壳聚糖季铵盐的合成及其在棉织物上的应用
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摘要
本文合成了一种适用于纤维素纤维织物的新一代抗菌剂QFR-105。该抗菌剂以壳聚糖和缩水甘油三甲基氯化铵(GTMAC)为主要原料制备而成，属壳聚糖季铵盐类化合物，可以借助于交联剂与纤维发生交联，使织物获得抗菌效果且具有一定的耐久性。研究了该抗菌剂的合成及应用工艺，测试了整理织物的抗菌性，开发出了环境友好抗菌棉织物。
QFR-105抗菌剂是一种微黄色的固体粉末，其水溶液为澄清、略带黄色的粘性液体。通过变化反应条件，测定产物的取代度和产率，得出最佳的反应条件。对抗菌剂的结构、物理和化学性能等作了分析测定。分别以戊二醛、交联剂EH、非离子粘合剂TK、反应性氨基硅油和N-羟甲基丙烯酰胺为交联剂，选用合适的催化剂，详细研究了该抗菌剂对棉织物的整理工艺，通过溴酚蓝染色和细菌减少百分率测定，得到了所研究织物的最佳工艺处方。
经QFR-105抗菌剂整理的织物的抗菌效果有一定的耐久性，按国家标准FZ／T02021-92《织物抗菌性能试验方法》测试，水洗5次后其抑菌率仍能达到80％以上。
In this paper, a new generation of antibacterial agents -QFR-105, which is suitable for the application of cotton fabrics, was synthesized by the reaction of glycidyltrimethyl ammonium chloride (GTMAC) with chitosan. The optimum synthesis conditions were selected by orthogonal experiments, and the structure of the quaternary ammonium chitosan derivative was confirmed by FT-IR and'H NMR spectrum.
The reaction product exists as white-to-brown power, and is easy to become soluble in water. Its solution is a kind of clear and transparent viscous liquid. The product is eco-friendly and can be applied- together with various crosslinkers or binders to impart the finishing fabrics durable antibacterial function. Several chemicals were used in the paper to compare and find the suitable additives in improving the washing durability of treated fabrics. By using 0.02% BPB as a qualitative analysis agent and by calculating the bacterial reduction rate on cotton fabrics, it was easy to find that the fabrics treated by QFR-105 shows superior antimicrobial activity compared with that by chitosan.
QFR-105抗菌剂是一种微黄色的固体粉末，其水溶液为澄清、略带黄色的粘性液体。通过变化反应条件，测定产物的取代度和产率，得出最佳的反应条件。对抗菌剂的结构、物理和化学性能等作了分析测定。分别以戊二醛、交联剂EH、非离子粘合剂TK、反应性氨基硅油和N-羟甲基丙烯酰胺为交联剂，选用合适的催化剂，详细研究了该抗菌剂对棉织物的整理工艺，通过溴酚蓝染色和细菌减少百分率测定，得到了所研究织物的最佳工艺处方。
经QFR-105抗菌剂整理的织物的抗菌效果有一定的耐久性，按国家标准FZ／T02021-92《织物抗菌性能试验方法》测试，水洗5次后其抑菌率仍能达到80％以上。
In this paper, a new generation of antibacterial agents -QFR-105, which is suitable for the application of cotton fabrics, was synthesized by the reaction of glycidyltrimethyl ammonium chloride (GTMAC) with chitosan. The optimum synthesis conditions were selected by orthogonal experiments, and the structure of the quaternary ammonium chitosan derivative was confirmed by FT-IR and'H NMR spectrum.
The reaction product exists as white-to-brown power, and is easy to become soluble in water. Its solution is a kind of clear and transparent viscous liquid. The product is eco-friendly and can be applied- together with various crosslinkers or binders to impart the finishing fabrics durable antibacterial function. Several chemicals were used in the paper to compare and find the suitable additives in improving the washing durability of treated fabrics. By using 0.02% BPB as a qualitative analysis agent and by calculating the bacterial reduction rate on cotton fabrics, it was easy to find that the fabrics treated by QFR-105 shows superior antimicrobial activity compared with that by chitosan.
引文
[1] 蒋挺大．壳聚糖．北京．化学工业出版社．2001．1～13
[2] 汪多仁．甲壳素、壳聚糖的生产和应用．印染助剂，2000，17(4)
[3] USP2002025945, Chitosan and method of preparing chitosan, Fan weiyu(US) et al.,2002
[4] 那海秋，张德智，等．壳聚糖的性质、制备及应用．辽宁化工，Vol．26，No．4
[5] 鲍萍等译．壳聚糖降低活性染色时的耗盐量．国外纺织技术，1999，8 {international dyer, 1998, 11(39～41))
[6] 陈维国，关立平．壳聚糖处理羊毛的染色性能研究．纺织学报，Vol．20，No．5
[7] 刘昌龄，唐志翔．脱乙酰甲壳质在涂料印花中的应用．丝绸，2000
[8] 吴丽莉，俞见勇．多元羧酸和壳聚糖对棉织物的抗菌防皱整理．现代纺织技术，2001．5
[9] 刘昌龄译．脱乙酰甲壳质在涂料印花中的应用．{S. A. Bahmani, G. C. East&Holme, J. S. D. C., 2000(3):94～99}
[10] 黄玉丽．壳聚糖在羊毛防毡缩整理中的应用．1998，6
[11] Gupta,K.C; Kumar, M.J.Macro.Chem.Phys.2000,4, 273
[12] 康战燕，庚丽华．甲壳素与壳聚糖在食品中的应用．山东科学，
1999，12(1)
[13] 黄丽萍，刘宗明．甲壳素、壳聚糖在农业上的应用．辽宁农业科学，1996．6
[14] 崔兆玉，于刚，等．壳聚糖引入桦木的防腐处理．东北林业大学学报，2002．2
[15] Muzzarelli, R.A.A. Carbohydrate Polymers, 1983,3, 53
[16] Reddy M; Belkacemi, K.; Corcuff, R. Postharvest Biol. Tec.2000,39.1
[17] Kulak,Z.;Niekraszewicz,A.;Struszczyk,H.Polim.2001,46,48
[18] Schmuhl, R.; Krieg, H. M.; Keizer, K. Water SA.,2001,27,1
[19] Onsoyen,E.Parfums, Cosmet.,Aromes, 1991,97,85
[20] Lang,G.and T.Clausen, The Use of Chitosan in Cosmetics, in Chitin and Chitosan, Sources, Chemistry, Biochemistry, Physical Properties and Application, G.Skjak-Braek, T.Anthonsen, and P.Sandford, Editors, 1989, Elsevier Applied Science: London.P139-147
[21] Hirano,S.; Hirochi,K.; Hayashi,K.; Mikami,T.; Tachibana, H. "Cosmetic and pharmaceutical uses of chitin and chitosan" , in Gebelein, C.G.; Cheng, T.C.; Yang,V.C..eds., Cosmet. Pharm. Appl. Poly., Plenum, New York, 1991,95
[22] 于姝丽，于爱华．抗菌纺织品的开发研制．辽宁丝绸，1995．4
[23] 黄占杰．无机抗菌剂的发展与应用．材料导报，1999，13．2
[24] 闵沽．无机抗菌剂及其纤维应用．合成纤维，2002，31．2
[25] 严玉蓉，赵耀明．无机抗菌材料．化工进展，2001，7
[26] 王建平．抗菌纤维与抗菌剂体系(二)． 合成纤维，No．3，2003
[27] 曹惠椿，徐超．抗菌纤维的研制．合成纤维，1999，28(3)．
[28] 杨俊玲．壳聚糖抗菌性的研究．纺织学报，2003，24(2)
[29] 吴丽莉，朱明娟，等．多元羧酸和壳聚糖对棉织物的抗菌防皱整理．山东纺织科技，2001，42(5)
[30] 杨冬芝，刘晓非．壳聚糖抗菌活性的影响因素．应用化学，2000，17(6)
[31] 郑连英，朱江峰．壳聚糖的抗菌性能研究．材料科学与工程，2000，18(2)
[32] 沈东风，贾之慎．不同分子量壳聚糖对草莓防腐效果的研究．食品科学，2000，21(7)
[33] Y.Shin, Molecular weight effect on antimicrobial activity of chitosan treated cotton fabrics, Journal of Applied Polymer Science, 2001 .Vol.80
[34] S.W.Fang,et al., Antifungal activity of chitosan and its preservative effect on low-sugar candied kumquat, J.Food Protect., 1994.2,Vol.56
[2] 汪多仁．甲壳素、壳聚糖的生产和应用．印染助剂，2000，17(4)
[3] USP2002025945, Chitosan and method of preparing chitosan, Fan weiyu(US) et al.,2002
[4] 那海秋，张德智，等．壳聚糖的性质、制备及应用．辽宁化工，Vol．26，No．4
[5] 鲍萍等译．壳聚糖降低活性染色时的耗盐量．国外纺织技术，1999，8 {international dyer, 1998, 11(39～41))
[6] 陈维国，关立平．壳聚糖处理羊毛的染色性能研究．纺织学报，Vol．20，No．5
[7] 刘昌龄，唐志翔．脱乙酰甲壳质在涂料印花中的应用．丝绸，2000
[8] 吴丽莉，俞见勇．多元羧酸和壳聚糖对棉织物的抗菌防皱整理．现代纺织技术，2001．5
[9] 刘昌龄译．脱乙酰甲壳质在涂料印花中的应用．{S. A. Bahmani, G. C. East&Holme, J. S. D. C., 2000(3):94～99}
[10] 黄玉丽．壳聚糖在羊毛防毡缩整理中的应用．1998，6
[11] Gupta,K.C; Kumar, M.J.Macro.Chem.Phys.2000,4, 273
[12] 康战燕，庚丽华．甲壳素与壳聚糖在食品中的应用．山东科学，
1999，12(1)
[13] 黄丽萍，刘宗明．甲壳素、壳聚糖在农业上的应用．辽宁农业科学，1996．6
[14] 崔兆玉，于刚，等．壳聚糖引入桦木的防腐处理．东北林业大学学报，2002．2
[15] Muzzarelli, R.A.A. Carbohydrate Polymers, 1983,3, 53
[16] Reddy M; Belkacemi, K.; Corcuff, R. Postharvest Biol. Tec.2000,39.1
[17] Kulak,Z.;Niekraszewicz,A.;Struszczyk,H.Polim.2001,46,48
[18] Schmuhl, R.; Krieg, H. M.; Keizer, K. Water SA.,2001,27,1
[19] Onsoyen,E.Parfums, Cosmet.,Aromes, 1991,97,85
[20] Lang,G.and T.Clausen, The Use of Chitosan in Cosmetics, in Chitin and Chitosan, Sources, Chemistry, Biochemistry, Physical Properties and Application, G.Skjak-Braek, T.Anthonsen, and P.Sandford, Editors, 1989, Elsevier Applied Science: London.P139-147
[21] Hirano,S.; Hirochi,K.; Hayashi,K.; Mikami,T.; Tachibana, H. "Cosmetic and pharmaceutical uses of chitin and chitosan" , in Gebelein, C.G.; Cheng, T.C.; Yang,V.C..eds., Cosmet. Pharm. Appl. Poly., Plenum, New York, 1991,95
[22] 于姝丽，于爱华．抗菌纺织品的开发研制．辽宁丝绸，1995．4
[23] 黄占杰．无机抗菌剂的发展与应用．材料导报，1999，13．2
[24] 闵沽．无机抗菌剂及其纤维应用．合成纤维，2002，31．2
[25] 严玉蓉，赵耀明．无机抗菌材料．化工进展，2001，7
[26] 王建平．抗菌纤维与抗菌剂体系(二)． 合成纤维，No．3，2003
[27] 曹惠椿，徐超．抗菌纤维的研制．合成纤维，1999，28(3)．
[28] 杨俊玲．壳聚糖抗菌性的研究．纺织学报，2003，24(2)
[29] 吴丽莉，朱明娟，等．多元羧酸和壳聚糖对棉织物的抗菌防皱整理．山东纺织科技，2001，42(5)
[30] 杨冬芝，刘晓非．壳聚糖抗菌活性的影响因素．应用化学，2000，17(6)
[31] 郑连英，朱江峰．壳聚糖的抗菌性能研究．材料科学与工程，2000，18(2)
[32] 沈东风，贾之慎．不同分子量壳聚糖对草莓防腐效果的研究．食品科学，2000，21(7)
[33] Y.Shin, Molecular weight effect on antimicrobial activity of chitosan treated cotton fabrics, Journal of Applied Polymer Science, 2001 .Vol.80
[34] S.W.Fang,et al., Antifungal activity of chitosan and its preservative effect on low-sugar candied kumquat, J.Food Protect., 1994.2,Vol.56