Synthesis of a well-defined polybromostyrene by living radical polymerization with a nitroxyl radical

Abstract

Radical polymerization of p‐bromostyrene 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 another 48 h at 125°C to afford the corresponding polybromostyrene with a narrow molecular weight distribution in high yield. 1H NMR study revealed that the polymer obtained had BPO and MTEMPO moieties at its head and tail, respectively. It was confirmed that the polymerization proceeded in accordance with living mechanism, because the molecular weight linearly increased with an increase of the conversion, and it was directly proportional to the reciprocal of the initial concentration of BPO. Furthermore, the polystyrene obtained in the present study could quantitatively act as the initiator for the polymerization of p‐bromostyrene in the living radical manner to afford the corresponding block copolymer, and vice versa. © 1996 John Wiley & Sons, Inc.

Halogeno‐modified polystyrene: monomer reactivity ratios, thermal behaviour and flammability

“…The homopolymers (PSt, PClSt, PBrSt and P5FSt) were obtained according to the procedure described in the literature . Monomer St (3.6 g, 34.6 mmol) or ClSt (1.2 g, 8.3 mmol) or BrSt (0.7 g, 3.8 mmol) or 5FSt (2.8 g, 14 mmol) was placed into a two‐necked flask.…”

Synthesis of polystyrene modified with fluorine atoms: Monomer reactivity ratios and thermal behavior

“…The homopolymers (PSt and PFSt) were obtained according to the procedure described in the literature . The monomer St (3.6 g, 34.6 mmol) or FSt (1.0 g, 8.4 mmol) and the initiator [0.5 or 1.0 mol% initiator (AIBN)] were placed into a two‐necked flask and then content was degassing and flushing by inert gas.…”

Controlled-Growth Free-Radical Polymerization of Methacrylate Esters: Reversible Chain Transfer versus Reversible Termination

“…The process relies on the use of a reagent (Ν·) which reversibly caps the propagating species (R-(M) n ») by radical-radical combination. Reagents that have been employed include various stable radicals, for example: Ν· = nitroxides (5,(13)(14)(15)(16)(17)(18)(19)(20)(21)(22) di -or triarylmethyl radicals (23)(24)(25)(26)(27) dithiocarbamyl radicals (72,(28)(29)(30)(31)(32)(33)(34)(35) borinate radicals (36) verdazyl radicals (37) triazolinyl radicals (38) inorganic radicals (39) and organometallic reagents, for example: Ν· = square planar cobalt complexes (40)(41)(42) organo aluminum complexes (43,44) One of the most widely studied processes is alkoxyamine-initiated polymerization (in this case Ν· is a nitroxide) (75). However, while many papers have now appeared on the synthesis of narrow polydispersity polystyrene and derivatives (5,(16)(17)(18)(19)(20)(21)(22), relatively little has appeared on the synthesis of other polymers.…”