Synthesis of well-defined polychlorostyrenes by living radical polymerization with 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl

Abstract

Radical polymerization of 2‐, 3‐, and 4‐chlorostyrenes (ClSts) was investigated with benzoyl peroxide (BPO) as an initiator, in the presence of 4‐methoxy‐2,2,6,6‐tetramethylpiperidine‐1‐oxyl (MTEMPO). The polymerization was performed in bulk for 3.5 h at 95°C and then continued for a defined time at 125°C to give the corresponding poly(ClSt)s with narrow polydispersity in high yield. It was found that the polymerization proceeded in accordance with a living mechanism in all cases, because the molecular weight of the resulting polymers was proportional to the conversion, and inversely proportional to the initial concentration of MTEMPO. Furthermore, the polymers obtained from 2‐ and 3‐ClSts quantitatively act as initiators for the polymerization in the living radical manner, of styrene to give the corresponding block copolymers, except for poly(4‐ClSt). The thermal stability of the living poly(ClSt)s was found to decrease in the order of 2‐ > 3‐ > 4‐ClSt on the basis of the results of their postpolymerizations. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2371–2378, 1997

Synthesis and characterization of the novel block copolymer poly(ε‐caprolactone)‐b‐poly(4‐vinyl pyridine) by the combination of coordination and controlled free‐radical polymerizations

“…In this way, the merits of various techniques can be combined, and more block polymers that can be hardly or trivially prepared via one mechanism become available. Because the applicable monomers have been expanded from the traditional styrene and its derivatives8, 9 to acrylic esters10 and some amine‐containing monomers, including dimethylacrylamide and vinyl pyridine,11, 12 in recent years, nitroxide‐mediated free‐radical polymerization, typically with 2,2,6,6‐tetramethylpiperidinyloxy (TEMPO) as the initiator, has become a versatile method for preparing polymers with well‐controlled molecular weights and narrow polydispersities. Also, the technique can be successfully used to make block copolymers.…”