Analytical Pyrolysis Of Synthetic Organic Polymers by Serban C. Moldoveanu

By Serban C. Moldoveanu

Analytical Pyrolysis of artificial natural Polymers is a follow-up to Analytical Pyrolysis of normal natural Polymers, that is quantity 20 of the sequence. the main target of the booklet is on useful purposes of analytical pyrolysis in artificial natural polymer id and characterization.

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CH ~CH ~CH ~ C H~ ',, ,cH~CH2~GH/CH2~GH~ CH3 ,, '"CHj ~CH2 /CH2 ~Cl-I" ~3H~GH2~cH~cH3 /CH 2 jCH2 "CH ~CH ~ C H " ,,' ,,, "CH/CH2"~'CH/CH2 Since larger free radicals are more stable than those with small molecules, the fragmentation in the middle of the polymeric chain is favored thermodynamically compared to the formation of small molecules. However, kinetic factors also may play a role in determining the abundance of a specific compound. The formation of small radicals from the end of a polymeric chain can be kinetically favored, and, as a result, formation of small radicals in the initiation step is more common than expected based on the thermodynamic criteria.

The nucleophilic substitution takes place with the attack of a reagent that brings an electron pair to the substrate. This pair is used to form a new bond. The leaving group retains its electron pair. Decarboxylation mechanism of aromatic acids is probably an electrophile substitution. Free radical substitutions are very common in pyrolytic reactions. An example of this type is the formation of biphenyl from benzene above 700 ~ C. This reaction can be viewed as an oxidation because of the hydrogen elimination.

P. C. Uden, Nomenclature and Terminology for Analytical Pyrolysis (IUPAC recommendations 1993), J. Anal. Appl. , 31 (1995) 251. 16. W. J. Irwin, J. Anal. Appl. , 1 (1979) 3. 17. W. J. Irwin, J. Anal. Appl. , 1 (1979) 89. 18. W. W. Wendland, Thermal Analysis, J. Wiley, New York, 1986 W. W. Wendland, Thermal Analysis, J. Wiley, New York, 1986. 19. L. S. Ettre, A. Zlatkis, The Practice of Gas Chromatography, Interscience, New York, 1967. 20. C. P. Fenimore, F. J. Martin, Modern Plastics 44 (1966) 141.

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