A macrocyclic aromatic thioether ketone: synthesis, structure and anionic ring-opening polymerisation

Abstract

Nucleophilic polycondensation at high concentration between benzene-1,3-dithiol and 4,4′-difluorobenzophenone affords not only linear polymer1 but also a significant yield (ca. 8%) of cyclic oligomers, mainly the [2+2] cyclodimer 2. Under high-dilution conditions 2 becomes by far the major reaction product. Macrocycle 2 has been isolated, structurally characterised by single-crystal X-ray methods and found to undergo rapid anionic ring-opening polymerisation in the melt (330–360 °C), affording a linear, high molecular weight poly(arylthioether ketone).

References

1. (a) J. A. Cella, J. J. Talley and J. M. Fukuyama, Polym. Prepr. Am. Chem. Soc., Div. Polym. Chem., 1989, 30(2), 581; (b) J. A. Cella, J. M. Fukuyama and T. L. Guggenheim, Polym. Prepr. Am. Chem. Soc., Div. Polym. Chem., 1989, 30(2), 142.
2. H. M. Colquhoun, C. C. Dudman, M. Thomas, C. A. O'Mahoney and D. J. Williams, J. Chem. Soc., Chem. Commun., 1990, 336.
3. (a) M. J. Mullins, E. P. Woo, D. J. Murray and M. T. Bishop, CHEMTECH, 1993,(August), 25; (b) D. Xie and H. W. Gibson, Polym. Prepr. Am. Chem. Soc., Div. Polym. Chem., 1994, 35(1), 401; (c) K. P. Chan, Y.-F. Wang, A. S. Hay, X. L. Hrnowski and R. J. Cotter, Macromolecules, 1995, 28, 6705; (d) Y. Ding and A. S. Hay, Macromolecules, 1996, 29, 3090 and references cited therein.
4. High Performance Polymers: Their Origin and Development, ed. R. B. Seymour and G. S. Kirshenbaum, Elsevier, New York, 1986.
5. Y.-F. Wang, K. P. Chan and A. S. Hay, Macromolecules, 1996, 29, 3717.
6. Y. E. Ovchinnikov, V. I. Nedelkin, S. I. Ovsyannikova and Y. T. Struchkov, Russ. Chem. Bull., 1994, 43, 1384.
7. H. M. Colquhoun, C. A. O'Mahoney and D. J. Williams, Polymer, 1993, 34, 218.
8. K. Hasebe, T. Asahi, A. Ishazawa and K. Izumi, Acta Crystallogr., Sect. C., 1989, 45, 2023.