纤维素增强环氧树脂复合材料热解特性研究

doi:10.11949/0438-1157.20231196

化工学报 ›› 2023, Vol. 74 ›› Issue (12): 4968-4978.DOI: 10.11949/0438-1157.20231196

纤维素增强环氧树脂复合材料热解特性研究

刘世君¹(), 郑安庆¹^,², 陈晓丽¹, 付娟¹(), 苏秋成¹

^1.中国科学院可再生能源重点实验室，广东省新能源与可再生能源研究开发重点实验室，中国科学院广州能源研究所，广东广州 510640
^2.中国科学技术大学能源科学与工程学院，广东广州 510640

收稿日期:2023-11-20 修回日期:2023-12-14 出版日期:2023-12-25 发布日期:2024-02-19
通讯作者: 付娟
作者简介:刘世君（1990—），男，硕士研究生，实验师，liusj@ms.giec.ac.cn
基金资助:
国家自然科学基金面上项目(52276221);中国科学院技术支撑人才项目(E2298501)

Study on pyrolysis characteristics of cellulose-enhanced epoxy resin composites

Shijun LIU¹(), Anqing ZHENG¹^,², Xiaoli CHEN¹, Juan FU¹(), Qiucheng SU¹

^1.CAS Key Laboratory of Renewable Energy，Guangdong Key Laboratory of New and Renewable Energy Research and Development, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China
^2.School of Energy Science and Engineering, University of Science and Technology of China, Guangzhou 510640, Guangdong, China

Received:2023-11-20 Revised:2023-12-14 Online:2023-12-25 Published:2024-02-19
Contact: Juan FU

摘要/Abstract

摘要：

天然纤维在许多领域可取代合成纤维应用于增强式复合材料中，在保证了一定强度与刚度的同时具有成本低、质量轻、降解易等优点，但目前对于天然复合材料热解回收方面的研究匮乏。鉴于此，本文通过热重分析仪（TG）和热裂解气相色谱质谱联用仪（Py-GC/MS）研究天然纤维素增强式环氧树脂复合材料热解反应动力学和产物生产特性。结果表明，在复合材料中，纤维素和环氧树脂的协同效应降低了复合材料的热稳定性，同时极大程度地降低了焦的残余量，最终显著降低了复合材料的热解活化能；另一方面，协同效应对快速热解产物的种类影响不明显，但能够显著影响产物产量和分布。

关键词: 纤维素, 环氧树脂, 热解, 反应动力学, 分布, 协同作用

Abstract:

Natural fibers can replace synthetic fibers in many fields, particularly in reinforced composite materials. They ensure a certain strength and stiffness while having the advantages of low cost, light mass, and easy degradation. However, there is currently a lack of research on pyrolysis recycling of natural composite materials. To address this gap, this study investigates the thermal decomposition kinetics and product characteristics of natural fiber-reinforced epoxy resin composites using thermal gravimetric analyzer (TGA) and pyrolysis gas chromatography-mass spectrometry (Py-GC/MS) experimental methods. The results indicate that the synergistic effect of cellulose and epoxy resin in the composite reduces its thermal stability and significantly decreases the residual char content, ultimately leading to a substantial reduction in the activation energy for the composite. On the other hand, the synergistic effect has a less noticeable impact on the types of products during rapid pyrolysis but significantly influences the yield and distribution of products.

Key words: cellulose, epoxy resin, pyrolysis, reaction kinetics, distributions, synergistic effect

中图分类号:

X 783.2

刘世君, 郑安庆, 陈晓丽, 付娟, 苏秋成. 纤维素增强环氧树脂复合材料热解特性研究[J]. 化工学报, 2023, 74(12): 4968-4978.

Shijun LIU, Anqing ZHENG, Xiaoli CHEN, Juan FU, Qiucheng SU. Study on pyrolysis characteristics of cellulose-enhanced epoxy resin composites[J]. CIESC Journal, 2023, 74(12): 4968-4978.

图/表 14

参考文献 32

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样品编号	原料配比/%（质量分数）		固化温度与时间
样品编号	DGEBA+DDM	纤维素	固化温度与时间
EP	100	0	100℃ 2 h+ 150℃ 2 h
EP-10Cell	90	10
EP-20Cell	80	20
EP-30Cell	70	30

样品编号	原料配比/%（质量分数）		固化温度与时间
样品编号	DGEBA+DDM	纤维素	固化温度与时间
EP	100	0	100℃ 2 h+ 150℃ 2 h
EP-10Cell	90	10
EP-20Cell	80	20
EP-30Cell	70	30

步骤	Starink积分法
1	获得至少在三种加热速率下转化率α与温度T的关系
2	在不同加热速率下选定α值时计算ln（β/T^1.92)的值
3	绘制在选定α值下ln（β/T^1.92)与1/T的关系，并确定活化能E

步骤	Starink积分法
1	获得至少在三种加热速率下转化率α与温度T的关系
2	在不同加热速率下选定α值时计算ln（β/T^1.92)的值
3	绘制在选定α值下ln（β/T^1.92)与1/T的关系，并确定活化能E

参数	升温速率/ (℃/min)	纤维素	EP	EP-10Cell		EP-20Cell		EP-30Cell
参数	升温速率/ (℃/min)	纤维素	EP	Exp.	Pred.	Exp.	Pred.	Exp.	Pred.
Y_char/%	5	0.37	17.63	7.93	15.53	5.89	13.43	9.38	11.33
	15	2.39	16.67	6.16	15.24	7.49	13.82	6.45	12.39
	30	5.41	15.43	7.90	14.43	7.08	13.43	10.61	12.42
T₀/℃	5	293.69	349.40	300.57	339.47	291.48	315.46	293.92	296.42
	15	308.45	370.71	322.75	367.43	312.82	348.60	314.78	313.23
	30	320.11	382.04	335.20	367.98	323.84	333.22	328.39	326.60
T_max/℃	5	322.50	375.00	365.00	375.00	362.50	375.00	365.00	375.00
	15	342.50	395.00	390	395.00	387.50	395.00	390	395.00
	30	360	407.50	407.50	407.50	405.00	407.50	407.50	407.50
T_f /℃	5	349.66	432.55	428.58	432.84	426.32	433.19	422.65	433.64
	15	370.83	454.20	452.43	454.45	450.27	454.77	446.96	455.21
	30	388.88	472.79	468.40	473.30	465.17	473.92	462.39	474.69
（dm/dT_max）/(%/℃)	5	-3.10	-1.90	-1.50	-1.71	-1.36	-1.53	-1.38	-1.34
	15	-2.67	-1.97	-1.53	-1.78	-1.34	-1.59	-1.43	-1.39
	30	-2.35	-1.84	-1.47	-1.66	-1.34	-1.48	-1.35	-1.31

纤维素增强环氧树脂复合材料热解特性研究

Study on pyrolysis characteristics of cellulose-enhanced epoxy resin composites

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参考文献 32

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样品	E₀/(kJ/mol)
纤维素	152.4
EP	192.4
EP-10Cell	145.1
EP-20Cell	140.5
EP-30Cell	137.8

种类编号	定义
LMW	低分子量物种
1-B	化合物具有一个没有氧或氮的单一苯环
1-B-O	含有一个含有氧的单个苯环的化合物
1-B-N	具有单一苯环和氮气特征的化合物
2-B	具有两个苯环而含氧或氮的化合物
2-B-O	具有两个苯环的化合物
2-B-N	具有两个苯环和氮的化合物
其他	未识别或杂质

产物类别	占比/%
产物类别	LMS	1-B	1-B-O	1-B-N	2-B	2-B-O	2-B-N	Others
EP	1.52	0.49	9.71	0.42	0.14	66.36	15.34	6.01
EP-10Cell	1.45	0.47	10.20	0.30	0.18	68.42	14.60	4.38
EP-20Cell	1.65	0.50	13.34	0.35	0.16	68.15	11.70	4.16
EP-30Cell	1.27	0.41	11.00	0.32	0.14	70.53	12.45	3.88

产物类别	含量/%
产物类别	p-Isopropenylphenol	Phenol	p-Cumenol	Phenol, 2-methyl-	p-Cresol
EP	41.49	30.00	16.54	8.44	3.53
EP-10Cell	39.54	30.90	16.47	9.13	3.96
EP-20Cell	40.84	32.04	16.26	8.14	2.71
EP-30Cell	40.92	31.77	16.40	7.84	3.06

产物类别	含量/%
产物类别	Phenol, 4,4′-(1-methylethylidene)bis-	2-(4′-Hydroxyphenyl)-2-(4′-methoxyphenyl)propane	4-(2-(4-(Ethynyloxy)phenyl)propan-2-yl)phenol	4-(2-(4-(2-Hydroxyethoxy)phenyl)propan-2-yl)phenol	4-(2-(4-(2-Hydroxypropoxy)phenyl)propan-2-yl)phenol
EP	63.79	13.09	12.15	6.59	4.39
EP-10Cell	69.45	16.32	9.38	1.70	3.15
EP-20Cell	73.52	14.36	7.22	1.72	3.18
EP-30Cell	72.49	14.77	7.86	1.80	3.08

产物类别	含量/%
产物类别	4,4′-Methylenebis(N-methylaniline)	Benzenamine, 4,4′- methylenebis(N,N-dimethyl-)	N,N-Dimethyl-4-(4-(methylamino)benzyl)aniline	Benzenamine, 4,4′-methylenebis-	Oxazole, 2-(4-methoxyphenyl)-5-phenyl-
EP	30.53	24.76	22.95	17.50	4.27
EP-10Cell	31.15	32.04	22.81	8.17	5.83
EP-20Cell	21.51	39.60	18.18	11.95	8.76
EP-30Cell	24.16	35.14	22.71	10.47	7.52

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