Abstract
Triphenylmethyl bromide in conjunction with iodine (Ph3CBr/I2 initiator) induced cationic polymerization of p-methoxystyrene (pMOS) in 1,2-dichloroethane at −15°C to yield long-lived (living-like) polymers. The long lifetime of the polymers was indicated by a linear progressive increase of their number-average molecular weight (Mn) with pMOS conversion and the further increase of Mn on the addition of a fresh pMOS feed to a completely polymerized solution. UV/visible spectoscopic analysis showed that iodine promotes the dissociation of Ph3CBr into the triphenylmethyl cation which in turn initiates the polymerization of pMOS. A mixture of triphenylmethyl thiocyanate (Ph3CSCN) and iodine also acted as an initiator for pMOS polymerization; the overall polymerization rate decreased in the following order: Ph3CBr/I2>Ph3CSCN/I2 > I2.
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We have recently found that the living polymerization of vinyl ethers by HI/I2 initiator proceeds in not only nonpolar but polar media such as methylene chloride as well: T. Higashimura, T. Enoki, and M. Sawamoto, to be published.
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Heublein, G., Spange, S., Sawamoto, M. et al. Cationic Polymerization of p-Methoxystyrene by the Triphenylmethyl Bromide/Iodine Initiating System: Formation of Long-Lived Polymers in Polar Solvent. Polym J 17, 1085–1090 (1985). https://doi.org/10.1295/polymj.17.1085
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DOI: https://doi.org/10.1295/polymj.17.1085