有机磷/硼杂化小分子阻燃改性环氧树脂

doi:10.11949/0438-1157.20201832

摘要/Abstract

摘要：

从二苯基次膦酰氯和苯基磷酰二氯出发，分别合成了含单个苯硼酸基团和含两个苯硼酸基团的两种有机磷/硼杂化小分子（缩写为：DPC-1B和PDS-2B）。两种杂化小分子与环氧树脂有着良好的相容性并可参与环氧固化，在比较低的添加量下便有较高的机械强度和优异的阻燃性能，且保持环氧的透明度。DPC-1B和PDS-2B添加量为2%（质量）时，复合材料氧指数从25.7%分别提高到了31.8%和31.5%，热释放速率峰值分别降低了26.5%与21.8%，UL-94阻燃等级均达到了V-0级。改性环氧树脂燃烧后的残炭分析表明，炭层外部连续紧密，内部多蓬松，硼磷共同作用形成致密炭层，隔绝热质传递，从而达到阻燃效果。

关键词: 有机化合物, 聚合物, 阻燃, 力学性能, 透明度

Abstract:

As a common polymer material, epoxy resin (EP) is flammable. Traditional EP usually loses its transparency after flame retardant incorporated. Besides, it is hard to obtain the satisfying flame-retardant efficiency with low loading amount. In this work, two kinds of flame retardant with organophosphorus/boron hybrid were successfully synthesized (abbreviated as: DPC-1B and PDS-2B) by simple reaction between diphenylphosphinyl chloride/phenylphosphoryl dichloride and 4-hydroxyphenylboric acid. After introduced 2.0%(mass) of DPC- 1B or PDS-2B, the EP composite reached V-0 rating in the UL-94 vertical burning test and the limited oxygen index (LOI) values increased from 25.7% to 31.8% and 31.5% respectively. Interestingly, the EP composite still presented excellent transparency. Furthermore, the peak heat release rate of the flame retardant EP decreased 26.5% and 21.8%. Due to the combination of boron and phosphorus, a dense carbon layer was formed, which insulated the heat and achieves the flame retardant effect. Accordingly, the two novel flame retardant demonstrate promising applications in the flame retardant of EP without sacrifice of transparency.

Key words: organic compounds, polymers, flame retardant, mechanical properties, transparency

中图分类号:

TQ 314.22

纪荣彬, 陈婷, 彭超华, 夏龙, 陈国荣, 罗伟昂, 曾碧榕, 许一婷, 袁丛辉, 戴李宗. 有机磷/硼杂化小分子阻燃改性环氧树脂[J]. 化工学报, 2021, 72(7): 3856-3868.

JI Rongbin, CHEN Ting, PENG Chaohua, XIA Long, CHEN Guorong, LUO Wei'ang, ZENG Birong, XU Yiting, YUAN Conghui, DAI Lizong. Flame retardant epoxy resin composites modified with organophosphorus and boron hybrid molecules[J]. CIESC Journal, 2021, 72(7): 3856-3868.

图/表 19

图1 DPC-1B的合成路线

Fig.1 Synthetic route of DPC-1B

图2 PDS-2B的合成路线

Fig.2 Synthetic route of PDS-2B

图3 DPC-1B的核磁氢谱(a)、磷谱(b)、碳谱(c)

Fig.3 1H (a), 31P (b) and 13C (c) NMR spectra of DPC-1B

图4 PDS-2B的核磁氢谱(a)、磷谱(b)、碳谱(c)

Fig.4 1H (a), 31P (b) and 13C (c) NMR spectra of PDS-2B

图5 阻燃剂DPC-1B与PDS-2B的红外谱图

Fig.5 FT-IR spectra of DPC-1B and PDS-2B

表1 DPC-1B、PDS-2B的热分解数据

Table 1 Thermal decomposition data of DPC-1B and PDS-2B

Samples	Nitrogen					Air
Samples	T_o/℃	T_max1/℃	T_max2/℃	T_max3/℃	W_re/%	T_o/℃	T_max1/℃	T_max2/℃	T_max3/℃	W_re/%
DPC-1B	120.80	134.40	288.31	432.73	11.53	116.75	143.36	290.43	400.11	19.62
PDS-2B	100.12	113.21	392.53	515.16	36.55	93.29	122.25	398.43	518.77	31.13

图6 DPC-1B、PDS-2B在氮气氛围和空气氛围下的TG曲线(a),(c)和DTG曲线(b), (d)

Fig.6 TG (a), (c) and DTG (b), (d) curves of DPC-1B and PDS-2B under nitrogen atmosphere and air atmosphere

图7 环氧树脂固化物在氮气气氛下的TGA(a)和DTG(b)曲线

Fig.7 TGA (a) and DTG (b) curves of cured epoxy resin

表2 环氧树脂固化物的热失重数据

Table 2 TGA data of cured epoxy resin

Samples	Nitrogen
Samples	T_o/℃	T_max/℃	W_re/%
EP	355.3	392.65	12.66
EP/1% DPC-1B	352.4	387.89	15.28
EP/2% DPC-1B	347.0	390.84	16.12
EP/1% PDS-2B	343.6	388.95	16.66
EP/2% PDS-2B	340.9	389.88	19.27

表3 阻燃剂/环氧树脂固化物的氧指数测试及UL-94垂直燃烧试验

Table 3 LOI and UL-94 vertical burning data of cured epoxy resin

Samples	LOI/%	UL-94
Samples	LOI/%	T₁/s	T₂/s	Dripping	Rating
EP	25.7	>30	—	Yes	NR
EP/2% DDP	28.9	17	11	No	V-1
EP/2% HPB	26.6	25	14	No	V-1
EP/2% PB	30.1	12	6	No	V-1
EP/1% DPC-1B	31.1	6	1	No	V-0
EP/2% DPC-1B	31.8	3	1	No	V-0
EP/1% PDS-2B	31.0	11	3	No	V-1
EP/2% PDS-2B	31.5	3	3	No	V-0

图8 EP、EP/1% DPC-1B、EP/2% DPC-1B、EP/1% PDS-2B和EP/2% PDS-2B的HRR(a)、THR(b)、SPR(c)和TSP(d)曲线

Fig.8 HRR (a), THR (b), SPR (c) and TSP (d) curves of EP, EP/1% DPC-1B, EP/2% DPC-1B, EP/1% PDS-2B and EP/2% PDS-2B

表4 环氧固化物的锥形量热试验的相关数据

Table 4 Cone calorimeter tests data of cured epoxy resin

Samples	TTI /s	PHRR/(kW/m²)	THR/(MJ/m²)	FIGRA/(kW/(m²·s))	SPR/(m²/s)	TSP/m²	Residue/%(mass)
EP	101	1042.5	128.5	5.75	0.16	20.7	10.3
EP/1% DPC-1B	99	908.3	117.4	4.88	0.17	22.4	17.0
EP/2% DPC-1B	101	766.5	103.7	4.16	0.20	21.5	24.2
EP/1% PDS-2B	100	958.7	110.8	5.26	0.16	19.6	20.0
EP/2% PDS-2B	99	815.1	106.7	4.40	0.16	19.2	23.6

图9 锥形量热测试后的残炭照片

Fig.9 Optical images of char residue after cone calorimeter tests

图10 EP、EP/1% DPC-1B、EP/2% DPC-1B、EP/1% PDS-2B和EP/2% PDS-2B由锥形量热测试所得内外炭层SEM图

Fig.10 SEM images of char residue internal and exterior obtained from cone calorimeter tests for EP, EP/1% DPC-1B, EP/2% DPC-1B, EP/1% PDS-2B and EP/2% PDS-2B

图11 EP、EP/2% DPC-1B和EP/2% PDS-2B残炭的红外光谱图

Fig.11 FT-IR spectra of EP, EP/2% DPC-1B and EP/2% PDS-2B char

图12 DPC-1B和PDS-2B受热后的变化

Fig.12 Changes of DPC-1B and PDS-2B after heating

图13 环氧树脂固化物的光学照片(a)、紫外-可见光谱(b)；环氧树脂预聚体的DSC固化曲线(c)

Fig.13 The optical photographs (a) and UV-Vis spectra(b) of cured epoxy resin; Curing curves of EP cured tested by DSC (c)

图14 环氧树脂固化物的DMA曲线(a)和tanδ曲线(b)

Fig.14 DMA (a) and tanδ (b) curves of cured epoxy resin

表5 环氧树脂固化物的弯曲强度和弯曲模量

Table 5 Three-point bending test data of cured epoxy resin

Samples	Flexural strength/MPa	Elasticity modulus/(N/mm²)
EP	87.39	2045.9
EP/1% DPC-1B	98.13	2230.1
EP/2% DPC-1B	103.45	2328.4
EP/1% PDS-2B	114.80	2357.5
EP/2% PDS-2B	126.34	2391.3

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