In situ Cu(0) catalyzed SET-LRP: The first attempt.

In this work, single electron transfer-living radical polymerization (SET-LRP) was catalyzed by in situ Cu(0) generated from copper sulphate pentahydrate (CuSO4·5H2O) and hydrazine hydrate (N2H4·H2O) at 25 °C. The polymerization occurred smoothly with moderate controllability: the polymerization rates increased by the increases of N2H4·H2O, and the initiator concentration had an optimal value on the polymerization rate; the number-average molecular weights ( Mn,GPC) increased with monomer conversions and polydispersities were below 1.40. The Mn,GPC deviated much from theoretical ones with about 50% polymer chain-end fidelities. Some side reactions stemming from the strong reduction performance of N2H4·H2O were responsible for the mildly controlled polymerizations. This polymerization can be conducted in SET-LRP unfavorable solvents or in bulk, such as toluene and tetrahydrofuran, owing to the H2O contained in CuSO4·5H2O and N2H4·H2O. On account of the utilization of CuSO4·5H2O, an inactive Cu(II) compounds in LRP area, this work confirmed from experimental level that it was Cu(0) which acted as activator and mediator in SET-LRP. This work provided a first example of in situ Cu(0) catalyzing SET-LRP with CuSO4·5H2O as a copper source. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 [ABSTRACT FROM AUTHOR]