微波辅助羧甲基玉米淀粉的制备及其上浆性能
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摘要
为获得对纯棉高支纱线具有优良上浆效果的浆料,以玉米淀粉为原料,一氯乙酸为醚化剂,氢氧化钠为催化剂,微波辅助制备了一种亲水改性淀粉浆料羧甲基玉米淀粉(CMCS)。借助红外光谱仪和扫描电子显微镜对产物的分子结构和颗粒形态进行分析,并对其理化特性及对纯棉纤维的黏附性进行研究。结果表明:玉米淀粉大分子上成功引入了羧甲基取代基团, CMCS颗粒出现不同程度破损,完整性遭到破坏;CMCS的特性黏数和表观黏度降低,流动性增强,其溶解性、膨胀性和糊透明度提高,抗凝沉性增强,蓝值下降,直链淀粉发生降解;CMCS的糊化温度下降,糊化性能和糊加工性能得到改善;CMCS黏附性能相比于原淀粉最高可增加27.9%,并且随着取代度的提高,黏附性逐渐增强。对9.67 tex纯棉纱上浆实验结果表明,CMCS浆纱的力学性能显著提高,其浆纱的断裂增强率与耐磨增强率分别比原淀粉浆纱增加了118.5%和88.7%,伸长率降低了29.7%。
In order to obtain an excellent sizing effect for cotton high-count yarn, a hydrophilic modified starch size-carboxymethyl corn starch(CMCS) was synthesized from natural corn starch, chloroacetic acid and sodium hydroxide as raw material, etherifying reagent and catalyst by a microwave-assisted process. The molecular structure and granular morphology of the products were characterized by FT-IR and SEM. The results show that carboxymethyl groups are successfully introduced into corn starch macromolecule and starch granules are damaged by varying levels and their integrity is destroyed. The studies for physicochemical properties of CMCS show that the intrinsic viscosity and apparent viscosity of CMCS decrease, rheological property is enhanced, the solubility, swelling power, paste clarity and retrogradation resistance are improved, the blue value reduces, suggesting the degradation of amylase. The gelatinization temperature decreases, which indicates that gelatinization properties and paste processing performance are improved. The results of the adhesion experiment show that the adhesion force of CMCS is enhanced by as much as 27.9% compared with nature corn starch(NCS), and the adhesion force increases with the increase of degree of substitution. The results of sizing experiments on 9.67 tex pure cotton yarns show that the mechanical properties of CMCS sized yarns are significantly improved, the tensile strength enhancement and abrasion resistance enhancement increase by 118.5% and 88.7%, respectively, and the elongation reduction is 29.7% lower than that of NCS sized yarns.
In order to obtain an excellent sizing effect for cotton high-count yarn, a hydrophilic modified starch size-carboxymethyl corn starch(CMCS) was synthesized from natural corn starch, chloroacetic acid and sodium hydroxide as raw material, etherifying reagent and catalyst by a microwave-assisted process. The molecular structure and granular morphology of the products were characterized by FT-IR and SEM. The results show that carboxymethyl groups are successfully introduced into corn starch macromolecule and starch granules are damaged by varying levels and their integrity is destroyed. The studies for physicochemical properties of CMCS show that the intrinsic viscosity and apparent viscosity of CMCS decrease, rheological property is enhanced, the solubility, swelling power, paste clarity and retrogradation resistance are improved, the blue value reduces, suggesting the degradation of amylase. The gelatinization temperature decreases, which indicates that gelatinization properties and paste processing performance are improved. The results of the adhesion experiment show that the adhesion force of CMCS is enhanced by as much as 27.9% compared with nature corn starch(NCS), and the adhesion force increases with the increase of degree of substitution. The results of sizing experiments on 9.67 tex pure cotton yarns show that the mechanical properties of CMCS sized yarns are significantly improved, the tensile strength enhancement and abrasion resistance enhancement increase by 118.5% and 88.7%, respectively, and the elongation reduction is 29.7% lower than that of NCS sized yarns.
引文
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[10] 陈俊芳. 安徽板栗淀粉的理化性质及其糊化特性的研究山[D]. 合肥:安徽农业大学,2010:1-10.CHEN Junfang. Study on properties of physicoehemistry and gelatinization of chestnut starches from Anhui[D]. Hefei: Anhui Agriculture University,2010:1-10.
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[12] 李洁, 田翠华, 项丽霞, 等. 莲藕淀粉糊化温度测定方法的比较[J]. 中国粮油学报, 2007, 22(3): 70-72.LI Jie, TIAN Cuihua, XIANG Lixia, et al. Antioxidation of Berberine hydrochloride to oils and fat[J]. Journal of the Chinese Cereals and Oils Association, 2007, 22(3): 70-72.
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[14] 赵思明. 稻米淀粉特性与老化机理研究[D]. 武汉:华中农业大学,2001:1-20.ZHAO Siming. Study on the properties and retrogradation mechanism of rice starch[D]. Wuhan: Huazhong Agricultural University,2001:1-20.
[15] SANGSEETHONG K, KETSILP S, SRIROTH K. The role of reaction parameters on the preparation and properties of carboxymethyl cassava starch [J]. Starch-Stärke, 2005, 57(2): 84-93.
[16] 徐忠, 缪铭, 王鹏, 等. 羧甲基玉米多孔淀粉的制备及性能研究[J]. 食品科学, 2006, 26(10): 116-120.XU Zhong, MIAO Ming, WANG Peng, et al. Study on preparation and properties of carboxymethyl corn porous starch[J]. Food Science, 2006, 26(10): 116-120.
[17] ANDERSON A K, GURAYA H S. Effects of microwave heat-moisture treatment on properties of waxy and non-waxy rice starches [J]. Food Chemistry, 2006, 97(2): 318-323.
[18] KITTIPONGPATANA O S, SIRITHUNYALUG J, LAENGER R. Preparation and physicochemical properties of sodium carboxymethyl mungbean starches [J]. Carbohydrate Polymers, 2006, 63(1): 105-112.
[19] 罗志刚, 于淑娟, 杨连生. 微波场对小麦淀粉性质的影响[J]. 化工学报, 2007,58(11): 2871-2875.LUO Zhigang, YU Shujuan, YANG Liansheng. Effect of microwave irradiation on properties of wheat starches[J]. CIESC Journal, 2007,58(11): 2871-2875.
[20] WANG Y, JU B, ZHANG S. Viscosity properties of acetylated carboxymethyl starch [J].Carbohydrate Polymers, 2012, 90(1): 696-702.
[21] 王洪燕. 抗性淀粉的制备, 性质及其应用研究[D]. 无锡:江南大学, 2007:1-15.WANG Hongyan. Study on preparation, properties and application of resistant starch[D]. Wuxi: Jiangnan University, 2007:1-15.
[22] 徐忠. 马铃薯羧甲基淀粉糊化特性研究[J]. 食品科学, 2001, 22(2): 25-28.XU Zhong. Study on gelatinization characteristics of potato carboxymethyl starch [J]. Food Science, 2001, 22(2): 25-28.
[23] BHATTACHRYYA D, SINGHAL R S, KULKARNI P R. A comparative account of conditions for synthesis of sodium carboxymethyl starch from corn and amaranth starch [J]. Carbohydrate Polymers, 1995, 27(4): 247-253.
[24] YANG W, HATTORI M, TAKAHASHI K. Functional changes of carboxymethyl potato starch by conjugating with amino acids [J]. Bioscience Biotechnology and Biochemistry, 1995, 59: 203-220.
[25] ZHIFENG Y J Z. Research on the adhesion behaviors of acetylated starch to fibre substrates for warp sizing [J]. Cotton Textile Technology, 2004, 9: 100.
[26] LI M, ZHU Z, PAN X. Effects of starch acryloylation on the grafting efficiency, adhesion, and film properties of acryloylated starch-g-poly (acrylic acid) for warp sizing [J]. Starch-Stärke, 2011, 63(11): 683-691.
[27] HEBEISH A, HIGAZY A, El-SHAFEI A, et al. Synthesis of carboxymethyl cellulose (CMC) and starch-based hybrids and their applications in flocculation and sizing [J]. Carbohydrate Polymers, 2010, 79(1): 60-69.
[2] 陈思,邱夷平,施楣梧,等. 用于天然纤维素纤维纱线的无浆料浆纱技术[J]. 纺织学报,2016,37(2):85-91.CHEN Si,QIU Yiping,SHI Meiwu,et al. Size-free sizing process for cellulose yarns[J]. Journal of Textile Research,2016,37(2):85-91.
[3] 祝志峰,荣瑞萍. 无PVA上浆研究进展[J]. 棉纺织技术,2011,39(2):129-132.ZHU Zhifeng,RONG Ruiping. Sizing research development without PVA[J].Cotton Textile Technology,2011,39(2):129-132.
[4] CHANSHYAM 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,2006,66:435-443.
[5] SHI H X, YIN Y Z, JIAO S F. Preparation and characterization of carboxymethyl starch under ultrasound-microwave synergistic interaction[J]. Journal of Applied Polymer Science,2014,131(20):1366-1373.
[6] 邹丽霞,邹建国,冯荣华. 微波法合成羧甲基淀粉[J]. 化工进展,2003,22(12):1319-1322.ZOU Lixia, ZOU Jianguo, FENG Ronghua. Preparation of carboxymethyl starch using microwave method[J]. Chemical Industry and Engineering Progress,2003,22(12):1319-1322.
[7] 汪源浩,具本植,张淑芬.高黏度、高热稳定性羧甲基淀粉己酸酯的溶液性质[J]. 化工学报,2013,64(1):275-282.WANG Yuanhao,JU Benzhi,ZHANG Shufen. Aqueous solution properties of carboxymethyl starch hexanoate with high viscosity and thermal stability[J]. CIESC Journal,2013,64(1):275-282.
[8] 李雪晶,马嘶鸣,赵景峰,等. 高粘度羧甲基淀粉钠的应用和市场前景[J]. 化工进展,2002,21(7):511-513.LI Xuejing, MA Siming, ZHAO Jingfeng, et al. Application and market trend of high viscosity carboxy methyl starch sodium[J]. Chemical Industry and Engineering Progress,2002,21(7):511-513.
[9] 王瑞,张昊,王建坤,等. 接枝淀粉理化特性对其上浆性能的影响[J]. 纺织学报,2014,35(1):72-77.WANG Rui, ZHANG Hao, WANG Jiankun,et al. Effects of grafted starch physicochemical properties on sizing performance[J]. Journal of Textile Research,2014,35(1):72-77.
[10] 陈俊芳. 安徽板栗淀粉的理化性质及其糊化特性的研究山[D]. 合肥:安徽农业大学,2010:1-10.CHEN Junfang. Study on properties of physicoehemistry and gelatinization of chestnut starches from Anhui[D]. Hefei: Anhui Agriculture University,2010:1-10.
[11] MAZURS E G, SCHOCH T J, KITE F E. Graphical analysis of the Brabender viscosity curves of various starches [J]. Cereal chemistry, 1957, 34(3): 141-152.
[12] 李洁, 田翠华, 项丽霞, 等. 莲藕淀粉糊化温度测定方法的比较[J]. 中国粮油学报, 2007, 22(3): 70-72.LI Jie, TIAN Cuihua, XIANG Lixia, et al. Antioxidation of Berberine hydrochloride to oils and fat[J]. Journal of the Chinese Cereals and Oils Association, 2007, 22(3): 70-72.
[13] 朱旻鹏,李新华,刘爱华. 十二烯基琥珀酸淀粉酯性质的研究[J]. 食品科学, 2005, 26(6): 101-105.ZHU Minpeng, LI Xinhua, LIU Aihua. Studies on property of starch sodium dodecenyl succinate[J]. Food Science, 2005, 26(6): 101-105.
[14] 赵思明. 稻米淀粉特性与老化机理研究[D]. 武汉:华中农业大学,2001:1-20.ZHAO Siming. Study on the properties and retrogradation mechanism of rice starch[D]. Wuhan: Huazhong Agricultural University,2001:1-20.
[15] SANGSEETHONG K, KETSILP S, SRIROTH K. The role of reaction parameters on the preparation and properties of carboxymethyl cassava starch [J]. Starch-Stärke, 2005, 57(2): 84-93.
[16] 徐忠, 缪铭, 王鹏, 等. 羧甲基玉米多孔淀粉的制备及性能研究[J]. 食品科学, 2006, 26(10): 116-120.XU Zhong, MIAO Ming, WANG Peng, et al. Study on preparation and properties of carboxymethyl corn porous starch[J]. Food Science, 2006, 26(10): 116-120.
[17] ANDERSON A K, GURAYA H S. Effects of microwave heat-moisture treatment on properties of waxy and non-waxy rice starches [J]. Food Chemistry, 2006, 97(2): 318-323.
[18] KITTIPONGPATANA O S, SIRITHUNYALUG J, LAENGER R. Preparation and physicochemical properties of sodium carboxymethyl mungbean starches [J]. Carbohydrate Polymers, 2006, 63(1): 105-112.
[19] 罗志刚, 于淑娟, 杨连生. 微波场对小麦淀粉性质的影响[J]. 化工学报, 2007,58(11): 2871-2875.LUO Zhigang, YU Shujuan, YANG Liansheng. Effect of microwave irradiation on properties of wheat starches[J]. CIESC Journal, 2007,58(11): 2871-2875.
[20] WANG Y, JU B, ZHANG S. Viscosity properties of acetylated carboxymethyl starch [J].Carbohydrate Polymers, 2012, 90(1): 696-702.
[21] 王洪燕. 抗性淀粉的制备, 性质及其应用研究[D]. 无锡:江南大学, 2007:1-15.WANG Hongyan. Study on preparation, properties and application of resistant starch[D]. Wuxi: Jiangnan University, 2007:1-15.
[22] 徐忠. 马铃薯羧甲基淀粉糊化特性研究[J]. 食品科学, 2001, 22(2): 25-28.XU Zhong. Study on gelatinization characteristics of potato carboxymethyl starch [J]. Food Science, 2001, 22(2): 25-28.
[23] BHATTACHRYYA D, SINGHAL R S, KULKARNI P R. A comparative account of conditions for synthesis of sodium carboxymethyl starch from corn and amaranth starch [J]. Carbohydrate Polymers, 1995, 27(4): 247-253.
[24] YANG W, HATTORI M, TAKAHASHI K. Functional changes of carboxymethyl potato starch by conjugating with amino acids [J]. Bioscience Biotechnology and Biochemistry, 1995, 59: 203-220.
[25] ZHIFENG Y J Z. Research on the adhesion behaviors of acetylated starch to fibre substrates for warp sizing [J]. Cotton Textile Technology, 2004, 9: 100.
[26] LI M, ZHU Z, PAN X. Effects of starch acryloylation on the grafting efficiency, adhesion, and film properties of acryloylated starch-g-poly (acrylic acid) for warp sizing [J]. Starch-Stärke, 2011, 63(11): 683-691.
[27] HEBEISH A, HIGAZY A, El-SHAFEI A, et al. Synthesis of carboxymethyl cellulose (CMC) and starch-based hybrids and their applications in flocculation and sizing [J]. Carbohydrate Polymers, 2010, 79(1): 60-69.