环三磷腈-DOPO大分子阻燃剂的合成及阻燃环氧树脂性能

doi:10.7503/cjcu20190257

摘要/Abstract

摘要：

通过取代反应、缩合反应和加成反应等合成了一种无机-有机杂化大分子阻燃剂六-[4-(N-苯基氨基-DOPO-次甲基)苯氧基]环三磷腈(DOPO-PCP), 并利用傅里叶变换红外光谱、 ¹H和 ³¹P核磁共振波谱对其进行结构表征. 将DOPO-PCP用于环氧树脂(DGEBA)阻燃, 得到环氧树脂阻燃固化物, 通过极限氧指数(LOI)、垂直燃烧测试(UL-94)、热重分析与锥形量热(Cone)测试等对阻燃环氧树脂固化物的热稳定性及燃烧性能进行分析; 利用扫描电子显微镜及Mapping观察并分析了燃烧碳层的形貌与元素分布. 研究结果表明, 产物的结构符合设计的DOPO-PCP分子结构; 当DOPO-PCP在DGEBA中添加量(质量分数)达12.2%时, 磷含量为1.3%, 制得的阻燃环氧树脂固化物垂直燃烧测试通过UL-94 V-0级, LOI值为36.2%; Cone测试结果表明, DOPO-PCP的添加有效降低了DGEBA燃烧时热量与烟气的释放, 且在高温下碳残余量显著增加. 研究表明DOPO-PCP兼具气相和凝固相阻燃机理, 对DGEBA有良好的阻燃性能.

关键词: 环三磷腈-DOPO大分子, 阻燃剂, 环氧树脂

Abstract:

A novel inorganic-organic hybrid macromolecule flame retardant, hexa-[4-(N-phenylamino-DOPO-methenyl)-phenoxyl]-cyclotriphosphazene(DOPO-PCP, DOPO=9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide) was synthesized successfully through three-step reactions including substitution, condensation and addition. The chemical structure of DOPO-PCP was characterized by Fourier transform infrared spectroscopy, ¹H and ³¹P nuclear magnetic resonance spectroscopies. All the results conformed the functional groups of the DOPO-PCP designed. Then the thermal stability of DOPO-PCP, pure epoxy(DGEBA) and their composites was analyzed by thermogravimetric analysis, and the properties of flame-retarded cured epoxy were investigated by limited oxygen index(LOI), UL-94 vertical burning test and Cone calorimeter test. Among all the samples, P-1.3 passed UL-94 V-0 level test and its LOI value reached 36.2%, while the phosphorus content in it was only 1.3%. In cone calorimeter test, the heat release rate(HRR) and the smoke production rate(SPR) of P-1.3 went down obviously, meanwhile, its residual char mass increased significantly, demonstrating that DOPO-PCP was favored to flame-retarded DGEBA. Furthermore, the SEM images showed the excellent compatibility between the additives and DGEBA matrix, which made for the formation of the continuous char layer. The mapping photographs displayed the uniform distribution of phosphorus and nitrogen elements in intumescent char layer. As a result, DOPO-PCP was evaluated as a higher efficiency flame retardant by synergistic flame retardant mechanism in both gas phase and the solidification phase.

Key words: Cyclotriphosphazene-DOPO macromolecule(DOPO=9, 10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide), Flame retardant, Epoxy resin

中图分类号:

O631.3

TrendMD:

江民文,尹晨辉,李胜,李晓丽. 环三磷腈-DOPO大分子阻燃剂的合成及阻燃环氧树脂性能. 高等学校化学学报, 2019, 40(12): 2615.

Minwen JIANG,Chenhui YIN,Sheng LI,Xiaoli LI. Synthesis of DOPO-based Cyclotriphosphazene Macromolecule Flame Retardant and Its Performance in Flame-retarded Epoxy Resin ^†. Chem. J. Chinese Universities, 2019, 40(12): 2615.

图/表 15

Scheme 1 Synthetic routes of DOPO-PCP

Fig.1 FTIR spectra of HAPCP(a), HPA-PCP(b) and DOPO-PCP(c)

Fig.2 1H NMR spectrum of DOPO-PCP

Fig.3 31P NMR spectrum of DOPO-PCP

Table 1 Formulations and flame retardancy for epoxy resins thermosets

Sample	m(DGEBA)/g	m(DDS)/g	m(DOPO-PCP)/g	w(DOPO-PCP)(%)	w(P)(%)	LOI(%)	UL-94 rating
Sample	m(DGEBA)/g	m(DDS)/g	m(DOPO-PCP)/g	w(DOPO-PCP)(%)	w(P)(%)	LOI(%)	3.0 mm	Dripping
DGEBA	100	31	0	0	0	21.7	Fail	NO
P-1.0	100	31	13.5	9.3	1.0	35.4	V-1	NO
P-1.1	100	31	15.0	10.3	1.1	35.5	V-1	NO
P-1.2	100	31	16.6	11.2	1.2	35.8	V-1	NO
P-1.3	100	31	18.1	12.1	1.3	36.2	V-0	NO

Fig.4 TGA(A) and DTG(B) curves of DOPO-PCP(a), DGEBA(b) and P-1.3(c)

Table 2 Thermal degradation data of DOPO-PCP, DGEBA and P-1.3

Sample	$T 1 % *$ /℃	$T 5 % *$ /℃	R_{peak 1}/T_{peak 1} (%·min^-1/℃)	R_{peak 2}/T_{peak 2} (%·min^-1/℃)	Mass fraction at 700 ℃(%)
DOPO-PCP	246.6	287.1	3.01/303.3	468.9	46.1
DGEBA	350.4	385.4	20.87/418.8		15.4
P-1.3	277.5	338.7	13.93/387.3		28.2

Table 2 Thermal degradation data of DOPO-PCP, DGEBA and P-1.3

Sample	$T 1 % *$ /℃	$T 5 % *$ /℃	R_{peak 1}/T_{peak 1} (%·min^-1/℃)	R_{peak 2}/T_{peak 2} (%·min^-1/℃)	Mass fraction at 700 ℃(%)
DOPO-PCP	246.6	287.1	3.01/303.3	468.9	46.1
DGEBA	350.4	385.4	20.87/418.8		15.4
P-1.3	277.5	338.7	13.93/387.3		28.2

Table 3 Cone calorimeter data forDGEBA and P-1.3

Sample	DGEBA	P-1.3
TTI/s	63	51
Av-EHC/(MJ·kg^-1)	24.43	17.93
Peak _1-HRR/(kW·m^-2)	857.9	252.4
t_{Peak 1-HRR}/s	120	60
Peak_2-HRR/(kW·m^-2)		352.1
t_{Peak 2-HRR}/s		185
THR/(MJ·m^-2)	93.0	51.1
Peak _1-SPR/(m²·s^-1)	0.36	0.20
t_{Peak 1-SPR}/s	115	60
Peak _2-SPR/(m²·s^-1)		0.19
t_{Peak 2-SPR}/s		170
TSP/(m²·kg^-1)	36.85	26.14

Fig.5 HRR(A) and THR(B) curves of DGEBA(a) and P-1.3(b)

Fig.6 SPR(A) and TSP(B) curves of DGEBA(a) and P-1.3(b)

Fig.7 Residual char mass curves of DGEBA(a) and P-1.3(b)

Fig.8 Digital photos of the char residues after cone calorimeter tests (A) Top view, DGEBA; (B) main view, P-1.3; (C) top view, P-1.3.

Fig.9 SEM images of char residue of DGEBA(A) and P-1.3(B) after Cone calorimeter tests

Fig.10 SEM images of fracture surfaces of DGEBA(A) and P-1.3(B)

Fig.11 Merged EDX elements mapping images of P-1.3 after cone calorimeter tests (A) N; (B) P.

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