生物基聚酰胺56纤维的热降解动力学及其热解产物

doi:10.13475/j.fzxb.20200908307

纺织学报 ›› 2021, Vol. 42 ›› Issue (04): 1-7.doi: 10.13475/j.fzxb.20200908307

• 特约专栏:生物基聚酯和聚酰胺纤维 • 下一篇

生物基聚酰胺56纤维的热降解动力学及其热解产物

杨婷婷¹^,², 高远博¹^,², 郑毅³, 王学利⁴, 何勇¹^,²^,⁴()

1.东华大学材料科学与工程学院, 上海 201620
2.东华大学纤维材料改性国家重点实验室, 上海 201620
3.上海凯赛生物技术股份有限公司, 上海 201203
4.东华大学纺织科技创新中心, 上海 201620

收稿日期:2020-09-30 修回日期:2020-12-23 出版日期:2021-04-15 发布日期:2021-04-20
通讯作者: 何勇
作者简介:杨婷婷(1995—),女,博士生。主要研究方向为生物基聚酰胺聚合与成形动力学机制。
基金资助:
国家重点研发计划资助项目(2017YFB0309400)

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. 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

摘要/Abstract

摘要：

生物基聚酰胺56(PA56)纤维是由生物基1,5-戊二胺和石油基1,6-己二酸聚合制备而成的新型生物基材料。为探究生物基PA56纤维的热稳定性,分别在氮气氛围中测定其在不同升温速率下的热降解过程,并计算其热降解动力学参数,同时分析了生物基PA56纤维在热降解过程中的主要热降解气相产物。结果表明:生物基PA56纤维的热失重曲线及热降解动力学参数对升温速率具有显著依赖性,采用Kissinger法、Flynn-Wall-Ozawa法和Coasts-Redfern法获得的生物基PA56纤维的活化能分别为235.00、217.23和232.18 kJ/mol,可推测其热降解机制为F1型,热降解过程中产生的主要气相产物为CO₂、环戊酮和1,5-戊二胺。

关键词: 生物基聚酰胺56纤维, 热稳定性, 热降解动力学, 热降解动力学参数, 热解气相产物

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

中图分类号:

TS151

杨婷婷, 高远博, 郑毅, 王学利, 何勇. 生物基聚酰胺56纤维的热降解动力学及其热解产物[J]. 纺织学报, 2021, 42(04): 1-7.

YANG Tingting, GAO Yuanbo, ZHENG Yi, WANG Xueli, HE Yong. Thermal degradation kinetics and pyrolysis products of bio-based polyamide 56 fiber[J]. Journal of Textile Research, 2021, 42(04): 1-7.

图/表 12

图1

图2

表1

图3

表2

图4

表3

Coasts-Redfern法计算得到的活化能及相关系数"

动力学机制类型	g(α)	10 ℃/min		15 ℃/min		20 ℃/min		25 ℃/min
动力学机制类型	g(α)	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	$1 - 23 α$ -(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

表3

图5

图6

图7

图8

表4

参考文献 10

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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

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

物质编号	热解气相产物	m/z	不同温度时的相对含量
物质编号	热解气相产物	m/z	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

生物基聚酰胺56纤维的热降解动力学及其热解产物

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

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