Pyrolysis mechanism and kinetics of calixarene based on TG analysis

doi:10.19491/j.issn.1001-9278.2022.01.014

Abstract

Abstract:

Thermogravimetry analysis was conducted to investigate the pyrolysis status and mechanism of calixarene and 4?tert?butylcalixarene under a nitrogen atmosphere. Meanwhile， the reaction activation energy and the optimal mechanism function equation of the two pyrolysis processes were obtained using a thermal decomposition kinetics method. The results indicated that the overall structure of 4?tert?butylcalixarene was more stable due to the strong interaction between the C—H σ and C＝C π bonds. Calixarene exhibited excellent char forming performance， and 4?tert?butylcalixarene presented an excellent thermal stability. Their decomposition temperatures are very suitable for the use of polymer materials， Moreover， the pyrolysis kinetic analysis demonstrated that the activation energies of calixarene were determined to be 179.14 and 192.84 kJ/mol through calculation using the Kissinger′s and Flynn?wall?Ozawa′s methods， respectively. The activation energies of 4?tert?butylcalixarene were calculated to be 291.61 and 312.14 kJ/mol using the Kissinger′s and Flynn?wall?Ozawa′s methods， respectively. According to the Coats?Redfern method， the pyrolysis mechanism function of calixarene was determined to be g（α）=［-ln（1-α）］^1/3 and its reaction order n was 1/3. Its non?isothermal pyrolysis mechanism belongs to random nucleation and subsequent growth reaction. The pyrolysis mechanism function of 4?tert?butylcalixarene was g（α）=α^1/3 and its reaction order n was 1/3.

Key words: calixarene, 4?tert?Butylcalix［8］arene, thermogravimetry, thermal decomposition, kinetics

CLC Number:

TQ314.2

ZHANG Dingran, LU Lingang. Pyrolysis mechanism and kinetics of calixarene based on TG analysis[J]. China Plastics, 2022, 36(1): 92-99.

Figures/Tables 13

References 15

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β/℃·min^-1	材料类别	T_{5 %}/℃	T_max/℃	R_max/%·℃^-1
10	杯［8］芳烃	257.09	348.69	0.645 9
10	对叔丁基杯［8］芳烃	408.00	413.37	2.266 7
20	杯［8］芳烃	266.79	360.58	0.544 0
20	对叔丁基杯［8］芳烃	410.07	421.40	1.571 5
30	杯［8］芳烃	334.51	369.05	0.518 9
30	对叔丁基杯［8］芳烃	413.28	424.90	1.263 2
40	杯［8］芳烃	303.50	372.00	0.482 0
40	对叔丁基杯［8］芳烃	414.13	432.14	0.857 1

β/℃·min^-1	材料类别	T_{5 %}/℃	T_max/℃	R_max/%·℃^-1
10	杯［8］芳烃	257.09	348.69	0.645 9
10	对叔丁基杯［8］芳烃	408.00	413.37	2.266 7
20	杯［8］芳烃	266.79	360.58	0.544 0
20	对叔丁基杯［8］芳烃	410.07	421.40	1.571 5
30	杯［8］芳烃	334.51	369.05	0.518 9
30	对叔丁基杯［8］芳烃	413.28	424.90	1.263 2
40	杯［8］芳烃	303.50	372.00	0.482 0
40	对叔丁基杯［8］芳烃	414.13	432.14	0.857 1

β/ ℃·min^-1	T_p/K	T_p^-1/ ×10^-3K^-1	ln（β/T_p²）/ K^-1·min^-1	E_K/ kJ·mol^-1
10	621.70	1.609	-10.562	179.14
20	633.59	1.578	-9.907
30	642.05	1.558	-9.528
40	645.00	1.550	-9.250

β/ ℃·min^-1	T_p/K	T_p^-1/ ×10^-3K^-1	ln（β/T_p²）/ K^-1·min^-1	E_K/ kJ·mol^-1
10	621.70	1.609	-10.562	179.14
20	633.59	1.578	-9.907
30	642.05	1.558	-9.528
40	645.00	1.550	-9.250

β/ ℃·min^-1	T_p/K	T_p^-1/ ×10^-3K^-1	ln（β/T_p²）/ K^-1·min^-1	E_K/ kJ·mol^-1
10	686.38	1.457	-10.760	291.61
20	694.41	1.440	-10.090
30	697.90	1.433	-9.695
40	705.14	1.418	-9.428