张玥,李海峰,李欣达,黎欢,余木火
ZHANG Yue,LI Hai-feng,LI Xin-da,LI Huan,YU Mu-huo(State Key Laboratory for Modification of Chemical Fibers and Polymer Materials

• 1:东华大学材料科学与工程学院 纤维材料改性国家重点实验室

摘要(Abstract)：

以离子液体1-丁基-3-甲基咪唑氯盐([Bmim]C)l作反应介质,采用马来酸酐对纤维素进行原位化学改性。利用双螺杆挤出机的剪切作用来提高纤维素在[Bmim]Cl中的溶解效率,并促进马来酸酐与纤维素的酯化反应。红外光谱(FTIR)结果证明了纤维素马来酸酯的生成,导致纤维素的氢键网络结构破坏,同时也破坏了纤维素的规整度,降低了纤维素的结晶度。热重分析(TGA)结果显示:马来酸酐支链阻碍了纤维素主链的运动,使改性纤维素的热稳定性明显高于未改性纤维素。当马来酸酐与纤维素质量比为0.8、螺杆转速为50 r/min时,改性纤维素在[Bmim]Cl中的溶解度达到20%,是未改性纤维素溶解度的2倍。
Cellulose is chemically modified with maleic anhydride(MA) by in-situ reactive extrusion.1-Nbutyl-3-methylimidazolium chloride([Bmim]Cl) is applied as reaction medium.Owing to the high shear stress of twin-screw extruder,the dissolving efficiency of cellulose in [Bmim]Cl as well as the modification effect of MA is improved effectively.Fourier transform infrared spectrscope(FTIR) results show that the formation of MA side chain in cellulose maleate obviously destroys the regularity of cellulose chains and reduces the crystallinity of cellulose.Thermal gravimetric analysis(TGA) results show that the resistance of cellulose segment motion in the cellulose maleate suppresses the degradation of cellulose in [Bmim]Cl and improves the thermal stability of cellulose maleate.The hydrogen bond network in cellulose maleate is destructed efficiently and intermolecular force of cellulose maleate is decreased with the increase of MA content.As a result,the concentration of cellulose in spinning solution can be up to 20 % when the MA content is 80 % with respect to the weight of cellulose and the screw speed is 50 rpm,which is almost double of the concentration of unmodified cellulose.

关键词(KeyWords)： 纤维素;离子液体;原位化学改性;马来酸酐;挤出
cellulose,ionic liquid,in-situ chemical modification,maleic anhydride,extrusion

Abstract:

Keywords:

基金项目(Foundation): 上海市博士后科研资助计划(基金号12R21410100)

作者(Author): 张玥,李海峰,李欣达,黎欢,余木火
ZHANG Yue,LI Hai-feng,LI Xin-da,LI Huan,YU Mu-huo(State Key Laboratory for Modification of Chemical Fibers and Polymer Materials

DOI: 10.16090/j.cnki.hcxw.2013.06.007

参考文献(References)：

• [1]张金明,张军.基于纤维素的先进功能材料[J].高分子学报,2010(12):1376-1398.
• [2]Edgar K,Heinze T,Liebert T.Cellulose solvents:for analysis,shaping and chemical modification[M].Washington DC:American Chemical Society,2009.
• [3]Klemm D,Philpp B,Heinze T,et al.Comprehensive Cellulose Chemistry:Fundamentals and Analytical Methods[M].Weinheim:Wiley-VCH Verlag GmbH,1998.
• [4]Krassig H A.Cellulose:structure,accessibility and reactivity[M].Yverdon:Gordon and Breach Science Publisher,1993.
• [5]王刚,相涛,郑毅.我国黏胶纤维行业水污染防治技术现状分析[J].废物处理与综合利用,2007,21(3):176-180.
• [6]程春祖,徐纪刚,骆强,等.纤维素在N-甲基吗啉-N-氧化物/水溶液中的溶胀与溶解性能[J].合成纤维,2012,41(7):15-19.
• [7]Barthel S,Heinze T.Acylation and carbanilation of cellulose in ionic liquids[J].Green Chemistry,2006,8(3):301-306.
• [8]蔡涛,张慧慧,杨瑜榕,等.凝固浴浓度对离子液体法纤维素纤维结构以及性能的影响[J].合成纤维,2011,40(3):13-16.
• [9]Guo Y,Zhou J P,Song Y B,et al.An efficient and environmentally friendly method for the synthesis of cellulose carbamate by microwave heating[J].Macromol Rapid Commun,2009,30,1504-1508.
• [10]王怀芳,朱平,张传杰.氢氧化钠/尿素/硫脲溶剂体系对纤维素溶解性能研究[J].合成纤维,2008,37(7):28-32.
• [11]Swatloski R P,Spear S K,Holbrey J D,et al.Dissolution of cellulose with ionic liquid[J].Journal of the American Chemical Society,2002,124:4974-4975.
• [12]Heinze T,Schwikal K,Barthel S.Ionic liquids as reaction medium in cellulose functionalization[J].Macromolecular Bioscience,2005,(5):520-525.
• [13]张秀成,邓长勇,刘文广,等.气-固反应法酯化改性纤维素[J].东北林业大学学报,2010,38(1):99-102.