【作者】 王春梅；

【导师】 何瑾馨；

【作者基本信息】 东华大学 ， 纺织化学与染整工程， 2011， 博士

【摘要】 环糊精(cyclodextrins)简称CDs,是由淀粉在葡萄糖基转移酶催化下得到的六个以上D-吡喃葡萄糖单元以1,4-糖苷键连结的环状低聚糖化合物。它具有特殊的内部疏水空腔结构,能包合合适的客体形成较稳定的包合物。根据所含葡萄糖单元数的不同,常见的环糊精有三种：α-环糊精(α—CD)、β-环糊精(β-CD)和γ-环糊精(γ-CD),分别是由6、7、8个葡萄糖单元连接而成。β-CD因其生产工艺简单、价格低、空腔尺寸合适而受到人们的重视,已在食品、化妆品、医药、分析及有机化学领域得到广泛应用。近年来,作为一种无毒、可降解、的绿色助剂,在纺织品上的应用也越来越广泛。本文通过接枝交联、溶胶-凝胶和化学改性三种方法将β-CD固着到织物上,赋予纺织品芳香、抗菌、抗紫外等功能。接枝交联采用的交联剂有乙二醛和柠檬酸(CA)；溶胶-凝胶法采用了纳米YiO2和纳米ZnO两种溶胶；对β-CD进行的化学改性主要是磺化和羧甲基改性及预聚反应。主要研究内容和结论如下：研究了以30%的乙二醛为交联剂,采用轧烘焙和冷轧堆两种工艺,将β-CD接枝到棉织物上进行芳香防皱整理的工艺。探讨了乙二醛、β-CD和催化剂的用量及焙烘温度等对整理效果的影响。通过正交实验优化的轧烘焙工艺条件为：β-CD的质量浓度70g/L,30%乙二醛质量浓度为50g/L, CA质量浓度为2g/L,焙烘温度为140℃。棉织物接枝p-CD后,吸香留香性能和折皱回复角明显提高,强力保留率在75%以上,白度略有下降。通过正交实验优化的冷轧堆工艺条件为：β-CD质量浓度35g/L,30%乙二醛质量浓度15g/L,催化剂MgCl2·6H2O质量浓度17g/L, CA质量浓度为2g/L。比较两种工艺,采用轧烘焙法整理的织物上的香精含量比冷轧堆法整理的高,抗皱性能好,但白度下降。采用轧堆法时,β-CD、乙二醛的用量比轧烘焙法低得多,且节省能源。研究了羊毛、真丝织物以CA为交联剂、次亚磷酸钠(SHP)为催化剂,采用轧烘焙工艺接枝β-CD的工艺。探讨了β-CD、CA、SHP用量、焙烘温度及焙烘时间对接枝效果的影响。实验发现,由于真丝、羊毛织物上所含的反应性基团数量不一样,接枝β-CD的条件不完全一样,接枝后对织物性能的影响也有差别。真丝最佳整理工艺为：β-CD质量浓度80g/L, CA质量浓度80g/L, SHP质量浓度40g/L,焙烘温度160℃,焙烘时间2min。经过整理后的织物,增重率和吸香性能明显提高,折皱回复角、白度和强力略有改善。羊毛最佳整理工艺为：β-CD质量浓度80g/L, CA质量浓度80g/L,焙烘温度160℃,焙烘时间3min,不需加催化剂SHP。加入β-CD整理后的织物,增重率和吸香性能明显提高,白度略有改善,折皱回复角和强力保留率比不加p-CD整理的织物低。研究了纳米Ti02、纳米ZnO溶胶的制备工艺,采用溶胶-凝胶法将纳米TiO2/β-CD、纳米ZnO/β-CD负载到棉织物上,探讨了织物的性能。纳米Ti02溶胶的合成工艺为：n[Ti(OC4H9)4]:n[HN(CH2CH2OH)2]: n(CH3CH2OH):n(H2O)为1：0.8：20：0.6,室温反应1h后,再80℃回流1h。制得的溶胶平均粒径为14.3nm。纳米ZnO溶胶的合成工艺为：n[Zn(Ac)2·2H2O]:n[HN(CH2CH2OH)2]: n(NaOH):n(C2H5OH)为1:1.5：1：114,在80℃的温度下反应45min。制得的溶胶平均粒径为73.7nm。在纳米溶胶中加入p-CD,采用轧烘焙的方法整理到织物上,结果表明,整理织物具有优良的抗紫外性、抗菌性以及对甲醛的光催化降解性,而强力和白度变化不大。加入p-CD能提高织物的吸香性能,增强纳米粒子光催化降解甲醛能力和抗菌性。但纳米ZnO溶胶整理的织物耐洗性较差,加入粘合剂可得到一定程度的改善。采用共沉淀法制备了p-CD与苯甲酸、香兰素的包合物,探讨了主客体比例、溶剂的用量、包合时间、包合温度等因素对包合物性能的影响。采用CA为交联剂,以SHP作为催化剂将包合物固着到棉织物上。p-CD与香兰素的最佳包合工艺是：n (β-CD)：n(香兰素)为1：1,包合温度为50℃,包合时间是2h。香兰素包合物与棉织物接枝工艺条件为：CA质量浓度80g/L,包合物质量浓度60g/L, SHP质量浓度40g/L,焙烘温度160℃,焙烘时间3min。β-CD与苯甲酸的最佳包合工艺是：n (β-CD):n(苯甲酸)为1：2,v(水)：v(乙醇)为80：20,包合温度为50℃,包合时间为2h。苯甲酸包合物与棉织物接枝工艺条件为：CA质量浓度50g/L,包合物质量浓度60g/L, SHP质量浓度40g/L,焙烘温度160℃,焙烘时间4min。由于香兰素与苯甲酸分子结构上差异,p-CD对苯甲酸的包合率大于对香兰素的包合率。分别用浓硫酸和氯乙酸对p-CD进行磺化和羧甲基化改性。无需添加交联剂,通过提高p-CD与羊毛、真丝纤维的结合力,将具有包络作用的p-CD固着到织物上,使浸香整理后织物上的香精含量增加,且具有缓释性。用磺化及羧甲基化p-CD与香精的包合物整理织物,随着包合物浓度的增加,织物上香精的含量增加,而且整理效果优于直接用这两种衍生物整理织物再进行浸香整理的效果。但整理织物的耐水洗牢度较差。为了增加织物上p-CD的接枝量,用环氧氯丙烷为交联剂,在碱性介质中合成了水溶性的p-环糊精预聚体(β-CDP)。以CA为交联剂,SHP为催化剂,采用轧烘焙的工艺将β-CDP接枝到棉织物上。研究了CA、β-CDP及SHP的浓度、焙烘温度和时间等因素对织物性能的影响,确定了最佳接枝工艺为：β-CDP质量浓度为30g/L,CA质量浓度为50g/L, SHP质量浓度为30g/L,焙烘温度为180。C,焙烘时间2.5min。结果表明,β-CDP既较好地保持了p-CD的包络、缓释的能力,又兼具聚合物良好的机械强度、稳定性和化学可调性。采用β-CDP比直接用p-CD的整理效果好,接枝后织物的吸香和缓释性能明显提高,白度、强力和折皱回复角略有改善。为了赋予棉织物多种特殊功能,利用p-CD和壳聚糖(CTS)对棉织物进行整理,CTS质量浓度为2g/L,β-CD的质量浓度为30g/L时,整理织物对香精和甲苯的吸附量最大。CTS分子量越大,整理织物对香精和甲苯的吸附量越大,而低分子量的CTS整理的棉织物抑菌性能好。加入交联剂可提高p-CD在织物上的耐洗性。为了进一步提高整理效果,合成了接枝p-CD的壳聚糖(CD-CTS),发现在棉织物以CA为交联剂的防皱整理中,添加CD-CTS比单独添加CTS或CTS与p-CD的混合物整理后织物的防皱和吸香性能好。最佳整理工艺为：CA质量浓度80g/L, SHP质量浓度50g/L, CD-CTS质量浓度3g/L,三乙醇胺质量浓度25g/L,焙烘温度为180℃,焙烘时间为3min。整理后的棉织物折皱回复角提高了105°,吸香性能提高到2.5倍多,对金黄葡萄球菌和大肠杆菌有明显的抑菌效果,且白度和断裂强力下降程度略有改善。本文的研究表明,接枝p-CD的织物在多功能织物的开发方面具有良好的应用前景。更多还原

【Abstract】 Cyclodextrins (CDs), which are cyclic oligosaccharides having more than six glucose units linked byα-(1,4)-glycosidic bonds. CDs can be obtained through the enzymatic degradation of starch by Bacillus maceran. Their toroidal shape and the presence of internal hydrophobic hollow cavity produce the extraordinary capability to include a wide variety of different molecules which fit into their cone-shaped hydrophobic cavity and to form stable inclusion compounds. According to the number of glucose units in the CD ring, we distinguishα-CD,β-CD andγ-CD, which contians six, seven, and eight glucopyranose units, respectively.β-CD is commercially most interesting because of its simple production, availability, cavity diameter, and price.β-CD and its derivatives are successfully exploited in different fields, such as food manufacturing, cosmetics, pharmaceuticals, and analytical and organic chemistry. In recent years, thanks to its benign toxicological and ecological properties,β-CD has become important as auxiliaies for textile finishing.In this paperβ-CD was fixed on the fabric by three methods, namely cross-linking grafting, sol-gel and chemical modification. It can bring some special factions to fabrics shch as fragrance, antibacterial and uvioresistant properties. Glyoxal and citric acid (CA) were used as cross linking agents. The nano-TiO2 and nano-ZnO sol were studied in the sol-gel method.β-CD was modified by sulfonation, carboxymethylation and prepolymerization. Contents and conclusions of the studies are mainly as follows.β-CD was grafted onto cotton fabric using 30% of glyoxal solution as a cross-linking agent by pad-dry-cure and cold pad-batch process. The effects of glyoxal,β-CD, catalyst dosage, curing temperature on the grafting yield ofβ-CD were studied. The optimum pad-dry-cure process was determined by orthogonal experiments: 70g/L ofβ-CD,50g/L of glyoxal,2g/L of CA and cured at 140℃for 3min. The results showed that the fragrance inclusion and reservation property of grafted cotton fabric was improved, the wrinkle recovery angle was markedly increased, the breaking strength retention was over 75%, and the whiteness was slightly decreased. The optimum cold pad-batch process was determined by orthogonal experiments:35g/L ofβ-CD,15g/L of glyoxal,17g/L MgCI2·6H2O,2g/L of CA. Compared the pad-dry-cure process with cold pad-batch process, It was found that the fabric treated by pad-dry-cure process had higher content of fragrance and wrinkle recovery angle, lower whiteness. In cold pad-batch process less dosage of glyoxal andβ-CD were used to treat the fabric, It can save energy.(3-CD was grafted onto wool and silk fabric using CA as a cross-linking agent and sodium hypophosphite (SHP) as a catalyst by pad-dry-cure process. The effects of the concentration of (3-CD, CA, and SHP, cured temperature and time on the properties of finished fabric were studied. The difference of wool and silk in treating process and property was found. The optimum conditions for silk were as follows:β-CD 80g/L, CA 80g/L, SHP 40g/L, cured at 160℃for 2min. The results indicated that the addition of (3-CD can increase weight gain of fabrics and improve the ability to include fragrance markedly. The wrinkle recovery angle, whiteness and breaking strength were also improved slightly. The optimum conditions for wool were as follows:β-CD 80g/L, CA 80g/L, cured at 160℃for 3min. The results indicated that the addition ofβ-CD can increase weight gain of fabrics and improve the ability to include fragrance markedly. The whiteness was also improved slightly, but the wrinkle recovery angle and breaking strength were slightly decreased.Nano-TiO2 and nano-ZnO sol solution were prepared with Ti(OC4H9)4 and Zn(Ac)2·2H2O as raw material, respectively. Nano-TiO2/β-CD nano-ZnO andβ-CD were loaded on the cotton fabrics by sol-gel method. The properties of treated fabrics were studied. The optimum synthesis process of Nano-TiO2 sol was established as the molar ratio of Ti(OC4H9)4:HN(CH2CH2OH)2 CH3CH2OH:H2O was 1:0.8:20:0.6, reacted 80℃for 1h and then reflux reacted for another 1h. The average particle size of the sol was 14.3 nm. The optimum synthesis process of Nano-ZnO sol was established as the molar ratio of Zn(Ac)2·2H2O:HN(CH2CH2OH)2:NaOH:C2H5OH was 1:1.5:1:114, reacted at 80℃for 45min. The average particle size of the sol was 73.7nm.β-CD was added into the sol, and cotton fabric treaded with the sol by pad-dry-cure technique. Based on the tests of anti-UV, photocatalysis, antibacterial and weight gain rate after adsorbing essence, the results showed that the treated cotton fabrics added withβ-CD had better adsorbability to essence, anti-bacterial activity, photocatalytic degradation to formaldehyde and excellent anti-UV property. However, the fixation fastness of the nano-ZnO sol on the fabric was bad, it can be improved by adding the adhesives.The inclusion complexes of benzoic acid withβ-CD and vanillin withβ-CD were prepared by the coprecipitation method. The effects of the molar ratio of guest compound to host compound, dosage of solvent, inclusion temperature and time on the properties of inclusion complexes were studied. The inclusion complex was grafted onto cotton fabric by CA as a cross-linking agent and SHP as a catalyst. The optimum inclusion-forming condition of vanillin withβ-CD was established as the molar ratio ofβ-CD to vanillin was 1:1, with the inclusion temperature at 50℃for 2h. The optimum grafting process of vanillin inclusion complex was CA 80 g/L, the inclusion complex 60 g/L, SHP 40g/L, cured at 160℃for 3min. The optimum inclusion-forming condition of benzoic acid withβ-cyclodextrin was established as the molar ratio ofβ-CD to benzoic acid was 1:2, the volume ratio of water to absolute ethanol was 80:20, with the inclusion temperature at 50℃for 2h. The optimum grafting process of benzoic acid inclusion complex was CA 80 g/L, the inclusion complex 60 g/L, SHP 40g/L, cured at 160℃for 4min. The inclusion ratio ofβ-CD to benzoic acid was higher than that to vanillin because of the difference on their molecular structure.The sulfonated and carboxymethylβ-CD derivatives were prepared with concentrated sulphuric acid and monochloroacetic acid, respectively. They could form ionic bonds directly with wool and silk fabric without adding cross-linking agent. Their applications in perfume finishing on wool and silk fabrics were discussed. The results indicated that fabrics finished withβ-CD derivatives could include more perfume and release it slowly, and fabrics finished with perfume complexes ofβ-CD derivatives had more perfume than that finished with P-CD derivatives. However, the fixation fastness needs to be raised.In order to improved the grafting rate ofβ-CD on cotton fabric, solubleβ-CD prepolymer (β-CDP) which was prepared with epichlorohydrin as cross-linking agent in an alkaline medium was grafted onto cotton fiber using CA as a cross-linking agent and SHP as a catalysts by the pad-dry-cure technique. The effects of the concentration of CA,β-CDP and SHP, curing temperature and time on the properties of finished fabric were studied. The optimum grafting conditions were as follows:β-CDP 30g/L, CA 50g/L, SHP 30g/L, cured at 180℃for 2.5min. The results showed thatβ-CDP kept the ability ofβ-CD to inclusion, slow release and had good mechanical strength, stability and chemical adjustable. The property of the fabric grafted with P-CDP was better than that withβ-CD. The P-CDP grafted fabric has improved fragrance absorption and controlled release ability, with whiteness, breaking strength and wrinkle recovery angle enhanced slightly.In order to impart multifunctions to cotton fabric,β-CD and chitosan (CTS) were finished on cotton fabric. The results indicated that the maximum adsorption of finished fabrics was obtained when the dosage of CTS was 2g/L andβ-CD was 30g/L. The fabric finished with chitosan of higher molecular weights had better adsorption ability and lower antibiotic activity. The adsorption of washed fabric could be improved by using cross-linking agent. In order to improve the properties of the finished fabric, chitosan grafted withβ-CD (CD-CTS) was prepared, which was applied to the durable press finishing of cotton fabric finished with CA as a crosslinker and SHP as a catalyst. The results showed that the effect of treatment of CD-CTS was superior to that of CTS and CTS blended withβ-CD. The optimum process was determined by orthogonal experiments as follows:CA 80g/L, SHP 50g/L, CD-CTS 3g/L, cured at 180℃for 3 min. The wrinkle recovery angle of finished fabric increased by 105°, the store perfume properties increased to over 2.5 times. The finished fabric had the inhibition to Staphylococcus aureus and Escherichia coli and its breaking strength and whiteness were also improved.It is summarized that the fabrics grafted withβ-CD have wide perspective and practicability on the development of multfunctional fabrics.更多还原