摘要
超临界CO_2染色技术具有染色时间短、效果好、低污染等传统水染工艺无法比拟的优点,是一种新型的“绿色”染色技术。染料在超临界CO_2中的溶解度与染色效果有直接的关系,添加共溶剂可望改善染色的效果。
本文选用乙醇和水作为共溶剂,在自行研制的超临界CO_2染色装置中,采用分散红54分别在添加和未添加共溶剂的超临界CO_2中对涤纶织物进行了染色实验,染色温度范围为70-120℃,压力范围为14-24 MPa。
实验结果表明,采用分散红54在本实验装置中对涤纶染色60 min即可达到上染平衡。纯SCCO_2体系中,分散红54在涤纶中的上染量随着温度的升高而增大。上染量随压力变化的趋势分两种情况:低温时,上染量随着压力的增加变化不大,温度较高时则随着压力升高而显著增大,22 MPa左右达到最大值。
共溶剂对染色效果有着显著的影响。低温(70℃)添加共溶剂能有效提高染料在织物中的上染量,乙醇的效果要好于水。随着温度的升高,共溶剂效应逐渐减弱,高温(110℃)添加乙醇,上染量基本不再增加,添加水则反而降低染料的上染量。
分散红54在织物与超临界CO_2间的分配系数随着温度和压力的升高而增大。低温添加共溶剂有助于提高染料的分配系数,但随着温度的升高,共溶剂的存在将越来越有利于染料朝流体相分配,温度越高,分配系数下降的幅度越大。
采用“卷层法”对超临界CO_2和超临界CO_2/共溶剂混合体系中染料在涤纶织物中的扩散情况进行了考察,并采用染色——扩散模型研究了染料在涤纶织物中扩散过程,发现温度升高,染料的上染速率和扩散速率均增加,但上染速率的增加幅度要大于扩散速率,从而导致染料向涤纶内部的扩散较浅。添加共溶剂将有助于染料在织物中的扩散。
Compared with traditional dyeing process, as an innovative and“green”technology, supercritical carbon dioxide dyeing has many advantages such as less dyeing time, good dyeing effect and less pollution. Dye solubilities in supercritical carbon dioxide are important to the dye uptake on the fabric and the addition of cosolvent in the supercritical carbon dioxide can improve the dyeing effect. A flow-type dyeing apparatus was employed to dye terylene fabric with disperse red 54 in supercritical carbon dioxide with and without ethanol or water as cosolvent at temperature rage from 70 to 120℃and pressure from 14 to 24 MPa.
The results revealed that dyeing for 60 min can ensure the dyeing equilibrium on the terylene fabric. In pure supercritical carbon dioxide dyeing system, the dye uptake increased with temperature and pressure, the maximum uptake appeared at 22 MPa when the temperature was high, but the changes in dye uptake were not obvious with pressure when the temperature was relatively low.
The dye uptake was found significantly affected by the cosolvent. The addition of cosolvent would greatly enhance the dye uptake at low temperature and ethanol was more effective than water. The cosolvent effect on dye uptake decreased with increasing temperature. When the temperature was relatively high, adding ethanol would’t help to increase the dye uptake. Moreover adding water would even lead to a decrease in dye uptake at the same condition.
The partition coefficients of disperse red 54 between the fabric and supercritical carbon dioxide rose with the increase of temperature or pressure and also increased with the addition of cosolvent at low temperature. But the presence of cosolvent favours the dye partition towards the fluid phase and lead to the big decrease of the partition coefficients at higher temperature.
The“film roll method”was used to study the behavior of dye permeating terylene fabric in supercritical carbon dioxide with and without cosolvent. The homogenous reaction and diffusion model was employed to study the dye duffusion in the terylene fabric. The results indicated that the dyeing and diffusion rate of dye both increased with increasing temperature and the increase of dyeing rate was bigger than that of diffusion rate, which led to a week diffusion in the fabric.The diffusion was effectively enhanced by the presence of cosolvent.
引文
[1]姜方新,兰尧中.印染废水处理技术研究进展[J].云南师范大学学报, 2002, 22(2): 24-27.
[2]黄猛.我国绿色纺织品的现状及发展趋势[J].棉纺织技术, 2000, (2): 31-35.
[3] Kazarian S G, Vincent M F, West B L, et al. Partitioning of solutes and cosolvents between supercritical CO_2 and polymer phases[J]. Journal of Supercritical Fluids, 1998, 13(1-3): 107-112.
[4] Knittel D, Saus W, Schollmeyer E. Application of supercritical carbon dioxide in finishing processes[J]. Journal of the Textile Institute, 1993, 84(4): 534-552.
[5] Muthukumaran P, Gupta R B, Sung H D, et al. Dye solubility in supercritical carbon dioxide. Effect of hydrogen bonding with cosolvents[J]. Korean Journal of Chemical Engineering, 1999, 16(1): 111-117.
[6] Bae H K, Jeon J H, Lee H. Influence of co-solvent on dye solubility in supercritical carbon dioxide[J]. Fluid Phase Equilibria, 2004, 222: 119-125.
[7] Tsai C C, Lin H M, Lee M J. Solubility of disperse yellow 54 in supercritical carbon dioxide with or without cosolvent[J]. Fluid Phase Equilibria, 2007, 260: 287-294.
[8] Tsai C C, Lin H M, Lee M J. Solubility of CI Disperse Violet 1 in supercritical carbon dioxide with or without cosolvent[J]. Journal of Chemical and Engineering Data, 2008, 53(9): 2163-2169.
[9] Saus W, Knittel D, Schollmeyer E. Dyeing of textiles in supercritical carbon-dioxide[J]. Textile Research Journal, 1993, 63(3): 135-142.
[10] Gebert B, Saus W, Knittel D, et al. Dyeing natural fibers with disperse dyes in supercritical carbon-dioxide[J]. Textile Research Journal, 1994, 64(7): 371-374.
[11] Knittel D, Saus W, Schollmeyer E. Water-free dyeing of textile accessories using supercritical carbon dioxide[J]. Indian Journal of Fibre & Textile Research, 1997, 22(3): 184-189.
[12] Sicardi S, Frigerio M A. Method of dyeing natural fibres with a dyeing medium compromising supercritical carbon dioxide[P]. Italy: WO01/004410A1, 2001-01-18.
[13]解谷声.超临界二氧化碳流体的染色加工[J].辽宁丝绸, 2003, (4): 33-37.
[14] Chang K H, Bae H K, Shim J J. Dyeing of PET textile fibers and films in supercritical carbon dioxide[J]. Korean Journal of Chemical Engineering, 1996, 13(3): 310-316.
[15] Banchero M, Ferri A, Manna L. The phase partition of disperse dyes in the dyeing of polyethylene terephthalate with a supercritical CO_2/methanol mixture[J]. Journal of Supercritical Fluids, 2009, 48(1): 72-78.
[16]黄振仁,廖传华.超临界CO_2流体萃取技术[M].北京:化学工业出版社, 2004. 15.
[17]朱自强.超临界流体技术[M].北京:化学工业出版社, 2000. 409-414.
[18]张镜澄.超临界流体萃取[M].北京:化学工业出版社, 2000. 6-17.
[19]俞成丙,吴文华.染料在共混丙纶中的吸附和扩散[J].中国纺织大学学报, 2000, 26(3): 102-105.
[20] Lin H M, Liu C Y, Cheng C H, et al. Solubilities of disperse dyes of blue 79, red 153, and yellow 119 in supercritical carbon dioxide[J]. Journal of Supercritical Fluids, 2001, 21(1): 1-9.
[21] Schnitzler J V, Eggers R. Mass transfers in polymers in a supercritical CO_2-atmosphere[J]. Journal of Supercritical Fluids, 1999, 16(1): 81-92.
[22]高淑珍,赵珍.生态染整技术[M].北京:化学工业出版社, 2003. 242-268.
[23] Berens A R. Transport of Plasticizing Penetrants in Glassy Polymers[A]. Koros W J. ACS Symposium Seres[C]. USA: 1990. 92.
[24] Tang M, Du T B, Chen Y P. Sorption and diffusion of supercritical carbon dioxide in polycarbonate[J]. Journal of Supercritical Fluids, 2004, 28(2-3): 207-218.
[25]罗巨涛.超临界CO_2在印染中的应用[J].现代纺织技术, 1995, (3): 42-45.
[26] Drew M J, Jordan C. The effect of supercritical CO_2 dyeing conditions of the morphology of polyester fibers[J]. Textile Chemist and Colorist, 1998, 30(6): 13-20.
[27] Min J, Park M, Jeon J, et al. Dye uptake of poly fiber in supercritical fluids[J]. Hwahak Konghak, 2004, 42(2): 213-216.
[28]蔚立玉,林春绵,王军良,等.涤纶织物在超临界二氧化碳中的染色实验[J].纺织学报, 2003, 24(6): 581-582.
[29]李志义,孟庭宇,张晓东,等.利用分散蓝60对涤纶进行超临界流体染色的实验研究[J].高校化学工程学报, 2006, 20(2): 203-207.
[30]鲍萍,戴瑾瑾.超临界CO_2流体流速对涤纶织物染色的影响[J].印染, 2004, (18): 13-14.
[31]宋赛赛,林春绵,周红艺,等.涤纶织物的预处理对超临界条件下分散染料染色效果的影响[J].浙江工业大学学报, 2006, 34(4): 377-380.
[32]张珍,余志成,林鹤鸣.超临界二氧化碳对涤纶纤维结构和性能的影响[J].丝绸, 2004, (3):34-36.
[33]龙家杰,陆同庆,张培群,等.超临界CO_2流体中涤纶织物的染色研究[J].毛纺科技, 2005, (9): 10-16.
[34]周明强,李青.超临界CO_2中分散红对超细涤纶的染色研究[J].染整技术, 2007, 29(10): 1-4.
[35] Jun J H. Effects of pressure and temperature on dyeing acrylic fibres with basic dyes in supercritical carbon dioxide[J]. Coloration Technology, 2005, 121(1): 25-28.
[36]文会兵,戴瑾瑾.超临界CO_2分散染料染聚乳酸纤维的研究[J].印染, 2006, (23): 11-13.
[37]杨文芳,王雷.超临界CO_2在PLA纤维染色中的应用[J].纺织学报, 2007, (10): 59-63.
[38] Schmidt A, Bach E, Schollmeyer E. The dyeing of natural fibers with reactive disperse dyes in supercritical carbon dioxide[J]. Dyes and Pigments, 2003, 56(1): 27-35.
[39] Bach E, Cleve E, Schollmeyer E. Past, present and future of supercritical fluid dyeing technology-an overview[J]. Rev.Prog.Color, 2002, 32: 88-101.
[40]陈颖.天然纤维的超临界CO_2染色[J].印染, 2003, (1): 44-45.
[41] Giehl A, Schafer K, Hocker H. Dyeing wool without water[J]. DWI Reports, 2000, 123: 460-465.
[42] Schollmeyer E, Knittel D. Dyeing process[P]. Germany: DE 3906724, 1990-09-13.
[43] Asozcan. Dyeing of Modified Cotton Fabrics With Disperse Dyes from Supercritical Carbon Dioxide[J]. Journal of the Society of Dyers and Colourists, 1998, 114(5-6): 169-173.
[44] Draper S L, Montero, Smith B. Solubility relationships for disperse dyes in supercritical carbon dioxide[J]. Dyes and Pigments, 2000, 45(3): 177-183.
[45]刘志伟,郑来九.羊毛织物超临界二氧化碳染色的研究[J].毛纺科技, 2005, (3): 9-12.
[46]郑来九,刘晶,马东霞.纤维素纤维超临界CO_2染色机理研究[J].纺织学报, 2004, 25(2): 11-13.
[47] Rossbach V, Hudson A. Newdyes used for dyeing.wool, silk, polyamide or cotton are azo, anthraquinone, quinizarin, coumarin or indigo dyes with sulfonyl, sulfonyl chloride, or sulfonamide group(s)[P]. Germany: DE 19937328, 2000-03-02.
[48] Holme I. New dyes for supercritical fluid dyeing[J]. International Dyer, 1999, 184(5): 27-30.
[49] Giehl A, Schafer K. Dyeing wool without water-The synthesis of fiber reactive disperse dyes for the coloration of wool from supercritical carbon dioxide[A]. 10th International Wool TextileResearch Conference Proceedings[C]. 2000. 356-360.
[50]李青,周明强,廖青.超临界CO_2染色技术在毛纺中的应用[J].毛纺科技, 2007, (8): 57-59.
[51]冉瑞龙,张莉莉,龙家杰,等.天然纤维在超临界CO_2流体中的染色研究[J].蚕学通讯, 2006, 26(2): 5-9.
[52]张晨,吴赞敏,张利贵.羊毛纤维的超临界天然染料染色研究[J].天津工业大学学报, 2007, 26(2): 47-49.
[53]侯爱芹,戴瑾瑾.二氧化碳在纺织领域应用的研究进展[J].纺织导报, 2004, (2): 76-78.
[54]何中琴.用超临界CO_2的无水染色法[J].印染译丛, 2000, 6(3): 51-57.
[55] Wagner B, Kautz C B, Schneide G M. Investigations on the solubility of anthraquinone dyes in supercritical carbon dioxide by a flow method[J]. Fluid Phase Equilibria, 1999, 158: 707-712.
[56]蒋勇,董擎之,杨玉英.聚对苯二甲酸丁二酯纤维在超临界二氧化碳介质中的染色研究[J].合成纤维工业, 2003, 12(6): 18-20.
[57] Bao P, Dai J J. Relationships between the Solubility of C.I.Disperse Red 60 and Uptake on PET in Supercritical CO_2[J]. Journal of Chemical and Engineering Data, 2005, 50(3): 838-842.
[58] Draper S L, Montero, Smith B. Solubility relationships for disperse dyes in supercritical carbon dioxide[J]. Dyes and Pigments, 2000, 45: 177-183.
[59] Guzel B, Akgerman A. Solubility of Disperse and Mordant Dyes in Supercritical CO_2[J]. Journal of Chemical and Engineering Data, 1999, 44(1): 83-85.
[60]鲁雪燕,徐明仙,林春绵,等.分散红343和分散蓝366及其混合物在超临界CO_2中的溶解度测定与关联[J].高校化学工程学报, 2009, 23(4): 553-558.
[61] Gordillo M D, Pereyra C, Martinez E J. Measurement and correlation of solubility of Disperse Blue 14 in supercritical carbon dioxide[J]. Journal of Supercritical Fluids, 2003, 27(1): 31-37.
[62] Coimbra P, Gil M H, Duarte C M M. Solubility of spiroindolinonaphthoxazine photochromic dye in supercritical carbon dioxide:Experimental determination and correlation[J]. Fluid Phase Equibria, 2005, 238(1): 120-128.
[63] Huang Z, Guo Y H, Sun G B, et al. Representing dyestuff solubility in supercritical carbon dioxide with several density-based correlations[J]. Fluid Phase Equilibria, 2005, 236(1-2): 136-145.
[64] Kazarian S G, Brantley N H, Eckert C A. Dyeing to be clean: use supercritical carbon dioxide[J]. Chemtech, 1999, 29(7): 36-41.
[65] Montero G A, Smith C B, Hendrix W A. Supercritical Fluid Technology in Textile Processing: An Overview[J]. Industrial & Engineering Chemistry Research, 2000, 39(12): 4806-4812.
[66] Tabata I, Lyu J, Cho S. Relationship between the solubility of disperse dyes and the equilibrium dye adsorption in supercritical fluid dyeing[J]. Coloration Technology, 2001, 117(6): 346-351.
[67] Shim J J, Park S, Kim C H. Polymer Sorption of Disperse Dyes in Supercritical Carbon Dioxide[A]. Proceedings of the 5th International Symposium on Supercritical Fluids[C]. USA: 2000.
[68] Sicardi S, Manna L, Banchero M. Comparison of dye diffusion in poly(ethylene terephthalate) films in the presence of a supercritical or aqueous solvent[J]. Industrial and Engineering Chemistry Research, 2000, 39(12): 4707-4713.
[69] Oezcan A. Adsorption behavior of a disperse dye on polyester in supercritical carbon dioxide[J]. Journal of Supercritical Fluids, 2005, 35(2): 133-139.
[70] Fleming O S, Stepanek F, Kazarian S G. Dye diffusion in polymer films subjected to supercritical CO_2: Confocal Raman microscopy and modeling[J]. Macromolecular Chemistry and Physics, 2005, 206(11): 1077-1083.
[71] Fleming O S, Kazarian S G, Bach E, et al. Confocal Raman study of poly(ethylene terephthalate) fibres dyed in supercritical carbon dioxide: dye diffusion and polymer morphology[J]. Polymer, 2005, 46(9): 2943-2949.
[72] Banchero M, Ferri A, Manna L, et al. Solubility of disperse dyes in supercritical carbon dioxide and ethanol[J]. Fluid Phase Equilibria, 2006, 243(1-2): 107-114.
[73] Giehl A, Gieβann M, Schafer K, et al. Dyeing wool without water—possibilities and limits of supercritical CO_2[A]. Wenclawiak B, Padberg S. 4th International Symposium Extraction for Sample Preparation-SFE-(X)SE-SPME—Book of abstracts[C]. USA: 1999. 29-30.
[74]马渝茳.纺织品染色[M].北京:中国纺织出版社, 2004. 352-354.
[75]肖新亮,古风才,赵桂英.实用分析化学(修订版)[M].天津:天津大学出版社, 2000. 209-210.
[76] Hirogaki K, Tabata I, Hisada K, et al. An investigation of the interaction of supercritical carbon dioxide with poly(ethylene terephthalate) and the effects of some additive modifiers on the interaction[J]. Journal of Supercritical Fluids, 2005, 36(2): 166-172.
[77] Montero G A, Butcher D L, Hendrix W A. Controlling the Mechanism of Dye Migration inSupercritical CO_2 Dyeing Processes. Effect of Dye-Bath Flow and Bath Turns on Dyeing Uniformity[J]. Confidential Research Note, 1999.
[78] Chrastil J. Solubility of solids and liquids in supercritical gases[J]. Journal of Physical Chemistry, 1982, 56(15): 3016-3021.
[79] Gonzalez J C, Vieytes M R, Botana A M, et al. Modified mass action law-based model to correlate the solubility ofsolids and liquids in entrained supercritical carbon dioxide[J]. Journal of Chromatography A, 2001, 910(1): 119-125.
[80]袁一.化学工程师手册[M].北京:机械工业出版社, 2000. 84-87.
[81]陈钟秀,顾飞燕,胡望月.化工热力学(第二版)[M].北京:化学工业出版社, 2000. 4-11.
[82] Sung H D, Shim J. Solubility of C.I.disperse red 60 and C.I.disperse blue 60 in supercritical carbon dioxide[J]. Journal of Chemical and Engineering Data, 1999, 44(5): 985-989.
[83]金咸穰.染整工艺实验[M].北京:中国纺织出版社, 1987. 83-87.
[84] Sicardi S, Manna M, Banchero M. Diffusion of disperse dyes in PET films during impregnation with a supercritical fluid[J]. Journal of Supercritical fluids, 2000, 17(2): 187-194.
[85] Crank J, Park G S. Diffusion in polymers[M]. London: Academic Press, 1968.
[86]许保玖,龙腾锐.当代给水与废水处理原理[M].北京:高等教育出版社, 2000. 60-64.
[87] Kazarian S G, Brantley N H, West B L, et al. In situ spectroscopy of polymers subjected to supercritical CO_2: Plasticization and dye impregnation[J]. Applied Spectroscopy, 1997, 51(4): 491-494. .
