Abstract
Anionic copolymerization of β-cyanopropionaldehyde (CPA, M1) with dimethylketene (DMK, M2) initiated by benzophenone-dilithium complex was carried out at 0°C and −78°C. The values of monomer reactivity ratio at −78°C were determined to be r1=0.6±0.1 and r2=0.04±0.03. The structure of the resulting copolymer was investigated by means of IR and NMR analyses. The main structure of the copolymer was found to consist of sequence I formed through the alternating addition of the C = O bond of CPA with the C = C bond of DMK. The copolymer which is rich in the CPA component is believed to contain sequence II in addition to I, but the former must be extremely limited. The DMK-rich copolymer has sequence III in addition to I.
These facts suggest that the selectivity of elementary reactions in the copolymerization process is relatively high but not complete, which might be explained in terms of the different preferable forms of ambident anions.
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Hashimoto, K., Sumitomo, H. Polymerization of β-Cyanopropionaldehyde. VIII. Anionic Copolymerization with Dimethylketene. Polym J 1, 190–197 (1970). https://doi.org/10.1295/polymj.1.190
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DOI: https://doi.org/10.1295/polymj.1.190