第2章-聚合物燃烧与成炭-2010.pptVIP

* * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * 北京理工大学 Gelation studies Mixtures containing 10 wt.% of additive in PVC were produced by low-temperature grinding. Gelation studies on the PVC/additive mixtures were carried out via solvent-free pyrolysis for 1 h at 190 ℃ under flowing argon. The soluble portion of residues was removed by Soxhlet extraction with THF (tetrahydrofuran). Following extraction, the crosslinked gel residue was recovered, dried, and weighed. Since additive-free control samples show no gelation under these conditions, formation of a gel indicates that the additive is promoting PVC crosslinking. 2.5 烟的形成及抑制 北京理工大学 2.5 烟的形成及抑制 北京理工大学 2.5 烟的形成及抑制 北京理工大学 2.5 烟的形成及抑制 北京理工大学 A conclusive answer to this question is, at present, unavailable. Nevertheless, we do know that synergism usually results from the operation of different mechanisms that are mutually reinforcing, and that several mechanisms of smoke suppression can be envisaged for the system under discussion. These include a Lewis-acid-promoted crosslinking caused by one or both of the additives themselves or by acids such as CuCl2, SnCl4, and MoO2Cl2 that may be formed in situ. Another possibility is reductive crosslinking brought about by Cu(0), which could either be formed directly or result from the valence disproportionation of Cu(I): 2Cu(I)?Cu(II)+Cu(0). Why does the synergism for smoke suppression occur with the copper additives? 2.5 烟的形成及抑制 北京理工大学 Conclusions Gelation data for PVC/copper-additive samples have strongly supported the theory that copper produces crosslinking in pyrolyzing PVC samples. Neither the original oxidation state of the metal nor the copper content of the additive appear to be particularly important in determining the degree of crosslinking. However, copper oxide compounds produce relatively high degrees of crosslinking. The cone ca