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.

Photo‐mediated metal free atom transfer radical polymerization of acrylamide in water

“…As shown in Figure (b), the M n ,GPC values increased with monomer conversion and agreed with the theoretical values in two cases. Compared with 5 μW/cm 2 , the M n ,GPC values were deviated from the theoretical ones when the light intensity was 3 μW/cm 2 , indicating the low initiation efficiency . Relatively low Đ values were observed in all cases.…”

“…Compared with 5 lW/cm 2 , the M n,GPC values were deviated from the theoretical ones when the light intensity was 3 lW/cm 2 , indicating the low initiation efficiency. 34 Relatively low -D values were observed in all cases. However, the -D values with a light intensity of 5 lW/cm 2 were less than that of 3 lW/cm 2 under the same experimental conditions.…”

In-situ syntheses of graft copolymers by metal-free strategies: combination of photoATRP and ROP

“…Traditional ATRP generally requires low oxidation state copper complexes as catalysts that mediate the process. Attempts have been focused on decreasing the required concentration of these complexes, which include simultaneous chemical reduction10 and photochemical methodologies [10][11][12][13][14][15][16][17]. More recently, several photocatalysts have been developed that mediate ATRP even in the absence of inorganic complexes [18][19][20][21][22][23][24][25].…”

Photoinitiated Metal Free Living Radical and Cationic Polymerizations

“…Combining photoinduced electron transfer reactions developed for the conventional systems with controlled polymerization techniques has recently revolutionized the synthesis of well-defined macromolecular architectures [6]. Many attempts have been devoted to apply photochemical systems to existing controlled/living polymerization methodologies by photochemically effecting initiation, mediation and control of these processes [7][8][9][10][11][12][13][14][15][16][17][18][19].…”