Abstract
Star homopolymers of some vinyl monomers such as methyl methacrylate, n‐butyl methacrylate and styrene (MMA, nBMA, St.) were prepared by using a N,N,N′N′‐tetramethylethylenediamine ligand/CuBr catalytic system via atom transfer radical polymerization (ATRP). A three armed benzene based core was successfully used as initiator. Low polydispersities and regular molecular weight values were obtained in most cases, especially at low conversions. MMA and BMA showed comparable behavior where controlled and true ATRP was observed even at high conversions. However, styrene monomer recorded irregular high polydispersities at high conversions in spite of the relatively low molecular weight values. Some block copolymers were obtained using MMA homopolymer as macroinitiator with the same strategy of ATRP. 1H‐NMR confirmed the structures of the resulting polymers. Transmission electron microscopy (TEM) proved the nano‐structure of the star polymers. The thermal behavior of the MMA star homo and copolymers was studied. The effect of the star shape on thermal behavior was very clear with respect to the linear ones.