多胺型可交联染料染色性能研究
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摘要
交联染料通过交联剂和染色纤维实现共价结合,因此交联染料不仅可使染色纤维有很好的湿处理牢度,还克服了活性染料存在的活性基团水解问题,大大提高染料利用率。
本文首先研究了多胺型可交联染料的溶解特性、分子大小和渗透性能,通过软件模拟和纤维切片的方式证实了染料可以对纤维达到透染的目的。研究了染液pH值、染色温度、染色时间以及染料结构等对染色性能影响。发现不含磺酸基的多乙烯多胺可交联染料适合浸染染色蛋白质纤维,其中交联染料PAD1在丝绸和羊毛上的竭染率最高,分别为99.8%和95.5%,不含磺酸基的聚乙烯胺可交联染料对蛋白质和纤维素纤维都可采用浸染染色的方式,竭染率最高的是交联染料PVD4,在棉和丝绸上可分别达到97.6%和99.3%；而含有磺酸基的两类多胺型可交联染料更适合轧染染色工艺。
分别以交联染料PAD1和PVD4为例,研究了多乙烯多胺可交联染料在丝绸和羊毛上以及聚乙烯胺可交联染料在棉纤维上的吸附动力学和吸附平衡模型。研究显示多乙烯多胺可交联染料和聚乙烯胺可交联染料在蛋白质纤维上的吸附过程遵循准二级动力学方程,以化学吸附为主,吸附平衡模型为Langmuir型,吸附过程是自发进行的：而聚乙烯胺可交联染料在棉纤维上的吸附过程遵循准一级动力学方程,以物理吸附为主,吸附平衡为Freundlich型,吸附过程是自发吸热的过程。
本文研究了固色pH值、交联剂用量、交联反应温度和反应时间等条件对交联固色性能影响,得出最佳固色条件,测定了染料的各项色牢度。结果表明不含磺酸基的多胺型可交联染料在棉、丝绸和羊毛纤维上都可得到近100%的交联反应率和优良的色牢度,耐洗牢度可达4-5级,耐摩擦牢度可达4级。采用色牢度法、DMF剥色法、红外差谱等方法,证明了多胺型可交联染料经交联剂固色后染料和纤维间共价键的存在。通过对交联剂水解速率、交联剂放置时间和交联剂循环使用次数对交联反应率影响的研究,发现本文所用的交联剂M不仅交联固色性能优良,而且稳定性良好。
通过测量染色织物折皱回复角的方法研究了两类可交联染料染色纤维的折皱回复性能,当交联染料用量为丝绸染色0.67g／L,棉纤维染色1g/L,交联剂用量20g/L时,与未染色纤维相比,多胺交联染色丝绸纤维的折皱回复性能与丁烷四酸整理的丝绸相当,交联染色棉纤维的折皱回复性能也有了较明显提高。交联染色纤维的抗皱性能还可随交联剂用量和交联染料用量的提高而提高,而且交联染料的交联固色性能、织物手感和强力性质不受影响。
Crosslinking dyes can form covalent bonds with dyed fibers by crosslinking agent. The advantages of crosslinking dye are avoiding the hydrolysis of reactive dyes and at same time keeping good fastness properties, which can improve the dye utilization obviously.
The solubility, molecule size and penetrability of polyamine crosslinking dyes were studied in the paper. The methods of software simulation and fiber slice validated that crosslinking dyes could obtain good dye penetrability. The effect of pH value, dyeing temperature, dyeing time and structure of dyes on dyeing properties was investigated in detail. We found that polyethylene polyamine crosslinking dyes without sulphonic groups suited exhaustion dyeing manner on protein fibers, and Exhaustion of PAD1 were 99.8% and 95.5% on silk and wool respectively; polyvinylamine crosslinking dyes without sulphonic groups suited exhaustion dyeing manner on cotton and silk fibers, and Exhaustion of PVD4 were 97.6% and 99.3% on cotton and silk, respectively. Padding method was more suitable for two kinds of crosslinking dyes with sulphonic groups.
Take PAD1 and PVD4 for examples, the model of adsorption kinetics and adsorption equilibrium of polyethylene polyamine and polyvinylamine crosslinking dyes on silk, wool and cotton were discussed respectively. The results showed that the adsorption of polyethylene polyamine and polyvinylamine crosslinking dyes on silk and wool which followed pseudo second-order kinetics equation gave priority to chemisorption and adsorption equilibrium was Langmuir type. The adsorption process of polyvinylamine crosslinking dyes on cotton which belongs to pseudo first-order kinetics equation and Freundlich model is spontaneous, endothermic and dominated by physical adsorption.
Effect of pH value, amount of crosslinker, crosslinking reaction temperature and reaction time on crosslinking fixation of crosslinker was studied. The color fastness and fixing condition were discussed. The results indicated that approximately 100% crosslinking ratio and good fastness could be obtained. The washfastness, dry rubfastness reached 4-5 grade and 4 grade, respectively. The type of intermolecular force between crosslinking dyes and dyed fibers was investigated by colorfastness, DMF color stripping, dyeing of polypropene fiber and IR. spectra. The formation of covalent bonds between fibers and the crosslinking dyes was comfirmed. The hydrolysis ratio of crosslinking agent was calculated and the effect of storage time and recycle application of crosslinker M on crosslinking ratio was discussed. It was found that crosslinker M with excellent reactivity was stable.
Crease resistance of dyed fibers was investigated by measuring wrinkle recovery angles in this paper. When the concentration of the crosslinking dyes was 0.67 g/L on silk,1 g/L on cotton and that of the crosslinker was 20 g/L, the crease resistance of the dyed silk fabrics was comparable to that obtained from that finished with BTCA and that of the dyed cotton fabrics also was improved evidently. With the increase of the concentrations of both the crosslinking dyes and the crosslinker, the wrinkle resistance of the dyed fabrics was further improved. Furthermore, under those conditions, crosslinking fixation properties, the handle and tensile strength of the silk fabrics were still satisfactory.
本文首先研究了多胺型可交联染料的溶解特性、分子大小和渗透性能,通过软件模拟和纤维切片的方式证实了染料可以对纤维达到透染的目的。研究了染液pH值、染色温度、染色时间以及染料结构等对染色性能影响。发现不含磺酸基的多乙烯多胺可交联染料适合浸染染色蛋白质纤维,其中交联染料PAD1在丝绸和羊毛上的竭染率最高,分别为99.8%和95.5%,不含磺酸基的聚乙烯胺可交联染料对蛋白质和纤维素纤维都可采用浸染染色的方式,竭染率最高的是交联染料PVD4,在棉和丝绸上可分别达到97.6%和99.3%；而含有磺酸基的两类多胺型可交联染料更适合轧染染色工艺。
分别以交联染料PAD1和PVD4为例,研究了多乙烯多胺可交联染料在丝绸和羊毛上以及聚乙烯胺可交联染料在棉纤维上的吸附动力学和吸附平衡模型。研究显示多乙烯多胺可交联染料和聚乙烯胺可交联染料在蛋白质纤维上的吸附过程遵循准二级动力学方程,以化学吸附为主,吸附平衡模型为Langmuir型,吸附过程是自发进行的：而聚乙烯胺可交联染料在棉纤维上的吸附过程遵循准一级动力学方程,以物理吸附为主,吸附平衡为Freundlich型,吸附过程是自发吸热的过程。
本文研究了固色pH值、交联剂用量、交联反应温度和反应时间等条件对交联固色性能影响,得出最佳固色条件,测定了染料的各项色牢度。结果表明不含磺酸基的多胺型可交联染料在棉、丝绸和羊毛纤维上都可得到近100%的交联反应率和优良的色牢度,耐洗牢度可达4-5级,耐摩擦牢度可达4级。采用色牢度法、DMF剥色法、红外差谱等方法,证明了多胺型可交联染料经交联剂固色后染料和纤维间共价键的存在。通过对交联剂水解速率、交联剂放置时间和交联剂循环使用次数对交联反应率影响的研究,发现本文所用的交联剂M不仅交联固色性能优良,而且稳定性良好。
通过测量染色织物折皱回复角的方法研究了两类可交联染料染色纤维的折皱回复性能,当交联染料用量为丝绸染色0.67g／L,棉纤维染色1g/L,交联剂用量20g/L时,与未染色纤维相比,多胺交联染色丝绸纤维的折皱回复性能与丁烷四酸整理的丝绸相当,交联染色棉纤维的折皱回复性能也有了较明显提高。交联染色纤维的抗皱性能还可随交联剂用量和交联染料用量的提高而提高,而且交联染料的交联固色性能、织物手感和强力性质不受影响。
Crosslinking dyes can form covalent bonds with dyed fibers by crosslinking agent. The advantages of crosslinking dye are avoiding the hydrolysis of reactive dyes and at same time keeping good fastness properties, which can improve the dye utilization obviously.
The solubility, molecule size and penetrability of polyamine crosslinking dyes were studied in the paper. The methods of software simulation and fiber slice validated that crosslinking dyes could obtain good dye penetrability. The effect of pH value, dyeing temperature, dyeing time and structure of dyes on dyeing properties was investigated in detail. We found that polyethylene polyamine crosslinking dyes without sulphonic groups suited exhaustion dyeing manner on protein fibers, and Exhaustion of PAD1 were 99.8% and 95.5% on silk and wool respectively; polyvinylamine crosslinking dyes without sulphonic groups suited exhaustion dyeing manner on cotton and silk fibers, and Exhaustion of PVD4 were 97.6% and 99.3% on cotton and silk, respectively. Padding method was more suitable for two kinds of crosslinking dyes with sulphonic groups.
Take PAD1 and PVD4 for examples, the model of adsorption kinetics and adsorption equilibrium of polyethylene polyamine and polyvinylamine crosslinking dyes on silk, wool and cotton were discussed respectively. The results showed that the adsorption of polyethylene polyamine and polyvinylamine crosslinking dyes on silk and wool which followed pseudo second-order kinetics equation gave priority to chemisorption and adsorption equilibrium was Langmuir type. The adsorption process of polyvinylamine crosslinking dyes on cotton which belongs to pseudo first-order kinetics equation and Freundlich model is spontaneous, endothermic and dominated by physical adsorption.
Effect of pH value, amount of crosslinker, crosslinking reaction temperature and reaction time on crosslinking fixation of crosslinker was studied. The color fastness and fixing condition were discussed. The results indicated that approximately 100% crosslinking ratio and good fastness could be obtained. The washfastness, dry rubfastness reached 4-5 grade and 4 grade, respectively. The type of intermolecular force between crosslinking dyes and dyed fibers was investigated by colorfastness, DMF color stripping, dyeing of polypropene fiber and IR. spectra. The formation of covalent bonds between fibers and the crosslinking dyes was comfirmed. The hydrolysis ratio of crosslinking agent was calculated and the effect of storage time and recycle application of crosslinker M on crosslinking ratio was discussed. It was found that crosslinker M with excellent reactivity was stable.
Crease resistance of dyed fibers was investigated by measuring wrinkle recovery angles in this paper. When the concentration of the crosslinking dyes was 0.67 g/L on silk,1 g/L on cotton and that of the crosslinker was 20 g/L, the crease resistance of the dyed silk fabrics was comparable to that obtained from that finished with BTCA and that of the dyed cotton fabrics also was improved evidently. With the increase of the concentrations of both the crosslinking dyes and the crosslinker, the wrinkle resistance of the dyed fabrics was further improved. Furthermore, under those conditions, crosslinking fixation properties, the handle and tensile strength of the silk fabrics were still satisfactory.
引文
[1]刘敬来.天然纤维的发展概述.黑龙江纺织[J].2006,(1)：5-6.
[2]Dawson T L. It must be green:meeting society's environmental concerns. Coloration Technology[J].2008,124, (2):67-78.
[3]Eileen W,王利伟.天然纤维优点集锦.产业用纺织品[J].2003,21,(3)：37-40.
[4]张淑芬,杨锦宗.活性染料的现状与展望.染料与染色[J].2008,45,(1)：1-7.
[5]张壮余,吴祖望.染料应用：第一版[M].北京：化学工业出版社,1991.
[6]Parton K. The dyeing of wool:past, present and future. Journal of the Society of Dyers and Colourists[J].1998,114, (1):8-10.
[7]Ahmed N S E. The use of sodium edate in the dyeing of cotton with reactive dyes. Dyes and Pigments[J].2005,65, (3):221-225.
[8]Mughal M J, Naeem M, AleemA, et al. Effect of a cationising agent on the conventional reactive dyeing of cotton. Coloration Technology[J].2008,124, (1):62-65.
[9]Kampyli V, Phillips D A S, Renfrew A H M. Reactive dyes containing a 4-m-carboxypyridinium-1,3,5-triazine-2-oxide reactive group:exhaust dyeing of cotton under alkaline and neutral fixation conditions. Dyes and Pigments [J].2004, 61, (2):165-175.
[10]Taylor J A. Reactive mono:azo dyes of 1-amino 8-hydroxy naphthalene series|used for dyeing amino-or hydroxyl gp.-contg. textiles such as wool, silk or cellulosics: W09422961-A; EP692003-A; W09422961-A1; AU9461457-A; ZA9401504-A; EP692003-A1; TW273564-A; JP8508312-W; US5614613-A; CN1120344-A; EP692003-B1; DE69410606-E; ES2116585-T3; CN1046751-C[P].1994.
[11]Buch H M, Hahnle R, Springer H, et al. New reactive dyestuff cpds. with cyanamido triazinyl-amino substit|used for dyeing or printing wool, silk and esp. cotton: WO9013604-A1; DE3930704-A1; EP471702-A; BR9007365-A; JP4505174-W; US5227475-A; EP471702-B1; DE59004049-G; ES2062522-T3; JP95113089-B2; KR9511364-B1 [P].1990.
[12]Agarwal D, Sen K, Gulrajani M L. Dyeing of silk with bifunctional reactive dyes: The relationship between exhaustion and fixation. Journal of the Society of Dyers and Colourists[J].1997,113, (5-6):174-178.
[13]Sawada K, Ueda M. Dyeing of protein fiber in a reverse micellar system. Dyes and Pigments[J].2003,58, (2):99-103.
[14]Chaudhary A N, Smith B. Synthesis and properties of cationized wool. Aatcc Review[J].2003,3, (1):27-29.
[15]Garcia J, Postle R, Pailthorpe M T. Changes in the Chemical-Composition of Wool During Dyeing and Finishing and Their Effects on Fabric Properties. Textile Research Journal[J].1995,65, (8):477-485.
[16]宋心远.活性染料染色新技术(三).纺织导报[J].2007,(11)：73-75.
[17]李英玲,张淑芬,杨锦宗.多胺型交联染料在丝、棉纤维上的超高固色效应研究.精细化工[J].2008,25,(6)：595-599.
[18]Lei X P, Lewis D M, Shen X M, et al. Crosslinking nucleophilic dyes on wool. Dyes and Pigments[J].1996,30, (4):271-281.
[19]胡志勇.可交联高分子染料的合成与染色性能研究：博士学位论文[D].大连：大连理工大学，2002.
[20]Li Y L, Zhang S F, Yang J Z, et al. Synthesis and application of novel crosslinking polyamine dyes with good dyeing performance. Dyes and Pigments [J].2008,76, (2): 508-514.
[21]Lutzel G. Dye fixation by means of polyfunctional crosslinking agents. Journal of the Society of Dyers and Colourists[J].1966,82, (8):293-299.
[22]侯文杰,蒋嵩,张淑芬.交联染料的研究进展.染料与染色[J].2004,41,(3)：129-130.
[23]Hensel H R, Lutzel G. New cotton dye. Angewandte Chemie International Edition[J]. 1965,4, (4):312-321.
[24]Egger W B, Kissling B, Robinson T. Economic durable cellulosics dyeings with reactant-fixable dyes. American Dyestuff Reporter[J].1982,71, (9):55-61.
[25]Lewis DM, Wang Y N, Lei X P. Level Fast Dyeing of Wool with Nucleophilic Aminoalkyl Dyes and Cross-Linking Agents.1. Using a Trifunctional Cross-Linking Agent, Journal of the Society of Dyers and Colourists[J].1995,111, (1-2):12-18.
[26]Lei X P, Lewis D M, Wang Y N. Level fast dyeing of wool with nucleophilic aminoalkyl dyes and crosslinking agents.2. Using bifunctional crosslinking agents. Journal of the Society of Dyers and Colourists[J].1995,111, (12):385-390.
[27]Lei X P, Lewis D M, Wang Y N. The production of level fast dyeings on wool with nucleophilic dyes and a crosslinking agent. Journal of the society of dyers and colorist[J].1992,108, (9):383-387.
[28]周璐瑛.交联染色体系的染整一步法研究.染料工业[J].1989,(5)：33-37.
[29]应燮元.新型交联染料的应用.上海染料[J].1987,(4)：17-22.
[30]章杰.交链染料的研究-棉用染料的一种创新.染料工业[J].1987,(6)：1-9.
[31]Murdock K C. Heteroalkylenebisanthraquinone:US4278605[P].1981.
[32]Larry B F, Spartanburg. Polymeric anthraquinone derived colorants:US4137243[P]. 1979.
[33]Phillip E S, Hu C T. Method for dyeing human hair with cationic polymeric dyes: US4182612[P].1980.
[34]Crounse N N. Novel monoazo and disazo colorants:US4376729[P].1983.
[35]顾丹.一类新型含可交联基团的交联染料的合成与应用研究：硕士学位论文[D].大连：大连理工大学,1997.
[36]Li Y L, Tang Y F, Zhang S F, et al. Synthesis and application of crosslinking blue anthraquinone polyamine dye with high fixation. Textile Research Journal [J].2007, 77, (9):703-709.
[37]Tang Y F, Zhang S F, Yang J Z, et al. Synthesis of a new, yellow crosslinking polyvinylamine dye and its crosslinking/dyeing process through a crosslinker. Journal of Applied Polymer Science[J].2006,102, (2):1568-1573.
[38]Elachari A, Coqueret X, Lablachecombier A, et al. Preparation of Polyvinylamine from Polyacrylamide-a Reinvestigation of the Hofmann Reaction. Makromolekulare Chemie-Macromolecular Chemistry and Physics[J].1993,194, (7):1879-1891.
[39]Hiroo T, Ryoichi S. Preparation of polyvinylamine by the Hofmann degradation of polyacrylamide. Bull. Chem. Soc. Jpn.[J].1976,49, (10):2821-2823.
[40]Hiroo T. Hofmann reaction of polyacrylamide:relationship between reaction condition and degree of polymerization of polyvinylamine. J. Polym. Sci. Polym. Chem. Ed. [J].1979,17:1239-1245.
[41]Ahmida E A, Xavier C, Alain L C, et al. Preparation of polyvinylamine from polyacrylamide:a reinvestigation of the Hofmann reaction. Makromol. Chem. [J].1993,194:1879-1891.
[42]唐炳涛.聚胺型可交联高分子染料的合成与应用：博士学位论文[D].大连：大连理工大学,2005.
[43]Hu Z Y, Zhang S F, Yang J Z, et al. Some properties of aqueous-solutions of poly(vinylamine chloride). Journal of Applied Polymer Science [J].2003,89, (14): 3889-3893.
[44]胡志勇,张淑芬,杨锦宗.聚乙烯胺的合成及其在染料中的应用.染料工业[J].2001,38,(6)：31-33.
[45]Tang B T, Zhang S F, Yang J Z, et al. Synthesis of a novel water-soluble crosslinking polymeric dye with good dyeing properties. Dyes and Pigments[J],2006,68, (1): 69-73.
[46]Tang B T, Zhang S F, Yang J Z, et al. Synthesis and dyeing performance of a novel yellow crosslinking polymeric dye. Coloration Technology[J].2004,120, (4): 180-183.
[47]Cheng H, Kai S. Easy-care finishing of silk fabrics with a novel multifunctional epoxide. Part 1. Journal of the Society of Dyers and Colourists[J].1998,114, (12): 359-362.
[48]Hu C, Sun K. Easy-care finishing of silk fabrics with epoxy resin EPTA. American Dyestuff Reporter[J].1998,87, (3):42-45.
[49]Moon S J, Kang T J. Effects of epoxide and silicone polymers on the mechanical and performance properties of wool fabric. Textile Research Journal[J].2000,70, (12):1063-1069.
[50]Cai Z S, Wang F A, Yang S J. Crease resistant finishing of silk fabrics with silicone-containing epoxide A. Journal of China Textile University[J].2000,17, (2):56-60.
[51]Omura N, Isobe K. Nitrogen atom-containing polysiloxanes, their preparation and use in fabric finishing agent compositions:EP1063344[P].2000.
[52]汤艳峰.交联染色用交联剂的合成及应用性能研究：博士学位论文[D].大连：大连理工大学,2006.
[53]Tang Y F, Li Y L, Zhang S F, et al. Fixation of a tetraethylene pentamine dye on cotton and silk by bifunctional crosslinkers. Coloration Technology [J].2006,122, (2):82-85.
[54]Zollonger H. Color Chemistry[M]. Beijing:化学工业出版社,2005.
[55]杨锦宗.活性染料与反应性染色.大连理工大学学报[J].1999,39,(2)：235-242.
[56]Lewis D M. New Possibilities to Improve Cellulosic Fiber Dyeing Processes with Fiber-Reactive Systems. Journal of the Society of Dyers and Colourists[J].1993, 109, (11):357-364.
[57]尤克非,章忠秀,孙淑娟.SW型活性染料对羊毛的染色性能研究.毛纺科技[J].2007,(2)：25-28.
[58]Ma W, Zhang S F, Yang J Z. Cationization of cotton and salt-free dyeing them with reactive dyes. Dyestuffs and Coloration[J].2004,41, (6):340-345.
[59]New asymmetric dioxazine compounds and their salts useful as reactive dyes capable of dyeing cellulose fibers clear violet-blue with excellent repeatability and color fastness:JP2002003736-A[P].2002.
[60]Wang L L, Ma W, Zhang S F, et al. Preparation of cationic cotton with two-bath pad-bake process and its application in salt-free dyeing. Carbohydrate Polymers [J]. 2009,78, (3):602-608.
[61]Montazer M, Malek R M A, Rahimi A. Salt free reactive dyeing of cationized cotton. Fibers and Polymers[J].2007,8, (6):608-612.
[62]冯福建,成万辉.直接交联染料在针织物染色中的应用.针织工业[J].1994,(3)：24-28.
[63]Lewis D M, Shao J Z. A New Approach to the Dyeing of Silk with Sulphatoethylsulphone Dyes. Journal of the Society of Dyers and Colourists[J].1995,111, (5):146-150.
[64]阎克路.染整工艺学教程第一分册[M].北京：中国纺织出版社,2005.
[65]Uddin F, Lomas M. Catalyst systems for crease recovery finishing prior to pigment printing. Coloration Technology[J].2004,120, (5):254-259.
[66]Yang Y Q, Li S Q. Dyeability of silk fabric finished for durable press with trimethylolmelamine. American Dyestuff Reporter[J],1993,82, (8):22-28.
[67]Xu W L, Cui W G, Li W B, et al. Two-step durable press treatment of cotton fabric. Coloration Technology [J].2001,117, (6):352-355.
[68]Schramm C, Rinderer B. Multifunctional carboxylic acids in DP finishing with BTCA and CA. Textile Chemist and Colorist & American Dyestuff Reporter[J].2000,32, (4):50-54.
[69]Voncina B, le Marechal A M, Voncina D B. Evaluation of analytical methods for the determination of free formaldehyde on textile substrate. Journal of the Textile Institute[J].2007,98:533-538.
[70]Yang Y Q, Li S Q. Crease resistant finishing of silk fabric with BTCA. Text. Chem. Color. [J].1994,26, (5):25-29.
[71]Hebeish A, Hashem M, Abdel-Rahman A, et al. Improving easy care nonformaldehyde finishing performance using polycarboxylic acids via precationization of cotton fabric. Journal of Applied Polymer Science[J].2006,100, (4):2697-2704.
[72]Schramm C, Rinderer B, Bobleter 0. Quantitative determination of BTCA bound to cellulosic material by means of isocratic HPLC. Textile Research Journal [J].1998, 68, (11):821-827.
[73]Yang C Q, Xu L, Li S Q, et al. Nonformaldehyde durable press finishing of cotton fabrics by combining citric acid with polymers of maleic acid. Textile Research Journal[J].1998,68, (6):457-464.
[74]Choi H M, Park M J, Oh K W. Nonformaldehyde crease-resistant finishing of silk with glyoxal. Textile Chemist and Colorist[J].1998,30, (12):41-45.
[75]张广知.棉织物的乙二醛抗皱整理.染整技术[J].2005,27,(7)：6-11.
[76]Blanchard E J, Reinhardt R M. Determining specif ic dyeing characteristics of cotton fabric. American Dyestuff Reporter[J].1989,78, (2):30,32,34,37.
[77]Cai Z S, Jiang G C, Qiu Y P. Chemical modification of bombyx mori silk with epoxide EPSIB. Journal of Applied Polymer Science[J].2004,91, (6):3579-3586.
[78]Melinikov B N, Sirokova M K, Kutaceva N S, et al. Simultaneous dyeing and finishing of cellulosic fabrics|using soln. contg. precondensate of thermo-reactive resin, acrylic acid amide, ammonium chloride and organic dye:DD253552-A[P].1988.
[79]Bashurina I Y U, Kalinnikov Y U A, Melnikov B N. Colouration and crease-resistant finishing of cotton fabric|effected simultaneously using reactive dye and polyvinyl acetate emulsion after treatment with liq. ammonia:SU1359380-A[P]. 1988.
[80]Ibrahim N A, Allam E, El-Hosamy M B, et al. Combined dyeing and resin finishing of wool/viscose and cotton/wool blends. Polymer-Plastics Technology and Engineering[J].2006,45, (4):455-462.
[81]Raheel M, Guo C. Single-step dyeing and formaldehyde-free durable press finishing of cotton fabric. Textile Research Journal[J].1998,68, (8):571-577.
[82]Malik S K, Kumar S. Simultaneous dyeing and finishing of cotton fabric using reactive dyes and citric acid. Indian Journal of Fibre & Textile Research [J].2005, 30, (4):444-450.
[83]Dong Y C, Wang J J, Liu P F. Dyeing and finishing of cotton fabric in a single bath with reactive dyes and citric acid. Coloration Technology [J].2001,117, (5): 262-265.
[84]Choi H M. A semi-continuous single-step dyeing and finishing treatment of cotton using polycarboxylic acids and reactive dyes. Cellulose Chemistry and Technology[J].1998,32, (5-6):483-495.
[85]Dong W, Xu J, Huang J. Pore structure characterization of cotton fiber by nitrogen adsorption. Journal of Textile Research[J].2007,28, (6):5-7.
[86]张月华,徐安英.蚕丝纤维超细结构的研究.国外丝绸[J].2003,(6)：1,2,40.
[87]Kim S H, Nam Y S, Lee T S, et al. Silk fibroin nanofiber. Electrospinning, properties, and structure. Polymer Journal[J].2003,35, (2):185-190.
[88]池海涛,李宏伟,陈英.羊毛染整加工中低温等离子体技术应用现状,第七届功能性纺织品及纳米技术研讨会论文集[C].2007：pp 136-138.
[89]Ho Y S, McKay G. Pseudo-second order model for sorption processes. Process Biochemistry[J].1999,34, (5):451-465.
[90]Chairat M, Rattanaphani S, Bremner J B, et al. Adsorption kinetic study of lac dyeing on cotton. Dyes and Pigments[J],2008,76, (2):435-439.
[91]Dogan M, Ozdemir Y, Alkan M. Adsorption kinetics and mechanism of cationic methyl violet and methylene blue dyes onto sepiolite. Dyes and Pigments[J].2007,75: 701-713.
[92]Dogan M, Alkan M. Adsorption kinetics of methyl violet onto perlite. Chemosphere[J]. 2003,50, (4):517-528.
[93]Ozcan A, Oncu E M, Ozcan A S. Kinetics, isotherm and thermodynamic studies of adsorption of Acid Blue 193 from aqueous solutions onto natural sepiolite. Colloids and Surfaces a-Physicochemical and Engineering Aspects[J].2006,277, (1-3): 90-97.
[94]Nollet H, Roels M, Lutgen P, et al. Removal of PCBs from wastewater using fly ash. Chemosphere[J].2003,53, (6):655-665.
[95]Chairat M, Rattanaphani S, Bremner J B, et al. An adsorption and kinetic study of lac dyeing on silk. Dyes and Pigments[J].2005,64, (3):231-241.
[96]Ghiaci M, Kalbasi R J, Abbaspour A. Adsorption isotherms of non-ionic surfactants on Na-bentonite (Iran) and evaluation of thermodynamic parameters. Colloids and Surfaces a-Physicochemical and Engineering Aspects [J].2007,297, (1-3):105-113.
[97]Kweon H, Ha H C, Um I C, et al. Physical properties of silk fibroin/chitosan blend films. Journal of Applied Polymer Science[J].2001,80, (7):928-934.
[98]宋心远,沈煜如.活性染料染色的理论和实践[M].北京：纺织工业出版社,1991.
[99]黄旭明,金雅,蔡再生.液体活性染料的水解性分析及水解控制.纺织科技进展[J].2005,(6)：17-19.
[100]何海兰.染料[M].北京：化学工业出版社,2004.
[101]Hunger K. Industrial dyes:chemistry, properties, applications[M]. WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim,2003.
[102]Kabra R, Parab A. Formaldehyde free low temperature-cure cross-linking agent. Colourage[J].2004,51, (11):41-43.
[103]罗巨涛,陈利丽,宋金星.全棉细平布抗皱整理.印染[J].2006,32,(22)：23-26.
[104]Schramm C, Vukusic S B, Katovic D. Non-formaldehyde durable press finishing of dyed fabrics:evaluation of cotton-bound polycarboxylic acids. Coloration Technology[J].2002,118, (5):244-249.
[2]Dawson T L. It must be green:meeting society's environmental concerns. Coloration Technology[J].2008,124, (2):67-78.
[3]Eileen W,王利伟.天然纤维优点集锦.产业用纺织品[J].2003,21,(3)：37-40.
[4]张淑芬,杨锦宗.活性染料的现状与展望.染料与染色[J].2008,45,(1)：1-7.
[5]张壮余,吴祖望.染料应用：第一版[M].北京：化学工业出版社,1991.
[6]Parton K. The dyeing of wool:past, present and future. Journal of the Society of Dyers and Colourists[J].1998,114, (1):8-10.
[7]Ahmed N S E. The use of sodium edate in the dyeing of cotton with reactive dyes. Dyes and Pigments[J].2005,65, (3):221-225.
[8]Mughal M J, Naeem M, AleemA, et al. Effect of a cationising agent on the conventional reactive dyeing of cotton. Coloration Technology[J].2008,124, (1):62-65.
[9]Kampyli V, Phillips D A S, Renfrew A H M. Reactive dyes containing a 4-m-carboxypyridinium-1,3,5-triazine-2-oxide reactive group:exhaust dyeing of cotton under alkaline and neutral fixation conditions. Dyes and Pigments [J].2004, 61, (2):165-175.
[10]Taylor J A. Reactive mono:azo dyes of 1-amino 8-hydroxy naphthalene series|used for dyeing amino-or hydroxyl gp.-contg. textiles such as wool, silk or cellulosics: W09422961-A; EP692003-A; W09422961-A1; AU9461457-A; ZA9401504-A; EP692003-A1; TW273564-A; JP8508312-W; US5614613-A; CN1120344-A; EP692003-B1; DE69410606-E; ES2116585-T3; CN1046751-C[P].1994.
[11]Buch H M, Hahnle R, Springer H, et al. New reactive dyestuff cpds. with cyanamido triazinyl-amino substit|used for dyeing or printing wool, silk and esp. cotton: WO9013604-A1; DE3930704-A1; EP471702-A; BR9007365-A; JP4505174-W; US5227475-A; EP471702-B1; DE59004049-G; ES2062522-T3; JP95113089-B2; KR9511364-B1 [P].1990.
[12]Agarwal D, Sen K, Gulrajani M L. Dyeing of silk with bifunctional reactive dyes: The relationship between exhaustion and fixation. Journal of the Society of Dyers and Colourists[J].1997,113, (5-6):174-178.
[13]Sawada K, Ueda M. Dyeing of protein fiber in a reverse micellar system. Dyes and Pigments[J].2003,58, (2):99-103.
[14]Chaudhary A N, Smith B. Synthesis and properties of cationized wool. Aatcc Review[J].2003,3, (1):27-29.
[15]Garcia J, Postle R, Pailthorpe M T. Changes in the Chemical-Composition of Wool During Dyeing and Finishing and Their Effects on Fabric Properties. Textile Research Journal[J].1995,65, (8):477-485.
[16]宋心远.活性染料染色新技术(三).纺织导报[J].2007,(11)：73-75.
[17]李英玲,张淑芬,杨锦宗.多胺型交联染料在丝、棉纤维上的超高固色效应研究.精细化工[J].2008,25,(6)：595-599.
[18]Lei X P, Lewis D M, Shen X M, et al. Crosslinking nucleophilic dyes on wool. Dyes and Pigments[J].1996,30, (4):271-281.
[19]胡志勇.可交联高分子染料的合成与染色性能研究：博士学位论文[D].大连：大连理工大学，2002.
[20]Li Y L, Zhang S F, Yang J Z, et al. Synthesis and application of novel crosslinking polyamine dyes with good dyeing performance. Dyes and Pigments [J].2008,76, (2): 508-514.
[21]Lutzel G. Dye fixation by means of polyfunctional crosslinking agents. Journal of the Society of Dyers and Colourists[J].1966,82, (8):293-299.
[22]侯文杰,蒋嵩,张淑芬.交联染料的研究进展.染料与染色[J].2004,41,(3)：129-130.
[23]Hensel H R, Lutzel G. New cotton dye. Angewandte Chemie International Edition[J]. 1965,4, (4):312-321.
[24]Egger W B, Kissling B, Robinson T. Economic durable cellulosics dyeings with reactant-fixable dyes. American Dyestuff Reporter[J].1982,71, (9):55-61.
[25]Lewis DM, Wang Y N, Lei X P. Level Fast Dyeing of Wool with Nucleophilic Aminoalkyl Dyes and Cross-Linking Agents.1. Using a Trifunctional Cross-Linking Agent, Journal of the Society of Dyers and Colourists[J].1995,111, (1-2):12-18.
[26]Lei X P, Lewis D M, Wang Y N. Level fast dyeing of wool with nucleophilic aminoalkyl dyes and crosslinking agents.2. Using bifunctional crosslinking agents. Journal of the Society of Dyers and Colourists[J].1995,111, (12):385-390.
[27]Lei X P, Lewis D M, Wang Y N. The production of level fast dyeings on wool with nucleophilic dyes and a crosslinking agent. Journal of the society of dyers and colorist[J].1992,108, (9):383-387.
[28]周璐瑛.交联染色体系的染整一步法研究.染料工业[J].1989,(5)：33-37.
[29]应燮元.新型交联染料的应用.上海染料[J].1987,(4)：17-22.
[30]章杰.交链染料的研究-棉用染料的一种创新.染料工业[J].1987,(6)：1-9.
[31]Murdock K C. Heteroalkylenebisanthraquinone:US4278605[P].1981.
[32]Larry B F, Spartanburg. Polymeric anthraquinone derived colorants:US4137243[P]. 1979.
[33]Phillip E S, Hu C T. Method for dyeing human hair with cationic polymeric dyes: US4182612[P].1980.
[34]Crounse N N. Novel monoazo and disazo colorants:US4376729[P].1983.
[35]顾丹.一类新型含可交联基团的交联染料的合成与应用研究：硕士学位论文[D].大连：大连理工大学,1997.
[36]Li Y L, Tang Y F, Zhang S F, et al. Synthesis and application of crosslinking blue anthraquinone polyamine dye with high fixation. Textile Research Journal [J].2007, 77, (9):703-709.
[37]Tang Y F, Zhang S F, Yang J Z, et al. Synthesis of a new, yellow crosslinking polyvinylamine dye and its crosslinking/dyeing process through a crosslinker. Journal of Applied Polymer Science[J].2006,102, (2):1568-1573.
[38]Elachari A, Coqueret X, Lablachecombier A, et al. Preparation of Polyvinylamine from Polyacrylamide-a Reinvestigation of the Hofmann Reaction. Makromolekulare Chemie-Macromolecular Chemistry and Physics[J].1993,194, (7):1879-1891.
[39]Hiroo T, Ryoichi S. Preparation of polyvinylamine by the Hofmann degradation of polyacrylamide. Bull. Chem. Soc. Jpn.[J].1976,49, (10):2821-2823.
[40]Hiroo T. Hofmann reaction of polyacrylamide:relationship between reaction condition and degree of polymerization of polyvinylamine. J. Polym. Sci. Polym. Chem. Ed. [J].1979,17:1239-1245.
[41]Ahmida E A, Xavier C, Alain L C, et al. Preparation of polyvinylamine from polyacrylamide:a reinvestigation of the Hofmann reaction. Makromol. Chem. [J].1993,194:1879-1891.
[42]唐炳涛.聚胺型可交联高分子染料的合成与应用：博士学位论文[D].大连：大连理工大学,2005.
[43]Hu Z Y, Zhang S F, Yang J Z, et al. Some properties of aqueous-solutions of poly(vinylamine chloride). Journal of Applied Polymer Science [J].2003,89, (14): 3889-3893.
[44]胡志勇,张淑芬,杨锦宗.聚乙烯胺的合成及其在染料中的应用.染料工业[J].2001,38,(6)：31-33.
[45]Tang B T, Zhang S F, Yang J Z, et al. Synthesis of a novel water-soluble crosslinking polymeric dye with good dyeing properties. Dyes and Pigments[J],2006,68, (1): 69-73.
[46]Tang B T, Zhang S F, Yang J Z, et al. Synthesis and dyeing performance of a novel yellow crosslinking polymeric dye. Coloration Technology[J].2004,120, (4): 180-183.
[47]Cheng H, Kai S. Easy-care finishing of silk fabrics with a novel multifunctional epoxide. Part 1. Journal of the Society of Dyers and Colourists[J].1998,114, (12): 359-362.
[48]Hu C, Sun K. Easy-care finishing of silk fabrics with epoxy resin EPTA. American Dyestuff Reporter[J].1998,87, (3):42-45.
[49]Moon S J, Kang T J. Effects of epoxide and silicone polymers on the mechanical and performance properties of wool fabric. Textile Research Journal[J].2000,70, (12):1063-1069.
[50]Cai Z S, Wang F A, Yang S J. Crease resistant finishing of silk fabrics with silicone-containing epoxide A. Journal of China Textile University[J].2000,17, (2):56-60.
[51]Omura N, Isobe K. Nitrogen atom-containing polysiloxanes, their preparation and use in fabric finishing agent compositions:EP1063344[P].2000.
[52]汤艳峰.交联染色用交联剂的合成及应用性能研究：博士学位论文[D].大连：大连理工大学,2006.
[53]Tang Y F, Li Y L, Zhang S F, et al. Fixation of a tetraethylene pentamine dye on cotton and silk by bifunctional crosslinkers. Coloration Technology [J].2006,122, (2):82-85.
[54]Zollonger H. Color Chemistry[M]. Beijing:化学工业出版社,2005.
[55]杨锦宗.活性染料与反应性染色.大连理工大学学报[J].1999,39,(2)：235-242.
[56]Lewis D M. New Possibilities to Improve Cellulosic Fiber Dyeing Processes with Fiber-Reactive Systems. Journal of the Society of Dyers and Colourists[J].1993, 109, (11):357-364.
[57]尤克非,章忠秀,孙淑娟.SW型活性染料对羊毛的染色性能研究.毛纺科技[J].2007,(2)：25-28.
[58]Ma W, Zhang S F, Yang J Z. Cationization of cotton and salt-free dyeing them with reactive dyes. Dyestuffs and Coloration[J].2004,41, (6):340-345.
[59]New asymmetric dioxazine compounds and their salts useful as reactive dyes capable of dyeing cellulose fibers clear violet-blue with excellent repeatability and color fastness:JP2002003736-A[P].2002.
[60]Wang L L, Ma W, Zhang S F, et al. Preparation of cationic cotton with two-bath pad-bake process and its application in salt-free dyeing. Carbohydrate Polymers [J]. 2009,78, (3):602-608.
[61]Montazer M, Malek R M A, Rahimi A. Salt free reactive dyeing of cationized cotton. Fibers and Polymers[J].2007,8, (6):608-612.
[62]冯福建,成万辉.直接交联染料在针织物染色中的应用.针织工业[J].1994,(3)：24-28.
[63]Lewis D M, Shao J Z. A New Approach to the Dyeing of Silk with Sulphatoethylsulphone Dyes. Journal of the Society of Dyers and Colourists[J].1995,111, (5):146-150.
[64]阎克路.染整工艺学教程第一分册[M].北京：中国纺织出版社,2005.
[65]Uddin F, Lomas M. Catalyst systems for crease recovery finishing prior to pigment printing. Coloration Technology[J].2004,120, (5):254-259.
[66]Yang Y Q, Li S Q. Dyeability of silk fabric finished for durable press with trimethylolmelamine. American Dyestuff Reporter[J],1993,82, (8):22-28.
[67]Xu W L, Cui W G, Li W B, et al. Two-step durable press treatment of cotton fabric. Coloration Technology [J].2001,117, (6):352-355.
[68]Schramm C, Rinderer B. Multifunctional carboxylic acids in DP finishing with BTCA and CA. Textile Chemist and Colorist & American Dyestuff Reporter[J].2000,32, (4):50-54.
[69]Voncina B, le Marechal A M, Voncina D B. Evaluation of analytical methods for the determination of free formaldehyde on textile substrate. Journal of the Textile Institute[J].2007,98:533-538.
[70]Yang Y Q, Li S Q. Crease resistant finishing of silk fabric with BTCA. Text. Chem. Color. [J].1994,26, (5):25-29.
[71]Hebeish A, Hashem M, Abdel-Rahman A, et al. Improving easy care nonformaldehyde finishing performance using polycarboxylic acids via precationization of cotton fabric. Journal of Applied Polymer Science[J].2006,100, (4):2697-2704.
[72]Schramm C, Rinderer B, Bobleter 0. Quantitative determination of BTCA bound to cellulosic material by means of isocratic HPLC. Textile Research Journal [J].1998, 68, (11):821-827.
[73]Yang C Q, Xu L, Li S Q, et al. Nonformaldehyde durable press finishing of cotton fabrics by combining citric acid with polymers of maleic acid. Textile Research Journal[J].1998,68, (6):457-464.
[74]Choi H M, Park M J, Oh K W. Nonformaldehyde crease-resistant finishing of silk with glyoxal. Textile Chemist and Colorist[J].1998,30, (12):41-45.
[75]张广知.棉织物的乙二醛抗皱整理.染整技术[J].2005,27,(7)：6-11.
[76]Blanchard E J, Reinhardt R M. Determining specif ic dyeing characteristics of cotton fabric. American Dyestuff Reporter[J].1989,78, (2):30,32,34,37.
[77]Cai Z S, Jiang G C, Qiu Y P. Chemical modification of bombyx mori silk with epoxide EPSIB. Journal of Applied Polymer Science[J].2004,91, (6):3579-3586.
[78]Melinikov B N, Sirokova M K, Kutaceva N S, et al. Simultaneous dyeing and finishing of cellulosic fabrics|using soln. contg. precondensate of thermo-reactive resin, acrylic acid amide, ammonium chloride and organic dye:DD253552-A[P].1988.
[79]Bashurina I Y U, Kalinnikov Y U A, Melnikov B N. Colouration and crease-resistant finishing of cotton fabric|effected simultaneously using reactive dye and polyvinyl acetate emulsion after treatment with liq. ammonia:SU1359380-A[P]. 1988.
[80]Ibrahim N A, Allam E, El-Hosamy M B, et al. Combined dyeing and resin finishing of wool/viscose and cotton/wool blends. Polymer-Plastics Technology and Engineering[J].2006,45, (4):455-462.
[81]Raheel M, Guo C. Single-step dyeing and formaldehyde-free durable press finishing of cotton fabric. Textile Research Journal[J].1998,68, (8):571-577.
[82]Malik S K, Kumar S. Simultaneous dyeing and finishing of cotton fabric using reactive dyes and citric acid. Indian Journal of Fibre & Textile Research [J].2005, 30, (4):444-450.
[83]Dong Y C, Wang J J, Liu P F. Dyeing and finishing of cotton fabric in a single bath with reactive dyes and citric acid. Coloration Technology [J].2001,117, (5): 262-265.
[84]Choi H M. A semi-continuous single-step dyeing and finishing treatment of cotton using polycarboxylic acids and reactive dyes. Cellulose Chemistry and Technology[J].1998,32, (5-6):483-495.
[85]Dong W, Xu J, Huang J. Pore structure characterization of cotton fiber by nitrogen adsorption. Journal of Textile Research[J].2007,28, (6):5-7.
[86]张月华,徐安英.蚕丝纤维超细结构的研究.国外丝绸[J].2003,(6)：1,2,40.
[87]Kim S H, Nam Y S, Lee T S, et al. Silk fibroin nanofiber. Electrospinning, properties, and structure. Polymer Journal[J].2003,35, (2):185-190.
[88]池海涛,李宏伟,陈英.羊毛染整加工中低温等离子体技术应用现状,第七届功能性纺织品及纳米技术研讨会论文集[C].2007：pp 136-138.
[89]Ho Y S, McKay G. Pseudo-second order model for sorption processes. Process Biochemistry[J].1999,34, (5):451-465.
[90]Chairat M, Rattanaphani S, Bremner J B, et al. Adsorption kinetic study of lac dyeing on cotton. Dyes and Pigments[J],2008,76, (2):435-439.
[91]Dogan M, Ozdemir Y, Alkan M. Adsorption kinetics and mechanism of cationic methyl violet and methylene blue dyes onto sepiolite. Dyes and Pigments[J].2007,75: 701-713.
[92]Dogan M, Alkan M. Adsorption kinetics of methyl violet onto perlite. Chemosphere[J]. 2003,50, (4):517-528.
[93]Ozcan A, Oncu E M, Ozcan A S. Kinetics, isotherm and thermodynamic studies of adsorption of Acid Blue 193 from aqueous solutions onto natural sepiolite. Colloids and Surfaces a-Physicochemical and Engineering Aspects[J].2006,277, (1-3): 90-97.
[94]Nollet H, Roels M, Lutgen P, et al. Removal of PCBs from wastewater using fly ash. Chemosphere[J].2003,53, (6):655-665.
[95]Chairat M, Rattanaphani S, Bremner J B, et al. An adsorption and kinetic study of lac dyeing on silk. Dyes and Pigments[J].2005,64, (3):231-241.
[96]Ghiaci M, Kalbasi R J, Abbaspour A. Adsorption isotherms of non-ionic surfactants on Na-bentonite (Iran) and evaluation of thermodynamic parameters. Colloids and Surfaces a-Physicochemical and Engineering Aspects [J].2007,297, (1-3):105-113.
[97]Kweon H, Ha H C, Um I C, et al. Physical properties of silk fibroin/chitosan blend films. Journal of Applied Polymer Science[J].2001,80, (7):928-934.
[98]宋心远,沈煜如.活性染料染色的理论和实践[M].北京：纺织工业出版社,1991.
[99]黄旭明,金雅,蔡再生.液体活性染料的水解性分析及水解控制.纺织科技进展[J].2005,(6)：17-19.
[100]何海兰.染料[M].北京：化学工业出版社,2004.
[101]Hunger K. Industrial dyes:chemistry, properties, applications[M]. WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim,2003.
[102]Kabra R, Parab A. Formaldehyde free low temperature-cure cross-linking agent. Colourage[J].2004,51, (11):41-43.
[103]罗巨涛,陈利丽,宋金星.全棉细平布抗皱整理.印染[J].2006,32,(22)：23-26.
[104]Schramm C, Vukusic S B, Katovic D. Non-formaldehyde durable press finishing of dyed fabrics:evaluation of cotton-bound polycarboxylic acids. Coloration Technology[J].2002,118, (5):244-249.