The reaction of Wilkinson's salt, CIRh(PP₃₎₃, and poly(methyl methacrylate) (PMMA) has been studied. Char formation is observed, and some 30% of the reaction product is nonvolatile at 600°C. In order to understand the pathway of this reaction, the reaction of dimethylglutarate (DMG) and CIRh(PP₃)₃ has been studied. A pathway is proposed in which the initial step is the oxidative addition of the rhodium species into a carbon—oxygen bond of the DMG molecule. Six different products have been isolated from this reaction and can be seen to result from the oxidative insertion. This pathway also seems to apply to the PMMA reaction and leads to an interpretation of the results of this reaction and permits one to understand the role of this, and similar, compounds as flame retardants.

References

1 N. Grassie and H. W. Melville, Disc. Far. Soc., 2, 378 (1947).
10.1039/df9470200378
Web of Science® Google Scholar
2 N. Grassie and H. W. Melville, Proc. Roy. Soc. Lond. A., 199, 14 (1949).
10.1098/rspa.1949.0122
CAS Web of Science® Google Scholar
3 N. Grassie and H. W. Melville, Proc. Roy. Soc. Lond. A., 199, 24, (1949).
10.1098/rspa.1949.0123
CAS Web of Science® Google Scholar
4 H. H. G. Jellinek and M. D. Luh, J. Phys. Chem., 70, 3632 (1966).
10.1021/j100883a051
Web of Science® Google Scholar
5 I. C. McNeill, Eur. Polym. J., 4, 21 (1968).
10.1016/0014-3057(68)90004-9
CAS Web of Science® Google Scholar
6 G. Bagby, R. S. Lehrley, and J. C. Robb, Polymer, 10, 83 (1969).
10.1016/0032-3861(69)90087-1
Web of Science® Google Scholar
7 R. J. Gritter, M. Seeger, and D. E. Johnson, J. Polym. Sci., Polym. Chem. Ed., 16, 169 (1978).
10.1002/pol.1978.170160117
CAS Web of Science® Google Scholar
8 F. Cullis and M. M. Hirschler, The Combustion of Organic Polymers, Clarendon, Oxford, 1981, p. 139–141.
Google Scholar
9 I. C. McNeill, in Developments in Polymer Degradation, N. Grassie Ed., Applied Science, London, 1977, Vol. 1, p. 43.
Google Scholar
10 S. L. Madorsky, Thermal Degradation of Organic Polymers, Wiley, New York, 1964.
Google Scholar
11 J. R. MacCollum, Makromol. Chem., 83, 137 (1965).
10.1002/macp.1965.020830111
Google Scholar
12 W. H. Starnes, Jr., in Developments in Polymer Degradation, N. Grassie, Ed., Applied Science, London, 1981, Vol. 3, p. 135.
Google Scholar
13 S. J. Sirdesai and C. A. Wilkie, J. Appl. Polym. Sci., to appear.
Google Scholar
14 J. J. Maurer, D. J. Eustace, and C. T. Ratcliffe, Macromolecules, 20, 196 (1987).
10.1021/ma00167a035
CAS Web of Science® Google Scholar
15 M. Lewin, Z. Aizenstat, and J. Blum, J. Organometal. Chem., 184, 255 (1980).
10.1016/S0022-328X(00)83492-0
CAS Web of Science® Google Scholar
16 R. L. Augustine and J. E. Van Peppen. J. Chem. Soc., Chem. Commun., 1970, 1486.
Google Scholar
17 C. Dudley and G. Read, Tet. Let., 1972, 5273.
Google Scholar
18 T. Suebsaeng, C. E. Brown, and C. A. Wilkie, J. Polym. Sci., Polym. Chem. Ed., 26, 2705 (1988).
10.1002/pola.1988.080261007
CAS Web of Science® Google Scholar
19 J. A. Landgrebe, in Theory and Practice in the Organic Laboratory, 2nd ed., D. C. Heath, Lexington, MA, 1977.
Google Scholar
20 W. Kiem, J. Organometal. Chem., 14, 179 (1968).
10.1016/S0022-328X(00)92654-8
Web of Science® Google Scholar
21 A. J. Deeming and B. L. Shaw, J. Chem. Soc. A, 1969, 597.
Google Scholar
22 A. M. Abeysekera, R. Grigg, J. Trocha-Grimshaw, and V. Viswanatha, J. Chem. Soc. Perkin I, 1977, 1395.
Google Scholar
23 R. T. Conley, in Infrared Spectroscopy, 2nd ed., Allyn and Bacon, Boston, 1972.
Google Scholar
24 J. W. Diesveld, E. M. Menger, H. T. Edzes, and W. S. Veeman, J. Am. Chem. Soc., 102, 7936 (1980).
10.1021/ja00547a021
Web of Science® Google Scholar
25 R. C. Dickson, in Organometallic Chemistry of Rhodium and Iridium, Academic, New York, 1983.
Google Scholar
26 P. Hughes, in Comprehensive Organometallic Chemistry, Pergamon, New York, Vol. 5.
Google Scholar
27 F. Faraone, J. Chem. Soc., Dalton Trans., 1975, 541.
Google Scholar
28 G. Camino, N. Grassie, and I. C. McNeill, J. Polym. Sci., Polym. Chem. Ed., 16, 95 (1978).
10.1002/pol.1978.170160110
CAS Web of Science® Google Scholar
29 W. C. Still, M. Kahn, and A. Mitra, J. Org. Chem., 43, 2923 (1978).
10.1021/jo00408a041
CAS Web of Science® Google Scholar

Citing Literature

Volume37, Issue6

20 February 1989

Pages 1595-1603

Mechanism of poly(methyl methacrylate) fire retardation by Wilkinson's salt

Abstract

References

Citing Literature

References

Information

About Wiley Online Library

Help & Support

Opportunities

Connect with Wiley

Mechanism of poly(methyl methacrylate) fire retardation by Wilkinson's salt

Abstract

References

Citing Literature

References

Related

Information