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
计量
- 文章访问数: 972
- HTML全文浏览量: 306
- PDF下载量: 33
- 被引次数: 0
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

HTML全文

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

下载: 全尺寸图片幻灯片

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

下载: 全尺寸图片幻灯片

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

下载: 全尺寸图片幻灯片

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

下载: 全尺寸图片幻灯片

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

下载: 全尺寸图片幻灯片

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

下载: 全尺寸图片幻灯片

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

下载: 全尺寸图片幻灯片

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.

下载: 导出CSV

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℃.

下载: 导出CSV

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.

下载: 导出CSV

参考文献(31)

[1]	王玉忠, 陈力. 新型阻燃材料[J]. 新型工业化, 2016, 6(1):38-61. doi: 10.3969/j.issn.2095-6649.2016.01.003 WANG Yuzhong, CHEN Li. New flame retardant materials[J]. The Journal of New Induatrialization,2016,6(1):38-61(in Chinese). doi: 10.3969/j.issn.2095-6649.2016.01.003
[2]	廖利敏, 李建凤, 黄茜. 阻燃材料的研究及应用综述[J]. 山东化工, 2019, 48(17):87-88. doi: 10.3969/j.issn.1008-021X.2019.17.037 LIAO Limin, LI Jianfeng, HUANG Xi. Research and application of flame retardant materials[J]. Shandong Chemical Industry,2019,48(17):87-88(in Chinese). doi: 10.3969/j.issn.1008-021X.2019.17.037
[3]	MA T, GUO C. Synergistic effect between melamine cyanurate and a novel flame retardant curing agent containing a caged bicyclic phosphate on flame retardancy and thermal behavior of epoxy resins[J]. Journal of Analytical and Applied Pyrolysis,2017,124:239-246. doi: 10.1016/j.jaap.2017.02.001
[4]	李娟, 刘青, 曹佳丽, 等. 阻燃环氧树脂研究进展[J]. 合成树脂及塑料, 2016, 33(6):76-80. LI Juan, LIU Qing, CAO Jiali, et al. Research progress of flame retardant epoxy resin[J]. China Synthetic Resin and Plastics,2016,33(6):76-80(in Chinese).
[5]	VElENCOSO M M, BATTING A, MARKWART J C, et al. Molecular firefighting-how modern phosphorus chemistry can help solve the flame retardancy task[J]. Angewandte Chemie International Edition,2018,57(33):10450-10467.
[6]	CHIU S H, WU C L, LEE H T, et al. Synthesis and characterization of novel flame retardant polyurethanes containing designed phosphorus units[J]. Journal of Polymer Research,2016,23(10):205.
[7]	LI J J, DUAN R T, ZHANG J B, et al. Phosphorus-containing poly(ethylene terephthalate): Solid-state polymerization and its sequential distribution[J]. Industrial & Engineering Chemistry Research,2013,2(15):5326-5333.
[8]	王志国, 梁兵, 刘徐越. 磷氮阻燃剂PDAB-DOPO的制备及阻燃环氧树脂复合材料性能研究[J]. 化工新型材料, 2018, 46(12):68-71. WANG Zhiguo, LIANG Bing, LIU Xuyue. Preparation of phosphorous-nitrigen PDAB-DOPO and its flame retardant epoxy resin[J]. New Chemical Materials,2018,46(12):68-71(in Chinese).
[9]	程振宁, 汪凌峰, 李皓, 等. 2-羧乙基苯基次膦酸阻燃/固化环氧树脂[J]. 塑料, 2016, 45(2):54-57. CHENG Zhenning, WANG Lingfeng, LI Hao, et al. 2-carboxyethyl phenylphosphinic acid flame retardant/cured epoxy resin[J]. Plastics,2016,45(2):54-57(in Chinese).
[10]	刘学清, 刘继延, 蔡少君, 等. 甲基丁基次膦酸铝/环氧树脂阻燃复合材料性能研究[J]. 塑料工业, 2012, 40(2):79-82. LIU Xueqing, LIU Jiyan, CAI Shaojun, et al. Study on properties of aluminum methyl butylphosphinate/epoxy resin composite[J]. China Plastics Industry,2012,40(2):79-82(in Chinese).
[11]	邹政平, 肖啸, 田杰, 等. 无卤阻燃型环氧树脂的研究进展[J]. 合成树脂及塑料, 2020, 37(1):97-102. ZOU Zhengping, XIAO Xiao, TIAN Jie, et al. Research progress of halogen-free flame retardant epoxy resin[J]. China Synthetic Resin and Plastics,2020,37(1):97-102(in Chinese).
[12]	吴伟国. 含P、N、Si的阻燃环氧树脂的研究进展[J]. 合成材料老化与应用, 2017, 46(5):120-125. WU Weiguo. Research progress of flame retardant epoxy resins containing P, N, and Si[J]. Synthetic Materials Aging and Application,2017,46(5):120-125(in Chinese).
[13]	董美丽, 武保林, 胡泊. 有机磷阻燃剂对环氧树脂性能的影响[J]. 消防科学与技术, 2017, 36(12):1698-1702. doi: 10.3969/j.issn.1009-0029.2017.12.020 DONG Meili, WU Baolin, HU Po. The effect of organic-phosphorus flame retardant on the performance of epoxy resin[J]. Fire Science and Technology,2017,36(12):1698-1702(in Chinese). doi: 10.3969/j.issn.1009-0029.2017.12.020
[14]	袁智慧, 牛永平, 汪小伟, 等. 环氧树脂增韧机理及研究进展[J]. 热固性树脂, 2019, 34(6):65-70. YUAN Zhihui, NIU Yongping, WANG Xiaowei, et al. Toughening mechanism and research progress of epoxy resin[J]. Thermosetting Resin,2019,34(6):65-70(in Chinese).
[15]	胡芳芳, 聂小安. 碳纳米管增强环氧树脂基复合材料研究进展[J]. 热固性树脂, 2019, 34(1):60-65. HU Fangfang, NIE Xiaoan. Research progress of carbon nanotube reinforced epoxy-based composites[J]. Thermosetting Resin,2019,34(1):60-65(in Chinese).
[16]	YUAN P, TAN D Y, ANNABI-BERGAYA F. Properties and applications of halloysite nanotubes: Recent research advances and future prospects[J]. Applied Clay Science,2015,112-113:75-93. doi: 10.1016/j.clay.2015.05.001
[17]	ATTIA N F, HASSAN M A, NOUR M A, et al. Flame-retardant materials: Synergistic effect of halloysite nanotubes on the flammability properties of acrylonitrile-butadiene-styrene composites[J]. Polymer International,2014,63(7):1168-1173. doi: 10.1002/pi.4653
[18]	EMAD S G, YOONA R, SHIMA H, et al. Halloysite nanotubes as smart flame retardant and economic reinforcing materials: A review[J]. Thermochimica Acta,2018,669:173-184. doi: 10.1016/j.tca.2018.09.017
[19]	BOONKONGKAEW M, SIRISINHA K. Halloysite nanotubes loaded with liquid organophosphate for enhanced flame retardancy and mechanical properties of polyamide 6[J]. Journal of Materials Science,2018,53(14):10181-10193. doi: 10.1007/s10853-018-2351-z
[20]	丁勇, 罗远芳, 薛锋, 等. 改性埃洛石复配聚磷酸铵对硅橡胶阻燃性能和力学性能的影响[J]. 高分子材料科学与工程, 2017, 33(10):58-64, 71. DING Yong, LUO Yuanfang, XUE Feng, et al. Effect of modified halloysite compound ammonium polyphosphate on flame retardancy and mechanical properties of silicone rubber[J]. Polymeric Materials Science and Engineering,2017,33(10):58-64, 71(in Chinese).
[21]	王亚飞, 赵静, 蔡学明, 等. 聚丙烯/埃洛石纳米管复合材料的力学性能及阻燃性能[J]. 中国塑料, 2016, 30(8):39-42. WANG Yafei, ZHAO Jing, CAI Xueming, et al. Mechanical and flame retardant properties of polypropylene/halloysite nanotube composites[J]. China Plastics,2016,30(8):39-42(in Chinese).
[22]	中国国家标准化管理委员会. 塑料燃烧性能试验方法氧指数法: GB/T 2406—1993[S]. 北京: 中国标准出版社, 1994. Standardization Administration of of the people’s Republic of China. Plastics: Determination of fammability by oxygen index: GB/T 2406—1993[S]. Beijing: China Standards Press, 1994(in Chinese).
[23]	中国国家标准化管理委员会. 塑料燃烧性能的测定水平法和垂直法: GB/T 2408—2008[S]. 北京: 中国标准出版社, 2009. Standardization Administration of of the people’s Republic of China. Plastics: Determination of burning characteristics: Horizontal and vertical test: GB/T 2408—2008[S]. Beijing: China Standards Press, 2009(in Chinese).
[24]	International Organization for Standardization. Reaction-to-fire tests: Heat release, smoke production and mass loss rate Part 1: Heat release rate (cone calorimeter method): ISO 5660—1∶2002[S]. Geneva: International Organization for Standardization, 2002.
[25]	中国国家标准化管理委员会. 塑料拉伸性能的测定: GB/T 1040—2006[S]. 北京: 中国标准出版社, 2007. Standardization Administration of of the people’s Republic of China. Plastics: Determination of tensile properties: GB/T 1040—2006[S]. Beijing: China Standards Press, 2007(in Chinese).
[26]	中国国家标准化管理委员会. 塑料悬臂梁冲击强度的测定: GB/T 1843—2008[S]. 北京: 中国标准出版社, 2009. Standardization Administration of of the people’s Republic of China. Plastics: Determination of izod impact strength: GB/T 1843—2008[S]. Beijing: China Standards Press, 2009(in Chinese).
[27]	TAN Z W, SUN J, ZHANG M, et al. Phosphorus-containing polymers from THPS Ⅱ: Synthesis and property of phosphorus-containing hyperbranched aromatic-aliphatic polyamides[J]. Designed Monomers and Polymers,2015,18(3):222-231. doi: 10.1080/15685551.2014.999461
[28]	ZHENG T C, NI X Y. Loading organophosphorous flame retardant to halloysite nanotubes for modifying UV-curable epoxy resin[J]. RSC Advances,2016,6(62):57122-57130. doi: 10.1039/C6RA08178A
[29]	刘聪, 罗远芳, 贾志欣, 等. PVC/改性埃洛石纳米管纳米复合材料的制备与性能[J]. 华南理工大学学报(自然科学版), 2011, 39(6):71-76. LIU Cong, LUO Yuanfang, JIA Zhixin, et al. Preparation and properties of PVC/modified halloysite nanotube nanocomposites[J]. Journal of South China University of Technology (Natural Science Edition),2011,39(6):71-76(in Chinese).
[30]	DENG S Q, ZHANG J N, YE L, et al. Toughening epoxies with halloysite nanotubes[J]. Polymer,2008,49(23):5119-5127. doi: 10.1016/j.polymer.2008.09.027
[31]	ZENG S S, CHRISTOPHER R, LIU J J, et al. Facile hydroxylation of halloysite nanotubes for epoxy nanocomposite applications[J]. Polymer,2014,55(25):6519-6528. doi: 10.1016/j.polymer.2014.10.044