Abstract
Anionic copolymerizations of trans-stilbene (M2) with butadiene (M1), isoprene (M1), and 2,3-dimethylbutadiene (M1) were studied in tetrahydrofuran (THF) at 0°C and in benzene at 40°C by means of n-butyllithium (n-BuLi) as an initiator. All the copolymerizations in THF gave alternating copolymers, and the rate of the consumption of M1 decreased as follows: butadiene>isoprene>2,3-dimethylbutadiene. The copolymerizations with isoprene and 2,3-dimethylbutadiene in THF spontaneously stopped, and the unchanged M1 monomers remained when the concentration of n-BuLi was low, where the final yields were lower in the copolymerization with 2,3-dimethylbutadiene with the same concentration of n-BuLi. The final yields increased with an increase in n-BuLi and decreased with increasing [M2]0/[M1]0 ratio. The copolymerization with butadiene was completed without the remaining M1 monomer. In all cases the electronic spectra of the reaction mixtures in THF showed no peak near 540 mμ in the initial stage of the reactions, but a new peak appeared near 540 mμ in time. The order of the optical densities of the peak after a prolonged time was 2,3-dimethylbutadiene>isoprene>butadiene. The microstructures of the dienes in the homopolymers and alternating copolymers which were polymerized in THF were determined by NMR spectroscopy. The alternating copolymers had more 1,4-structure than the corresponding homopolymers, and the 1,4-content in the formers decreased in the following order: 2,3-dimethylbutadiene>isoprene>butadiene. The dienes, however, were completely consumed in the copolymerizations in benzene. In the copolymerizations with butadiene and isoprene, little trans-stilbene was incorporated into the copolymers, but a considerable amount of trans-stilbene was copolymerized with 2,3-dimethylbutadiene.
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Yuki, H., Okamoto, Y., Tsubota, K. et al. Anionic Copolymerizations of trans-Stilbene with Butadiene, Isoprene, and 2,3-Dimethylbutadiene. Polym J 1, 147–154 (1970). https://doi.org/10.1295/polymj.1.147
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DOI: https://doi.org/10.1295/polymj.1.147
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