Abstract
Living cationic copolymerization of isobutyl vinyl ether with p-methoxystyrene was effected by an equimolar mixture of hydrogen iodide and iodine (HI/I2 initiator) at −15°C in nonpolar solvents (carbon tetrachloride and toluene). Isobutyl vinyl ether reacted faster than p-methoxystyrene. The products were random copolymers with a nearly monodisperse molecular weight distribution (MWD) (Mw/Mn=1.1–1.2). Their number-average molecular weight (Mn) increased in proportion to total monomer conversion. The iodine-initiated copolymerization under similar conditions led to long-lived (but not perfectly living) copolymers with a narrow MWD (Mw/Mn=1.2–1.3). In contrast, boron trifluoride etherate induced a conventional transfer-dominant copolymerization. The Mn of the copolymers obtained with the HI/I2 initiator was almost independent of the monomer feed ratio, but in the BF3OEt2-initiated non-living process, the polymer molecular weight decreased sharply with increasing isobutyl vinyl ether content in the feed. These findings show the living copolymerization by HI/I2 to be free from the cross-transfer usually involved in the conventional cationic copolymerization of vinyl monomers.
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Since the formula weight of the pMOS repeat unit is greater than that of the IBVE repeat unit (13. vs. 100), the Mn of the pMOS–IBVE copolymers should increase with increasing pMOS content in the feed, if no chain-breaking reactions are involved in the copolymerization. The discrepancy between this expectation and the independence of the observed Mn values on the PMOS/IBVE feed ratio is probably due to that they were determined by SEC on the basis of a polystyrene calibration.
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Sawamoto, M., Ohtoyo, T., Higashimura, T. et al. Living Cationic Copolymerization of Isobutyl Vinyl Ether with P-Methoxystyrene by Hydrogen Iodide/Iodine Initiating System. Polym J 17, 929–933 (1985). https://doi.org/10.1295/polymj.17.929
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DOI: https://doi.org/10.1295/polymj.17.929
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