木薯羧甲基淀粉的机械活化固相化学法制备、表征及其特性
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摘要
以木薯淀粉为原料,氯乙酸钠为醚化剂,氢氧化钠为催化剂,采用机械活化固相化学反应法制备羧甲基淀粉。以取代度为评价指标,通过单因素和正交试验设计优化确定最佳制备工艺,采用傅里叶红外光谱(Fourier transform infrared spectroscopy,FTIR)、X-射线衍射(X-ray diffraction,XRD)、扫描电镜(scanning electron microscope,SEM)对羧甲基淀粉的结构进行表征,并考察羧甲基淀粉的理化特性。结果表明,最佳工艺参数为淀粉与氯乙酸钠物质的量比1∶1、反应温度50℃、反应时间1.5 h、氢氧化钠溶液质量分数18.8%、搅拌速率380 r/min、球磨介质堆体积500 m L,在此条件下制备的羧甲基淀粉取代度为0.540 1。FTIR、XRD、SEM检测进一步证实木薯淀粉发生了羧甲基化反应。理化特性结果显示,羧甲基淀粉的黏度升高,溶解度增大,吸水性、保水性、冻融稳定性、抗酸碱性、抗酶解性等均得到较好的提高。
Carboxymethyl cassava starch was synthesized from cassava starch with monochloroacetate(MCA) as an etherifying agent and sodium hydroxide(Na OH) as a catalyst by mechanical activation-assisted solid-state reaction.Onefactor-at-a-time and orthogonal array design methods were used to optimize the preparation conditions for higher degree of substitution(DS).The structure of carboxymethyl cassava starch was characterized by Fourier transform infrared spectroscopy(FTIR),X-ray diffraction(XRD) and scanning electron microscope(SEM) and its physicochemical propertieswere systematically investigated.The optimal process parameters that provided maximum DS of 0.540 1 were obtained as follows: molar ratio of starch to sodium chloroacetate 1:1,reaction temperature 50 ℃,reaction time 1.5 h,sodium hydroxide concentration 18.8%,stirring speed 380 r/min,and volume of ball milling medium 500 m L.The etherification reaction of cassava starch was confirmed by FTIR,XRD and SEM.Results of the physicochemical properties showed that the solubility of carboxymethyl cassava starch and the viscosity of starch paste and were significantly increased; water-absorbing capacity,water-retaining capacity,freeze-thaw stability,and acid,alkali and enzyme resistance were also improved compared with the native starch.
Carboxymethyl cassava starch was synthesized from cassava starch with monochloroacetate(MCA) as an etherifying agent and sodium hydroxide(Na OH) as a catalyst by mechanical activation-assisted solid-state reaction.Onefactor-at-a-time and orthogonal array design methods were used to optimize the preparation conditions for higher degree of substitution(DS).The structure of carboxymethyl cassava starch was characterized by Fourier transform infrared spectroscopy(FTIR),X-ray diffraction(XRD) and scanning electron microscope(SEM) and its physicochemical propertieswere systematically investigated.The optimal process parameters that provided maximum DS of 0.540 1 were obtained as follows: molar ratio of starch to sodium chloroacetate 1:1,reaction temperature 50 ℃,reaction time 1.5 h,sodium hydroxide concentration 18.8%,stirring speed 380 r/min,and volume of ball milling medium 500 m L.The etherification reaction of cassava starch was confirmed by FTIR,XRD and SEM.Results of the physicochemical properties showed that the solubility of carboxymethyl cassava starch and the viscosity of starch paste and were significantly increased; water-absorbing capacity,water-retaining capacity,freeze-thaw stability,and acid,alkali and enzyme resistance were also improved compared with the native starch.
引文
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[31]范庆松.干法制备高取代度羧甲基淀粉及应用性能研究[D].大连:大连理工大学,2006:27-28.
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[2]BROUILLET F,BATAILLE B,CARTILIER L.High-amylose sodium carboxymethyl starch matrices for oral susained drug-release:formulation aspects and in vitro drug-release evaluation[J].Iternational Journal of Pharmaceutics,2008,356(1/2):52-60.DOI:10.1016/j.ijpharm.2007.12.039.
[3]GHANSHYAM S C,SAROJ C J,MONIKA V.Post functionalization of carboxymethylated starch and acrylonitrile based networks through amidoximation for use as ion sorbents[J].Carbohydrate Polymers,2006,66(4):435-443.DOI:10.1016/j.carbpol.2006.03.030.
[4]张慧,侯汉学,董海洲,等.羧甲基淀粉制备干法工艺[J].食品与发酵工业,2005,31(1):10-14.
[5]范庆松,具本植,张淑芬,等.干法制备高取代度高黏度羧甲基淀粉[J].精细化工,2005,22(增刊1):112-114.
[6]王磊,温其标.半干法快速合成羧甲基淀粉的研究[J].食品科技,2006,31(11):165-168.DOI:10.3969/j.issn.1005-9989.2006.11.046.
[7]陈振华,陈鼎.机械合金化与固液反应球磨[M].北京:化学工业出版社,2005:492.
[8]罗永春,毛松科,阎汝煦,等.机械球磨固相化学反应制备AlH3及其放氢性能[J].物理化学学报,2009,25(2):237-241.DOI:10.3866/PKU.WHXB20090207.
[9]陈渊,杨家添,黄祖强,等.机械活化固相化学反应制备木薯醋酸酯淀粉[J].食品与发酵工业,2013,39(7):135-141.
[10]胡华宇,黄红铭,张燕娟,等.机械活化固相法制备月桂酸淀粉酯的工艺研究[J].江苏农业科学,2012,40(10):225-227.DOI:10.3969/j.issn.1002-1302.2012.10.084.
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[13]冼学权,黄爱民,胡华宇,等.机械活化固相法制备棕榈酸淀粉酯及其性能研究[J].广东农业科学,2015(15):72-76.DOI:10.3969/j.issn.1004-874X.2015.15.013.
[14]胡华宇,罗袁伟,张燕娟,等.木薯酒糟机械活化固相醋酸酯化改性研究[J].江苏农业科学,2013,41(8):266-268.DOI:10.3969/j.issn.1002-1302.2013.08.102.
[15]谭义秋.机械活化木薯淀粉羧甲基化产物的结构表征[J].食品科学,2010,31(13):74-77.
[16]谭义秋,赵汉民,农克良,等.机械活化木薯淀粉羧甲基化产物糊性质的研究(Ⅰ)[J].食品科学,2010,31(3):102-105.
[17]谭义秋,黄祖强,农克良.机械活化木薯淀粉羧甲基化产物糊性质的研究(Ⅱ)[J].食品科学,2011,32(15):30-33.
[18]谭义秋,黄祖强,农克良,等.木薯羧甲基淀粉对铜离子的吸附性能[J].化学研究与应用,2010,22(2):171-175.DOI:10.3969/j.issn.1004-1656.2010.02.009.
[19]谭义秋,黄祖强.木薯羧甲基淀粉对Cu(Ⅱ)的吸附行为和机理[J].精细化工,2012,29(1):57-61;90.
[20]谭义秋,赵汉民,周树年,等.机械活化木薯淀粉干法制备羧甲基淀粉的研究[J].粮食与饲料工业,2009(9):20-23.DOI:10.3969/j.issn.1003-6202.2009.09.007.
[21]谭义秋,黄祖强,农克良.高取代度木薯羧甲基淀粉的合成及表征[J].过程工程学报,2010,10(1):173-178.
[22]张友松.变性淀粉生产与应用手册[M].北京:中国轻工业出版社,2001:648-655.
[23]张杨.羧甲基玉米淀粉钠-硬脂酸淀粉酯的制备、性质及应用[D].无锡:江南大学,2012:13
[24]徐忠.张亚丽.马铃薯羧甲基淀粉的理化性质及结构分析研究[J].黑龙江商学院学报(自然科学版),2000,16(4):7-12.DOI:10.3969/j.issn.1672-0946.2000.04.002.
[25]冯承,张燕萍.滚筒法制备的交联-羧甲基木薯淀粉的性能研究[J].粮食与饲料工业,2005(4):23-25.DOI:10.3969/j.issn.1003-6202.2005.04.010.
[26]王占忠,刘钟栋,陈肇锬,等.小麦交联淀粉的制备工艺研究[J].中国粮油学报,2004,19(1):26-30.DOI:10.3321/j.issn:1003-0174.2004.01.008.
[27]钟振声,钟艳萍,孙昂.马铃薯交联-羧甲基淀粉的结构与性能[J].华南理工大学学报(自然科学版),2011(3):22-27.
[28]毛杰.交联-羧甲基淀粉的制备及其理化特性研究[D].合肥:合肥工业大学,2005:21-24.
[29]陈渊,韦庆敏,杨家添,等.机械活化甘蔗渣制备羧甲基纤维素及性能表征[J].农业工程学报,2015,31(23):301-302.DOI:10.11975/j.issn.1002-6819.2015.23.040.
[30]刘亚伟,张海俊,田景霞,等.高取代度羧甲基淀粉的制备研究[J].粮油食品科技,2008,16(3):47-48.DOI:10.3969/j.issn.1007-7561.2008.03.017.
[31]范庆松.干法制备高取代度羧甲基淀粉及应用性能研究[D].大连:大连理工大学,2006:27-28.
[32]WANG L F,PAN S Y,HU H,et al.Synthesis and properties of carboxymethyl kudzu root starch[J].Carbohydrate Polymers,2010,80(1):174-179.DOI:10.1016/j.carbpol.2009.11.008.
[33]陈渊,黄祖强,谢祖芳,等.机械活化醋酸酯淀粉的制备及其生物降解塑料膜性能[J].农业工程学报,2011,27(5):298-304.DOI:10.3969/j.issn.1002-6819.2011.05.053.