Mechanism and kinetics of thermo-dehydrochlorination of poly(vinyl chloride)
The effect of chain defects in PVC on the rate of thermo-dehydrochlorination (TDHC) has shown that allylic chlorine is a major initiation site during TDHC. On this basis a radical mechanism of TDHC, including initiation, propagation, termination and the generation of new allylic chlorine, is propose...
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| Veröffentlicht in: | Polymer degradation and stability 1988, Vol.22 (1), p.31-41 |
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| Hauptverfasser: | , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
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| Zusammenfassung: | The effect of chain defects in PVC on the rate of thermo-dehydrochlorination (TDHC) has shown that allylic chlorine is a major initiation site during TDHC. On this basis a radical mechanism of TDHC, including initiation, propagation, termination and the generation of new allylic chlorine, is proposed. A kinetic equation for TDHC is deduced:
dξ
dt
=
1000
δ(1−δ)
k
1
∗[H
0]
The probability parameter for the formation of stable polyene sequences, δ, is discussed and a value of 0·154 is obtained for δ from experimental data. The activation energy for TDHC is 117·5 kJ/mol. |
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| ISSN: | 0141-3910 1873-2321 |
| DOI: | 10.1016/0141-3910(88)90054-7 |