含磷液氧相容环氧树脂的热降解行为

李娟子; 严佳; 陈铎; 崔运广; 高畅; 黄昊; 武湛君

doi:10.13801/j.cnki.fhclxb.20230515.003

含磷液氧相容环氧树脂的热降解行为

doi: 10.13801/j.cnki.fhclxb.20230515.003

李娟子^{1, 2},
严佳^2, ,,
陈铎¹,
崔运广²,
高畅¹,
黄昊¹,
武湛君²

1.
大连理工大学　材料科学与工程学院，大连 116024
2.
大连理工大学　航空航天学院，大连 116024

基金项目: 国家重点研发项目(2018YFA0702800)

详细信息

通讯作者:
严佳，博士，副教授，硕士生导师，研究方向为材料物理与化学　E-mail: jyan@dlut.edu.cn

中图分类号: TQ322.41；TB332
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- 文章访问数: 505
- HTML全文浏览量: 198
- PDF下载量: 28
- 被引次数: 0
出版历程
- 收稿日期: 2023-03-02
- 修回日期: 2023-05-08
- 录用日期: 2023-05-10
- 网络出版日期: 2023-05-15
- 刊出日期: 2024-01-01

Thermal degradation behaviors of phosphorus-containing liquid oxygen-compatible epoxy resin

LI Juanzi^{1, 2},
YAN Jia^{2
, ,},
CHEN Duo¹,
CUI Yunguang²,
GAO Chang¹,
HUANG Hao¹,
WU Zhanjun²

1.
School of Materials Science and Engineering, Dalian University of Technology, Dalian 116024, China
2.
School of Aeronautics and Astronautics, Dalian University of Technology, Dalian 116024, China

Funds: National Key Research and Development Program of China (2018YFA0702800)

摘要

摘要: 碳纤维/环氧树脂复合材料液氧贮箱对重型火箭和空天飞机等新一代航天器减重具有重要意义。然而，环氧树脂与液氧不相容制约了其应用。采用热重分析、Kissinger方法、Coasts-Redfern方法、热重-红外-气质联用技术对10-(2, 5-二羟基苯基)-10-氢-9-氧杂-10-磷杂菲-10-氧化物(ODOPB)改性液氧相容环氧树脂(ODOPB-EP)的热降解行为及机制进行了研究。结果表明：ODOPB-EP的热降解机制为相边界反应，对应的降解机制函数g(α)=1−(1−α)^1/3，α为转化率。在热降解过程中，树脂先从C—N和C—O弱键处断裂，随着温度升高，释放出苯酚及其衍生物等芳香类物质，且ODOPB在树脂中会分解产生联苯等物质，在这个过程中会伴随着含磷自由基的释放，在气相能起到淬灭作用，有利于提高树脂的液氧相容性，为探明聚合物的液氧相容机制提供了理论基础。
- 环氧树脂 /
- 液氧相容性 /
- 热降解 /
- 热重-红外-气质联用 /
- 相容机制
Abstract: The liquid oxygen tanks that made of carbon fiber/epoxy resin composites are vital for weight reduction in new generation spacecraft such as heavy rockets and space shuttles. However, the incompatibility of epoxy resin with liquid oxygen limits their application. Thermogravimetric analyser, the Kissinger method, the Coasts-Redfern method and thermogravimetric-infrared-gas chromatography/mass spectrometry were used to investigate the thermal degradation behaviors and mechanism of 10-(2, 5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphafi-10-oxide (ODOPB)-modified liquid oxygen-compatible epoxy resin (ODOPB-EP). The results show that the thermal degradation mechanism of ODOPB-EP is a phase boundary reaction, corresponding to the degradation mechanism function g(α)=1−(1−α)^1/3, α is conversion rate. During the thermal degradation process, the resin breaks from the weak bonds of C—N and C—O. With the increase of temperature, aromatic substances such as phenol and its derivatives are released. Besides, ODOPB part in resin produces biphenyl and other substances, accompanied by the release of phosphorus-containing radicals. The phosphorus-containing radicals could exert quenching effects, which is conducive to improving the compatibility of the resin with liquid oxygen. This study provides a theoretic basis for verifying the compatible mechanism of polymers with liquid oxygen.
- epoxy resin /
- liquid oxygen compatibility /
- thermal degradation /
- TG-FTIR-GC/MS /
- compatible mechanism

HTML全文

图 1 9, 10-二氢-9-氧-10-磷杂菲-10-氧化物-1, 4-苯二酚改性液氧相容环氧树脂(ODOPB-EP)的合成路线

Figure 1. Synthesis route of liquid oxygen compatible epoxy resin modified with 10-(2, 5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphafi-10-oxide (ODOPB-EP)

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图 2 ODOPB-EP的红外图谱

Figure 2. FTIR spectrum of ODOPB-EP

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图 3 不同升温速率下ODOPB-EP在氮气气氛下的热重曲线

Figure 3. TG and DTG curves of ODOPB-EP under N₂ atmosphere at various heating rates

T_max—Temperature corresponding to maximum thermal degradation rate

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图 4 不同升温速率下ODOPB-EP在空气气氛下的热重曲线

Figure 4. TG and DTG curves of ODOPB-EP under air atmosphere at various heating rates

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图 5 Kissinger法拟合的ln(β/${{{T}}_{{{\rm{max}}}}^{{2}}} $)~1/T_max关系曲线

Figure 5. Plot of ln(β/${{{T}}_{{{\rm{max}}}}^{{2}}} $) versus 1/T_max according to Kissinger method

β—Heating rate

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图 6 Coasts-Redfern方法拟合的ln[g(α)/T²]对1/T关系曲线

Figure 6. Plot of ln[g(α)/T²] versus 1/T according to Coasts-Redfern method

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图 7 ODOPB-EP在氮气气氛下的三维TG-FTIR图谱

Figure 7. Three-dimensional TG-FTIR spectra of ODOPB-EP under N₂ atmosphere

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图 8 不同温度下ODOPB-EP热解气相产物的红外图谱

Figure 8. FTIR spectra of pyrolytic volatiles for ODOPB-EP at various temperatures

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图 9 ODOPB-EP在氮气氛围不同温度下热解气相产物的气质总离子流图谱

Figure 9. GC/MS total ion chromatograms of the pyrolytic compounds from ODOPB-EP at different temperatures under N₂ atmosphere

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图 10 ODOPB-EP的降解路径

Figure 10. Pyrolytic process of ODOPB-EP

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图 11 ODOPB在550℃的降解气相产物质谱图及降解路径

Figure 11. Mass chromatograms of the pyrolytic compounds from ODOPB and the pyrolytic process of ODOPB at 550℃

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图 12 ODOPB-EP的动态热机械性能分析(DMA)结果

Figure 12. Results of dynamic mechanical analysis (DMA) for ODOPB-EP

T_g—Glass transition temperature; tanδ—Loss factor

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表 1 ODOPB-EP在氮气和空气下的热重数据

Table 1. TG and DTG data of ODOPB-EP under N₂ and air atmosphere

Atmosphere	Heating rate/ (℃·min⁻¹)	T_5%/℃	T_max/℃		Residue at 800℃/%
Atmosphere	Heating rate/ (℃·min⁻¹)	T_5%/℃	T_max1	T_max2	Residue at 800℃/%
N₂	5	371.1	389.4	—	18.7
	10	376.1	400.6	—	17.8
	15	388.3	405.8	—	16.8
	20	397.6	421.3	—	16.6
Air	5	319.4	382.7	581.7	0.70
	10	335.6	394.6	599.7	0.72
	15	353.3	405.3	618.2	0.88
	20	358.1	415.6	627.3	1.52
Note: T_5%—Temperature corresponding to mass loss 5% of material.

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表 2 Coasts-Redfern方法计算不同机制模型的活化能及相关系数^{[22- 23]}

Table 2. Activation energy and correlation coefficient calculated by Coasts-Redfern method^[22-23]

Kinetic mechanism models	g(α)	5℃/min		10℃/min		15℃/min		20℃/min
Kinetic mechanism models	g(α)	E/(kJ·mol⁻¹)	r	E/(kJ·mol⁻¹)	r	E/(kJ·mol⁻¹)	r	E/(kJ·mol⁻¹)	r
F₁	−ln(1−α)	158.71	0.875	157.11	0.915	180.91	0.911	186.19	0.906
F₂	1/(1-α)	58.89	0.986	56.94	0.974	65.85	0.978	68.02	0.980
F₃	1/(1−α)²	129.07	0.988	124.82	0.976	144.33	0.980	149.08	0.983
A₂	[−ln(1−α)]^1/2	73.72	0.856	73.08	0.900	84.13	0.896	86.58	0.891
A₃	[−ln(1−α)]^1/3	45.39	0.835	45.07	0.882	51.88	0.878	53.37	0.873
A₄	[−ln(1−α)]^1/4	31.22	0.808	31.07	0.860	35.75	0.855	36.77	0.849
R₂	1−(1−α)^1/2	142.04	0.843	140.97	0.889	162.24	0.885	166.93	0.879
R₃	1−(1−α)^1/3	147.40	0.854	146.17	0.872	168.25	0.894	173.13	0.889
D₁	α²	265.41	0.822	263.87	0.872	303.57	0.867	312.26	0.862
D₂	(1−α)ln(1-α)+α	284.33	0.842	282.23	0.888	324.80	0.884	334.17	0.879
D₃	[1−(1−α)^1/3]²	306.08	0.864	303.28	0.906	349.14	0.902	359.31	0.897
D₄	(1−2α/3)−(1−α)^2/3	291.55	0.849	289.22	0.895	332.88	0.890	342.51	0.885
Notes: g(α)—Degradation mechanism function; α—Conversion rate; E—Activation energy; r—Degree of fit.

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表 3 不同温度下ODOPB-EP的热分解气相产物

Table 3. Pyrolytic compounds of ODOPB-EP under different temperatures

Peak	Compounds	m/z	Peak	Compounds	m/z
1		92	9		121
2		106	10		136
3		94	11		160
4		108	12		134
5		107	13		158
6		121	14		174
7		122	15		154
8		122	16		172
Note: m/z—Mass-to-charge ratio.

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