埃洛石复配2-羧乙基苯基次膦酸对环氧树脂阻燃及力学性能的影响

吕佳帅男; 狄凯莹; 蔡鹏麟; 陈晓婷

doi:10.13801/j.cnki.fhclxb.20200603.003

埃洛石复配2-羧乙基苯基次膦酸对环氧树脂阻燃及力学性能的影响

doi: 10.13801/j.cnki.fhclxb.20200603.003

天津科技大学　化工与材料学院，天津 300457

详细信息

通讯作者:
陈晓婷，博士，副教授，硕士生导师，研究方向为纳米阻燃技术、阻燃剂开发及应用等　E-mail：chenxt@tust.edu.cn

中图分类号: TQ323.5
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出版历程
- 收稿日期: 2020-03-26
- 录用日期: 2020-06-02
- 网络出版日期: 2020-06-03
- 刊出日期: 2021-01-15

Effects of halloysite nanotubes and 2-carboxyethyl phenylphosphonic acid on flame retardant and mechanical properties of epoxy resin

College of Chemical Engineering and Materials, Tianjin University of Science and Technology, Tianjin 300457, China

摘要

摘要: 将埃洛石纳米管(HNTs)与2-羧乙基苯基次磷酸(CEPPA)复配并用于环氧树脂(EP)阻燃改性，制备了CEPPA-HNTs/EP复合材料。研究了HNTs与CEPPA的配比对CEPPA-HNTs/EP复合材料热稳定性、阻燃性及力学性能的影响。TG分析表明，CEPPA与HNTs复配可提高CEPPA-HNTs/EP复合材料的热稳定性，促进成炭并降低分解速率。锥形量热和极限氧指数分析表明，加入HNTs可降低EP热释放速率，而CEPPA对提高EP的极限氧指数作用更显著。残炭的红外分析及SEM结果表明，燃烧过程中CEPPA与HNTs反应生成硅铝磷酸盐促进凝聚相的脱水交联，形成更致密的炭层。力学性能分析表明，当HNTs与EP和CEPPA与EP的质量比分别为6%和4%时，CEPPA-HNTs/EP复合材料的拉伸强度和冲击强度分别提高了19.4%和17.3%，冲击断面的SEM图像显示CEPPA-HNTs/EP复合材料呈韧性断裂。
- 环氧树脂 /
- 埃洛石纳米管(HNTs) /
- 2-羧乙基苯基次膦酸(CEPPA) /
- 阻燃 /
- 力学性能
Abstract: Halloysite nanotubes (HNTs) were compounded with 2-carboxyethyl phenylphosphonic acid (CEPPA) and used for modification of epoxy (EP) to prepare CEPPA-HNTs/EP composite. The effects of the ratios of CEPPA and HNTs on the thermal stability, flame retardancy and mechanical properties of the CEPPA-HNTs/EP composite were studied. TG analysis shows that the combination of CEPPA and HNTs can improve the thermal stability of the CEPPA-HNTs/EP composites, promote the carbonization and reduce the decomposition rate. The analyses of cone and limiting oxygen index show that adding HNTs can reduce the heat release rate, while CEPPA has a more significant effect on the increasing of oxygen index. The FTIR and SEM of the carbon residue show that the reaction of CEPPA and HNTs during the combustion produce silica-aluminate, which promotes the dehydration and cross-linking of the condensed phase. The analysis of mechanical properties shows that when mass ratio of HNTs to EP is 6%, mass ratio of CEPPA to EP is 4%, the tensile strength and impact strength of CEPPA-HNTs/EP composite are increased by 19.4% and 17.3%, respectively. SEM morphologies of impact sections of CEPPA-HNTs/EP composite show the characteristics of ductile fracture.
- epoxy resin /
- halloysite nanotubes (HNTs) /
- 2-carboxyethyl phenylphosphonic acid (CEPPA) /
- flame retardant /
- mechanical properties

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图 1 EP、HNTs/EP、CEPPA/EP和CEPPA-HNTs/EP复合材料在N₂和空气的TG和DTG曲线

Figure 1. TG and DTG curves of EP, HNTs/EP, CEPPA/EP and CEPPA-HNTs/EP composites in N₂ and air

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图 2 EP、CEPPA/EP和CEPPA-HNTs/EP复合材料的热释放速率(HRR)和热释放总量(THR)曲线

Figure 2. Heat release rate (HRR) and total heat release (THR) curves of EP, CEPPA/EP and CEPPA-HNTs/EP composites

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图 3 EP、HNTs/EP和CEPPA-HNTs/EP复合材料燃烧后残炭的FTIR图谱

Figure 3. FTIR spectra of char of EP, HNTs/EP and CEPPA-HNTs/EP composites after burning

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图 4 EP (a)、10HNTs/EP (b)、4CEPPA-6HNTs/EP (c)、10CEPPA/EP (d)复合材料燃烧后残炭的SEM图像

Figure 4. SEM images of residual carbon after combustion of EP (a), 10HNTs/EP (b), 4CEPPA-6HNTs/EP (c), 10CEPPA/EP (d) composites

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图 5 EP、HNTs/EP、CEPPA/EP和CEPPA-HNTs/EP复合材料的拉伸强度

Figure 5. Tensile strength of EP, HNTs/EP, CEPPA/EP and CEPPA-HNTs/EP composites

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图 6 EP、HNTs/EP、CEPPA/EP和CEPPA-HNTs/EP复合材料的冲击强度

Figure 6. Impact strength of EP, HNTs/EP, CEPPA/EP and CEPPA-HNTs/EP composites

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图 7 EP (a)、HNTs/EP (b)、CEPPA-HNTs/EP (c)和CEPPA/EP (d)复合材料冲击断面的SEM图像

Figure 7. SEM images of impact section of EP (a), HNTs/EP (b), CEPPA-HNTs/EP (c) and CEPPA/EP (d) composites

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表 1 2-羧乙基苯基次膦酸-埃洛石纳米管/环氧树脂(CEPPA-HNTs/EP)复合材料的配比(与EP的质量比)

Table 1. Formulation of 2-carboxyethyl phenylphosphonic acid-halloysite nanotubes/epoxy (CEPPA-HNTs/EP) composites (Mass ratio to EP)

Sample	Component/%
Sample	EP	CEPPA	h-HNTs	MeHHPA
EP	100	0	0	80
10HNTs/EP	100	0	10	80
2CEPPA-8HNTs/EP	100	2	8	80
4CEPPA-6HNTs/EP	100	4	6	80
6CEPPA-4HNTs/EP	100	6	4	80
8CEPPA-2HNTs/EP	100	8	2	80
10CEPPA/EP	100	10	0	80
Notes: h-HNTs—Surface hydroxylated HNTs; MeHHPA—Methylhexahydrophthalic anhydride.

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表 2 EP、HNTs/EP、CEPPA/EP和CEPPA-HNTs/EP复合材料的TG、极限氧指数(LOI)及垂直燃烧(UL-94)测试结果

Table 2. TG, limiting oxygen index (LOI) and vertical burning (UL-94) test values of EP, HNTs/EP, CEPPA/EP and CEPPA-HNT/EP composites

Sample	N₂ atmosphere				Air atmosphere					LOI/ %	UL-94
Sample	T_i/ ℃	T_max/ ℃	R_max/ (%·min⁻¹)	C at 700℃/%	T_i/ ℃	T_max1/ ℃	T_max2/ ℃	R_max/ (%·min⁻¹)	C_700℃/%	LOI/ %	UL-94
EP	351	408	21.5	4.1	332	409	549	18.0	1.0	22.7	—
10HNTs/EP	360	403	19.3	14.7	346	406	558	17.0	8.0	24.9	V-1
2CEPPA-8HNTs/EP	366	406	19.6	14.4	341	405	561	16.9	3.5	25.5	V-1
4CEPPA-6HNTs/EP	362	405	17.3	15.0	339	407	561	16.2	2.2	26.4	V-0
6CEPPA-4HNTs/EP	359	405	17.5	13.9	334	405	567	16.4	1.8	27.6	V-0
8CEPPA-2HNTs/EP	357	404	16.5	13.8	335	401	566	16.1	2.8	28.9	V-0
10CEPPA/EP	346	405	16.5	10.8	327	404	567	16.0	3.0	29.4	V-1
Notes: T_i—5% mass loss temperature; T_max—Peak temperature of DTG cures; R_max—Maximum rate of mass loss; C_700℃—Char yield at 700℃.

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表 3 EP、CEPPA/EP和CEPPA-HNTs/EP复合材料的锥形量热测试结果

Table 3. Data of cone calorimeter test of EP, CEPPA/EP and CEPPA-HNTs/EP composites

Sample	TTI/s	PHRR/(kW·m⁻²)	THR/(MJ·m⁻²)	EHC/(MJ·kg⁻¹)
EP	22	733.0	50.9	27.43
4CEPPA-6HNTs/EP	8	448.2	45.4	22.00
10CEPPPA/EP	10	568.5	40.6	22.97
Notes: TTI—Time to ignition; PHRR—Peak heat release rate; THR—Total heat release; EHC—Effective heat of combustion.

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