热塑性聚酯弹性体复合材料的制备与阻燃性能

刘天明; 赵东; 沈育才; 江国栋; 王庭慰

doi:10.13801/j.cnki.fhclxb.20230724.004

热塑性聚酯弹性体复合材料的制备与阻燃性能

doi: 10.13801/j.cnki.fhclxb.20230724.004

刘天明¹,
赵东^{1, 2, ,},
沈育才^1, ,,
江国栋¹,
王庭慰^{1, 2, ,}

1.
南京工业大学　材料科学与工程学院，南京 211816
2.
江苏先进无机功能复合材料协同创新中心，南京 211816

基金项目: 江苏省高等学校基础科学(自然科学)研究面上项目(22KJB430028)；国家自然科学基金面上项目(22175088)；江苏高校优势学科建设工程项目(PAPD)；江苏省研究生科研与实践创新计划项目(SJCX23_0442)

详细信息

通讯作者:
赵东，博士，讲师，研究方向为阻燃高分子复合材料　E-mail: dongzhao@njtech.edu.cn；

沈育才，博士，教授，硕士生导师，研究方向为功能化高分子复合材料　E-mail: ycshen@njtech.edu.cn；

王庭慰，博士，教授，博士生导师，研究方向为生物高分子复合材料　E-mail: wangtw@njtech.edu.cn

中图分类号: TQ333.93；TB332
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出版历程
- 收稿日期: 2023-05-12
- 修回日期: 2023-06-27
- 录用日期: 2023-07-12
- 网络出版日期: 2023-07-25
- 刊出日期: 2024-03-01

Preparation and flame retardancy of thermoplastic polyester elastomer composites

LIU Tianming¹,
ZHAO Dong^{1, 2
, ,},
SHEN Yucai^{1
, ,},
JIANG Guodong¹,
WANG Tingwei^{1, 2
, ,}

1.
School of Materials Science and Engineering, Nanjing University of Technology, Nanjing 211816, China
2.
Jiangsu Collaborative Innovation Center for Advanced Inorganic Functional Composites, Nanjing 211816, China

Funds: Natural Science Foundation of the Jiangsu Higher Education Institutions of China (22KJB430028); National Natural Science Foundation of China (22175088); Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD); Postgraduate Research & Practice Innovation Program of Jiangsu Province (SJCX23_0442)

摘要

摘要: 由于热塑性聚酯弹性体(TPEE)极易燃烧，严重阻碍了其在电子电气、电线护套、充电桩等领域的应用，为解决此问题，以二乙基次磷酸铝(AlPi)和三聚氰胺聚磷酸盐(MPP)为阻燃剂，添加到TPEE中，采用密炼和热压成型方法制备出高阻燃性TPEE复合材料。采用极限氧指数(LOI)测试、垂直燃烧(UL-94)测试、锥形量热(CONE)测试等对TPEE复合材料的阻燃性能进行了测试。结果表明：AlPi和MPP复配可以实现TPEE的高效阻燃，添加22wt%复配阻燃剂的TPEE材料的LOI由19.3%提升至31.5%，UL-94达到V-0级，总热释放和峰值热释放速率下降27.6%和64.8%。采用热失重分析仪(TGA)、扫描电子显微镜、力学性能测试仪及电绝缘性能测试仪等对TPEE材料的热稳定性、力学性能、电性能及其烧蚀前后的微观形貌进行了表征。结果表明：复配阻燃剂的阻燃机制为膨胀炭层凝聚相阻隔型阻燃，且促进了TPEE分解成炭；力学性能、电绝缘性能和微观形貌测试表明复配的AlPi和MPP能够提升TPEE材料的电绝缘性，但其与TPEE相容性较差，导致TPEE材料的力学性能下降。
- 热塑性聚酯弹性体 /
- 二乙基次磷酸铝 /
- 三聚氰胺聚磷酸盐 /
- 阻燃性能 /
- 电绝缘性能
Abstract: Thermoplastic polyester elastomer (TPEE) is extremely flammable, which seriously hinders its application in the fields of electronics and electrical, wire sheath, charging station, etc. TPEE composites with high flame retardancy were prepared by adding aluminum diethylphosphinate (AlPi) and melamine polyphosphate (MPP) flame retardant into TPEE matrix through internal mixing and hot pressing process. The flame retardancy of the TPEE composites was studied by limiting oxygen index (LOI), vertical burning (UL-94) and cone calorimeter (CONE) tests. The results show that AlPi combined with MPP can achieve high-efficiency flame retardancy of TPEE composites. In addition, the TPEE composite with 22wt%AlPi and MPP passed the UL-94 V-0 rating and its LOI value increase from 19.3% to 31.5%, accompanied with 27.6% reduction in the total heat release and 64.8% reduction of the peak heat release rate compared to pure TPEE. The thermal stabilities, mechanical properties, and electrical properties of the TPEE composites, as well as the microscopic morphology of the composites before and after ablation were studied by thermogravimetric analyzer (TGA), SEM, universal testing machine and electrical insulation test. The results indicate that the flame retardant mechanism of the composite flame retardant system is the barrier action of intumescent char layer in the condense phase. The composite flame retardant system can promote the decomposition of TPEE into carbon. The mechanical properties, electrical insulation properties and microtopography tests show that the combination of AlPi and MPP can improve the electrical insulation performance, but reduce the mechanical properties of TPEE composites due to their poor compatibility with TPEE matrix.
- thermoplastic polyester elastomer /
- aluminum diethylphosphinate /
- melamine pyrophosphate /
- flame retardancy /
- electrical insulation property

HTML全文

图 1 TPEE (a)、3MPP-9AlPi/TPEE (b)、4.25MPP-12.75AlPi/TPEE (c)和5.5MPP-16.5AlPi/TPEE (d)在30% LOI下的测试图片

Figure 1. Digital photos of TPEE (a), 3MPP-9AlPi/TPEE (b), 4.25MPP-12.75AlPi/TPEE (c) and 5.5MPP-16.5AlPi/TPEE (d) under the LOI of 30%

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图 2 所制备的TPEE复合材料与其他文献报道的阻燃TPEE复合材料的阻燃性能比较^{[1-5, 7, 10, 12]}

Figure 2. Flame retardancy comparison of as-prepared TPEE composites with other previously reported flame retardant TPEE composites^{[1-5, 7, 10, 12]}

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图 3 MPP-AlPi/TPEE复合材料的热释放率(HRR) (a)、总热释放(THR) (b)、质量损失率(MLR) (c)和TPEE (d)、3MPP-9AlPi/TPEE (e)、4.25MPP-12.75AlPi/TPEE (f)、5.5MPP-16.5AlPi/TPEE (g)复合材料在锥形量热实验后的残炭照片

Figure 3. Heat release rate (HRR) (a), total heat release (THR) (b), mass loss rate (MLR) (c) of MPP-AlPi/TPEE composite materials and carbon residue photos of TPEE (d), 3MPP-9AlPi/TPEE (e), 4.25MPP-12.75AlPi/TPEE (f) and 5.5MPP-16.5AlPi/TPEE (g) after cone calorimetry test

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图 4 MPP-AlPi/TPEE复合材料、AlPi和MPP的TGA (a)及DTG (b)测试曲线

Figure 4. TGA (a) and DTG (b) curves of MPP-AlPi/TPEE composites, AlPi and MPP

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图 5 TPEE (a)、3MPP-9AlPi/TPEE (b)和5.5MPP-16.5AlPi/TPEE (c)的断面微观形貌及4.25MPP-12.75AlPi/TPEE (d)和5.5MPP-16.5AlPi/TPEE (e)在锥形量热实验后的微观形态

Figure 5. SEM images of shear cross-section microstructure of TPEE (a), 3MPP-9AlPi/TPEE (b), 5.5MPP-16.5AlPi/TPEE (c) and micromorphology of carbon layer of 4.25MPP-12.75AlPi/TPEE (d) and 5.5MPP-16.5AlPi/TPEE (e) after cone calorimetry test

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图 6 MPP-AlPi/TPEE 复合材料的拉伸强度和断裂伸长率

Figure 6. Tensile strength and elongation at break of MPP-AlPi/TPEE composites

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表 1 三聚氰胺聚磷酸盐(MPP)-二乙基次磷酸铝(AlPi)/热塑性聚酯弹性体(TPEE)复合材料的配方

Table 1. Formulations of melamine polyphosphate (MPP)-aluminum diethylphosphinate (AlPi)/thermoplastic polyester elastomer (TPEE) composites

Sample	TPEE/wt%	AlPi/wt%	MPP/wt%
TPEE 3MPP-9AlPi/TPEE 4.25MPP-12.75AlPi/TPEE 5.5MPP-16.5AlPi/TPEE	100 88 83 78	0.00 9.00 12.75 16.50	0.00 3.00 4.25 5.50
Note: Each sample contains an additional 2% antioxidant 1010.

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表 2 不同MPP-AlPi/TPEE复合材料的极限氧指数(LOI)及垂直燃烧(UL-94)测试结果

Table 2. Limiting oxygen index (LOI) and vertical burning (UL-94) test results of different MPP-AlPi/TPEE composites

Sample	LOI/%	UL-94	Driping	t₁/s	t₂/s
TPEE	19.3	No rating	Yes	—^a	—^a
3MPP-9AlPi/TPEE	26.3	No rating	Yes	—^a	—^a
4.25MPP-12.75AlPi/TPEE	27.6	V-0	No	2.3	5.7
5.5MPP-16.5AlPi/TPEE	31.5	V-0	No	0.0	1.1
Notes: t₁—Self-extinguishing time after the first ignition; t₂—Self-extinguishing time after the second ignition; —^a: After ignition, the sample continues to burn until it is completely burned out.

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表 3 不同MPP-AlPi/TPEE复合材料的锥形量热数据

Table 3. Cone calorimetric data of different MPP-AlPi/TPEE composites

Sample	TTI/s	T_p/s	PHRR/ (kW·m^–2)	THR/ (MJ·m^–2)	CO yield/ (kg·kg^–1)	CO₂ yield/ (kg·kg^–1)	Residue/ %	FGI	FPI
TPEE	33	65	529.0±5.8	41.4±2.6	0.04±0.01	1.82±0.01	4.2±0.1	8.1	0.‍06
3MPP-9AlPi/TPEE	40	105	277.1±3.2	34.9±2.1	0.18±0.02	1.43±0.02	10.1±0.1	2.6	0.14
4.25MPP-12.75AlPi/TPEE	39	116	260.7±2.8	36.0±2.3	0.21±0.01	1.43±0.01	10.6±0.2	2.3	0.15
5.5MPP-16.5AlPi/TPEE	41	114	186.3±2.4	30.0±1.8	0.20±0.01	1.43±0.01	28.0±0.1	1.6	0.22
Notes: TTI—Ignition time; T_p—Time to reach peak heat release rate; PHRR—Peak heat release rate; FGI—Fire growth index; FPI—Fire performance index.

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表 4 MPP-AlPi/TPEE复合材料在空气中的TGA数据

Table 4. TGA data of MPP-AlPi/TPEE composites in air

Sample	T_5%/℃	T_max/℃	DTG_max/(%·℃^–1)	Residue at 700℃ (Exp.)/wt%	Residue at 700℃ (Cal.)/wt%
TPEE	333.1	393.1	1.9	0.5	—
AlPi	435.6	445.6	2.2	24.0	—
MPP	351.7	411.1	1.0	21.0	—
3MPP-9AlPi/TPEE	342.1	390.0	1.8	4.1	3.2
4.25MPP-12.75AlPi/TPEE	347.1	391.2	1.7	5.1	4.4
5.5MPP-16.5AlPi/TPEE	348.2	392.2	1.6	7.0	5.5
Notes: T_5%—Initial degradation temperature of the composite; T_max—Temperature at maximum mass loss rate; DTG_max—Maximum mass loss rate; Exp.—Experimental value; Cal.—Calculated value.

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表 5 MPP-AlPi/TPEE复合材料的杨氏模量

Table 5. Young's modulus of MPP-AlPi/TPEE composites

Sample	Young's modulus/MPa
TPEE	4.32±0.23
3MPP-9AlPi/TPEE	4.26±0.26
4.25MPP-12.75AlPi/TPEE	7.01±0.55
5.5MPP-16.5AlPi/TPEE	45.48±1.58

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表 6 MPP-AlPi/TPEE复合材料的体积电阻率

Table 6. Volume resistivity of MPP-AlPi/TPEE composites

Sample	Volume resistivity/(10¹¹Ω·m)
TPEE	3.41±0.34
3MPP-9AlPi/TPEE	6.21±0.46
4.25MPP-12.75AlPi/TPEE	8.59±0.57
5.5MPP-16.5AlPi/TPEE	16.90±8.90

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