氨基化棉短绒纤维素的制备和性能
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摘要
以棉短绒,甲基丙烯酸缩水甘油酯(glycidyl methacrylate, GMA)为原料,采用自由基共聚合成纤维素聚合物(cellulose-g-GMA),再利用乙二胺(EDA)进行化学修饰,制备了氨基棉短绒纤维素复合材料(cellulose-g-GMA-EDA)。通过红外光谱(FT-IR)、扫描电镜(SEM)、热重分析(TG)、X射线衍射分析(XRD)和元素分析等手段对其结构表征,并进一步研究了产物对二甲酚橙染料的去除率和吸附量。实验结果表明:棉纤维素分子中引入了氨基,成功合成了氨基棉短绒纤维素,接枝聚合物Cellulose-g-GMA的环氧值最高达2.79 mmol/g,在m(cellulose-g-GMA)∶m(EDA)=2∶5,反应温度为100℃,反应时间为11 h的条件下,得接枝率为55%的氨基纤维素吸附材料,对二甲酚橙染料去除率达89.7%,吸附动力学符合准二级动力学模型,吸附等温线符合Freundlich模型,最大吸附量为7.2 mg/g。
Amino cotton linters cellulose composite(Cellulose-g-GMA-EDA) was prepared with cotton linters, glycidyl methacrylate(GMA) and ethylenediamine(EDA) by means of free radical graft copolymerization. The structure of the product was characterized by FT-IR, SEM, TG, XRD and elemental analysis. The removal rate and the amount of adsorption were further studied. The experimental result shows that the epoxy value of the graft polymer Cellulose-g-GMA was up to 2.79 mmol/g. At cellulose-g-GMA/EDA=2∶5, when the reaction temperature was 100 ℃, and the reaction time was 11 h, the aminocellulose adsorption material with grafting ratio of 55% was obtained, which had a removal rate of 89.7% for the xylenol orange dye. The adsorption kinetics accords with the quasi-secondary kinetic model. The adsorption isotherm conformed to the Freundlich model, and the maximum adsorption capacity was 7.2 mg/g.
Amino cotton linters cellulose composite(Cellulose-g-GMA-EDA) was prepared with cotton linters, glycidyl methacrylate(GMA) and ethylenediamine(EDA) by means of free radical graft copolymerization. The structure of the product was characterized by FT-IR, SEM, TG, XRD and elemental analysis. The removal rate and the amount of adsorption were further studied. The experimental result shows that the epoxy value of the graft polymer Cellulose-g-GMA was up to 2.79 mmol/g. At cellulose-g-GMA/EDA=2∶5, when the reaction temperature was 100 ℃, and the reaction time was 11 h, the aminocellulose adsorption material with grafting ratio of 55% was obtained, which had a removal rate of 89.7% for the xylenol orange dye. The adsorption kinetics accords with the quasi-secondary kinetic model. The adsorption isotherm conformed to the Freundlich model, and the maximum adsorption capacity was 7.2 mg/g.
引文
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[2] Wang S,Lu A,Zhang L.Recent advances in regenerated cellulose materials[J].Progress in Polymer Science,2016,53:S007967001500074X.
[3] Chang S C,Condon B,Edwards J V.Preparation and characterization of aminobenzyl cellulose by two step synthesis from native cellulose[J].Fibers and Polymers,2010,11(8):1101-1105.
[4] Li Hui.Preparation of cellulose amine resin and study on adsorption of chromium ion[J].Beijing:Beijing Forestry University,2009(in Chinese).李辉.纤维素胺基树脂制备及对铬离子吸附的研究[D].北京:北京林业大学,2009.
[5] Matsui Y,Fujie M,Sakate H.Host—guest complexation of 6-deoxy-6-(1-pyridinio) derivatives of α-cyclodextrin (cyclomaltohexaose) with inorganic anions in aqueous solution[J].Carbohydrate Research,1989,192:91-95.
[6] Takano T,Ishikawa J,Kamitakahara H,et al.The application of microwave heating to the synthesis of 6-amino-6-deoxycellulose[J].Carbohydrate Research,2007,342(16):2456-2460.
[7] Heinze T,Nikolajski M,Daus S,et al.Protein-like oligomerization of carbohydrates[J].Angewandte Chemie International Edition,2011,50(37):8602-8604.
[8] Raji C,Anirudhan T S.Batch Cr(Ⅵ) removal by polyacrylamide-grafted sawdust:kinetics and thermodynamics[J].Water Research,1998,32(12):3772-3780.
[9] And I G S,Anirudhan T S.Synthesis,characterization,and application as a mercury(ii) sorbent of banana stalk (musa paradisiaca)-polyacrylamide grafted copolymer bearing carboxyl groups[J].Industrial & Engineering Chemistry Research,2002,41(22):5341-5352.
[10] O’Connell D W,Birkinshaw C,O’Dwyer T F.A chelating cellulose adsorbent for the removal of Cu(Ⅱ) from aqueous solutions[J].Journal of Applied Polymer Science,2010,99(6):2888-2897.
[11] Fernández M J,Casinos I,Guzmán G M.Grafting of a vinyl acetate/methyl acrylate mixture onto cellulose.effect of temperature and nature of substrate[J].Macromolecular Chemistry & Physics,1990,191(6):1287-1299.
[12] Anirudhan T S,Senan P.Adsorptive potential of sulfonated poly(glycidylmethacrylate)-grafted cellulose for separation of lysozyme from aqueous phase:mass transfer analysis,kinetic and equilibrium profiles[J].Colloids & Surfaces A Physicochemical & Engineering Aspects,2011,377(1):156-166.
[13] Alberti A,Bertini S,Gastaldi G.Electron beam-irradiated textile cellulose fibers[J].European Polymer Journal,2005,41(8):1787-1797.
[14] Shukla S R,Athalye A R.Graft-copolymerization of glycidyl methacrylate onto cotton cellulose[J].Journal of Applied Polymer Science,2010,54(3):279-288.
[15] Deng S,Renbi Bai A,Chen J P.Aminated polyacrylonitrile fibers for lead and copper removal[J].Langmuir,2003,19(12):5058-5064.
[16] Filho E C D S,Melo J C P D,Airoldi C.Preparation of ethylenediamine-anchored cellulose and determination of thermochemical data for the interaction between cations and basic centers at the solid/liquid interface[J].Carbohydr Res,2006,341(17):2842-2850.
[17] Hermans P H,Weidinger A.Quantitative X-ray investigations on the crystallinity of cellulose fibers.a background analysis[J].Journal of Applied Physics,1948,19(5):491-506.
[18] Inagaki T,Siesler H W,Mitsui K,et al.Difference of the crystal structure of cellulose in wood after hydrothermal and aging degradation:a NIR spectroscopy and XRD study[J].Biomacromolecules,2010,11(9):2300-2305.
[19] Segal L,Creely J J,Martin Jr A E,et al.An empirical method for estimating the degree of crystallinity of native cellulose using the X-ray diffractometer[J].Textile Research Journal,1959,29(10):786-794.
[20] Bai Qian,Wang Wei,Liang Tao,et al.Preparation and asorption properties of aminated macroporous regenerated cellulose membranes[J].Cellulose Science and Technology,2017,25(2):30-37 (in Chinese).白倩,王玮,梁涛,等.胺基化多孔再生纤维素膜的制备及其吸附性能的研究[J].纤维素科学与技术,2017,25(2):30-37.
[21] Zhang Conglu.Chitosan modification in ionic liquids and adsorption properties of modified materials [D].Shenyang:Northeastern University ,2014 (in Chinese) .张聪璐.离子液体中壳聚糖改性及改性材料的吸附性能研究[D].沈阳:东北大学,2014.