聚酰亚胺/绢云母复合材料的制备及表征  

Preparation and Characterization of Polyimide /Sericite Mica Composites

作　　者：张起[1] 李笃信[1] 赖登旺[1] 游一兰[1] 欧宝立[2] 雷霆[1] 

机构地区：[1]中南大学粉末冶金国家重点实验室,长沙410083 [2]湖南科技大学化学化工学院,湘潭411201

出　　处：《高分子学报》2014年第3期369-377,共9页Acta Polymerica Sinica

基　　金：中南大学中央高校基本科研业务费专项资金(项目号2012zzts075);粉末冶金国家重点实验室专项基金(基金号20120613Z);湖南省自然科学基金(基金号13JJA004)资助项目

摘　　要：首先采用加热和酸浸、硝酸锂处理、十六烷基三甲基溴化铵（HDTMAB）阳离子交换等多步反应制备了有机绢云母，随后通过原位聚合插层法合成了不同种类的聚酰亚胺（PI）/绢云母复合材料.研究了反应温度及有机阳离子HDTMAB加入量对绢云母改性效果的影响，采用X-射线衍射（XRD）、傅里叶变换红外光谱（FTIR）和扫描电子显微镜（SEM）对改性前后的绢云母进行了系统的分析.结果表明，改性反应温度为180 ℃，有机阳离子加入量为15倍的阳离子交换容量（CEC）时插层效果最理想，在此条件下，绢云母 d002晶面间距从0.99 nm扩大到2.77 nm.通过XRD和高分辨透射电子显微镜（HRTEM）对复合材料的微观结构进行了研究，采用热重分析（TGA）和力学性能测试研究了复合材料的热性能，拉伸强度、杨氏模量和断裂伸长率.结果表明，用原样绢云母制备的PI/原样绢云母复合材料是一种简单物理混合物，而PI/有机绢云母复合材料是一种剥离型纳米复合材料，同时，有机绢云母含量为1%-7%的纳米复合材料在2θ=0.5°-10°的衍射角范围内，均没有出现明显的衍射峰，表明有机绢云母的d002晶面间距被扩大到4.42 nm以上.绢云母与PI质量比为5：100时，PI/有机绢云母纳米复合材料的拉伸强度、杨氏模量、断裂伸长率是PI/原样绢云母复合材料相应值的1.79，1.40和1.83倍.纳米复合材料的T5（质量损失5%时的温度）随着有机绢云母含量的增加而显著提高，当有机绢云母含量为7%时，纳米复合材料的T5相比纯PI可提高36 ℃.The sericite mica was first treated by heating and acid dipping followed by LiNO3 treatment.The organophilic clay was subsequently achieved by inorganic-organic ion exchange in the hydrothermal reaction of LiNO3-treated sericite mica with intercalating agent-hexadecyltrimethylammonium bromide solution.Finally, a series of polyimide （PI）/sericite mica composites were prepared via in situ polymerization reaction.The effects of the reaction temperature and the amount of intercalating agent added on the modification of sericite mica were investigated.The structures of modified and original sericite mica were systemically characterized with X-ray diffraction （XRD）, Fourier transform infrared spectroscopy （FTIR） and scanning electron microscopy （SEM）, showing the best intercalating effect was observed when the reaction temperature was 180 ℃ and the amount of intercalating agent added was fifteenfold the cation exchange capacity （CEC）.Under the above reaction conditions, the d002 basal spacing of the sericite mica was increased from 0.99 nm to 2.77 nm.The structure of the composites was investigated by XRD and high resolution transmission electron microscopy （HRTEM）, and the thermal stability and the mechanical properties were studied by means of thermogravimetric analysis （TGA） and mechanical property measurements, indicating that the PI/original sericite mica composite was a simple physical blend of PI and pure sericite mica, while the PI/organic sericite mica nanocomposites was an exfoliated structure with 5 wt% loading, and the nanocomposites with the content of 1 wt%-7 wt% organophilic sericite mica exhibited no observable peaks in the range of 0.5°-10° （2θ）, which revealed that majority of the d002-spacing of organophilic sericite mica had been intercalated to a distance of more than 4.42 nm （2θ〈1°）.When the mass ratio of sericite mica and PI was 5：100, the tensile strength, Young＇s modulus and elongation at break of the PI/organic sericite mica nanocomposites are 1

关 键 词：绢云母 改性 十六烷基三甲基溴化铵 聚酰亚胺 复合材料 

分 类 号：TB332[一般工业技术—材料科学与工程]