表面修饰纳米晶纤维素及其在双马来酰亚胺树脂中的应用  

Surface modification of nano crystalline cellulose and application in bismaleimide resin

作　　者：巩桂芬[1] 邢韵 李泽 辛浩 曹景飞 罗艳梅 GONG Guifen;XING Yun;LI Ze;XIN Hao;CAO Jingfei;LUO Yanmei(College of Material Science and Engineering,Harbin University of Science and Technology,Harbin 150040,China)

机构地区：[1]哈尔滨理工大学材料科学与工程学院,哈尔滨150040

出　　处：《复合材料学报》2020年第6期1334-1343,共10页Acta Materiae Compositae Sinica

基　　金：国家自然科学基金(51372128)。

摘　　要：采用硫酸水解法制备了纳米晶纤维素(NCC),以N,N-羰基二咪唑(CDI)为活化剂,甲代烯丙基醇(MPO)为改性剂,通过化学取代得到含有烯丙基碳酸酯的纳米晶纤维素(PCNCC);以4,4′-二氨基二苯甲烷双马来酰亚胺(MBMI)、3,3′-二烯丙基双酚A(BBA)及双酚A双烯丙基醚(BBE)为原料制备了复合材料基体(MBAE)。采用FTIR、XRD、TEM和碘值法等对化学修饰的产物进行分析和表征。结果表明,当PCNCC中烯丙基碳酸酯的取代率为16.4%时,既能保持晶型不变,同时能在BBE中稳定悬浮;PCNCC中烯丙基碳酸酯的取代率过小或过大时均不适宜用作PCNCC/MBAE复合材料的增强相。利用原位聚合法将PCNCC掺杂在MBAE基体中制备PCNCC/MBAE复合材料,考察PCNCC质量分数对PCNCC/MBAE复合材料力学性能、介电性能及热性能的影响规律。结果显示,当PCNCC质量分数为0.2 wt%时,PCNCC/MBAE复合材料的弯曲强度和弯曲模量分别为148.1 MPa和6 GPa,较MBAE基体分别提高了50.5%和82.9%;冲击强度为13.9 kJ/m^2,较MBAE基体提高54.8%;玻璃化转变温度Tg由纯MBAE的240.4℃提高到257.8℃。此时PCNCC/MBAE复合材料的介电常数明显提高,而介电损耗达到最低值。为扩展纳米晶纤维素及双马来酰亚胺树脂的应用提供了理论依据。The nano crystalline cellulose(NCC)was prepared through a sulfuric acid hydrolysis process,Then NCC was chemically modified with N,N-carbonyldiimidazole(CDI)and 2-Methyl-2-propen-1-ol(MPO)to obtain propenyl carbonate NCC(PCNCC).4,4′-diamino diphenyl methane bismaleimide(MBMI),3,3′-diallyl bisphenol A(BBA)and bisphenol-A diallyl ether(BBE)were used to synthesize MBMI-BBA-BBE(MBAE)matrix.The modification results were characterized by FTIR,XRD,TEM and iodine value method.When the replacement rate of PCNCC is 16.4%,the modified PCNCC preserve their type and high degree of crystallization,The PCNCC stably suspend in BBE;PCNCC with too low or too high replacement rate are not suitable for fillers in PCNCC/MBAE composites.The PCNCC/MBAE composites were prepared by doing PCNCC in an MBAE matrix by in-situ polymerization.The effects of modified PCNCC mass fraction on the mechanic properties,dielectric properties and thermal properties of PCNCC/MBAE composites were investigated.A strong interaction is observed between the PCNCC and MBAE,When the mass fraction of PCNCC is 0.2 wt%,the flexural strength and modulus of PCNCC/MBAE composite are 148.1 MPa and 6 GPa,increased by 50.5%and 82.9%than that of MBAE matrix.The impact strength of PCNCC/MBAE composite is 13.9 kJ/m^2,increased by 54.8%than that of MBAE matrix,respectively.The glass transition temperature Tg value from 240.4℃of the pure MBAE to 257.8℃.The dielectric constant of PCNCC/MBAE composite increases and the dielectric loss reaches the lowest value.The improvement of mechanical properties and thermal stability of PCNCC/MBAE composites provides theoretical data for the expansion of nano cystalline cellulose and bismaleimide resin applications.

关 键 词：纳米晶纤维素 化学改性 4 4′-二氨基二苯甲烷双马来酰亚胺(MBMI) 复合材料 性能 

分 类 号：TB332[一般工业技术—材料科学与工程] O636[理学—高分子化学]