Citation: Shi-fu Liao, Cong Deng, Sheng-chao Huang, Jing-yu Cao, Yu-zhong Wang. An Efficient Halogen-free Flame Retardant for Polyethylene: Piperazinemodified Ammonium Polyphosphates with Different Structures[J]. Chinese Journal of Polymer Science, ;2016, 34(11): 1339-1353. doi: 10.1007/s10118-016-1855-8 shu

An Efficient Halogen-free Flame Retardant for Polyethylene: Piperazinemodified Ammonium Polyphosphates with Different Structures

Center for Degradable and Flame-Retardant Polymeric Materials, College of Chemistry, State Key Laboratory of Polymer Materials Engineering, National Engineering Laboratory of Eco-Friendly Polymeric Materials(Sichuan);Analytical and Testing Center, Sichuan University, Chengdu 610064, China

Corresponding author: Cong Deng, dengcong@scu.edu.cn Yu-zhong Wang, yzwang@scu.edu.cn
Received Date: 25 May 2016
Revised Date: 21 June 2016
Accepted Date: 28 June 2016

Fund Project: AAAAA AAAAA

In this study, piperazine-modified ammonium polyphosphates (PA-APPs) with hierarchical structure were synthesized through ion exchange reaction. ¹H nuclear magnetic resonance (¹H-NMR), Fourier transform infrared spectra (FTIR), elemental analysis (EA), and inductively coupled plasma atomic emission spectroscopy (ICP-AES) confirmed that the PA-APPs with different structures were prepared successfully. Then these flame retardants were used alone as monocomponent intumescent flame retardant for low-density polyethylene (LDPE). Combustion tests demonstrated that the flameretardant efficiency of PA-APP containing about 7 wt% carbon (PA-APP₇) was significantly higher than that of the other PAAPPs with more or less carbon. The flame-retarded LDPE system with 30 wt% PA-APP₇ passed the UL-94 V-0 rating, and had the oxygen index (LOI) of 33.0%. Thermal analysis illustrated that the thermal decomposition behavior of PA-APP changed with incorporating different contents of PA. For all these PA-APPs, PA-APP₇ showed higher thermal stability than the other PA-APP flame retardants. All the experimental results proved that PA-APP₇ could reach the balance of an acid source, a blowing source, and a charring source as a mono-component intumescent flame retardant for LDPE. Further, it led to the formation of a compact intumescent char layer containing the structures of rich P-O-P, P-N-C, C=C, etc. during burning which in turn resulted in the excellent flame-retardant efficiency of PA-APP₇.
- Ammonium polyphosphate,
- Piperazine,
- Flame retardant,
- Polyethylene
1. [1]
  Abraham, D., George, K.E. and Joseph Francis, D., Eur. Polym. J., 1990, 26:197 doi: 10.1016/0014-3057(90)90188-A
2. [2]
  Ajji, A., Sammut, P. and Huneault, M.A., J. Appl. Polym. Sci., 2003, 88:3070 doi: 10.1002/(ISSN)1097-4628
3. [3]
  Gao, H., Hu, S., Han, H. and Zhang, J., J. Appl. Polym. Sci., 2011, 122:3263 doi: 10.1002/app.34398
4. [4]
  Bourbigot, S. and Duquesne, S., J. Mater. Chem., 2007, 17:2283 doi: 10.1039/b702511d
5. [5]
  Hu, X.P., Li, W.Y. and Wang, Y.Z., J. Appl. Polym. Sci., 2004, 94:1556 doi: 10.1002/(ISSN)1097-4628
6. [6]
  Xie, F., Wang, Y.Z., Yang, B. and Liu, Y., Macromol. Mater. Eng., 2006, 291:247 doi: 10.1002/(ISSN)1439-2054
7. [7]
  Azizi, H., Barzin, J. and Morshedian, J., Express Polym. Lett., 2007, 1:378 doi: 10.3144/expresspolymlett.2007.53
8. [8]
  Bourbigot, S., Le Bras, M., Duquesne, S. and Rochery, M., Macromol. Mater. Eng., 2004, 289:499 doi: 10.1002/(ISSN)1439-2054
9. [9]
  Hippi, U., Mattila, J., Korhonen, M. and Seppälä, J., Polymer, 2003, 44:1193 doi: 10.1016/S0032-3861(02)00856-X
10. [10]
  Lu, K., Cao, X., Liang, Q., Wang, H., Cui, X. and Li, Y., Ind. Eng. Chem. Res., 2014, 53:8784 doi: 10.1021/ie5008147
11. [11]
  Gao, Y., Wu, J., Wang, Q., Wilkie, C.A. and O'Hare, D., J. Mater. Chem. A., 2014, 2:10996 doi: 10.1039/c4ta01030b
12. [12]
  Witkowski, A., Stec, A.A. and Hull, T.R., Polym. Degrad. Stab., 2012, 97:2231 doi: 10.1016/j.polymdegradstab.2012.08.003
13. [13]
  Shi, L., Li, D.Q., Wang, J.R., Li, S.F., Evans, D.G. and Duan, X., Clays Clay Miner., 2005, 53:294 doi: 10.1346/CCMN.2005.0530309
14. [14]
  Braun, U., Schartel, B., Fichera, M.A. and Jaeger, C., Polym. Degrad. Stab., 2007, 92:1528 doi: 10.1016/j.polymdegradstab.2007.05.007
15. [15]
  Mueller, P., Fuhr, O. and Doering, M., Heteroat. Chem, 2013, 24:252 doi: 10.1002/hc.2013.24.issue-4
16. [16]
  Zhang, T., Yan, H., Shen, L., Fang, Z., Zhang, X., Wang, J. and Zhang, B., RSC Adv., 2014, 4:48285 doi: 10.1039/C4RA09243K
17. [17]
  Huang, G., Yang, J., Wang, X., Gao, J. and Liang, H., J. Mater. Chem. A., 2013, 1:1677 doi: 10.1039/C2TA00246A
18. [18]
  Molyneux, S., Stec, A.A. and Hull, T.R., Polym. Degrad. Stab., 2014, 106:36 doi: 10.1016/j.polymdegradstab.2013.09.013
19. [19]
  Rakotomalala, M., Wagner, S. and Doering, M., Mater., 2010, 3:4300 doi: 10.3390/ma3084300
20. [20]
  Paul, K.T., Hull, T.R., Lebek, K. and Stec, A.A., Fire Saf. J., 2008, 43:243 doi: 10.1016/j.firesaf.2007.10.003
21. [21]
  Wang, D., Liu, Y., Wang, D.Y., Zhao, C.X., Mou, Y.R. and Wang, Y.Z., Polym. Degrad. Stab., 2007, 92:1555 doi: 10.1016/j.polymdegradstab.2007.05.001
22. [22]
  Liu, X.Q., Wang, D.Y., Wang, X.L., Chen, L. and Wang, Y.Z., Polym. Degrad. Stab., 2011, 96:771 doi: 10.1016/j.polymdegradstab.2011.02.022
23. [23]
  Ciesielski, M., Schaefer, A. and Doering, M., Polym. Adv. Technol., 2008, 19:507
24. [24]
  Bourbigot, S., Le Bras, M., Dabrowski, F., Gilman, J.W. and Kashiwagi, T., Fire Mater., 2000, 24:201 doi: 10.1002/(ISSN)1099-1018
25. [25]
  Tian, N., Wen, X., Jiang, Z., Gong, J., Wang, Y., Xue, J. and Tang, T., Ind. Eng. Chem. Res., 2013, 52:10905 doi: 10.1021/ie401058u
26. [26]
  Li, B., Jia, H., Guan, L., Bing, B. and Dai, J., J. Appl. Polym. Sci., 2009, 114:3626 doi: 10.1002/app.v114:6
27. [27]
  Wang, B., Qian, X., Shi, Y., Yu, B., Hong, N., Song, L. and Hu, Y., Composites Part B, 2015, 69:22 doi: 10.1016/j.compositesb.2014.09.015
28. [28]
  Nie, S., Zhang, M., Yuan, S., Dai, G., Hong, N., Song, L., Hu, Y. and Liu, X., J. Therm. Anal. Calorim., 2011, 109:999
29. [29]
  Camino, G., Costa, L. and Trossarelli, L., Polym. Degrad. Stab., 1985, 12:203 doi: 10.1016/0141-3910(85)90089-8
30. [30]
  Camino, G., Costa, L. and Luda di Cortemiglia, M.P., Polym. Degrad. Stab., 1991, 33:131 doi: 10.1016/0141-3910(91)90014-I
31. [31]
  Li, B. and Xu, M., Polym. Degrad. Stab., 2006, 91:1380 doi: 10.1016/j.polymdegradstab.2005.07.020
32. [32]
  Nie, S., Hu, Y., Song, L., He, Q., Yang, D. and Chen, H., Polym. Adv. Technol., 2008, 19:1077 doi: 10.1002/pat.v19:8
33. [33]
  Shao, Z.B., Deng, C., Tan, Y., Chen, M.J., Chen, L. and Wang, Y.Z., ACS Appl. Mater. Interfaces, 2014, 6:7363 doi: 10.1021/am500789q
34. [34]
  Shao, Z.B., Deng, C., Tan, Y., Yu, L., Chen, M.J., Chen, L. and Wang, Y.Z., J. Mater. Chem. A., 2014, 2:13955 doi: 10.1039/C4TA02778G
35. [35]
  Shao, Z.B., Deng, C., Tan, Y., Chen, M.J., Chen, L. and Wang, Y.Z., Polym. Degrad. Stab., 2014, 106:88 doi: 10.1016/j.polymdegradstab.2013.10.005
36. [36]
  Gottlieb, H.E., Kotlyar, V. and Nudelman, A., J. Org. Chem., 1997, 62:7512 doi: 10.1021/jo971176v
37. [37]
  Wu, Z.P., Shu, W.Y. and Hu, Y.C., J. Appl. Polym. Sci., 2007, 103:3667 doi: 10.1002/(ISSN)1097-4628
38. [38]
  Deng, C., Zhao, J., Deng, C.L., Lv, Q., Chen, L. and Wang, Y.Z., Polym. Degrad. Stab., 2014, 103:1 doi: 10.1016/j.polymdegradstab.2014.03.001
39. [39]
  Liu, G., Chen, W. and Yu, J., Ind. Eng. Chem. Res., 2010, 49:12148 doi: 10.1021/ie1014102
40. [40]
  Camino, G., Costa, L. and Trossarelli, L., Polym. Degrad. Stab., 1985, 12:213 doi: 10.1016/0141-3910(85)90090-4
41. [41]
  Yan, Y.W., Chen, L., Jian, R.K., Kong, S. and Wang, Y.Z., Polym. Degrad. Stab., 2012, 97:1423 doi: 10.1016/j.polymdegradstab.2012.05.013
42. [42]
  Deng, C.L., Deng, C., Zhao, J., Li, R.M., Fang, W.H. and Wang, Y.Z., Chinese J. Polym. Sci., 2015, 33:203 doi: 10.1007/s10118-015-1575-5
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