碳纳米管改性环氧树脂的导热和阻燃性能

doi:10.11944/j.issn.1000-0518.2017.01.160178

摘要/Abstract

摘要：

以双酚A二缩水甘油醚(DGEBA)环氧树脂(Epoxy Resin,EP)为基体、甲基六氢苯酐(MHHPA)为固化剂、以多壁碳纳米管(MWCNTs)为添加剂制备了环氧树脂/碳纳米管纳米复合材料。通过对微观结构、玻璃化转变温度(T_g)、热失重、热导率和锥形量热测试结果分析,研究了质量分数少于1.5%的MWCNTs对环氧树脂的导热和阻燃性能影响,结果表明,MWCNTs质量分数为1.5%时,复合材料发生团聚;纳米复合材料随着MWCNTs质量分数的增加T_g值先增加后降低;失重5%时,对应的温度先增加后降低,残炭量增加;样品的热导率呈现先升高后降低的趋势,当MWCNTs质量分数为1%时,复合材料的热导率最大;MWCNTs加入后环氧树脂的总释热量减少,释烟量增加,阻燃性得到一定程度的提高。

关键词: 环氧树脂, 碳纳米管, 导热性能, 阻燃性能

Abstract:

Epoxy resin(EP) nanocomposites have been regarded as high performance materials with the advantages of organic polymers, inorganic materials and nanoparticles. Herein, DGEBA/MWCNTs nanocomposites were prepared based on diglycidyl ether of bisphenol-A(DGEBA),methylhexahydrophthalic anhydride(MHHPA) as curing agent, and multi-walled carbon nanotubes(MWCNTs) as additive.The effect of MWCNTs(mass fraction less than 1.5%) on thermal and flame retardancy of DGEBA epoxy resin was explored by DGEBA/MWCNTs nanocomposites structure, thermal properties, thermal conductivity and cone calorimeter analysis. MWCNTs formed cluster when their mass fraction is 1.5%. With increasing the content of MWCNTs, the glass transition temperature(T_g) and the temperature at which 5% mass loss of the composites increase initially and then decrease, at the same time the residual carbon content increases. Thermal conductivity of the composite exhibits a trend of rising initially and then decreasing afterwards. The maximal thermal conductivity appears when the mass fraction of MWCNTs reaches 1%. The total heat release volume of these composites decreases and the total volume of smoke release increases compared to those of epoxy resin. Cone calorimeter tests show that the incorporation of MWCNTs into epoxy thermosets can improve its flame retardancy to some extent.

Key words: epoxy resin, multi-walled carbon nanotubes, thermal conductivity, flame retardancy

张丽丽, 丁慧敏, 张继堂, 许东华, 李志锋. 碳纳米管改性环氧树脂的导热和阻燃性能[J]. 应用化学, 2017, 34(1): 46-53.

ZHANG Lili, DING Huimin, ZHANG Jitang, XU Donghua, LI Zhifeng. Thermal Conductivity and Flame Retardancy of Carbon Nanotube Modified Epoxy Resin[J]. Chinese Journal of Applied Chemistry, 2017, 34(1): 46-53.

参考文献

[1]	Ray S S,Okamoto M.Polymer/layered Silicate Nanocomposites:A Review from Preparation to Processing[J]. Prog Polym Sci,2003,28(11):1539-1541.
[2]	Emmanuel P G.Polymer Layered Silicate Nanocomposites[J]. Adv Mater,1996,8(1):1-9.
[3]	BI Hong,WU Xianliang,LI Minquan.Electroless Plating Preparation and Microwave Absorbing Properties of Co-coated Carbon Nanotubes/Epoxy Composite[J]. Aerosp Mater Technol,2005,35(2):34-37(in Chinese). 毕红,吴先良,李民权. 镀钴碳纳米管/环氧树脂基复合材料的制备及其微波吸收特性研究[J]. 宇航材料工艺,2005,35(2):34-37.
[4]	YUAN Guanming,LI Xuanke,ZHANG Mingjin,et al. Effect of Carbon Nanotubes on the Mechanical Properties of Epoxy Resin[J]. Aerosp Mater Technol,2005,35(2):38-41(in Chinese). 袁观明,李轩科,张铭金,等. 碳纳米管对环氧树脂力学性能的影响[J]. 宇航材料工艺,2005,35(2):38-41.
[5]	HONG Xiaobin,XIE Kai,XIAO Jiayu.Curing Reaction of Organic Silane Modified Bisphenol F Epoxy Resin[J]. Chinese J Appl Chem,2007,24(11):1264-1267(in Chinese). 洪晓斌,谢凯,肖加余. 有机硅改性双酚F环氧树脂固化反应[J]. 应用化学,2007,24(11):1264-1267.
[6]	Park S J,Jeong H J,Nah C.A Study of Oxyfluorination of Multi-walled Carbon Nanotubes on MechanicalInterfacial Properties of Epoxy Matrix Nanocomposites[J]. Mater Sci Eng A,2004,38(1):13-16.
[7]	Tian L,Pinnavaia T J.Clay-reinforced Epoxy Nanocomposites[J]. Chem Mater,2002,52(9):2216-2219.
[8]	Lebaron P C,Wang Z,Pinnavaia T J.Polymer-layered Silicate Nanocomposites:An Overview[J]. Appl Clay Sci,1999,15(1):11-29.
[9]	WANG Jianguo.Study on the Structure and Properties of Multi-walled Carbon Nanotubes/Epoxy Resin Composites[D]. Hangzhou:Zhejiang University,2006 (in Chinese). 王建国. 多壁碳纳米管/环氧树脂复合材料结构与性能的研究[D]. 杭州:浙江大学,2006.
[10]	Im J S,Lee S K,In S J,et al. Improved Flame Retardant Properties of Epoxy Resin by Fluorinated MMT/MWCNT Additives[J]. J Anal Appl Pyrolysis,2010,89(2):225-232.
[11]	Dutta A,Penumadu D,Files B.Nanoindentation Testing for Evaluating Modulus and Hardness of Single-walled Carbon Nanotube-reinforced Epoxy Composites[J]. J Mater Res,2004,9(1):158-164.
[12]	ZANG Pengyuan,XUE Hua,CAI Jing,et al. Synthesis and Characterization of Multi-branch and Iron-Filled Carbon Nanotubes[J]. Chinese J Inorg Chem,2011,27(8):1625-1629(in Chinese). 臧鹏远,薛华,蔡婧,等. 多分叉和铁填充碳纳米管的合成与表征[J]. 无机化学学报,2011,27(8):1625-1629.
[13]	GUO Zhansheng,DU Shanyi,ZHANG Boming,et al. Cure Kinetics and Chemorheological Behavior of Epoxy Resin Used in Advanced Composites[J]. Acta Mater Compos Sin,2004,21(4):146-151(in Chinese). 郭战胜,杜善义,张博明,等. 先进复合材料用环氧树脂的固化反应和化学流变[J]. 复合材料学报,2004,21(4):146-151.
[14]	ZENG Xiaoliang,LIU Jia,XIONG Yuanqin,et al. Progress in Research on High Heat Resistance of Epoxy Resins[J]. Chem Ind Prog,2009,28(6):986-990(in Chinese). 曾小亮,刘甲,熊远钦,等. 高耐热性环氧树脂的研究进展[J]. 化工进展,2009,28(6):986-990.
[15]	HONG Bin,WANG Tianzhen.Market Analysis of Epoxy Applications[J]. Thermoset Resin,2011,26(3):54-58(in Chinese). 洪彬,王天祯. 环氧树脂应用领域市场分析[J]. 热固性树脂,2011,26(3):54-58.
[16]	Wu K,Song L,Hu Y,et al. Synthesis and Characterization of a Functional Polyhedral Oligomericsilses Quioxaneand Its Flame Retardancy in Epoxy Resin[J]. Prog Org Coat,2009,65(4):490-497.
[17]	Mercado L A,Galià M,Reina J A.Silicon-containing Flame Retardant Epoxy Resins:Synthesis, Characterization and Properties[J]. Polym Degrad Stab,2006,91(11):2588-2594.
[18]	Kaynak C,Nakas G I,Isitman N A. Mechanical Properties, Flammability and Char Morphology of Epoxy Resin/Montmorillonite Nanocomposites[J]. Appl Clay Sci,2009,46(3):319-324.
[19]	Kaya E,Tano?lu M,Okur S. Layered Clay/Epoxy Nanocomposites:Thermomechanical, Flame Retardancyand Optical Properties[J]. J Appl Poly Sci,2008,109(2):834-840.
[20]	Duan J K,Kim C,Jiang P K,et al. Nano-AlN Functionalization by Silane Modification for the Preparation of Covalent-Integrated Epoxy/Poly(ether imide) Nanocomposites[J]. J Appl Polym Sci,2010,115(5):2734-2746.
[21]	ZENG Lingke,QI Xiaoling,WANG Hui,et al. Study on the Thermal Conductivity of Oxide Thermoelectric Materials[J]. Bull Chinese Ceram Soc,2009,28(3):525-530 (in Chinese). 曾令可,漆小玲,王慧,等. 氧化物热电材料热导率的研究[J]. 硅酸盐通报,2009,28(3):525-530.
[22]	XIAO Lin,LI Xiaozhao,ZHAO Xiaobao,et al. Laroratory of Influences of Moisture Content and Porosity on Thermal Conductivity of Soils[J]. J PLA Univ Sci Tech(Nat Sci Edn),2008,9(3):241-247(in Chinese). 肖琳,李晓昭,赵晓豹,等. 含水量与孔隙率对土体热导率影响的室内实验[J]. 解放军理工大学学报:自然科学版,2008,9(3):241-247.
[23]	Wei L,Kuo P K,Thomas R L,et al. Thermal Conductivity of Isotopically Modified Single Crystal Diamond[J]. Phys Rev Lett,1993,70(24):3764-3767.
[24]	Anthony T R,Banholzer W F,Fleiseher J F,et al. Thermal Diffusivity of Isotopically Enriched 12 C Diamond[J]. Phys Rev B,1990,42(2):1104-1111.