Journal of Textile Research ›› 2021, Vol. 42 ›› Issue (04): 1-7.doi: 10.13475/j.fzxb.20200908307

• Invited Column: Bio-based Polyester and Polyamide Fiber •     Next Articles

Thermal degradation kinetics and pyrolysis products of bio-based polyamide 56 fiber

YANG Tingting1,2, GAO Yuanbo1,2, ZHENG Yi3, WANG Xueli4, HE Yong1,2,4()   

  1. 1. College of Materials Science and Engineering, Donghua University, Shanghai 201620, China
    2. State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University, Shanghai 201620, China
    3. Cathay Biotech Inc., Shanghai 201203, China
    4. Innovation Center for Textile Science and Technology, Donghua University, Shanghai 201620, China
  • Received:2020-09-30 Revised:2020-12-23 Online:2021-04-15 Published:2021-04-20
  • Contact: HE Yong E-mail:yhe@dhu.edu.cn

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Abstract:

Bio-based polyamide 56 (PA56) fiber was prepared by bio-based 1,5-pentanediamine and petroleum-based 1,6-adipic acid. In order to explore the thermal stability of the new type of bio-based material, the thermal degradation process of the bio-based PA56 fiber were measured under nitrogen at different heating rates, and the thermal degradation kinetic parameters were calculated. In addition, the main pyrolysis gas phase products of bio-based PA56 fiber in the thermal degradation process were analyzed. The results show that the thermal weight loss curve and kinetic parameters of bio-based polyamide 56 fiber are dependent on the heating rates. The activation energy of bio-based PA56 fiber obtained by Kissinger method, Flynn-Wall-Ozawa method and Coasts-Redfern method are 235.00, 217.23 and 232.18 kJ/mol, respectively, suggesting that the thermal degradation mechanism is F1 type. The main pyrolysis gas phase products are CO2, cyclopentanone and 1,5-pentanediamine in the thermal degradation process.

Key words: bio-based polyamide 56 fiber, thermal stability, thermal degradation kinetics, thermal degradation kinetic parameter, pyrolysis gas phase product

CLC Number: 

  • TS151

Fig.1

TG (a) and DTG (b) curves of bio-based PA56 fibers at different heating rates under nitrogen atmosphere"

Fig.2

Plot of ln(β/T2) versus 1/T according to Kissinger method"

Tab.1

Activation energy and correlation coefficient calculated by Kissinger method"

β/(℃·min-1) T/℃ E/(kJ·mol-1) lnA 相关系数R
10 441.0 235.00 32.01 0.994
15 450.4
20 455.0
25 458.2

Fig.3

Plot of lgβ and 1 000/T according to Flynn-Wall-Ozawa method"

Tab.2

Activation energy calculated by Flynn-Wall-Ozawa method"

质量损失率α 斜率 活化能/
(kJ·mol-1)		 活化能平均值/
(kJ·mol-1)
0.1 -10.69 194.51 217.23
0.2 -11.77 214.16
0.3 -12.57 228.72
0.4 -12.70 231.09
0.5 -12.45 226.54
0.6 -12.25 222.90
0.7 -12.08 219.81
0.8 -11.76 213.98
0.9 -11.01 200.34

Fig.4

Plot of ln(g(α)/T2) and 1 000/T according to Coasts-Redfern method"

Tab.3

Activation energy and correlation coefficient calculated by Coasts-Redfern method"

动力学机制
类型		 g(α) 10 ℃/min 15 ℃/min 20 ℃/min 25 ℃/min
E/(kJ·mol-1) R E/(kJ·mol-1) R E/(kJ·mol-1) R E/(kJ·mol-1) R
A2 (-ln(1-α))12 123.96 0.999 126.61 0.700 116.94 0.997 129.98 0.998
A3 (-ln(1-α))13 86.55 0.999 87.33 0.510 81.95 0.998 90.67 0.998
A4 (-ln(1-α))14 67.85 0.999 67.69 0.364 64.45 0.998 70.01 0.999
R1 α 173.69 0.977 178.22 0.839 162.36 0.960 181.50 0.967
R2 1-(1-α)12 201.87 0.993 208.07 0.876 189.17 0.983 211.43 0.987
R3 1-(1-α)13 212.60 0.996 219.45 0.886 199.40 0.989 222.83 0.992
D1 α2 335.64 0.975 347.67 0.941 312.75 0.957 350.98 0.964
D2 (1-α)ln(1-α)+α 369.84 0.987 383.89 0.956 345.25 0.973 387.26 0.978
D3 (1-(1-α)13)2 413.46 0.996 430.14 0.967 386.84 0.988 433.64 0.991
D4 1-23α-(1-α)23 384.18 0.991 402.21 0.985 358.91 0.979 402.50 0.984
F1 -ln(1-α) 236.19 0.999 222.66 0.999 221.92 0.997 247.93 0.998
F2 1/(1-α) 161.90 0.838 170.21 0.854 155.44 0.873 171.88 0.858
F3 1/(1-α)2 312.08 0.828 330.53 0.845 298.91 0.865 331.74 0.849

Fig.5

Three-dimensional TG-IR spectra of bio-based PA56 fibers under nitrogen atmosphere"

Fig.6

IR spectra of pyrolysis volatiles for bio-based PA56 fibers at different temperatures"

Fig.7

Absorbance of main pyrolysis volatiles for bio-based PA56 fibers versus temperature"

Fig.8

Py-GC/MS chromatograms of PA56 under different pyrolysis temperatures"

Tab.4

Possible pyrolytic compounds of PA56 under different pyrolysis temperatures"

物质
编号		 热解气相产物 m/z 不同温度时的相对含量
455 ℃ 500 ℃ 550 ℃
1 CO2 44 11.96 25.35 29.33
吡啶 79 0.35 — —
2 氨基环戊烷 85 — 0.36 —
环戊烯 68 — — 1.31
3 环戊酮 84 46.60 40.97 38.78
4 四氢吡啶 83 4.75 7.29 —
5 1,5-戊二胺 102 25.48 8.58 3.40
6 1H-吲哚-3-甲醛 159 0.74 0.53 0.45
7 7-羟基-1-氮杂环烷-2-酮 185 3.21 4.47 6.13
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