DBU/DMSO/CO_2溶剂体系中纤维素聚离子液体的合成及性质
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摘要
针对环境污染以及石油资源的不可再生问题,开发环境友好、来源广泛且易改性的可再生资源具有十分重要的意义。本研究采用DBU/DMSO/CO_2可逆离子液体溶解体系对生物质资源中最多的纤维素进行溶解活化,再用2,3-吡啶二羧酸酐对其进行化学改性,以制备出吡啶阳离子基纤维素聚离子液体,并探索反应温度、物质的量比、反应时间对取代度的影响。结果表明,在2,3-吡啶二羧酸酐与纤维素脱水葡萄糖单元(AGU)物质的量比为1.2∶1、反应温度为80℃、反应时间为4 h时,得到了最高取代度(2.18)的产物。采用傅里叶变换红外光谱仪和核磁共振仪表征了纤维素聚离子液体的结构,采用同步式热分析仪测试了其热性能,其初始分解温度最高为152℃。采用本研究方法制备纤维素聚离子液体的操作过程简单,基本无环境污染及副产物,对开发新的纤维素衍生物具有一定的指导意义。
In view of environmental pollution and the non-renewable problem of petroleum resources, it is of great significance to develop renewable resources that are environmentally friendly and widely available for modification.The present study, one of the most abundant biomass resources, cellulose, was dissolved and activated in the DBU/DMSO/CO_2 reversible ionic liquid dissolution system, and then was chemically modified by 2,3-pyridine dicarboxylic anhydride to synthesize pyridine cationic cellulose polyionic liquid. The impact of reaction temperature, molar ratio and reaction time on the degree of substitution was studied. As can be seen from the results, the product achieved the highest substitution degree of 2.18, under the molar ratio of 2,3-pyridine dicarboxylic anhydride to cellulose anhydroglucose unit(AGU) of 1.2∶1, the reaction temperature of 80 ℃, and the reaction time of 4 h. Fourier transform infrared spectroscope(FTIR) and nuclear magnetic resonance(NMR) were employed to characterize the structure of cellulose polyionic liquid. In addition, the synchronous thermal analyzer was adopted to measure the thermal properties of the cellulose polyionic liquid, and its initial decomposition temperature of 152 ℃ was obtained. The proposed approach for preparing cellulose polyionic liquid exhibited simple operation process, no environmental pollution and by-products generally, showing certain guiding significance for the development of new cellulose derivatives.
In view of environmental pollution and the non-renewable problem of petroleum resources, it is of great significance to develop renewable resources that are environmentally friendly and widely available for modification.The present study, one of the most abundant biomass resources, cellulose, was dissolved and activated in the DBU/DMSO/CO_2 reversible ionic liquid dissolution system, and then was chemically modified by 2,3-pyridine dicarboxylic anhydride to synthesize pyridine cationic cellulose polyionic liquid. The impact of reaction temperature, molar ratio and reaction time on the degree of substitution was studied. As can be seen from the results, the product achieved the highest substitution degree of 2.18, under the molar ratio of 2,3-pyridine dicarboxylic anhydride to cellulose anhydroglucose unit(AGU) of 1.2∶1, the reaction temperature of 80 ℃, and the reaction time of 4 h. Fourier transform infrared spectroscope(FTIR) and nuclear magnetic resonance(NMR) were employed to characterize the structure of cellulose polyionic liquid. In addition, the synchronous thermal analyzer was adopted to measure the thermal properties of the cellulose polyionic liquid, and its initial decomposition temperature of 152 ℃ was obtained. The proposed approach for preparing cellulose polyionic liquid exhibited simple operation process, no environmental pollution and by-products generally, showing certain guiding significance for the development of new cellulose derivatives.
引文
1 Ragauskas A J,Williams C K,Davison B H,et al.Science,2006,311(5760),484.
2 Kim D H,Park S Y,Kim J,et al.Journal of Applied Polymer Science,2010,117(6),3588.
3 Regiani A M,Frollini E,Marson G A,et al.Journal of Polymer Science Part A Polymer Chemistry,2015,37(9),1357.
4 Heinze T,Dicke R,Koschella A,et al.Macromolecular Chemistry & Physics,2000,201(6),627.
5 Cai J,Zhang L,Zhou J,et al.Macromolecular Rapid Communications,2004,25(17),1558.
6 Wang H,Gurau G,Rogers R D.Chemical Society Reviews,2012,41(4),1519.
7 Cao Y,Wu J,Zhang J,et al.Chemical Engineering Journal,2009,147(1),13.
8 Cao Y,Li H,Zhang Y,et al.Journal of Applied Polymer Science,2010,116(1),547.
9 Xie H,Yu X,Yang Y,et al.GreenChem,2014,16(5),2422.
10 Macfarlane D R,Forsyth M,Howlett P C,et al.Nature Reviews Mate-rials,2016,1(2),15005.
11 Lu J,Yan F,Texter J.Progress in Polymer Science,2009,34(5),431.
12 Yuan J,Mecerreyes D,Antonietti M.Progress in Polymer Science,2013,38(7),1009.
13 Gu H,Yan F,Texter J.Macromolecular Rapid Communications,2016,37(14),1218.
14 Doebbelin M,Azcune I,Bedu M,et al.Chemistry of Materials,2012,24(9),1583.
15 Tang J,Tang H,Sun W,et al.Journal of Polymer Science Part A Polymer Chemistry,2005,43(22),5477.
16 Hu H,Yuan W,Lu L,et al.Journal of Polymer Science Part A Polymer Chemistry,2014,52(15),2104.
17 Gao K K,Du J H,Zhang L H,et al.Cellulose Science and Technology,DOI:10.16561/j.cnki.xws.2018.02.07(in Chinese).高可可,杜杰毫,张丽华,等.纤维素科学与技术,DOI:10.16561/j.cnki.xws.2018.02.07.
18 Du J H,Wen Y,Chen H X,et al.Scientia Sinica:Chimica,2018,48(5),512(in Chinese).杜杰毫,文玥,陈华鑫,等.中国科学:化学,2018,48(5),512.
19 Chen Q,Peng C,Xie H B,et al.RSC Advances,2015,5(55),44598.
20 Roberta D S,Agnese D L,Giuseppe M,et al.Journal of Porphyrins & Phthalocyanines,DOI:10.1142/S1088424607000898.
21 Priya K,Buvaneswari G.Materials Research Bulletin,2009,44(6).1209.
2 Kim D H,Park S Y,Kim J,et al.Journal of Applied Polymer Science,2010,117(6),3588.
3 Regiani A M,Frollini E,Marson G A,et al.Journal of Polymer Science Part A Polymer Chemistry,2015,37(9),1357.
4 Heinze T,Dicke R,Koschella A,et al.Macromolecular Chemistry & Physics,2000,201(6),627.
5 Cai J,Zhang L,Zhou J,et al.Macromolecular Rapid Communications,2004,25(17),1558.
6 Wang H,Gurau G,Rogers R D.Chemical Society Reviews,2012,41(4),1519.
7 Cao Y,Wu J,Zhang J,et al.Chemical Engineering Journal,2009,147(1),13.
8 Cao Y,Li H,Zhang Y,et al.Journal of Applied Polymer Science,2010,116(1),547.
9 Xie H,Yu X,Yang Y,et al.GreenChem,2014,16(5),2422.
10 Macfarlane D R,Forsyth M,Howlett P C,et al.Nature Reviews Mate-rials,2016,1(2),15005.
11 Lu J,Yan F,Texter J.Progress in Polymer Science,2009,34(5),431.
12 Yuan J,Mecerreyes D,Antonietti M.Progress in Polymer Science,2013,38(7),1009.
13 Gu H,Yan F,Texter J.Macromolecular Rapid Communications,2016,37(14),1218.
14 Doebbelin M,Azcune I,Bedu M,et al.Chemistry of Materials,2012,24(9),1583.
15 Tang J,Tang H,Sun W,et al.Journal of Polymer Science Part A Polymer Chemistry,2005,43(22),5477.
16 Hu H,Yuan W,Lu L,et al.Journal of Polymer Science Part A Polymer Chemistry,2014,52(15),2104.
17 Gao K K,Du J H,Zhang L H,et al.Cellulose Science and Technology,DOI:10.16561/j.cnki.xws.2018.02.07(in Chinese).高可可,杜杰毫,张丽华,等.纤维素科学与技术,DOI:10.16561/j.cnki.xws.2018.02.07.
18 Du J H,Wen Y,Chen H X,et al.Scientia Sinica:Chimica,2018,48(5),512(in Chinese).杜杰毫,文玥,陈华鑫,等.中国科学:化学,2018,48(5),512.
19 Chen Q,Peng C,Xie H B,et al.RSC Advances,2015,5(55),44598.
20 Roberta D S,Agnese D L,Giuseppe M,et al.Journal of Porphyrins & Phthalocyanines,DOI:10.1142/S1088424607000898.
21 Priya K,Buvaneswari G.Materials Research Bulletin,2009,44(6).1209.