Study on Thermal Decomposition Kinetics of Calixarene

doi:10.19491/j.issn.1001-9278.2021.09.005

Abstract

Abstract:

The thermal stability of calixarene and p?tert?butylcalixarene was studied by thermogravimetric analysis （TG） under a nitrogen atmosphere， and their apparent activation energy were calculated using the Kissinger’s and Flynn?wall?Ozawa’s methods. The thermal decomposition kinetic mechanisms and models were determined from the Coats?Redfern method. The apparent activation energy of calixarene was determined to be 166.64 kJ/mol and 175.79 kJ/mol through the Kissinger’s and Flynn?wall?Ozawa’s methods， respectively. The apparent activation energy of 4?tert?butylcalixarene were calculated to be 153.97 kJ/mol and 166.81 kJ/mol through the Kissinger’s and Flynn?wall?Ozawa’s methods， respectively. The results indicated that the thermal properties of two compounds were relatively stable in nitrogen， and their decomposition temperatures had a strong adaptability to polymer materials. The thermal decomposition mechanism function and reaction order of calixarene were determined to be g（α）=［-ln（1-α）］^3/2 and n =3/2， respectively. Its non?isothermal thermal decomposition mechanism belongs to the random nucleation and subsequent growth reaction. The thermal decomposition mechanism function and reaction order of 4?tert?butylcalixarene were determined to be g（α）=［-ln（1-α）］^2/3 and n=2/3， respectively. Its non?isothermal thermal decomposition mechanism belongs to the random nucleation and subsequent growth reaction. The thermal decomposition mechanism function and reaction order of 4?tert?butylcalixarene for the thermal decomposition process of benzene ring were determined to be g（α）=α² and n=2， respectively. Its non?isothermal thermal decomposition mechanism belongs to the one?dimensional diffusion reaction.

Key words: calixarene, 4?tert?Butylcalixarene, thermogravimetry, thermal decomposition, kinetics

CLC Number:

TQ314.2

ZHANG Dingran, LU Lingang. Study on Thermal Decomposition Kinetics of Calixarene[J]. China Plastics, 2021, 35(9): 27-33.

Figures/Tables 10

References 15

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β/℃·min^-1	材料	T_{5 %}/ ℃	T_max/℃	R_max/%·℃^-¹
10	杯［4］芳烃	313.4	383.5	-0.9813
10	对叔丁基杯［4］芳烃	180.8	188.9、390.9	-0.586 2、-1.390 9
20	杯［4］芳烃	321.2	405.7	-0.9776
20	对叔丁基杯［4］芳烃	188.2	194.0、399.5	-0.249 7、-1.265 5
30	杯［4］芳烃	339.0	415.2	-0.812 8
30	对叔丁基杯［4］芳烃	192.3	197.7、404.1	-0.196 6、-1.260 1
40	杯［4］芳烃	317.5	422.9	-0.715 2
40	对叔丁基杯［4］芳烃	197.4	204.6、411.5	-0.166 4、-0.833 6

β/℃·min^-1	材料	T_{5 %}/ ℃	T_max/℃	R_max/%·℃^-¹
10	杯［4］芳烃	313.4	383.5	-0.9813
10	对叔丁基杯［4］芳烃	180.8	188.9、390.9	-0.586 2、-1.390 9
20	杯［4］芳烃	321.2	405.7	-0.9776
20	对叔丁基杯［4］芳烃	188.2	194.0、399.5	-0.249 7、-1.265 5
30	杯［4］芳烃	339.0	415.2	-0.812 8
30	对叔丁基杯［4］芳烃	192.3	197.7、404.1	-0.196 6、-1.260 1
40	杯［4］芳烃	317.5	422.9	-0.715 2
40	对叔丁基杯［4］芳烃	197.4	204.6、411.5	-0.166 4、-0.833 6

β/ ℃·min^-1	T_p/K	（1/T_p）/ 1×10^-3 K^-1	ln（β/T_p²）/ k^-1·min^-1	E_K/kJ·mol^-1
10	665.49	1.502	-10.698	166.64
20	678.70	1.473	-10.044
30	688.21	1.453	-9.666
40	695.86	1.437	-9.401

β/ ℃·min^-1	T_p/K	（1/T_p）/ 1×10^-3 K^-1	ln（β/T_p²）/ k^-1·min^-1	E_K/kJ·mol^-1
10	665.49	1.502	-10.698	166.64
20	678.70	1.473	-10.044
30	688.21	1.453	-9.666
40	695.86	1.437	-9.401

β/℃·min^-1	T_p/K	（1/T_p） /1×10^-3 K^-1	ln（β/T_p²） /k^?1·min^-1	E_K/kJ·mol^-1
10	461.91	2.165	-9.968	153.97
20	466.97	2.141	-9.297
30	470.73	2.124	-8.907
40	477.61	2.094	-8.649