ANALYSIS OF THE KINETICS OF THE THERMAL-DECOMPOSITION OF POLY(1,6-BIS-N-CARBAZOLYL-2,4-HEXADIYNE) OBTAINED USING THERMOGRAVIMETRIC ANALYSIS

被引:4
作者
BRADNER, FP [1 ]
SHAPRIO, JS [1 ]
机构
[1] MACQUARIE UNIV,SCH CHEM,N RYDE,NSW 2109,AUSTRALIA
关键词
TGA; POLY(1,6-BIS-N-CARBAZOLYL-2,4-HEXADIYNE); KINETICS; THERMAL DECOMPOSITION;
D O I
10.1016/0032-3861(92)90281-Z
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
The thermal decomposition of crystalline poly(1,6-bis-N-carbazolyl-2,4-hexadiyne) was examined by thermogravimetric analysis (t.g.a.) using both isothermal and temperature-programmed methods over a temperature range of 400 600-degrees-C. Extents of decomposition versus time data were fitted to an Avrami-Erofeyev equation with the exponent equal to three. Two consecutive processes were observed, each with its own Arrhenius parameters. An independent study, reported by us elsewhere, involving a flow system, leads to results consistent with the parameters obtained by t.g.a. reported in this investigation. Differences in reactivity between polymer crystals prepared by heating and by gamma-radiation have been noted and discussed. Levels of imperfection of the crystals, determined by the choice of polymerization method, appear to correlate with the observed pre-exponential factors. The numerical value of the activation energy found for the second kinetic regime, which is attributed to the chemical process itself, is consistent with a process of bond breaking at the methylene carbazole bond being the rate-determining step of the decomposition.
引用
收藏
页码:4366 / 4374
页数:9
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