含磷/氮/硫环交联磷腈微纳米管的合成及对环氧树脂的阻燃作用

doi:10.7503/cjcu20170227

高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (12): 2337.doi: 10.7503/cjcu20170227

含磷/氮/硫环交联磷腈微纳米管的合成及对环氧树脂的阻燃作用

赵师师¹, 贺梦¹, 宋文尧¹, 张冲¹, 徐建中¹, 马海云^1,²()

1. 河北大学化学与环境科学学院,保定 071002
2. 河北省分析科学技术重点实验室, 保定 071002

收稿日期:2017-04-13 出版日期:2017-12-10 发布日期:2017-11-07
作者简介:联系人简介: 马海云, 男, 博士, 副教授, 主要从事高分子纳米材料研究. E-mail: coffee1123@126.com
基金资助:
高等学校博士学科点专项科研基金(新教师类)(批准号: 20131301120006)和教育部留学回国人员科研启动基金资助

Synthesis of a Phosphorus/Nitrogen/Sulphur Containing Phosphazene Micro-Nanotube and Its Flame Retardancy on Epoxy Nanocomposite^†

ZHAO Shishi¹, HE Meng¹, SONG Wenyao¹, ZHANG Chong¹, XU Jianzhong¹, MA Haiyun^1,^2,^*()

1. College of Chemistry & Environmental Science, Hebei University, Baoding 071002, China
2. Key Laboratory of Analytical Science and Technology of Hebei Province, Baoding 071002, China

Received:2017-04-13 Online:2017-12-10 Published:2017-11-07
Contact: MA Haiyun E-mail:coffee1123@126.com
Supported by:
Supported by the Research Fund for the Doctoral Program of Higher Education of China(No.20131301120006) and the Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministy, China

摘要/Abstract

摘要：

采用原位模板法, 以六氯环三磷腈(HCCP)和二羟基二苯砜(BPS)为原料合成了一种环状交联型不溶不熔的磷腈大分子——聚环三磷腈-二羟基二苯砜(PZS)微纳米管, 研究了PZS对环氧树脂(EP)的阻燃作用及阻燃机理. 利用红外光谱(FTIR)、扫描电子显微镜(SEM)及透射电子显微镜(TEM)对PZS微纳米管进行了表征; 采用热重分析(TG)考察了EP/PZS阻燃材料的热稳定性, 并通过极限氧指数(LOI)和微型量热分析(MCC)测试了EP/PZS的阻燃性能. 热降解实验结果表明, PZS微纳米管的加入使环氧树脂热降解温度降低, 但残炭率显著提高. PZS微纳米管可以显著提高环氧树脂的阻燃性能, 当阻燃剂添加量为5%时, 环氧树脂的残炭率提高了46%, 热释放速率峰值降低了约40%; LOI值从纯环氧树脂的26.0%提高到了30.6%. PZS微纳米管的加入还增强了环氧树脂的力学强度. 阻燃性能的显著提高和力学性能的改善归因于PZS微纳米管在环氧树脂基体中的良好分散, 以及燃烧炭化过程中生成的石墨化程度较高的类石墨烯结构的残炭, 具有较高的抗氧化能力. 研究结果表明, PZS微纳米管是一种优良、高效的具有潜在应用价值的阻燃剂.

关键词: 含磷/氮/硫交联磷腈微纳米管, 阻燃, 环氧树脂, 聚环三磷腈-二羟基二苯砜

Abstract:

A highly cross-linked poly(cyclotriphosphazene-co-4,4'-sulfonyldiphenol)(PZS) nanotubes were synthesized via an in situ template method using cyclotriphosphazene(HCCP) and 4,4'-sulfonyldiphenol(BPS) as raw materials. PZS micro-nanotubes were applied on epoxy resin(EP) and the flame retarded mechanism was studied. The PZS micro-nanotubes were characterized by SEM, TEM, EDS and element Mapping. The thermalstability of PZS/EP nanocomposites were explored through TG, as compared to that of EP, and the flammability was investigated by microscale combustion calorimeter(MCC) and limit oxygen index(LOI) tests. The TGA results showed that a decreased initial degradation temperature, the residue chars were greatly improved. The flame retardancy was significantly enhanced by the addition of PZS micro-nanotubes. The residue char was improved 46% and the heat release rate was reduced 40% under addition of PZS micro-nanotubes(5%). The LOI value was also improved from 26.0% to 30.6%. The mechanical strength was also improved by the addition of PZS micro-nanotubes. The improvement of flame retardancy can be ascribed to the good dispersion and the formation of graphene-like structure during combustion of PZS/EP nanocomposites. In conclusion, PZS micro-nanotube is a kind of excellent flame retardant with potential application value.

Key words: Phosphorus/Nitrogen/Sulphur containing phosphazene micro-nanotube, Flame retardancy, Epoxy, Poly(cyclotriphosphazene-co-4,4'-sulfonyldiphenol)

中图分类号:

O631.2

TrendMD:

赵师师, 贺梦, 宋文尧, 张冲, 徐建中, 马海云. 含磷/氮/硫环交联磷腈微纳米管的合成及对环氧树脂的阻燃作用. 高等学校化学学报, 2017, 38(12): 2337.

ZHAO Shishi, HE Meng, SONG Wenyao, ZHANG Chong, XU Jianzhong, MA Haiyun. Synthesis of a Phosphorus/Nitrogen/Sulphur Containing Phosphazene Micro-Nanotube and Its Flame Retardancy on Epoxy Nanocomposite^†. Chem. J. Chinese Universities, 2017, 38(12): 2337.

图/表 11

Scheme 1 Synthetic routes of the PZS nanotubes and EP/PZS nanocomposites

Fig.1 FTIR spectra of HCCP(a), BPS(b) and PZS nanotubes(c)

Fig.2 SEM(A), TEM(B), EDS(C) and element mapping(D) images of the PZS nanotubes

Fig.3 TG(A) and DTG(B) curves of PZS nanotubes, EP, EP/PZS nanocomposites at a heating rate of 10 ℃/min under N2 atmospherea. PZS; b. EP; c. EP/PZS-1%; d. EP/PZS-3%; e. EP/PZS-5%.

Table 1 Thermogravimetric properties of PZS nanotubes, EP and EP/PZS nanocomposites

Sample	T_5%/℃	T_max/℃	Char residue at 800 ℃/(%)	Sample	T_5%/℃	T_max/℃	Char residue at 800 ℃/(%)
Neat EP	366.4	381.4	15.4	EP/PZS-3%	330.3	381.2	20.5
PZS	395.0	503.9	46.0	EP/PZS-5%	324.6	342.9	22.5
EP/PZS-1%	341.6	382.4	17.8

Fig.4 LOI values(A) and HRR curves(B) of EP and PZS/EP nanocomposites a. EP; b. EP/PZS-1%; c. EP/PZS-3%; d. EP/PZS-5%.

Fig.5 Residue chars of EP and EP/PZS nanocomposites at the end of LOI tests(A) EP; (B)EP/PZS-1%; (C) EP/PZS-3%;(D) EP/PZS-5%.

Fig.6 SEM(A), TEM(B), HRTEM(C) and EDS(D) images of the chars of PZS nanotubes at a heating rate of 10 ℃/min under N2 atmosphere Inset of (C): TEM electron diffraction image.

Fig.7 XRD profiles(A) and FTIR spectra(B) of chars of EP(a) and PZS nanotubes(b)

Fig.8 Typical stress-strain curves of the EP and EP/PZS nanocompositesa. EP; b. EP/PZS-1%; c. EP/PZS-3%; d. EP/PZS-5%.

Fig.9 SEM images of fracture section of EP(A) and EP/PZS nanocomposites(3%)(B)

参考文献 22

[1]	Mariappan T., Wilkie C. A., Fire and Materials,2014, 38(5), 588—598
[2]	Rakotomalala M., Wagner S., Döring M., Materials,2010, 3(8), 4300—4327
[3]	Tan Y., Shao Z. B., Chen X. F., Long J. W., Chen L., Wang Y. Z., ACS Applied Materials & Interfaces,2015, 7(32), 17919—17928
[4]	Carja I. D., Serbezeanu D., Vlad-Bubulac T., Hamciuc C., Coroaba A., Lisa G., Lopez C. G., Soriano M. F., Perez V. F., Sanchez M. D. R., Journal of Materials Chemistry A,2014, 2(38), 16230—16241
[5]	Tang S., Wachtendorf V., Klack P., Qian L. J., Dong Y. P., Schartel B., RSC Advances, 2017, 7(2), 720—728
[6]	Zhao X. M., Xiao D., Alonso J. P., Wang D. Y., Materials & Design, 2017, 1145, 623—632
[7]	Ma C., Yu B., Hong N. N., Pan Y., Hu W. Z., Hu Y., Industrial & Engineering Chemistry Research,2016, 55(41), 10868—10879
[8]	Huang Y. W., Song S. Q., Yang Y., Cao K., Yang J. X., Chang G. J., Journal of Materials Chemistry A,2015, 3(31), 15935—15943
[9]	Qiu S. L., Xing W. Y., Feng X. M., Yu B., Mu X. W., Yuen R. K. K., Hu Y., Chemical Engineering Journal, 2017, 3095, 802—814
[10]	Wei Z. J., Liu W. Q., Li H. J., Ma S. Q., Yan Z. L., Acta Polymerica Sinica, 2012, 5(2), 148—153
	(魏振杰, 刘伟区, 李宏静, 马松琪, 闫振龙. 高分子学报, 2012, 5(2), 148—153)
[11]	Yang S., Zhang Q. X., Hu Y. F., Polymer Degradation and Stability,2016, 1335, 358—366
[12]	Jian R., Wang P., Duan W., Wang J., Zheng X., Weng J., Industrial and Engineering Chemistry Research, 2016, 55(44), 11520—11527
[13]	Qiu S. L., Xing W. Y., Mu X. W., Feng X. M., Ma C., Yuen R. K. K., Hu Y., ACS Applied Materials & Interfaces,2016, 8(47), 32528—32540
[14]	Yang S., Wang J., Huo S. Q., Wang J. P., Tang Y. S., Polymer Degradation and Stability,2016, 126, 9—16
[15]	Zhao B., Liang W. J., Wang J. S., Li F., Liu Y. Q., Polymer Degradation and Stability,2016, 133, 162—173
[16]	Fu J., Huang X., Zhu L., Tang X., Scripta Materialia, 2008, 58(12), 1047—1049
[17]	Jiang J., Chen H., Wang Z., Bao L., Qiang Y., Guan S., Chen J., Journal of Colloid and Interface Science, 2015, 452, 54—61
[18]	Li S. Y., Qiu S. L., Yu B., Tang G., Xing W. Y., Hu Y., RCS Advances, 2016, 6(4), 3025—3031
[19]	Qiu S., Li S., Tao Y., Feng X., Yu B., Mu X., Xing W., Hu Y., Jie G., RCS Advances, 2015, 5(90), 73775—73782
[20]	Fu J. W., Huang X. B., Huang Y. W., Pan Y., Zhu Y., Tang X. Z., Journal of Physical Chemistry C,2008, 112(43), 16840—16844
[21]	Ma H. Y., Tong L. F., Xu Z. B., Fang Z. P., Nanotechnology,2007, 18(37), 1—8
[22]	Maire J., Mering J., Chemical Physics Carbon, 1970, 6, 125—130

含磷/氮/硫环交联磷腈微纳米管的合成及对环氧树脂的阻燃作用

Synthesis of a Phosphorus/Nitrogen/Sulphur Containing Phosphazene Micro-Nanotube and Its Flame Retardancy on Epoxy Nanocomposite^†

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 11

参考文献 22

相关文章 15

编辑推荐

Metrics

本文评价

[1]	唐刚, 孙俊杰, 张冬欣, 伍强, 张贺新, 沈海峰, 陶熠, 刘秀玉. 磷杂菲改性腰果酚多元醇的合成及阻燃聚氨酯硬泡性能[J]. 高等学校化学学报, 2022, 43(4): 20210847.
[2]	高京, 何文涛, 王欣欣, 向宇姝, 龙丽娟, 秦舒浩. DOPO衍生物改性碳纳米管的制备及对聚乳酸阻燃性能的影响[J]. 高等学校化学学报, 2022, 43(3): 20210670.
[3]	董璐铭, 苏衍跃, 王春征, 乔亚飞, 陈雅君, 马海云. 微纳米钙钛矿型羟基锡酸钙的合成及对环氧树脂的阻燃性能[J]. 高等学校化学学报, 2021, 42(3): 937.
[4]	王鹏, 毛丹, 万家炜, 祁琪, 杜江, 王丹. 中空多壳层TiO₂填充对环氧树脂复合材料力学性能的影响[J]. 高等学校化学学报, 2021, 42(10): 3218.
[5]	沙迪, 禹旭敏, 赵将, 马小飞, 王汉夫, 刘芳芳, 邱雪鹏. 碳纤维三向织物/环氧树脂复合材料的制备与力学性能[J]. 高等学校化学学报, 2020, 41(4): 838.
[6]	殷平, 闫红强, 程捷, 方征平. 新型生物基苯并噁嗪的合成及性能[J]. 高等学校化学学报, 2019, 40(5): 1071.
[7]	韩涛, 蔡小霞, 李聪, 乔从德, 赵辉. 生物基氢化香豆素增韧环氧树脂的制备及性能[J]. 高等学校化学学报, 2019, 40(5): 1043.
[8]	王娜, 杨菲, 张静, 方庆红. 卡拉胶包覆APP微球阻燃水性环氧树脂[J]. 高等学校化学学报, 2019, 40(2): 385.
[9]	江民文,尹晨辉,李胜,李晓丽. 环三磷腈-DOPO大分子阻燃剂的合成及阻燃环氧树脂性能[J]. 高等学校化学学报, 2019, 40(12): 2615.
[10]	苏蕊, 汪亿晗, 陈长宝, 孙秀丽, 刘淑莹, 杨洪梅. 微波辅助离子液体分散液-液微萃取DART-Orbitrap质谱法测定环境水中的溴代阻燃剂[J]. 高等学校化学学报, 2018, 39(9): 1934.
[11]	钱艺豪, 张东杰, 成中军, 康红军, 刘宇艳. 亲水性形状记忆环氧树脂制备及表面浸润性调控[J]. 高等学校化学学报, 2018, 39(8): 1823.
[12]	王英楠, 戴雪岩, 徐天璐, 曲立杰, 张春玲. 环氧树脂/硅基-纳米SiO₂涂层的制备及防腐蚀性能[J]. 高等学校化学学报, 2018, 39(7): 1564.
[13]	卢林刚, 程哲, 丘新铭, 王会娅, 杨守生, 钱小东, 王学宝. 星型绿色磷腈阻燃剂的制备及阻燃环氧树脂性能[J]. 高等学校化学学报, 2018, 39(12): 2789.
[14]	黄海鸿, 张保玉, 赵志培. 超临界正丁醇对回收碳纤维复合材料的降解及表征[J]. 高等学校化学学报, 2017, 38(9): 1687.
[15]	刘子怡, 许苗军, 王琦, 李斌. 表面化学接枝改性阻燃棉织物的制备与性能[J]. 高等学校化学学报, 2017, 38(8): 1477.

含磷/氮/硫环交联磷腈微纳米管的合成及对环氧树脂的阻燃作用

Synthesis of a Phosphorus/Nitrogen/Sulphur Containing Phosphazene Micro-Nanotube and Its Flame Retardancy on Epoxy Nanocomposite†

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 11

参考文献 22

相关文章 15

编辑推荐

Metrics

本文评价

Synthesis of a Phosphorus/Nitrogen/Sulphur Containing Phosphazene Micro-Nanotube and Its Flame Retardancy on Epoxy Nanocomposite^†