RATE CONSTANTS OF THE REACTION OF SILYL MACRORADICALS GENERATED BY CHAIN CLEAVAGE OF POLY(DIHEXYL SILYLENE) WITH OLEFINIC MONOMERS

The flash photolysis of poly(dihexyl silylene), PDHeSi, in tetrahydrofuran solution at λ inc = 347 nm (flash length: 20 ns) and ambient temperature yields silyl macroradicals that strongly absorb light at 370 nm. Recording the decay of the optical density at λ obs = 370 nm rate constants of reaction...

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Bibliographic Details
Published in:Journal of macromolecular science. Part A, Pure and applied chemistry Pure and applied chemistry, 1999-08, Vol.36 (4), p.605-619
Main Authors: ALONSO, A., PEINADO, C., LOZANO, A. B., CATALINA, F., ZIMMERMANN, C., SCHNABEL, W.
Format: Article
Language:English
Subjects:
Main-Chain Cleavage
Olefinic Monomers
Poly(Dihexyl Silylene)
Silyl Macroradicals
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Summary:The flash photolysis of poly(dihexyl silylene), PDHeSi, in tetrahydrofuran solution at λ inc = 347 nm (flash length: 20 ns) and ambient temperature yields silyl macroradicals that strongly absorb light at 370 nm. Recording the decay of the optical density at λ obs = 370 nm rate constants of reactions of the silyl macroradicals were measured. The silyl macroradicals undergo a self reaction with a rate constant 2k R+R = 1.9×10 9 dm 3 mol (1 s (1) . Moreover, they are highly reactive towards olefinic monomers. The following rate constants k R+M (in units of dm 3 mol (1 s (1) were determined: 1.6×10 8 , styrene; 1.0 × 10 8 , acrylonitrile; 7.6×10 7 , methyl methacrylate; 6.5×10 7 , vinyl acetate; 1.6×10 7 , butyl acrylate; 7.3×10 6 , methacrylonitrile; < 10 5 , n-butyl vinyl ether.
ISSN:1060-1325
1520-5738
DOI:10.1081/MA-100101551