基于淀粉直接改性对热塑性淀粉塑化程度的影响
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摘要
以玉米淀粉为原料,经酸解或酸解酯化改性后,用甘油对其进行塑化处理,利用单螺杆挤出机制备改性热塑性淀粉,并通过X-射线衍射仪、差示扫描量热仪和扫描电镜对热塑性淀粉的塑化程度进行分析。结果表明,基于不同淀粉制得的热塑性淀粉呈现出不同的结晶结构,改性处理降低了热塑性淀粉的结晶度,增大了DSC吸热峰值,经挤出成型形成更加均一的连续相,塑化程度增大,特别是热塑性酸解酯化淀粉。TGA分析表明,热塑性淀粉的热稳定性随塑化程度的增大而降低。
Using corn starch as a raw material,we prepared acidolysis modified starch and acidolysis-esterification modified starch.Then,using glycerol as a plasticizer,we prepared different modified thermoplastic starch by extruding the starch with a single screw extruder.Furthermore,we analyzed the plasticizing degree of different modified thermoplastic starch by X-ray diffraction(XRD),differential scanning calorimeter(DSC),and scanning electron microscopy(SEM).The results show that the thermoplastic starch prepared with different matrix starch exhibits different crystalline structures,and the crystallinity of modified thermoplastic starch decreases while the endothermic peaks of DSC increase after modified treatment.Moreover,the modified thermoplastic starch shows a more homogeneous continuous phase by extrusion,and the plasticizing degree of thermoplastic starch increases,especially the acidolysis-esterification modified thermoplastic starch.TGA results show that the thermal stability of thermoplastic starch decreases as the plasticizing degree of starch increases.
Using corn starch as a raw material,we prepared acidolysis modified starch and acidolysis-esterification modified starch.Then,using glycerol as a plasticizer,we prepared different modified thermoplastic starch by extruding the starch with a single screw extruder.Furthermore,we analyzed the plasticizing degree of different modified thermoplastic starch by X-ray diffraction(XRD),differential scanning calorimeter(DSC),and scanning electron microscopy(SEM).The results show that the thermoplastic starch prepared with different matrix starch exhibits different crystalline structures,and the crystallinity of modified thermoplastic starch decreases while the endothermic peaks of DSC increase after modified treatment.Moreover,the modified thermoplastic starch shows a more homogeneous continuous phase by extrusion,and the plasticizing degree of thermoplastic starch increases,especially the acidolysis-esterification modified thermoplastic starch.TGA results show that the thermal stability of thermoplastic starch decreases as the plasticizing degree of starch increases.
引文
[1] MA X F,YU J G,WAN J J.Urea and ethanolamine as a mixed plasticizer for thermoplastic starch[J].Carbohydrate Polymers,2006,64(2):267-273.
[2] 程丽,吴馨,叶正涛.新型热塑性淀粉制备与性能研究[J].胶体与聚合物,2013,31(4):168-170.CHENG L,WU X,YE Z T.Preparation and properties of novel thermoplastic starch[J].Chinese Journal of Colloid &Polymer,2013,31(4):168-170.
[3] FORSELL P M,MIKKILA J M,MOATES G K,et al.Phase and glass transition behaviour of concentrated barley starch-glycerolwater mixtures,a model for thermoplastic starch[J].Carbohydrate Polymers,1997,34(4):275-282.
[4] LV S S,GU J Y,GAO J,et al.Effect of annealing on the thermal properties of poly(lactic acid)/starch blends[J].International Journal of Biological Macromolecules,2015,74:297-303.
[5] MA X F,YU J G.The plasticizers containing amide groups for thermoplastic starch[J].Carbohydrate Polymers,2004,57(2):197-203.
[6] 张坤玉,冉祥海,吴航,等.新型热塑性淀粉的制备和性能[J].高等学校化学学报,2009,30(8):1662-1667.ZHANG K Y,RAN X H,WU H,et al.Preparation and characterization of a nonel thermoplastic starch using dimethyl sulfoxide as the plasticizer[J].Chemical Journal of Chinese Universities,2009,30(8):1662-1667.
[7] 王礼建,董亚强,杨政,等.基于淀粉直接改性的热塑性淀粉塑料研究进展[J].材料导报,2015,29(17):63-67.WANG L J,DONG Y Q,YANG Z,et al.Progress of thermoplastic starch plastics derived viadirect modification of starch[J].Materials Review,2015,29(17):63-67.
[8] 谢新玲,熊海武,童张法,等.5种改性淀粉吸附Cu2+性能及动力学研究[J].功能材料,2017,48(2):2009-2012.XIE X L,XIONG H W,TONG Z F,et al.Adsorption properties and kinetics study of Cu2+removal using five kinds of modified starches[J].Journal of Functional Materials,2017,48(2):2009-2012.
[9] 赵奕玲,廖丹葵,张友全,等.超声波对木薯淀粉性质及结构的影响[J].过程工程学报,2007,7(6):1138-1143.ZHAO Y L,LIAO D K,ZHANG Y Q,et al.Effect of ultrasonic wave on the properties and structure of cassava starch[J].Chinese Journal of Process Engineering,2007,7(6):1138-1143.
[10] van SOEST J J G,VLIEGENTHART J F G.Crystallinity in starch plastics:consequences for material properties[J].Trends in Biotechnology,1997,15(6):208-213.
[11] WANG R C,CHEN C,GUO S T.Effects of drying methods on starch crystallinity of gelatinized foxtail millet(α-millet)and its eating quality[J].Journal of Food Engineering,2017,207:81-89.
[12] WAIGH T A,DONALD A M,HEIDELBACH F,et al.Analysis of the native structure of starch granules with small angle X-ray microfocus scattering[J].Biopolymers,1999,49(1):91-105.
[13] 左迎峰,顾继友,谭海彦,等.增塑时间对玉米淀粉塑化程度和TPS性能的影响[J].材料导报,2013,27(10):104-107.ZUO Y F,GU J Y,TAN H Y,et al.Effect of plasticizing time on plasticizing degree of corn starch and properties of TPS[J].Materials Review,2013,27(10):104-107.
[14] PARETA R,EDIRISINGHE M J.A novel method for the preparation of starch films and coatings[J].Carbohydrate Polymers,2006,63(3):425-431.
[15] YU J G,WANG N,MA X F.The effects of citric acid on the properties of thermoplastic starch plasticized by glycerol[J].Starch-Starke,2005,57(10):494-504.
[2] 程丽,吴馨,叶正涛.新型热塑性淀粉制备与性能研究[J].胶体与聚合物,2013,31(4):168-170.CHENG L,WU X,YE Z T.Preparation and properties of novel thermoplastic starch[J].Chinese Journal of Colloid &Polymer,2013,31(4):168-170.
[3] FORSELL P M,MIKKILA J M,MOATES G K,et al.Phase and glass transition behaviour of concentrated barley starch-glycerolwater mixtures,a model for thermoplastic starch[J].Carbohydrate Polymers,1997,34(4):275-282.
[4] LV S S,GU J Y,GAO J,et al.Effect of annealing on the thermal properties of poly(lactic acid)/starch blends[J].International Journal of Biological Macromolecules,2015,74:297-303.
[5] MA X F,YU J G.The plasticizers containing amide groups for thermoplastic starch[J].Carbohydrate Polymers,2004,57(2):197-203.
[6] 张坤玉,冉祥海,吴航,等.新型热塑性淀粉的制备和性能[J].高等学校化学学报,2009,30(8):1662-1667.ZHANG K Y,RAN X H,WU H,et al.Preparation and characterization of a nonel thermoplastic starch using dimethyl sulfoxide as the plasticizer[J].Chemical Journal of Chinese Universities,2009,30(8):1662-1667.
[7] 王礼建,董亚强,杨政,等.基于淀粉直接改性的热塑性淀粉塑料研究进展[J].材料导报,2015,29(17):63-67.WANG L J,DONG Y Q,YANG Z,et al.Progress of thermoplastic starch plastics derived viadirect modification of starch[J].Materials Review,2015,29(17):63-67.
[8] 谢新玲,熊海武,童张法,等.5种改性淀粉吸附Cu2+性能及动力学研究[J].功能材料,2017,48(2):2009-2012.XIE X L,XIONG H W,TONG Z F,et al.Adsorption properties and kinetics study of Cu2+removal using five kinds of modified starches[J].Journal of Functional Materials,2017,48(2):2009-2012.
[9] 赵奕玲,廖丹葵,张友全,等.超声波对木薯淀粉性质及结构的影响[J].过程工程学报,2007,7(6):1138-1143.ZHAO Y L,LIAO D K,ZHANG Y Q,et al.Effect of ultrasonic wave on the properties and structure of cassava starch[J].Chinese Journal of Process Engineering,2007,7(6):1138-1143.
[10] van SOEST J J G,VLIEGENTHART J F G.Crystallinity in starch plastics:consequences for material properties[J].Trends in Biotechnology,1997,15(6):208-213.
[11] WANG R C,CHEN C,GUO S T.Effects of drying methods on starch crystallinity of gelatinized foxtail millet(α-millet)and its eating quality[J].Journal of Food Engineering,2017,207:81-89.
[12] WAIGH T A,DONALD A M,HEIDELBACH F,et al.Analysis of the native structure of starch granules with small angle X-ray microfocus scattering[J].Biopolymers,1999,49(1):91-105.
[13] 左迎峰,顾继友,谭海彦,等.增塑时间对玉米淀粉塑化程度和TPS性能的影响[J].材料导报,2013,27(10):104-107.ZUO Y F,GU J Y,TAN H Y,et al.Effect of plasticizing time on plasticizing degree of corn starch and properties of TPS[J].Materials Review,2013,27(10):104-107.
[14] PARETA R,EDIRISINGHE M J.A novel method for the preparation of starch films and coatings[J].Carbohydrate Polymers,2006,63(3):425-431.
[15] YU J G,WANG N,MA X F.The effects of citric acid on the properties of thermoplastic starch plasticized by glycerol[J].Starch-Starke,2005,57(10):494-504.