Advanced Organic Chemistry. Structure and Mechanisms by Carey F., Sundberg R.

February 23, 2017 | Organic Chemistry | By admin | 0 Comments

By Carey F., Sundberg R.

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One of the most promising mass spectral techniques used in polymer analysis is matrix-assisted laser desorption ionization-mass spectroscopy or MALDI (typically done using a time-of-flight spectrometer and known as MALDI-TOF) [11]. In MALDI the analytes are not directly ionized. Only the matrix made from an aromatic compound containing oxo, hydroxyl, and carboxyl groups is ionized with the laser beam, followed by the charge transfer to the analyte. The technique offers a mild ionization for the macromolecules and an excellent way of polymer analysis.

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. Some pyrolytic reactions can be seen as a reverse (retrograde) addition. Diels-Alder reaction for example is known to be reversible, and retro Diels-Alder reactions are rather common. The retro-ene reaction (retro hydro-allyl addition) also can take place with the following mechanism: CH oH " H "'" Retro-aldol condensations also are known to take place during pyrolysis.

Ettre, A. Zlatkis, The Practice of Gas Chromatography, Interscience, New York, 1967. 20. C. P. Fenimore, F. J. Martin, Modern Plastics 44 (1966) 141. 21. E. M. Anderson, I. Ericsson, J. Anal. Appl. , 2 (1980) 97. 22. H. Itagaki, K. Horie, I. Mito, Prog. Polym. , 15 (1990) 361. 1 THE CHEMISTRY OF POLYMER THERMAL DECOMPOSITION - General aspects Thermal decomposition of polymers is a subject of considerable interest for many practical purposes. 6, a number of analytical techniques including analytical pyrolysis are used for polymer thermal characterization.

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