磷氮复合阻燃环氧树脂的制备及其阻燃性能

李亮; 蔡再生

doi:10.13801/j.cnki.fhclxb.20200319.003

磷氮复合阻燃环氧树脂的制备及其阻燃性能

doi: 10.13801/j.cnki.fhclxb.20200319.003

李亮^{1, 2,},
蔡再生^1, ,

1.
东华大学　化学化工与生物工程学院，上海 201620
2.
盐城工业职业技术学院　药品与健康学院，盐城 224005

基金项目: 江苏省高等学校自然科学研究计划面上项目(19KJD430009)；盐城工业职业技术学院自然科学项目(ygy1702)

详细信息

通讯作者:
蔡再生，博士，教授，博士生导师，研究方向为功能高分子材料　E-mail：zshcai@dhu.edu.cn

中图分类号: TB332
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- 被引次数: 0
出版历程
- 收稿日期: 2019-12-31
- 录用日期: 2020-03-10
- 网络出版日期: 2020-03-20
- 刊出日期: 2020-11-15

Preparation and performance of flame-retardant epoxy resin composite containing phosphorus and nitrogen

LI Liang^{1, 2
,},
CAI Zaisheng^{1
, ,}

1.
College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai 201620, China
2.
School of Pharmacy and Health, Yancheng Polytechnic College, Yancheng 224005, China

摘要

摘要: 为改善环氧树脂的阻燃性，成功合成了一种含苯砜基和磷杂菲杂环的阻燃添加剂(FRASP)。采用傅里叶变换衰减全反射红外光谱法(ATR-FTIR)、核磁共振(NMR)和元素分析等手段对FRASP的化学结构进行表征。将FRASP添加到双酚A型环氧树脂(DGEBA)中，经4,4’-二氨基二苯甲烷(DDM)固化后，制备出DGEBA-FRASP复合树脂。FRASP质量分数为9wt%的DGEBA-FRASP复合树脂的极限氧指数(LOI)达到35.9%，垂直燃烧(UL94)的等级为V-0级。残炭的形貌和激光拉曼光谱(LRS)分析显示，FRASP促进膨胀、致密、高石墨化程度的多孔炭层的生成。热重分析表明，FRASP改变了DGEBA-FRASP复合树脂的热降解过程，促进了DGEBA-FRASP复合树脂提前热分解，使最大失重率降低，并提高了残炭量。热裂解分析显示，DGEBA-FRASP复合树脂裂解过程中产生了含磷分子和不可燃气体，可稀释O₂并抑制燃烧过程中自由基链式反应。FRASP分子中P、N和S的协同作用，改善了DGEBA-FRASP复合树脂的阻燃性能。
- 热固性材料 /
- 热分析 /
- 阻燃剂 /
- 环氧树脂 /
- 协同效应
Abstract: A flame retardant additive with sulfone and phosphaphenanthrene groups (FRASP) was successfully synthesized for improving the flame retardancy of diglycidyl ether of bisphenol A type epoxy resins (DGEBA). The chemical structure of FRASP was characterized by attenuated total internal reflectance Fourier transform infrared spectroscopy (ATR-FTIR), nuclear magnetic resonance (NMR) and elemental analysis. FRASP was added into DGEBA, and the flame-retardant DGEBA-FRASP composite resins were prepared via thermal curing reaction between 4,4’-diaminodiphenyl methane (DDM) and the mixed DGEBA. When the mass fraction of FRASP is 9wt%, the limiting oxygen index (LOI) reaches 35.9%, and V-0 rating under the vertical combustion (UL94) test is achieved. The morphology and Laser Raman spectroscopy (LRS) analysis of char residues after UL94 test indicate that the addition of FRASP favor the generation of an intumescent, tight and high-graphitization degree char layer with porous structure inside. The thermosgravimetric analysis results reveal that FRASP changes the thermal degradation process of DGEBA-FRASP composite resins and the maximum mass loss rate decreases, which results in a higher residual char. Pyrolysis-gas chromatography/mass spectrometry analysis shows that the phosphorus fragments and nonflammable gas release during DGEBA-FRASP composite resins thermal decomposition, which can dilute the O₂ and act as free radical inhibitors in combustion. Owing to the synergistic effect of P, N and S in condensed and gas phase, the DGEBA-FRASP composite resins display improved flame-retardancy.
- thermosetting resin /
- thermal analysis /
- flame retardant /
- epoxy resin /
- synergism

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图 1 含苯砜基和磷杂菲杂环的阻燃添加剂(FRASP)的合成路线

Figure 1. Synthetic routes of flame retardant additive with sulfone and phosphaphenanthrene groups (FRASP)

DP—N-phenylsulfonyl dibenzimide; DMF—N,N-dimethylformamide

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图 2 对苯二甲醛、4,4’-二氨基二苯砜(DDS)、亚胺(DP)和FRASP的FTIR图谱

Figure 2. FTIR spectra of 1,4-Phthalaldehyde, 4,4’-diaminodiphenylsulfon (DDS), N-phenylsulfonyl dibenzimide (DP) and FRASP

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图 3 FRASP的³¹P-NMR and ¹H-NMR图谱

Figure 3. ³¹P-NMR and ¹H-NMR spectra of FRASP

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图 4 DGEBA和DGEBA-FRASP树脂在UL94测试时的图片

Figure 4. Digital photographs of DGEBA and DGEBA-FRASP resins in UL94 test

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图 5 DGEBA和DGEBA-FRASP树脂残炭的照片和SEM图像

Figure 5. Digital photographs and SEM images of char residue of DGEBA and DGEBA-FRASP resins

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图 6 N₂氛围下DGEBA和DGEBA-FRASP树脂热降解前(a)、残炭外部(b)和残炭内部(c)的图片

Figure 6. Digital photographs of DGEBA and DGEBA-FRASP resins before degradation(a) and exterior(b) and interior(c) of char residue after degradation in N₂

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图 7 DGEBA和DGEBA-FRASP树脂残碳的拉曼图谱

Figure 7. Raman spectra of char residue of DGEBA and DGEBA-FRASP resins

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图 8 FRASP、DGEBA和DGEBA-FRASP树脂在空气下的TG和DTG曲线

Figure 8. TG and DTG curves of FRASP, DGEBA and DGEBA-FRASP resins in air atmosphere

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图 9 FRASP、DGEBA和DGEBA-FRASP树脂在N₂下的TG和DTG曲线

Figure 9. TG and DTG curves of FRASP, DGEBA and DGEBA-FRASP resins in N₂ atmosphere

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图 10 FRASP的热裂解图谱

Figure 10. Pyrogram of FRASP

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图 11 DGEBA和DGEBA-FRASP9树脂的热裂解图谱

Figure 11. Pyrograms of DGEBA and DGEBA-FRASP9 resins

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表 1 双酚A型环氧树脂(DGEBA)-FRASP复合树脂的配方及FRASP的质量分数

Table 1. Formulas of diglycidyl ether of bisphenol A(DGEBA)-FRASP composite reins and mass fraction of FRASP

Sample	Composition/g			M_FRASP/wt%
Sample	DGEBA	DDM	FRASP	M_FRASP/wt%
Neat DGEBA	100	22	0	0
DGEBA-FRASP3	100	22	3.77	3
DGEBA-FRASP6	100	22	7.79	6
DGEBA-FRASP9	100	22	12.07	9
Notes: DDM—4,4-diaminodiphenyl methane; M_FRASP—Mass fraction of FRASP in DGEBA-FRASP composite resins.

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表 2 DGEBA和DGEBA-FRASP树脂的垂直燃烧(UL94)和极限氧指数(LOI)测试结果

Table 2. Vertical combustion (UL94) and limiting oxygen index (LOI) test results of DGEBA and DGEBA-FRASP resins

Sample	LOI/%	t₁ +t₂/s	Dripping	Rating
DGEBA	24.8	NR	Yes	No rating
DGEBA-FRASP3	33.7	6.1+6.3	No	V-1
DGEBA-FRASP6	34.5	4.3+3.0	No	V-0
DGEBA-FRASP9	35.9	2.3+1.9	No	V-0
Notes: t₁—Self-extinguishing time after the first ignition, take the average value of 2 sets of samples; t₂—Self-extinguishing time after the second ignition, take the average value of 2 sets of samples; NR—No ranking.

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表 3 FRASP、DGEBA和DGEBA-FRASP树脂在空气下的TGA数据

Table 3. TGA data of FRASP, DGEBA and DGEBA-FRASP resins in air atmosphere

Sample	T_5%/℃	T_max/℃	V_max/(%·℃^–1)	C_Y700/%
DGEBA	362.2	384.7	–1.45	1.90
FRASP	292.1	361.4	–0.46	43.41
DGEBA-FRASP3	343.8	374.6	–1.26	2.85
DGEBA-FRASP6	339.1	368.3	–1.14	3.72
DGEBA-FRASP9	332.4	363.2	–1.13	5.74
Notes: T_5%―Temperature at 5% mass loss; T_max―Temperature at the maximum mass loss rate; V_max―Maximum mass loss rate; C_Y700―Char yield at 700℃.

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表 4 FRASP、DGEBA和DGEBA-FRASP树脂在N₂下的TGA数据

Table 4. TGA data of FRASP, DGEBA and DGEBA-FRASP resins in N₂ atmosphere

Sample	T_5%/℃	T_max/℃	V_max/(%·℃^–1)	C_Y700/%
DGEBA	367.9	387.2	–1.76	16.58
FRASP	310.1	365.3	–0.81	33.40
DGEBA-FRASP3	357.8	382.1	–1.25	19.48
DGEBA-FRASP6	353.9	379.6	–1.19	21.27
DGEBA-FRASP9	341.3	377.1	–1.16	22.96

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