Preparation of Green Star-topology Phosphazene Flame Retardant and Properties of Flame-retardant Epoxy Resin†

doi:10.7503/cjcu20180339

Abstract

Abstract:

Based on the molecular structure design, a new type of flame retardant named six[4-(5,5-methyl-1,3,2-dioxanone endophosphoryl) phenoxy] cyclotriphosphazene(HDDCPPCP) was prepared by hexachloro-cyclotriphosphazene, p-hydroxybenzaldehyde, phosphorus oxychloride and neopentyl glycol. This new flame retardant, ammonium polyphosphate(APP) and multi walled carbon nanotubes(MWCNT) were added to epoxy resin(EP). After that, the HDDCPPCP/APP/MWCNT/EP flame-retardant composites were prepared. Limiting oxygen index(LOI), horizontal burning(UL-94), cone calorimetry(CONE), tensile, bending and impact methods were used to study the combustion, thermal and mechanical properties of the flame-retardant composites. The experimental results show that the combustion parameters of EP2(HDDCPPCP/APP/MWCNT/EP) composites perform better when the total mass of fraction of flame retardant system is 30% and the mass fraction of MWCNT is 2%. The LOI of EP2 is 42.8%, it shows good flame retardancy, smoke suppression and anti-poisoning properties. The peak heat release rate(pk-HRR), average heat release rate(av-HRR), average effective heat combustion(av-EHC), and average CO release rate(av-CO) of EP2 are respectively reduced by 92.5%, 93.0%, 65.2%, and 66.6% compared with EP0. EP2 have good tensile strength, break elongation, bending strength and bending modulus, which are respectively 110.46 MPa, 6.24%, 1259.99 MPa and 377.72 MPa.

Key words: Cyclophosphazene flame retardant, Epoxy resin, Flame retardancy, Mechanical property, Multi walled carbon nanotubes

CLC Number:

O634.5

TrendMD:

LU Lingang,CHENG Zhe,QIU Xinming,WANG Huiya,YANG Shousheng,QIAN Xiaodong,WANG Xuebao. Preparation of Green Star-topology Phosphazene Flame Retardant and Properties of Flame-retardant Epoxy Resin^†[J]. Chem. J. Chinese Universities, 2018, 39(12): 2789.

Figures/Tables 13

References 31

[1]	Han M.X., Xu M.J., Li B., Plastics,2015, 44(5), 65—73
	(韩明轩, 许苗军, 李斌. 塑料, 2015, 44(5), 65—73)
[2]	Song T., Li Z.S., Feng Q.L., Wang H., Liu J.G., Yang S.Y., Electronics & Packaging,2012, 12(1), 1—6
	(宋涛, 李志生, 封其立, 王超, 刘金刚, 杨士勇. 电子与封装, 2012, 12(1), 1—6)
[3]	Atay H.Y., Materials & Design, 2018, 5(5), 202
[4]	Xue B.X., Niu M., Li J.J., Yang Y.R., Dai J.M., Chinese J. Mater. Res.,2016, 30(8), 581—588
	(薛宝霞, 牛梅, 李京京, 杨雅茹, 戴晋明. 材料研究学报, 2016, 30(8), 581—588)
[5]	Wang J., Cai X.F., China Plastics,2011, 25(6), 7—13
	(王军, 蔡绪福. 中国塑料, 2011, 25(6), 7—13)
[6]	Qu H.Q., Wu W.H., Wu H.J., Xu J.Z., China Plastics,2010, 24(7), 7—12
	(屈红强, 武伟红, 武红娟, 徐建中. 中国塑料, 2010, 24(7), 7—12)
[7]	Ye L.J., Qian L.J., Tong S.P., Xu G.Z., China Plastics,2010, 24(3), 11—18
	(叶龙健, 钱立军, 佟芍朋, 许国志. 中国塑料, 2010, 24(3), 11—18)
[8]	Zheng G.D., Zhang Q.J., Deng H.Y., Jiang W.G., Yang X.P., Sui G., Acta Materiae Compositae Sinica,2015, 32(3), 640—648
	(郑国栋, 张清杰, 邓火英, 蒋文革, 杨小平, 隋刚. 复合材料学报, 2015, 32(3), 640—648)
[9]	Shen X.J., Meng L.G., Fu S.Y., Acta Materiae Compositae Sinica,2015, 32(1), 21—26
	(沈小军, 孟令轩, 付绍云. 复合材料学报, 2015, 32(1), 21—26)
[10]	He D., Zhao C.X., Wang Y., Li Y. T., Li S. L., Yue J.,Acta Polymerica Sinica, 2017, (5), 858—866
	(何达, 赵春霞, 王毅, 李云涛, 李姝靓, 岳杰. 高分子学报, 2017, (5), 858—866)
[11]	Wu Y., Zhu J., Wang X.H., Shao Z.H., Zhao D.Q., Zeng X.J., Polymer Materials Science & Engineering,2016, 32(3), 54—58
	(吴勇, 朱靖, 汪小憨, 邵振华, 赵黛青, 曾小军. 高分子材料科学与工程, 2016, 32(3), 54—58)
[12]	Li P., Fu H., Zhao O., Lai F., Cheng S.M., Mei G.Y., Zhao W., Ban D.M., Chem. J. Chinese Universities,2017, 38(2), 294—302
	(李霈, 付海, 赵欧, 来方, 陈仕梅, 梅贵友, 赵伟, 班大明. 高等学校化学学报, 2017, 38(2), 294—302)
[13]	Lu L.G., Chen Y.H., Wang S.H., Yang S.S., Dong X.L., Chinese J. Mater. Res.,2014, 28(6), 455—461
	(卢林刚, 陈英辉, 王舒衡, 杨守生, 董希琳. 材料研究学报, 2014, 28(6), 455—461)
[14]	GB/T2406.2-2009, Plastics-Determination of Burning Behaviour by Oxygen Index-Part 2: Ambient-Temperature Test, Standards Press of China, Beijing, 2010
	(中国国家标准化管理委员会, GB/T2406.2-2009, 塑料用氧指数法测定燃烧行为, 第2部分: 室温试验, 北京, 中国标准出版社, 2010)
[15]	GB/T2408-2008, Plastics-Determination of Burning Characteristics-Horizontal and Vertical Test, Standards Press of China, Beijing, 2009
	(中国国家标准化管理委员会, GB/T2408—2008, 塑料燃烧性能的测定－水平法和垂直法, 北京, 中国标准出版社, 2009)
[16]	GB/T1040-92, Plastics-Determination of Tensile Properties, Standards Press of China, Beijing, 1993
	(中国国家标准化管理委员会, GB/T1040-92, 塑料拉伸性能试验方法, 北京, 中国标准出版社, 1993)
[17]	GB/T1043-2008, Plastics-Determination of Charpy Impact Properties, Standards Press of China, Beijing, 2009
	(中国国家标准化管理委员会, GB/T1043-2008, 塑料简支梁冲击性能的测定, 北京, 中国标准出版社, 2009)
[18]	Wu Q., Zhang L.P., Zhang X., Zhong Y., Mao Z.P., Xu H., New Chemical Materials,2013, 41(12), 171—173
	(吴茜, 张琳萍, 张璇, 钟毅, 毛志平, 徐红. 化工新型材料, 2013, 41(12), 171—173)
[19]	Bao D.M., Liu J.P., Functional Materials,2013, 44(3), 396—400
	(宝冬梅, 刘吉平. 功能材料, 2013, 44(3), 396—400)
[20]	Zhou S.L., Synthesis and Flame Retardancy of a New Type of Phosphorus and Nitrogen Flame Retardant, Huazhong Normal University, Wuhan, 2003
	(周少林. 新型磷氮系阻燃剂的合成及其阻燃性能研究, 武汉: 华中师范大学, 2003)
[21]	Jimenez M., Duquesne S., Bourbigot S., Surface &Coatings Technology,2006, 201, 979—987
[22]	Wang Z.Z., Wang Y., Hu Y., Polymer Materials Science & Engineering,2009, 25(11), 86—89
	(王正洲, 王云, 胡源. 高分子材料科学与工程, 2009, 25(11), 86—89)
[23]	Riahipour R., Sahraei A.A., Werken N., Science & Engineering of Composite Materials,2017, 6(5), 166—170
[24]	Zhou T., Zhu A.P., Plastics Science and Technology,2014, 42(8), 38—43
	(周婷, 朱爱萍. 塑料科技, 2014, 42(8), 38—43)
[25]	Tian X.J., Wang Z.W., Yu Q., Gao J., Polymer Materials Science & Engineering,2014, 30(8), 31—36
	(田秀娟, 王忠卫, 于青, 高军. 高分子材料科学与工程, 2014, 30(8), 31—36)
[26]	Balandin A.A., Nature Materials, 2011, 10(8), 569
[27]	Colomer J.F., Piedigrosso P., Willems I., Journal of the Chemical Society Faraday Transactions,2017, 94(24), 3753—3758
[28]	Chen L., Zheng X., Fire Science and Technology,2016, 35(12), 1739—1741
	(陈亮, 郑雄. 消防科学与技术, 2016, 35(12), 1739—1741)
[29]	Li S., Wang X.H., Wang J., Xu B., Tan L., Yang Y.J., Zhang H., Fan H.J., Zhang X., Wang W.B., Chemistry and Adhesion,2017, 39(2), 98—101
	(李胜, 王晓慧, 王晶, 徐博, 谭蕾, 杨艳晶, 张惠, 樊慧娟, 张雪, 王文博. 化学与黏合, 2017, 39(2), 98—101)
[30]	Shu Y., Jiang X., Lin H.Q., Qu M.Z., Polymer Materials Science & Engineering,2016, 32(6), 90—95
	(舒颖, 姜晓, 林浩强, 瞿美臻. 高分子材料科学与工程, 2016, 32(6), 90—95)
[31]	Bi B., Wang X.B., Journal of Materials Engineering,2017, 45(5), 135—144
	(毕波, 王学宝. 材料工程, 2017, 45(5), 135—144)

Sample	Mass fraction(%)					LOI(%)	UL94-FH	UL94-FV
Sample	EP	m-PDA	HDDCPPCP	APP	MWCNT	LOI(%)	UL94-FH	UL94-FV
EP0	90.9	9.1	0	0	0	23.0	FH-2	No rating
EP1	63.6	6.4	10.0	20.0	0	43.8	FH-1	V-0
EP2	63.6	6.4	9.3	18.7	2	42.8	FH-1	V-0

Sample	Mass fraction(%)					LOI(%)	UL94-FH	UL94-FV
Sample	EP	m-PDA	HDDCPPCP	APP	MWCNT	LOI(%)	UL94-FH	UL94-FV
EP0	90.9	9.1	0	0	0	23.0	FH-2	No rating
EP1	63.6	6.4	10.0	20.0	0	43.8	FH-1	V-0
EP2	63.6	6.4	9.3	18.7	2	42.8	FH-1	V-0

Sample	TTI/s	pk-HRR/ (kW·m^-2)	av-HRR/ (kW·m^-2)	av-EHC/ (MJ·kg^-1)	av-MLR/ (g·s^-1)	av-SEA/ (m²·kg^-1)	av-CO/ (kg·kg^-1)
EP0	91	634.40(235 s)	261.30	20.43	0.12	1888.45	0.06
EP1	85	38.33(215 s)	10.97	4.42	0.02	2393.47	0.02
EP2	81	47.39(200 s)	18.26	7.11	0.02	2285.00	0.02

Sample	TTI/s	pk-HRR/ (kW·m^-2)	av-HRR/ (kW·m^-2)	av-EHC/ (MJ·kg^-1)	av-MLR/ (g·s^-1)	av-SEA/ (m²·kg^-1)	av-CO/ (kg·kg^-1)
EP0	91	634.40(235 s)	261.30	20.43	0.12	1888.45	0.06
EP1	85	38.33(215 s)	10.97	4.42	0.02	2393.47	0.02
EP2	81	47.39(200 s)	18.26	7.11	0.02	2285.00	0.02

Sample	FGI/(kW·m^-2·s^-1)	THRI_{6 min}/(MJ·m^-2)	TSPI_{6 min}/(m²·g·kg^-1·s^-1)	ToxPI_{6 min}/(g·s^-1)
EP0	2.70	3.85	7.44	4.21
EP1	0.18	2.64	6.11	3.33
EP2	0.24	2.73	6.98	3.53