废纸纤维环氧化改性及其反应动力学研究
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摘要
通过废纸纤维环氧基化改性,研究了反应温度和反应时间对改性纤维环氧值和取代度的影响。结果表明,废纸纤维的环氧基取代度随着反应温度的升高和反应时间的延长而增加。红外光谱分析显示改性后废纸纤维中有部分羟基被甲基环氧基团取代,谱图中出现了甲基、亚甲基以及醚键吸收峰的增强变化;X射线衍射分析表明纤维原有的结晶结构受到破坏,相对结晶度明显下降,改性纤维的结晶度为21.04%;TGA分析表明改性后纤维的热稳定性略有下降。确定了废纸纤维环氧基化在不同温度下的反应速率常数分别为k1=0.11(60℃),k2=0.25(70℃)、k3=0.35(80℃)。计算出了环氧基化反应的表观活化能为48.14kJ/mol。
Second fiber was epoxidated by using epichlorohydrin as etherifying agent.Effects of reaction time and reaction temperature on degree of substitution and epoxy value of the modified fiber were studied.It was indicated that they increases with prolonging of reaction time or increment of reaction temperature under 70 ℃.The characteristic absorption peaks of epoxidated fibers were observed from IR spectrum,which showed a lot of hydroxyls on the fiber surface were replaced by the methyl epoxy group of epichlorohydrin.The calculations based on XRD photo showed the crystallinity was reduced to 21.40% with the increased gap between molecular chains of modified fiber.TGA analysis indicated that thermal stability of fibers decreased slightly after modification.It was concluded in this paper that the rate constant of epoxidation of second fiber was ordered by 0.11,0.25,0.35 under reaction temperature of 60,70 and 80 ℃,respectively.Activation energy of fiber epoxidation was48.14 kJ/mol.
Second fiber was epoxidated by using epichlorohydrin as etherifying agent.Effects of reaction time and reaction temperature on degree of substitution and epoxy value of the modified fiber were studied.It was indicated that they increases with prolonging of reaction time or increment of reaction temperature under 70 ℃.The characteristic absorption peaks of epoxidated fibers were observed from IR spectrum,which showed a lot of hydroxyls on the fiber surface were replaced by the methyl epoxy group of epichlorohydrin.The calculations based on XRD photo showed the crystallinity was reduced to 21.40% with the increased gap between molecular chains of modified fiber.TGA analysis indicated that thermal stability of fibers decreased slightly after modification.It was concluded in this paper that the rate constant of epoxidation of second fiber was ordered by 0.11,0.25,0.35 under reaction temperature of 60,70 and 80 ℃,respectively.Activation energy of fiber epoxidation was48.14 kJ/mol.
引文
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[26] Xiu Huijuan.Research on natural plant fiber modification process by plasticizing and its promoting mechanism[D].Xi’an:Shaanxi University of Science&Technology,2013.修慧娟.天然植物纤维塑化改性工艺及促进机理研究[D].西安:陕西科技大学,2013.
[2] Zhan Huaiyu.Fiber chemistry and physics[M].Beijing:Science Press,2005(in Chinese).詹怀宇.纤维化学与物理[M].北京:科学出版社,2005.
[3] Ma Yaming.Grafting modification of ramie fiber and its composite materials[D].Xi'an:Xi'an Polytechnic University,2007(in Chinese).马亚明.苎麻纤维接枝改性及其复合材料研究[D].西安:西安工程大学,2007.
[4] Lu Bo.Natural fiber composite[M].Beijing:Chemical Industry Press,2005(in Chinese).鲁博.天然纤维复合材料[M].北京:化学工业出版社,2005.
[5] Zhang Lina.Natural polymer science and materials[M].Beijing:Science Press,2007(in Chinese).张俐娜.天然高分子科学与材料[M].北京:科学出版社,2007.
[6] TangAimin,Liang Wenzhi.The functionalization of cellulose[J].Polymer Bulletin,2000,(4):1-9(in Chinese).唐爱民,梁文芷.纤维素的功能化[J].高分子通报,2000,(4):1-9.
[7] Cho T S,Doh G H,Park S B.Conversion of chemically modified wood to thermoplastic material(I)chemical treatments for thermoplasticization[J].Research Reports of the Forestry Research Institute Seoul,1993,47:77.
[8] Huang Hui,Wang Yu,Wang Xiaodong.Research on internal plasticiztion of natural fiber materials[J].Jiangxi Forestry Science and Technology,2010,1:53-56(in Chinese).黄慧,王玉,王小东.天然纤维材料内部塑化研究综述[J].江西林业科技,2010,1:53-56.
[9] Kiguchi M.Chemical modification of wood surfaces by etherificationⅢ-some properties of self-bonded benzylated particleboard[J].Journal of the Japan Wood Research Society,1992,38(2):150.
[10] Kiguchi M.Chemical modification of wood surfaces by etherificationⅣ-Benzylation with solvent-dilution and vapor-phase methods[J].Journal of the Japan Wood Research Society,1993,39(1):80.
[11] Ohkoshi M.Bonding of wood by thermoplasticizing the surfaces II-possible cross-linking of wood by the graftcopolymerizing of styrene onto allylated surfaces[J].Journal of the Japan Wood Research Society,1991,37(10):917.
[12]Turkova J.Bioaffinity chromatography[M].Netherlands:Elsevier Science PubIishers,1993:215.
[13] Niu Dun,Wang Linshan,Wang Yuhong.Modification of rice straw by epichlorohy[J].Chinese Journal of Applied Chemistry,2005,22(9):1033-1035(in Chinese).牛盾,王林山,王育红.环氧氯丙烷改性稻草[J].应用化学,2005,22(9):1033-1035.
[14] Wu Xiaobin.Study on modification and rheological properties of rice epichlorohydrin[D].Shenyang:Northeastern University,2005(in Chinese).武晓滨.稻草环氧氯丙烷改性及其流变性研究[D].沈阳:东北大学,2005.
[15] Xiu Huijuan,Xiang Xinwei,Huang Min,et al.Preparation and characterization of thermoplastified fibers by alkylation reaction[J].Journal of shaanxi University of Science&Technology,2015,33(1):16-2(in Chinese).修慧娟,向欣维,黄敏,等.烷基化改性制备热塑性纤维材料的研究[J].陕西科技大学学报,2015,33(1):16-20.
[16] An Yong,Li Shiyong.The development on the epoxy resin mensurement method[J].Anwei Chemical,2003,29(4):7-9(in Chinese).安勇,李世荣.测定环氧值方法的改进[J].安微化工,2003,29(4):7-9.
[17] Wu Shigao,Li Shirong,Lu Juncai.Improved method for determining epoxy value[J].Journal of Wuhan Institute of Technology,2006,28(1):5-7(in Chinese).吴世高,李世荣,卢军彩.环氧值测定方法的改进[J].武汉工程大学学报,2006,28(1):5-7.
[18] Jorrand P,Perdrix S.Cellulose crystallinity index:measurement techniques and their impact on interpreting cellulase performance[J].Biotechnology for Biofuels,2010,3(1):10.
[19] Thygesen A,Oddershede J,Lilholt H,et al.On the determination of crystallinity and cellulose content in plant fibres[J].Cellulose,2005,12(6):563.
[20] Zheng Mingxia,Li Laiqing,Zheng Mingyue,et al.Effect of aikali pretreatment on cellulosic structural changes of corn stover[J].Environmental Science&Technology,2012,35(6):32-36(in Chinese).郑明霞,李来庆,郑明月,等.碱处理对玉米秸秆纤维素结构的影响[J].环境科学与技术,2012,35(6):32-36.
[21] Zhang Sufeng,Zhao Dongyan,Hou Chen.Strengthening of polyacrylonitrile sheets using polyamide epichlorohydrin resin[J].China Pulp&Paper,2018,37(4):25-29(in Chinese).张素凤,赵东艳,侯晨.聚酰胺环氧氯丙烷增强聚丙烯腈纤维纸的研究[J].中国造纸,2018,37(4):25-29.
[22] Sun Y,Lin L,Deng H,et al.Structural changes of bamboo cellulose in formic acid[J].Bioresources,2008,3(2):297-315.
[23] Kumar S,Negi Y S,Upadhyaya J S.Studies on characterization of corn cob based nanoparticles[J].Advanced Materials Letters,2010,1(3):246-253.
[24] French A D.Idealized powder diffraction patterns for cellulose polymorphs[J].Cellulose,2014,21(2):885-896.
[25] Zhang Xiangrong,Zhang Meiyun,Li Jinbao,et al.High value-added utilization of cellulose:microcrystalline cellulose preparation[J].China Pulp&Paper,2014,33(5):24-28(in Chinese).张向荣,张美云,李金宝,等.纤维素高值化利用制备微晶纤维素[J].中国造纸,2014,33(5):24-28.
[26] Xiu Huijuan.Research on natural plant fiber modification process by plasticizing and its promoting mechanism[D].Xi’an:Shaanxi University of Science&Technology,2013.修慧娟.天然植物纤维塑化改性工艺及促进机理研究[D].西安:陕西科技大学,2013.