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Polymer reactions, 8.Oxidative pyrolysis of poly(propylene)

 

作者: James C. W. Chien,   Joseph K. Y. Kiang,  

 

期刊: Die Makromolekulare Chemie  (WILEY Available online 1980)
卷期: Volume 181, issue 1  

页码: 47-57

 

ISSN:0025-116X

 

年代: 1980

 

DOI:10.1002/macp.1980.021810105

 

出版商: Hüthig&Wepf Verlag

 

数据来源: WILEY

 

摘要:

AbstractPoly(propylene) has been oxidized at temperatures between 240 and 289°C. The products were GC separated and on‐line identified by an interfaced GC peak identification system. The major products are CO2, H2O, acetaldehyde, acetone, butanal, formaldehyde, methanol and other ketones and aldehydes. Most of the products can be accounted for by well‐known reactions of alkoxyl and peroxyl radicals; the major products are derived from the secondary alkoxy and peroxy species. Oxygen starvation is manifested in diffusion limited products of olefins and dienes, and the increase of CO2and H2O formation in pure oxygen atmosphere. The first order rate constant at 240°C is 2,4·10−3S−1with an overall activation energy of ca. 16 kcal·mol−1(67 kJ·mol−1). If one assumes the oxidative pyrolysis to share the same reaction pathways as autoxidation at lower temperatures, then the observed rate constants and activation energy may be calculated from kinetic parameters measured earlier for autoxidation of poly(propylene) from 71 to 140°C. Good agreement was obtained implying a similarity of oxidative degradation of the polymers spanning a large

 

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