Abstract
Rhenium(V) iododioxobis(triphenylphosphine) [ReO2I(PPh3)2] proved an effective metal catalyst for living radical polymerization of styrene in conjunction with alkyl iodide as an initiator [R−I: CH3CH(Ph)I, (CH3)2C(CO2Et)I, and CH3CH(CO2Et)I] in the presence of Al(Oi-Pr)3. Compared to RuCl2(PPh3)3, the group 7 complex was highly effective for styrene, so as to induce the living polymerization even at 30 °C to yield well-controlled polystyrene, with M̄n up to ∼4 × 104 and very narrow molecular weight distributions (MWDs) (M̄w/M̄n = 1.19). The polystyrene thus obtained possessed one initiator moiety (R) at the α-end and one iodine atom at the ω-end, both from the initiator R−I, which indicates that the polymerization proceeds via activation of the C−I terminal, derived from R−I, by the Re(V) complex. Addition of methanol or water did not inhibit these polymerizations, while a stable nitroxide radical (TEMPO) immediately and completely quenched them. The quenching experiments thereby supported intervention of radical species in the Re(V)-mediated living polymerization.
Keywords
StyrenePolymerizationNitroxide mediated radical polymerizationPolymer chemistryRadical polymerizationChemistryPolystyreneLiving polymerizationAtom-transfer radical-polymerizationLiving free-radical polymerizationCopolymerPolymerOrganic chemistry
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Publication Info
- Year
- 1999
- Type
- article
- Volume
- 32
- Issue
- 8
- Pages
- 2420-2424
- Citations
- 137
- Access
- Closed
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Cite This
Yuzo Kotani,
Masami Kamigaito,
Mitsuo Sawamoto
(1999).
Re(V)-Mediated Living Radical Polymerization of Styrene: ReO<sub>2</sub>I(PPh<sub>3</sub>)<sub>2</sub>/R−I Initiating Systems.
Macromolecules
, 32
(8)
, 2420-2424.
https://doi.org/10.1021/ma981614f
Identifiers
- DOI
- 10.1021/ma981614f