Abstract
The microstructures of addition polymers composed of 1,4-benzenedithiol (BDT) and 1,4-diethynylbenzene (DEB) were studied by IR method. As model compounds for the assignment of the IR spectra, the compound [A] cis-cis and the compound [B] trans-trans were used
The characteristic absorption peak of the cis-linkage of the model compounds was assigned to be 1350 cm−1 (ε in 1 mol−1cm−1; 122.1 in CCl4) and that of the trans-linkage was 940 cm−1 (ε in 1 mol−1cm−1; 311.6 in CCl4) in the IR spectra. The microstructures of the polymers were quantitatively estimated by the following equations.
Ccis=7.80 ×10-3 D1350-2.10 ×10-4 D940and Ctrans=3.20 ×10 -3 D940-3.21 ×10-4 D1350
where Ccis and Ctrans mean the concentrations of the cis- and the trans-linkage in the polymers, and D1350 and D940 are the absorbances of the cis-linkage at 1350 cm−1 and the trans-linkage at 940 cm−1, respectively. The microstructures of polymers obtained in the toluene solution under UV-irradiation were found to be mainly the cis-structure, regardless of the polymerization temperature (0°C, cis 95%; 60°C, cis 88%). However, the cis-contents of the polymers obtained in solid state under UV-irradiation decreased with increasing polymerization temperature (0°C, cis 94%; 60°C, cis 81%; 80°C, cis 73%). The polymerization mechanism in the solid state may differ from that in solution. The arrangement and mobility of the reacting molecules in the crystalline solid probably affect the opening mode of the acetylenic triple bond. These phenomena are briefly discussed.
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Kobayashi, E., Ohashi, T. & Furukawa, J. Microstructure of an Addition Polymer Composed of 1,4-Benzenedithiol and 1,4-Diethynylbenzene. Polym J 21, 111–117 (1989). https://doi.org/10.1295/polymj.21.111
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DOI: https://doi.org/10.1295/polymj.21.111
