Ability of nitrones of various structures to control the radical polymerization of styrene mediated by in situ formed nitroxides
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Sciannamea, Valerie; Guerrero-Sanchez, Carlos; Schubert, Ulrich S.; Catala, Jean-Marie; Jerome, Robert; Detrembleur, Christophe
- Abstract:
- The ability of several nitrones to control the radical polymerization of styrene at 110 8C has been investigated by high-throughput
experimentation. The nitrone/free radical initiator pair dictates the structure of the nitroxide and the alkoxyamine formed in situ, which
determines the position of the equilibrium between the active and the dormant species operating in the nitroxide-mediated polymerization.
For the styrene polymerization to be controlled, the nitrone must be reacted with 2,20-azo-bis-isobutyronitrile (AIBN) at 85 8C, prior to
addition of styrene and polymerization at 110 8C. The effect of the nitrone structure on the kinetics of the styrene polymerization has been
emphasized. Amongst all the nitrones tested, those of the C-phenyl-N-tert-butylnitrone (PBN) type are the most efficient in terms of
polymerization rate, control of molecular weight and polydispersity. Electrophilic substitution of the phenyl group of PBN by either an
electrodonor or an electroacceptor group has only a minor effect on the polymerization kinetics. Importantly, the polymerization rate is not
governed by the thermal polymerization of styrene but by the alkoxyamine formed in situ during the pre-reaction step. The initiation
efficiency is, however, very low, consistent with a limited conversion of the nitrone into nitroxide and alkoxyamine.
- Year:
- 2005
- Type of Publication:
- Article
- Journal:
- Polymer
- Volume:
- 46
- Pages:
- 9632 - 9641