聚磷酸铵-三聚氰胺-三嗪成炭剂协同阻燃改性环氧树脂及玻璃纤维增强树脂复合材料

李想; 陈润华; 魏毅; 蔡欢欢; 刘万双

doi:10.13801/j.cnki.fhclxb.20201116.001

聚磷酸铵-三聚氰胺-三嗪成炭剂协同阻燃改性环氧树脂及玻璃纤维增强树脂复合材料

doi: 10.13801/j.cnki.fhclxb.20201116.001

李想^1,,
陈润华^1,,
魏毅^2,,
蔡欢欢^1,,
刘万双^2, ,

1.
中国船舶重工集团公司第七二五研究所，洛阳 471039
2.
东华大学民用航空复合材料协同创新中心，上海 201620

基金项目: 上海市自然科学基金(18ZR1400700)

详细信息

通讯作者:
刘万双，博士，副教授，硕士生导师，研究方向为环氧树脂及其纤维增强复合材料　E-mail：wsliu@dhu.edu.cn

中图分类号: TB332；TQ323.5
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出版历程
- 收稿日期: 2020-09-14
- 修回日期: 2020-10-22
- 录用日期: 2020-11-12
- 网络出版日期: 2020-11-16
- 刊出日期: 2021-09-01

Flame retardant epoxy resins and glass fiber reinforced epoxy composites synergistically modified by ammonium polyphosphate, melamine and triazine carbon-forming agent

LI Xiang^1
,,
CHEN Runhua^1
,,
WEI Yi^2
,,
CAI Huanhuan^1
,,
LIU Wanshuang^{2
, ,}

1.
Luoyang Ship Material Research Institute, Luoyang 471023, China
2.
Center for Civil Aviation Composites, Donghua University, Shanghai 201620, China

摘要

摘要: 采用聚磷酸铵(APP)与不同比例三聚氰胺(MA)和三嗪成炭剂(CFA)复配对环氧树脂进行阻燃改性。系统研究了不同配比阻燃剂(总量保持40wt%)的加入对环氧树脂流变特性、固化行为、热机械性能、力学性能及阻燃性能的影响。将优化后的阻燃改性环氧树脂用于制备玻璃纤维增强环氧树脂复合材料(GFRC)，对并其力学和阻燃性能进行了研究。结果表明，APP单独与MA或CFA复配改性环氧树脂并未表现出明显的协同阻燃效应，但它们组成的三元复配阻燃体系(30wt%APP-5wt%MA-5wt%CFA)具有良好的协同阻燃效应。相比未改性环氧树脂，APP-MA-CFA改性环氧树脂的极限氧指数(LOI)由18.0%提高到了50.2%，热释放峰值速率(PHRR)下降了84%，总热释放量(THR)下降了78%。树脂基体中加入阻燃剂后，GFRC的力学性能有所下降，尤其是层间剪切强度。同样地，基于APP-MA-CFA复配改性环氧树脂的GFRC表现出最佳阻燃性能，相比未改性的GFRC，其LOI值由22.8%提高到了66.0%，PHRR由354 kW/m²下降到93 kW/m²，THR由49.3 MJ/m²下降到22.8 MJ/m²。
- 热固性树脂 /
- 聚合物基复合材料 /
- 层压板 /
- 力学性能 /
- 阻燃性能
Abstract: Epoxy resins were modified by ammonium polyphosphate (APP) and its combination with different contents of melamine (MA) and triazine carbon-forming agent (CFA). The effects of flame retardants with different proportions(total content of 40wt%) on the rheological, curing, thermomechanical, mechanical and flame-retardant properties of epoxy resins were investigated systematically. The optimized flameretardant epoxy resin was used to fabricate glass fiber reinforced epoxy composite (GFRC), and the mechanical as well as flame retardancy of the resulting GFRC were studied. The results show that the epoxy resins modified by APP-MA and APP-CFA combinations do not show apparent synergistic flame retardancy effects, but the ternary APP-MA-CFA system (30wt%APP-5wt% MA-5wt%CFA) demonstrates superior synergistic flame retardancy effects. Compared with the unmodified epoxy resin, the epoxy resin modified by APP-MA-CFA exhibits an increase in limit oxygen index (LOI) from 18% to 50.2%, a 84% decrease in peak heat release rate (PHRR) and a 78% decrease in total hear release (THR). With the addition of flame retardants in the epoxy matrix, the GFRC shows deteriorative mechanical properties, especially for interlaminar shear strength. Again, the GFRC based on the epoxy matrix modified by APP-MA-CFA presents the best flame-retardant performance. Compared with the unmodified GFRC, the modified GFRC shows an increased LOI (from 22.8% to 66.0%), a decreased PHRR (from 354 kW/m² to 93 kW/m²) and a decreased THR (from 49.3 MJ/m² to 22.8 MJ/m²).
- thermosetting resins /
- polymer-matrix composites /
- laminates /
- mechanical properties /
- flame-retardant properties

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图 1 加入不同质量分数聚磷酸铵(APP)后环氧树脂黏度值

Figure 1. Viscosity values of epoxy resins with different contents of ammonium polyphosphate (APP)

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图 2 加入APP、三聚氰胺(MA)和三嗪成炭剂(CFA)后环氧树脂黏度值

Figure 2. Viscosity values of epoxy resins with the addition of APP, melamine (MA) and triazine carbon-forming agent (CFA)

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图 3 未改性和阻燃改性环氧树脂的DSC曲线

Figure 3. DSC curves of unmodified and flame retardant modified epoxy resins

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图 4 未改性和阻燃改性环氧树脂的储能模量(a)和损耗模量(b)随温度变化曲线

Figure 4. Storage modulus (a) and loss modulus (b) versus temperature curves of unmodified and flame retardant modified epoxy resins

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图 5 未改性和阻燃改性环氧树脂的拉伸强度(a)和拉伸模量(b)

Figure 5. Tensile strength (a) and modulus (b) of unmodified and flame retardant modified epoxy resins

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图 6 未改性和阻燃改性环氧树脂的热释放速率(a)和总热释放(b)随时间变化曲线

Figure 6. Heat release rate (a) and total heat release (b) versus time curves of unmodified and flame retardant modified epoxy resins

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图 7 40APP/EP (a)和30APP-5MA-CFA/EP (b)试样燃烧后照片；未改性环氧树脂((c)、(d))、40APP((e)、(f))和30APP-5MA-CF/EP ((g)、(h))试样燃烧后残炭在500和2 000倍下SEM图像

Figure 7. Images of 40APP/EP (a) and 30APP-5MA-CFA/EP (b) after combustion；SEM images of char residues after combustion for unmodified epoxy ((c), (d)), 40APP/EP ((e), (f)) and 30APP-5MA-CFA/EP ((g), (h)) at 500 and 2000 magnification

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图 8 未改性和阻燃改性玻璃纤维增强环氧树脂复合材料(GFRC)的弯曲强度(a)和弯曲模量(b)

Figure 8. Flexural strength (a) and modulus (b) of unmodified and flame retardant modified glass fiber reinforced epoxy composites (GFRC)

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图 9 未改性和阻燃改性GFRC的层间剪切强度

Figure 9. Interlaminar shear streng thof unmodified and flame retardant modified GFRC

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图 10 未改性和阻燃改性GFRC的热释放速率(a)和总热释放(b)随时间变化曲线

Figure 10. Heat release rate (a) and total heat release (b) versus time curves of unmodified and flame retardant modified GFRC

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表 1 未改性和阻燃改性环氧树脂组成配方

Table 1. Formulations of unmodified and flame retardant modified epoxy resins

Sample	EP828/wt%	Neopentyl diglycidyl ether/wt%	HTDA/wt%	APP/wt%	MA/wt%	CFA/wt%
Neat	30	20	10	0	0	0
20APP/EP	30	20	10	15	0	0
30APP/EP	30	20	10	26	0	0
40APP/EP	30	20	10	40	0	0
35APP-5MA/EP	30	20	10	35	5	0
30APP-10MA/EP	30	20	10	30	10	0
35APP-5CFA/EP	30	20	10	35	0	5
30APP-10CFA/EP	30	20	10	30	0	10
30APP-5MA-5CFA/EP	30	20	10	30	5	5
Notes: EP—Epoxy; HTDA—Methyl cyclohexandiamine; APP—Ammonium polyphosphate; MA—melamine; CFA—Triazine carbon-forming agent.

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表 2 不同含量APP改性环氧树脂的极限氧指数(LOI)和UL-94测试结果

Table 2. Limiting oxygen index (LOI) and UL-94 rating of epoxy resins with different APP contents

Sample	LOI/%	UL-94
Neat	18.0	No rating
20APP/EP	34.0	V0
30APP/EP	36.5	V0
40APP/EP	47.3	V0

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表 3 未改性和阻燃改性环氧树脂的DSC和动态力学分析测试数据

Table 3. DSC and dynamic mechanic alanalysis data of unmodified and flame retardant modified epoxy resins

Sample	ΔH/(J.g⁻¹)	T_i/℃	T_p/℃	Storage modulus at 30℃/MPa	T_g/℃
Neat	446	52	106	2675	94
40APP/EP	290	58	122	4064	108
35APP-5MA/EP	295	50	116	3854	108
30APP-10MA/EP	293	46	117	3651	107
35APP-5CFA/EP	283	53	109	3802	111
30APP-10CFA/EP	287	50	116	3458	110
30APP-5MA-5CFA/EP	275	52	110	3639	110
Notes: ΔH—Enthalpy change of curingreaction; T_i—Initial curing temperature; T_p—Peak temperature; T_g—Glass transition temperature.

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表 4 未改性和阻燃改性环氧树脂的LOI和UL-94测试结果

Table 4. LOI and UL-94 rating of unmodified and flame retardant modified epoxy resins

Sample	LOI/%	UL-94
Neat	18.0	No rating
40APP/EP	47.3	V0
35APP-5MA/EP	46.1	V0
30APP-10MA/EP	47.6	V0
35APP-5CFA/EP	46.7	V0
30APP-10CFA/EP	48.9	V0
30APP-5MA-CFA/EP	50.2	V0

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表 5 未改性和阻燃改性环氧树脂的锥形量热测试数据

Table 5. Data of cone calorimeter tests for unmodified and flame retardant modified epoxy resins

Sample	PHRR/(kW·m⁻²)	THR/(MJ·m⁻²)	av-ECH/(MJ·kg⁻¹)	av-CO/(kg·kg⁻¹)	av-CO₂/(kg·kg⁻¹)	Mass loss/%
Neat	1 055	107.0	18.30	0.21	1.99	98.6
40APP/EP	200	26.2	2.50	0.049	0.64	58.9
35APP-5MA/EP	211	27.5	2.33	0.035	0.52	61.5
30APP-10MA/EP	194	25.8	1.88	0.036	0.49	67.3
35APP-/5CFA/EP	249	27.0	4.37	0.051	0.61	40.3
30APP-10CFA/EP	192	25.0	2.06	0.035	0.50	61.3
30APP-5MA-CFA/EP	172	24.0	1.52	0.031	0.42	44.5
Notes: PHRR—Peak heat release rate; THR—Total heat release；av-ECH—Average effective heat of combustion；av-CO—Average release rate of CO；av-CO₂—Average release rate of CO₂.

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表 6 未改性和阻燃改性玻璃纤维增强环氧树脂复合材料(GFRC)的LOI、UL-94和锥形量热测试数据

Table 6. LOI, UL-94 rating and data of cone calorimeter tests for unmodified and flame retardant modified GFRC

Sample	LOI/%	UL-94	PHRR/(kW·m⁻²)	THR/(MJ·m⁻²)
Neat	22.8	No rating	354	49.3
40APP/EP	56.0	V0	114	31.2
30APP-5MA-5CFA/EP	66.0	V0	93	22.8

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