Influence of Polyphosphate Flame Retardant Couple with Ammonium Polyphosphate on Epoxy Resin†

doi:10.7503/cjcu20160599

Abstract

Abstract:

A novel polyphosphate flame retardant, poly(2-10-hydrogen-9-oxa-phosphaphenanthrene hydroquinone phenyl phosphate)(POPP), aimed at improving the flame retardancy of EP was prepared. POPP and ammonium polyphosphate(APP) at the mass ratio of 1:2 were added into EP to form a series of flame retardant modified epoxy resin(FR-EP). The chemical bond adsorptions of FR-EP were investigated by infrared spectroscopic analysis. The thermal stability was study by thermal gravimetric analysis(TGA). Flame retardant properties as well as burning behavior of epoxy resin composites have been investigated by limited oxygen index(LOI) and vertical burning test(UL-94). Fire properties of modified epoxy resin were test by Cone calorimeter. The morphological characteristics of char residue after Cone test were studied by scanning electron microscope(SEM). The result shows that POPP increase burning behavior at lower adding amount, which help epoxy resin to pass UL-94 V-0 at 5%. But POPP modified epoxy resin gave out only 24.2% of LOI value. POPP/APP flame retardant increase not only UL-94 grade but also much higher LOI value. A UL-94 V-0 grade was obtained when 5% POPP/APP were added into the epoxy matrix and 27.7% LOI value. When adding amount of POPP/APP are increased to 15%, a higher LOI value of 33.8% can be get. Results of TGA test indicate that decomposition temperature of FR-EP decrease along with increase of flame retardant amount. But modified samples give out more char residue. By incorporation of POPP/APP, THR, HRR, EHC, TSR and COP of FR-EP were reduced obviously, and promote char residue dramatically. PkHRR decrease from 831.5 kW/m² to 346.8 kW/m² at 15% of adding amount. Morphology study shows that good flame retardant property of FR-EP is contributed to well-formed char residue structure. These structures of char are net-like and type may prevent little burning product from moving out to the surface of matrix. Moreover, this char residue protects inner material from heat.

Key words: Epoxy resin, Phosphorus, Ammonium polyphospate, Intumescent flame retardant

CLC Number:

O634.5

TrendMD:

LI Pei, FU Hai, ZHAO Ou, LAI Fang, CHEN Shimei, MEI Guiyou, ZHAO Wei, BAN Daming. Influence of Polyphosphate Flame Retardant Couple with Ammonium Polyphosphate on Epoxy Resin^†[J]. Chem. J. Chinese Universities, 2017, 38(2): 294.

Figures/Tables 11

Scheme 1 Synthesis route of POPP

Table 1 Composition, LOI and UL94 vertical burning values of the samples

Sample	w_E-44(%)	w_m-PDA(%)	w_POPP(%)	w_APP(%)	LOI(%)	UL-94 rating	w_P(%)
EP-0	92	8	0	0	20.0	No rating	0
EP-a1	87	8	5	0	24.2	V-0	0.67
EP-a2	82	8	10	0	24.8	V-0	1.35
EP-a3	77	8	15	0	25.5	V-0	2.02
EP-b1	87	8	1.67	3.33	27.7	V-0	1.25
EP-b2	82	8	3.33	6.67	28.9	V-0	1.66
EP-b3	77	8	5	10	33.8	V-0	3.77

Fig.1 FTIR spectra of POPP(A), APP(B) and FR-EP(C) a. EP-0; b. EP-b1; c. EP-b2; d. EP-b3.

Fig.2 TGA(A, C) and DTG(B, D) curves of flame retardant and EP-0 (A, B) a. POPP; b. EP-0. (C, D) a. POPP; b. APP; c. POPP/APP.

Fig.3 TGA(A) and DTG(B) curves of EP-0(a), EP-b1(b), EP-b2(c) and EP-b3(d)

Table 2 Thermal gravimetric data of the EP with different content

Sample	T_5%/℃	T_10%/℃	T_50%/℃	T_max/℃	Residue(%)
POPP	393.23	449.88	567.42	510.94, 557.57	35.30
EP-0	362.76	374.81	411.90	398.44	15.03
EP-b1	328.78	344.83	392.99	388.17	20.55
EP-b2	316.95	334.03	386.93	378.10	22.49
EP-b3	308.82	327.4482	387.50	367.89	23.62

Table 3 Mechanical properties of the EP with different content

Sample	Breaking elongation(%)	Tensile strength/MPa	Elasticity modulus/MPa	Stress_max/MPa
EP-0	6.93	84.89	927.35	1398.73
EP-b1	6.45	76.12	1000.35	1141.82
EP-b2	6.05	64.57	879.90	968.57
EP-b3	4.22	40.30	1058.99	604.49

Fig.4 Cone calorimeter curves of EP-0(a), EP-b1(b) and EP-b3(c) (A) HRR; (B) EHC; (C) THR; (D) SPR; (E) COP; (F) TSR.

Table 4 Cone calorimeter data of EP-0, EP-b1 and EP-b3

Sample	TTI/s	PkHRR/ (kW·m^-2)	THR/ (MJ·m^-2)	Mass loss/g
EP-0	43	831.5	54.0	14.5
EP-b1	41	545.1	50.5	22.1
EP-b3	40	346.8	41.6	23.0

Fig.5 Photos of residues of cured epoxy resin samples after cone calorimeter tests(A) EP-0 in vertical view; (B) EP-b1 in vertical view; (C) EP-b3 in vertical view; (D) EP-b1 in level vision; (E) EP-b3 in level vision.

Fig.6 SEM images of char of EP-0(A), EP-b1(B) and EP-b3(C)

References 44

[1]	Wang C. S., Song J. Y., J. Appl. Polym. Sci., 1999, 73(3), 353—361
[2]	Lin C. H., Polym., 2004, 45(23), 7911—7926
[3]	Mariappan T., Wilkie C. A., Fire Mater., 2014, 38, 588—598
[4]	Sergei V.L., Edward D. W., Polym. Int., 2004, 53, 1901—1929
[5]	Chen Y. H., Wang Q., Adv. Powder. Technol., 2007, 18(8), 587—600
[6]	Li B., Xu M. J., Polym. Degrad. Stabil., 2006, 91(6), 1380—1386
[7]	Xie F., Wang. Y. Z., Yang B., Liu Y., Macromol Mater. Eng., 2006, 291(3), 247—253
[8]	Wang G. B., Gao. J. R., Jia J. H., Sheng W. J., Wang X., Acta Materiae Compositae Sinica,2010, 27(6), 45—52
	(黄国波, 高建荣, 贾建洪, 盛卫坚, 王旭. 复合材料学报, 2010, 27(6), 45—52)
[9]	Halpern Y., Denna M. M., Niswander R. H., Ind. Eng. Chem. Prod. Res. Dev., 1984, 23(2), 233—238
[10]	Shui Y. L., Lan H., Prog. Polym. Sci., 2002, 27(8), 1661—1712
[11]	Nie S. B., Hu Y., Song L., He Q. L., Yang D.D., Chen H., Polym. Advan. Technol., 2008, 19(8), 1077—1083
[12]	Thirumal M., Khastgir D., Singha N. K., Manjunath B. S., Naik Y. P., J. Appl. Polym. Sci., 2008, 110(5), 2586—2594
[13]	Wang Y. X., Jiang H. W., Acta. Polym. Sin., 2009, 4, 325—330
	(王宇旋, 姜宏伟. 高分子学报, 2009, 4, 325—330)
[14]	Wu N., Yang R.J., Hao J. W., Liu G. S.,Acta Polym. Sin., 2009, (12), 1205—1210
	(吴娜, 杨荣杰, 郝建薇, 刘国胜. 高分子学报, 2009, (12), 1205—1210)
[15]	Heinrich H., Stefan P., Polym. Inter., 2000, 49(10), 1106—1114
[16]	Liu J. C., Xu M. J., Li B., Chem. J. Chinese Universities,2015, 36(6), 1228—1235
	(刘建超, 许苗军, 李斌. 高等学校化学学报, 2015, 36(6), 1228—1235)
[17]	Ban D. M., Qi. H. L., Zhao O., Zhang Y. H., Liu Z. M., Wei W. L., The Manufacturing Methods and Applications of 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-xa-10-phosphaphenanthrene-10-oxide Based Polyphosphate Esters Flame Retardants, CN 102796253A,2012-11-28
	(班大明, 秦好丽, 赵欧, 张永航, 刘真美, 韦万丽. ODOPB基聚磷酸酯阻燃剂及其制备方法和用途, CN 102796253A, 2012-11-28)
[18]	Liu Y. J., Ma L., Polym. Mater. Sci. Eng., 2013, 34(12), 2903—2910
[19]	Bao C. L., Guo Y. Q., Song L., Kan Y. C., Qian X. D., Hu Y., J. Mater. Chem., 2011, 21, 13290—13298
[20]	Liao S. H, Liu P. L., Hsiao M. C., Teng C. C., Wang C. A., Ger M. D., Chiang C. L., Ind. Eng. Chem. Res., 2012, 51, 4573—4581
[21]	Annakutty K. S., Kishore K., Eur. Polym. J., 1993, 29(10), 1387—1390
[22]	Zhang D. F., Fan L. Z., Guo R. H., Fan Z. T., Chem. J. Chinese Universities,2014, 35(11), 2466—2471
	(张丹凤, 范楼珍, 郭瑞华, 樊择坛. 高等学校化学学报, 2014, 35(11), 2466—2471)
[23]	Gao M., Li G. F., Yang R. J., Chin. J. Process. Eng., 2008, 8(1), 182—186
	(高明, 李桂芬, 杨荣杰. 过程工程学报, 2008, 8(1), 182—186)
[24]	Krevelen D., Nijenhuis K.T.,Prop. Polym., 2009, 71—108
[25]	Lai X. J., Zeng X. R., Li H. Q., Liao F., Zhang H. L., Yin C. Y., J. Macromol. Sci. B,2012, 51(1), 35—47
[26]	Wen P. Y., Wang. X. F., Xing W. Y., Feng X. M., Yu B., Shi Y. Q., Tang G., Song L., Hu Y., Richard K. K. Yuen., Ind. Eng. Chem. Res., 2013, 52(48), 17015—17022
[27]	Song Y., Li J. C., Zhang X. J., Changzhou Univ.(Nat. Sci. Ed.)., 2015, 27(4), 20—25
	(宋艳, 李锦春, 张鑫. 常州大学学报(自然科学版), 2015, 27(4), 20—25)
[28]	Levchik S. V., Edward. D. W., Polym. Int., 2000, 49(10), 1033—1073
[29]	Wang D. Y., Costa F. R., Vyalikh A., Leuteritz A., Scheler U., Jehnichen D., Wagenknecht U., Hässler L., Heinrich G., Chem. Mater., 2009, 21, 4490—4497
[30]	Ran S. Y., Xu Y. Y., Guo Z. H., Fang Z. P., Chem. J. Chinese Universities,2013, 34(2), 467—473
	(冉诗雅, 许远远, 郭正虹, 方征平. 高等学校化学学报, 2013, 34(2), 467—473)
[31]	Wang F., Hao J.W., Li Z. S., Zou H. F.,Acta. Polym. Sin., 2015, (8), 897—905
	(王芳, 郝建薇, 李茁实, 邹红飞. 高分子学报, 2015, (8), 897—905)
[32]	Shan X. Y., Tai Q. L., Hu Y., Song L., Yuan G. J., Lu Z. M., Chem. J. Chinese Universities,2013, 34(10), 2431—2436
	(单雪影, 台启龙, 胡源, 宋磊, 袁国杰, 卢兆明. 高等学校化学学报, 2013, 34(10), 2431—2436)
[33]	Usta N., J. Appl. Polym. Sci., 2012, 124, 3372—3382
[34]	Wang X. B., Yang. S. S., Plast. Sci. Technol., 2010, 38(5), 47—49
	(王学宝, 杨守生. 塑料科技, 2010, 38(5), 47—49)
[35]	Dong Y. Q., Zhang L., Hou T. G., Chen H. L., Gao C. J., Chem. J. Chinese Universites,2007, 28(12), 2422—2426
	(董永全, 张林, 侯同刚, 陈欢林, 高从堦. 高等学校化学学报, 2007, 28(12), 2422—2426)
[36]	Sao B., Zhang Z. J., Wang Q. W., Song Y. M., Polym. Mater. Sci. Eng., 2008, 4, 93—96, 100
	(邵博, 张志军, 王清文, 宋永明. 高分子材料科学与工程, 2008, 4 93—96, 100)
[37]	Lu L. G., Yin D. M., Wang D. W., Xu X. N., Shu Z., J. China. Plas., 2008, 22(5), 38—43
	(卢林刚, 殷全明, 王大为, 徐晓楠, 舒仲俊. 中国塑料, 2008, 22(5), 38—43)
[38]	Wang F., Hao J.W., Li Z. S., Zou H. F.,Acta Polym. Sin., 2016, (7), 860—870
	(王芳, 郝建薇, 李茁实, 邹红飞. 高分子学报, 2016, (7), 860—870)
[39]	Le B.M., Camino. G., Bourbigot S., Royal. Soc. Chem.,Cambridge, 1998, 3—32
[40]	Li X., Ou Y. X., J. B. Inst. of Eng. Technol., 2001, 21(3), 388—391
	(李昕, 欧育湘. 北京理工大学学报, 2001, 21(3), 388—391)
[41]	Zhou Y., Hao J. W., Liu G. S., Du J. X., Chinese J. Inorg. Chem., 2013, 29(6), 1115—1122
	(周友, 郝建薇, 刘国胜, 杜建新. 无机化学学报, 2013, 29(6), 1115—1122)
[42]	Zhao C. X., Li Y. T., Xing Y. L., He D., Yue J., J. Appl. Polym Sci., 2014, 131(9), 40218—40225
[43]	Duquesne S., Bras M. L., Bourbigot S., Delobelr R., Camino G., Eling B., Lindsay C., Roels T., Vezin E J., Appl. Polym. Sci., 2001, 82, 3262—3274
[44]	Fang K.Y., Li. J., Ke C. H., Zhu Q. L., Tao K., Yan Q., Wang Y. Z.,Acta Polym. Sin., 2011, (1), 55—62
	(方科益, 李娟, 柯晨皓, 朱琦良, 陶慷, 严庆, 王玉忠. 高分子学报, 2011, (1), 55—62)