新型无卤膨胀/MH阻燃环氧树脂的制备及阻燃性能

doi:10.11868/j.issn.1001-4381.2015.05.009

摘要
图/表
参考文献
相关文章
Metrics

全文: PDF(1899 KB)

HTML ( 49 )
输出: BibTeX | EndNote (RIS)

摘要

通过极限氧指数(LOI)、水平垂直燃烧(UL-94)、锥形量热(cone)等方法,研究了纳米氢氧化镁(MH)添加到六(4-DOPO羟甲基苯甲酸)环三磷腈化合物(FR)、聚磷酸铵(APP)和环氧树脂(EP)后,制备的新型复合阻燃材料(FR/APP/MH/EP)的阻燃及力学性能.结果表明:在固定FR/APP比例为1/1的前提下,添加1%(质量分数)的MH时,复合阻燃材料EP2(10%FR/10%APP/1%MH/EP)的LOI值达到36.4%,其热释放速率(pk-HRR)、有效燃烧热平均值(av-EHC)、比消光面积平均值(av-SEA)、一氧化碳释放率平均值(av-CO)较纯环氧树脂(EP0)分别下降了79.8%,6.73%,47.2%,33.3%,相对于EP1(10%FR/10%APP/EP)分别下降了20.0%,69.6%,83.6%,58.6%,同时EP2的拉伸、弯曲、冲击强度较EP1也分别提高了47.6%,75.2%,196%;SEM分析表明EP2燃烧后能够形成一层均匀、致密、连续的炭层,具有良好的阻燃、抑烟、降毒效果.

	服务

	把本文推荐给朋友
	加入引用管理器
	E-mail Alert
	RSS
	作者相关文章
	卢林刚
	陈英辉
	程哲
	杨守生
	邵高耸

关键词 ：膨胀阻燃剂, 环氧树脂, 纳米氢氧化镁, 阻燃性能

Abstract：

The flame retarding and mechanical properties of new flame retardant composites(FR/APP/MH/EP) were studied using limited oxygen index (LOI) measurement,UL-94 and cone test. The new flame retardant composites were prepared by adding nano-magnesium hydroxide(MH) into six-(4-of DOPO hydroxymethyl phenoxy) cyclotriphosphazene (FR),polyphosphate (APP) and epoxy resin(EP). The results show that when fix the FR/APP 1:1, adding 1% mass fraction MH, the limited oxygen index(LOI) value of EP2 (10%FR/10%APP/1%MH/EP) can reach 36.4%, the peak heat release rate (pk-HRR),average effective heat of combustion (av-EHC),average specific extinction area (av-SEA),average CO release rate (av-CO) of EP2 are reduced by 79.8%,6.73%,47.2%,33.3%, respectively, compared with those of pure EP (EP0) and decrease 20.0%,69.6%,83.6%,58.6%, respectively, compared with those of EP1 (10%FR/10%APP/EP),meanwhile, the tensile,bending and impact strengths of EP2 increase 47.6%, 75.2% and 196%, separately, compared with those of EP1.SEM observation reveals that EP2 forms a uniform, compact and continuous charred layers after burning, which has good flame retarding,smoke suppression and the toxic effects.

Key words： intumescent flame retardant(IFR) epoxy resin nano-magnesium hydroxide flame retardancy

收稿日期: 2013-10-17 出版日期: 2015-05-20

基金资助:河北省自然科学基金资助项目(E2012507008);国家自然科学基金资助项目(21472241)

通讯作者: 卢林刚 E-mail: llg@iccas.ac.cn

作者简介: 卢林刚(1974—),男,教授,主要研究方向:阻燃材料及有机合成,联系地址:河北省廊坊市西昌路220号中国人民武装警察部队学院科研部(065000),llg@iccas.ac.cn

引用本文:

卢林刚, 陈英辉, 程哲, 杨守生, 邵高耸. 新型无卤膨胀/MH阻燃环氧树脂的制备及阻燃性能[J]. 材料工程, 2015, 43(5): 50-55.
Lin-gang LU, Ying-hui CHEN, Zhe CHENG, Shou-sheng YANG, Gao-song SHAO. Preparation and Flame Retardancy of Intumescent/MH Flame-retardant Epoxy Resins. Journal of Materials Engineering, 2015, 43(5): 50-55.

链接本文:

http://jme.biam.ac.cn/CN/10.11868/j.issn.1001-4381.2015.05.009 或 http://jme.biam.ac.cn/CN/Y2015/V43/I5/50

Fig.1 六(4-DOPO羟甲基苯氧基)环三磷腈(FR)的分子结构式^[11]

Table 1 纯EP及FR/APP/MH/EP复合材料的氧指数和UL94实验结果

Table 2 纯EP及FR/APP/MH/EP复合材料的35kW·m^-2辐射功率锥形量热仪(cone)实验数据

Fig.2 纯EP及FR/APP/MH/EP体系的热释放速率曲线

Table 3 纯EP及FR/APP/MH/EP复合材料燃烧性能指数

Table 4 纯EP和FR/APP/MH/EP力学性能测试结果

Fig.3 阻燃环氧树脂体系燃烧后炭层的数码照片
(a)EP0;(b)EP1;(c)EP2

Fig.4 阻燃环氧树脂体系燃烧后炭层的SEM照片
(a)EP0;(b)EP1;(c)EP2

1	王淑波, 王利生磷系阻燃环氧树脂研究[J]. 化学进展, 2007, 19 (1): 159- 164.
1	WANG Shu-bo, WANG Li-sheng Phosphorus-containing flame retardant epoxy resins[J]. Progress in Chemistry, 2007, 19 (1): 159- 164.
2	王正洲, 王云, 胡源聚磷酸铵及季戊四醇膨胀型阻燃环氧树脂的阻燃性能[J]. 高分子材料科学与工程, 2009, 25 (11): 86- 89.
2	WANG Zheng-zhou, WANG Yun, HU Yuan Intumescent flame retardation of epoxy resins containing ammonium polyphosphate and pentaerythritol[J]. Polymer Materials Science and Engineering, 2009, 25 (11): 86- 89.
3	马志领, 卢光玉膨胀型阻燃剂阻燃环氧树脂的阻燃性能及其影响因素[J]. 中国塑料, 2010, 24 (8): 45- 48.
3	MA Zhi-ling, LU Guang-yu Flame retardancy and influencing factors of epoxy resin flame retarded by intumescent flame retardant[J]. China Plastics, 2010, 24 (8): 45- 48.
4	卢林刚, 徐晓楠, 王大为, 等新型无卤膨胀阻燃聚丙烯的制备及阻燃性能[J]. 复合材料学报, 2013, 30 (1): 83- 89.
4	LU Lin-gang, XU Xiao-nan, WANG Da-wei, et al Preparation and flame retardancy of intumescent flame-retardant polypropylene[J]. Acta Materiae Compositae Sinica, 2013, 30 (1): 83- 89.
5	XIAO Wei-dong, HE Pei-xin, HU Gao-ping, et al Study on the flame-retardance and thermal stability of the acid anhydride-cured epoxy resin flame-retarded by triphenyl phosphate and hydrated alumina[J]. Journal Fire Sciences, 2001, 19 (5): 369- 377.
6	HUANG F, LIU Y Q, ZHANG X H, et al Effect of elastomeric nanoparticles on toughness and heat resistance of epoxy resins[J]. Macromolecular Rapid Communications, 2002, 23 (13): 786- 790.
7	MAUERER O New reactive, halogen-free flame retardant system for epoxy resins[J]. Polymer Degradation and Stability, 2005, 88 (1): 70- 73.
8	WANG C S, LEE M C Synthesis, characterization, and properties of multifunctional naphthalene-containing epoxy resins cured with cyanate ester[J]. Journal of Applied Polymer Science, 1999, 73 (9): 1611- 1622.
9	TAKAHASHI A, SATSU Y, NAGAI A, et al Heat-resistant epoxy-silicon hybrid materials for printed wiring boards[J]. IEEE Transactions on Electronics Packaging Manufacturing, 2005, 28 (2): 163- 167.
10	TAKAMATSU Y, DUNMEYER D, THOMAS EL, et al Preparation characterization and heat resistance studies of a holographic photopolymer based on SU-8 epoxy resin[J]. Optics Letters, 2008, 33 (1): 7- 9.
11	卢林刚, 王晓, 杨守生, 等单组分磷-氮膨胀阻燃剂的合成及成炭性能[J]. 高分子材料科学与工程, 2012, 28 (7): 10- 13.
11	LU Lin-gang, WANG Xiao, YANG Shou-sheng, et al Synthesis and charring of arborescent monomolecular P-N intumescent flame retardant[J]. Polymer Materials Science and Engineering, 2012, 28 (7): 10- 13.
12	周红军, 李设桥, 李翠金, 等纳米二氧化钛对环氧树脂固化反应的影响[J]. 热固性树脂, 2012, 27 (6): 11- 14.
12	ZHOU Hong-jun, LI She-qiao, LI Cui-jin, et al Influence of nano-TiO2 on the curing reaction of epoxy resin[J]. Thermosetting Resin, 2012, 27 (6): 11- 14.
13	FRANGIOSA P C, CATALANI L H Production of lifetime controlled plastics: copolymers of styrene and substituted butadienes[J]. Polymer Degradation and Stability, 2003, 82 (2): 207- 210.
14	王德花, 李荣勋, 刘光烨包覆红磷阻燃ABS的性能研究[J]. 中国塑料, 2007, 21 (11): 74- 77.
14	WANG De-hua, LI Rong-xun, LIU Guang-ye Performance of capsule red phosphorus flame-retarded ABS composites[J]. China Plastics, 2007, 21 (11): 74- 77.
15	张琦, 胡伟康, 田明, 等纳米氢氧化镁/橡胶复合材料的性能研究[J]. 橡胶工业, 2004, 51 (1): 14- 18.
15	ZHANG Qi, HU Wei-kang, TIAN Ming, et al Properties of nano-magnesium hydroxide/rubber composite[J]. China Rubber Industry, 2004, 51 (1): 14- 18.
16	张建军, 张靖宗, 纪全, 等 MWNTs-OH/PET纳米复合材料的燃烧性能与阻燃机理研究[J]. 功能材料, 2010, 41 (3): 394- 396.
16	ZHANG Jian-jun, ZHANG Jing-zong, JI Quan, et al Combustion property and flame-retardant mechanism of MWNTs-OH/PET composites[J]. Journal of Functional Materials, 2010, 41 (3): 394- 396.
17	李到, 胡静平, 秦艳, 等磷酸酯双三聚氰胺盐阻燃环氧树脂的燃烧性能和阻燃机理[J]. 功能高分子学报, 2007, 19-20 (1): 81- 86.
17	1): 81-86. LI Dao, HU Jing-ping, QIN Yan, et al Combustion behavior and pyrolysis of epoxy resins blended with caged bicyclic dimelamine phosphate[J]. Journal of Functional Polymers, 2007, 19-20 (1): 81- 86.

[1]	贾耀雄, 许良, 敖清阳, 张文正, 王涛, 魏娟. 不同热氧环境对T800碳纤维/环氧树脂复合材料力学性能的影响[J]. 材料工程, 2022, 50(4): 156-161.
[2]	许良, 涂宜鸣, 崔浩, 周松. 海水环境下老化周期对T800碳纤维/环氧树脂复合材料的影响[J]. 材料工程, 2022, 50(12): 89-94.
[3]	王牧, 曾夏茂, 苗霞, 魏浩光, 周仕明, 冯岸超. 三维石墨烯-吡咯气凝胶/环氧树脂复合材料的制备及其性能[J]. 材料工程, 2022, 50(1): 117-124.
[4]	张代军, 陈俊, 包建文, 钟翔屿, 陈祥宝. 树脂基体中热塑性树脂含量对碳纤维环氧复合材料Ⅱ型层间断裂韧性的影响[J]. 材料工程, 2021, 49(6): 178-184.
[5]	陈宇, 张代军, 李军, 温嘉轩, 陈祥宝. 三维结构石墨烯气凝胶/环氧树脂复合材料的制备和电磁屏蔽性能[J]. 材料工程, 2021, 49(5): 82-88.
[6]	周松, 贾耀雄, 许良, 边钰博, 涂宜鸣. 湿热环境对T800碳纤维/环氧树脂基复合材料力学性能的影响[J]. 材料工程, 2021, 49(10): 138-143.
[7]	王钰登, 郑亚萍, 宋珊, 姚东东. SiO₂无溶剂纳米流体粒径和含量对环氧树脂力学和热性能的影响[J]. 材料工程, 2021, 49(10): 156-163.
[8]	张成林, 董抒华, 李丽君, 田龙雨, 谭洪生. E-玻纤/环氧树脂预浸料固化动力学及其动态热力学性能[J]. 材料工程, 2020, 48(9): 152-157.
[9]	李为民, 彭超义, 杨金水, 邢素丽. PTFE/epoxy全有机超疏水涂层制备[J]. 材料工程, 2020, 48(7): 162-169.
[10]	李翰, 樊茂华, 王纳斯丹, 范保鑫, 冯振宇. 碳纤维环氧树脂复合材料热响应预报方法[J]. 材料工程, 2020, 48(5): 49-55.
[11]	侯桂香, 谢建强, 姚少巍, 张云杰, 蓝文. 生物基没食子酸环氧树脂/纳米氧化锌抗菌涂层的制备与性能[J]. 材料工程, 2020, 48(3): 34-39.
[12]	郑凌祺, 李刚, 杨小平, 李强, 石凌飞. 环糊精微球改性环氧树脂的制备及其碳纤维复合材料的X射线穿透性研究[J]. 材料工程, 2020, 48(11): 170-176.
[13]	顾善群, 刘燕峰, 李军, 陈祥宝, 张代军, 邹齐, 肖锋. 碳纤维/环氧树脂复合材料高速冲击性能[J]. 材料工程, 2019, 47(8): 110-117.
[14]	陈珂龙, 张桐, 崔溢, 王智勇. 超支化聚合物(HBPs)改性环氧树脂的研究进展[J]. 材料工程, 2019, 47(7): 11-18.
[15]	李曦. 二维和零维纳米材料协同增强的高性能纳米复合材料[J]. 材料工程, 2019, 47(4): 47-55.

Viewed

Full text

Abstract

Cited

Shared

Discussed