Abstract
The cationic homo- and copolymerizations of geometrical isomers of 2,4-hexadiene by various catalysts in toluene or nitroethane were investigated.The polymers obtained from three geometrical isomers were all of the trans-1,4 structure and the polymerizability of the isomeric monomers increased in the order: trans–trans <cis–cis <cis–trans isomer. With an estimation of activation parameters for this polymerization, the energy diagram for the cationic polymerization of these isomers was shown and reasons for the difference in cationic polymerizabilities were suggested.The monomer reactivity ratio of cis–trans to trans–trans isomers decreased from 1.51 in toluene (nonpolar solvent) to 1.43 in nitroethane (polar solvent). The rate of polymerization is greater in nitroethane than in toluene, as expected for cationic propagation. In the nonpolar solvent, toluene, the decrease of the monomer reactivity ratio and the increase in the polymerization rate for the WCl6 catalyst in comparison with that of BF3O(C2H5)2, suggest that the propagating cation obtained from WCl6 has a freer ionic character than that from BF3O(C2H5)2.The molecular weight of the polymers increased in the order: cis–cis <cis–trans <trans–trans, and this might be ascribed to an easy monomer transfer reaction caused in the most unstable cis–cis isomer and an easy self-termination of the propagating cation obtained from the most unstable cis–cis isomer.
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Kamachi, M., Matsumura, K. & Murahashi, S. The Polymerization of 2,4-Hexadiene. III. Cationic Polymerizability of 2,4-Hexadiene Isomers. Polym J 1, 499–504 (1970). https://doi.org/10.1295/polymj.1.499
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DOI: https://doi.org/10.1295/polymj.1.499
