溶解性可控的聚丙烯酰胺-co-乙烯胺型交联染料的合成及性能研究
|
摘要
本文设计合成了一系列溶解性可控的聚丙烯酰胺-co-乙烯胺型交联染料,详细研究了染料的分子结构中氨基与磺酸基比例、染料浓度以及电解质等对该类染料的溶解性能的影响规律,并将其用于指导染料在棉纤维上的染色研究。此类大分子染料与棉纤维之间通过交联剂发生化学交联反应,实现染料在棉纤维上高的染色固色率
论文以低分子量的聚丙烯酰胺为原料,通过对Hofmann降解反应的研究,证明在合成中低氨基含量的聚丙烯酰胺-co-乙烯胺时,碱用量可降至聚丙烯酰胺摩尔量的3.5倍,并在此碱量下得到了氨基含量低于80%的聚丙烯酰胺-co-乙烯胺的可控合成线性关系式。利用红外、13C NMR和元素分析对产物结构进行了表征。以此线性关系式为依据,合成了氨基含量为75%的聚丙烯酰胺-co-乙烯胺,作为大分子交联染料的主链。
以三聚氯氰和氨基芳磺酸类化合物为原料,设计合成了10个一氯均三嗪型芳磺酸衍生物3a～3j。将3a～3j接枝到聚丙烯酰胺-co-乙烯胺中,合成了10个含芳磺酸的聚丙烯酰胺-co-乙烯胺,即大分子中间体P-3a-P-3j。当取代度为33.3%以下时,反应效率92%以上。利用红外、电喷雾质谱和薄层色谱证明了产物结构正确。研究了大分子中间体的结构与溶液性能的关系,结果表明,其溶液性能主要受其分子结构中的氨基与磺酸基比例的影响。当氨基与磺酸基比例为1.4左右时,其溶解所需的pH值在8.0左右,氨基与磺酸基比例每降低1.3～1.5倍,其溶解所需的pH值降低约2-3。
在大分子中间体的溶液性能研究基础上,进行分子结构设计来匹配最佳偶合反应条件。选择取代度为20%以上的P-3j作为大分子偶合组分,与小分子重氮组分反应,合成了6支红色大分子染料Pd-R-a-Pd-R-f。利用红外和可见光光谱表征了合成产物。
同样,依据大分子中间体的溶液性能研究结果,论文还设计合成了含不同磺酸基个数的一氯均三嗪型发色体d-Y-4a-d-B-4j。并通过接枝法合成了10支分子结构中氨基与磺酸基比例可控的大分子染料Pd-Y-4a-d-B-4j,当染料的取代度在26.7%以下时,反应效率96%以上。利用红外、电喷雾质谱和薄层色谱证明了产物结构正确。以黄色大分子染料Pd-Y-4a-Pd-Y-4d为例,研究了该类染料的溶液性能,结果表明,在20～50g/L的浓度下,取代度为25.6%的大分子黄色染料中,发色体中磺酸基个数从1增加到4时,其溶解所需的pH值可从12降至7.5左右。
将该类染料的溶液性能研究结果用于指导染料的染色过程。采用轧染染色工艺,并通过交联剂M固色,该类染料在棉纤维上的固色率达到96%左右,干湿摩擦牢度为3-4级,水洗牢度4-5级。黄色、蓝色和红色染料的日晒牢度分别为4-5级、6级和2-3级。
In this thesis, a series of poly(acrylamide-co-vinylamine) crosslinking dyes with controllable solubility for cotton fibers were designed and synthesized. The effects of the ratio of amino to sulfonate groups in these dyes, concentration of dye solution and content of salt on solution properties of these dyes were studied in detail. The solution properties of these dyes were used to provide guidance in their dyeing process. High fixation could be achieved through covalent bonds between these dyes and cotton fibers by crosslinking agent.
Poly(acrylamide-co-vinylamine) with middle and low amino content was synthesized by Hofmann reaction of polyacrylamide with low molecular weight, in which NaOH dosage was only3.5times of that of polyacrylamide. The linear equation of controllable synthesis of poly(acrylamide-co-vinylamine) in which the amino content is below80%at this low NaOH dosage was obtained. The structure of the product was characterized by IR,13C-NMR and elemental analysis. The poly(acrylamide-co-vinylamine) with75%amino content which was used as main train of the macromolecular dyes was obtained under the directions of the linear equation.
Ten aryl sulfonate derivatives containing monochlorotriazine group3a-3j were designed and prepared using cyanuric chloride and aryl sulfonate as raw materials. Ten macromolecular intermediates P-3a-P-3j were synthesized by grafting reaction of poly(acrylamide-co-vinylamine) with aryl sulfonate derivatives3a-3j. When the degree of substitution (DS) of the macromolecular intermediate is below33.3%, the grafting efficiency is above92%. The structures of the synthesized products were confirmed by IR, ESI-MS and thin layer chromatography (TLC). The relationship between the structures of the macromolecular intermediates and their solution properties was investigated. The results showed that their solution properties were influenced mainly by the ratio of amino to sulfonate groups in their structures. They can be soluble at about pH8.0when their ratio of amino to sulfonate groups is1.4, and this ratio decreases by1.3～1.5times, the soluble pH of the macromolecular intermediate decreases by2-3.
Based on the studies of the solution properties of the macromolecular intermediates, the structures of the macromolecular intermediates were designed to match the optimal conditions in the couling reaction. Using P-3j with the DS above20%as macromolecular coupling component to react with diazonium salt, six macromolecular red dyes Pd-R-a～Pd-R-f were prepared. The structures of the synthesized dyes were confirmed by IR and visable spectrum.
According to the results of the solution properties of the macromolecular intermediates, chromophores containing monochlorotriazine group and different numbers of sulfonate groups (d-Y-4a～d-B-4j) were designed and synthesized. Ten macromolecular dyes Pd-Y-4a～Pd-B-4j with controllable ratio of amino and sulfonate groups were synthesized by grafting reaction of poly(acrylamide-co-vinylamine) with these chromophores. When the DS of the macromolecular dyes is below26.7%, the grafting efficiency is above96%. The structures of the synthesized products were confirmed by IR, ESI-MS and thin layer chromatography (TLC). Taking macromolecular yellow dyes for examples, solution properties of these dyes were studied. The results showed that at the concentration of20～50g/L and DS of25.6%, when the number of sulfonate group in the chromophore increases from1to4, the pH value in which the macromolecular yellow dyes can be soluble decreased from12to7.5.
The results of the solution properties of the macromolecular dyes were used to provide guidance in the dyeing process. The dyeing characteristics of these dyes were studies through padding operation. Using crosslinker M as a fixation agent, the fixation of these dyes on cotton fibers reached about96%. Dry and web rub fastness was both3-4grade, and wash fastness was4～5grade. The light fastness of yellow, blue and red dyes on cotton was4-5grade,6grade and2～3grade, respectively.
论文以低分子量的聚丙烯酰胺为原料,通过对Hofmann降解反应的研究,证明在合成中低氨基含量的聚丙烯酰胺-co-乙烯胺时,碱用量可降至聚丙烯酰胺摩尔量的3.5倍,并在此碱量下得到了氨基含量低于80%的聚丙烯酰胺-co-乙烯胺的可控合成线性关系式。利用红外、13C NMR和元素分析对产物结构进行了表征。以此线性关系式为依据,合成了氨基含量为75%的聚丙烯酰胺-co-乙烯胺,作为大分子交联染料的主链。
以三聚氯氰和氨基芳磺酸类化合物为原料,设计合成了10个一氯均三嗪型芳磺酸衍生物3a～3j。将3a～3j接枝到聚丙烯酰胺-co-乙烯胺中,合成了10个含芳磺酸的聚丙烯酰胺-co-乙烯胺,即大分子中间体P-3a-P-3j。当取代度为33.3%以下时,反应效率92%以上。利用红外、电喷雾质谱和薄层色谱证明了产物结构正确。研究了大分子中间体的结构与溶液性能的关系,结果表明,其溶液性能主要受其分子结构中的氨基与磺酸基比例的影响。当氨基与磺酸基比例为1.4左右时,其溶解所需的pH值在8.0左右,氨基与磺酸基比例每降低1.3～1.5倍,其溶解所需的pH值降低约2-3。
在大分子中间体的溶液性能研究基础上,进行分子结构设计来匹配最佳偶合反应条件。选择取代度为20%以上的P-3j作为大分子偶合组分,与小分子重氮组分反应,合成了6支红色大分子染料Pd-R-a-Pd-R-f。利用红外和可见光光谱表征了合成产物。
同样,依据大分子中间体的溶液性能研究结果,论文还设计合成了含不同磺酸基个数的一氯均三嗪型发色体d-Y-4a-d-B-4j。并通过接枝法合成了10支分子结构中氨基与磺酸基比例可控的大分子染料Pd-Y-4a-d-B-4j,当染料的取代度在26.7%以下时,反应效率96%以上。利用红外、电喷雾质谱和薄层色谱证明了产物结构正确。以黄色大分子染料Pd-Y-4a-Pd-Y-4d为例,研究了该类染料的溶液性能,结果表明,在20～50g/L的浓度下,取代度为25.6%的大分子黄色染料中,发色体中磺酸基个数从1增加到4时,其溶解所需的pH值可从12降至7.5左右。
将该类染料的溶液性能研究结果用于指导染料的染色过程。采用轧染染色工艺,并通过交联剂M固色,该类染料在棉纤维上的固色率达到96%左右,干湿摩擦牢度为3-4级,水洗牢度4-5级。黄色、蓝色和红色染料的日晒牢度分别为4-5级、6级和2-3级。
In this thesis, a series of poly(acrylamide-co-vinylamine) crosslinking dyes with controllable solubility for cotton fibers were designed and synthesized. The effects of the ratio of amino to sulfonate groups in these dyes, concentration of dye solution and content of salt on solution properties of these dyes were studied in detail. The solution properties of these dyes were used to provide guidance in their dyeing process. High fixation could be achieved through covalent bonds between these dyes and cotton fibers by crosslinking agent.
Poly(acrylamide-co-vinylamine) with middle and low amino content was synthesized by Hofmann reaction of polyacrylamide with low molecular weight, in which NaOH dosage was only3.5times of that of polyacrylamide. The linear equation of controllable synthesis of poly(acrylamide-co-vinylamine) in which the amino content is below80%at this low NaOH dosage was obtained. The structure of the product was characterized by IR,13C-NMR and elemental analysis. The poly(acrylamide-co-vinylamine) with75%amino content which was used as main train of the macromolecular dyes was obtained under the directions of the linear equation.
Ten aryl sulfonate derivatives containing monochlorotriazine group3a-3j were designed and prepared using cyanuric chloride and aryl sulfonate as raw materials. Ten macromolecular intermediates P-3a-P-3j were synthesized by grafting reaction of poly(acrylamide-co-vinylamine) with aryl sulfonate derivatives3a-3j. When the degree of substitution (DS) of the macromolecular intermediate is below33.3%, the grafting efficiency is above92%. The structures of the synthesized products were confirmed by IR, ESI-MS and thin layer chromatography (TLC). The relationship between the structures of the macromolecular intermediates and their solution properties was investigated. The results showed that their solution properties were influenced mainly by the ratio of amino to sulfonate groups in their structures. They can be soluble at about pH8.0when their ratio of amino to sulfonate groups is1.4, and this ratio decreases by1.3～1.5times, the soluble pH of the macromolecular intermediate decreases by2-3.
Based on the studies of the solution properties of the macromolecular intermediates, the structures of the macromolecular intermediates were designed to match the optimal conditions in the couling reaction. Using P-3j with the DS above20%as macromolecular coupling component to react with diazonium salt, six macromolecular red dyes Pd-R-a～Pd-R-f were prepared. The structures of the synthesized dyes were confirmed by IR and visable spectrum.
According to the results of the solution properties of the macromolecular intermediates, chromophores containing monochlorotriazine group and different numbers of sulfonate groups (d-Y-4a～d-B-4j) were designed and synthesized. Ten macromolecular dyes Pd-Y-4a～Pd-B-4j with controllable ratio of amino and sulfonate groups were synthesized by grafting reaction of poly(acrylamide-co-vinylamine) with these chromophores. When the DS of the macromolecular dyes is below26.7%, the grafting efficiency is above96%. The structures of the synthesized products were confirmed by IR, ESI-MS and thin layer chromatography (TLC). Taking macromolecular yellow dyes for examples, solution properties of these dyes were studied. The results showed that at the concentration of20～50g/L and DS of25.6%, when the number of sulfonate group in the chromophore increases from1to4, the pH value in which the macromolecular yellow dyes can be soluble decreased from12to7.5.
The results of the solution properties of the macromolecular dyes were used to provide guidance in the dyeing process. The dyeing characteristics of these dyes were studies through padding operation. Using crosslinker M as a fixation agent, the fixation of these dyes on cotton fibers reached about96%. Dry and web rub fastness was both3-4grade, and wash fastness was4～5grade. The light fastness of yellow, blue and red dyes on cotton was4-5grade,6grade and2～3grade, respectively.
引文
[1]侯毓汾,朱振华,王任之.染料化学[M].北京：化学工业出版社,1994.
[2]中国染料工业协会.中国染料工业“十二五”发展规划纲要(一)[J].印染,2011,18：47-50.
[3]Lewis D. M. Coloration in the next century[J]. Review of Progress in Coloration and Related Topics,1999,29:23-28.
[4]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[J].精细化工,2008,25(6)：595-599.
[5]Egger W B, Kissling B, Robison T. Economic durable cellulosics dyeings with reactant-fixable dyes[J]. American Dyestuff Reporter,1982,71(9):55-61.
[6]Lutzel G. Dye fixation by means of polyfunctional crosslinking agents[J]. Journal of the Society of Dyers and Colourists,1966,82 (8):293-299.
[7]侯文杰,蒋嵩,张淑芬,等.交联染料的研究进展[J].染料与染色,2004,41(3)：129-130.
[8]董志芳,陆琼.新型交联染料染色体系的研究[J].染料工业,1987,2：37-44.
[9]Lei X P, Lewis D M, Wang Y N. The production of level fast dyeings on wool with nucleophilic dyes and a crosslinking agent[J]. Journal of the society of dyers and colorist,1992,108(9):383-387.
[10]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[J]. Journal of the Society of Dyers and Colourists,1995,111(12):385-390.
[11]章杰.交链染料的研究-棉用染料的一种创新[J].染料工业,1987,6：1-9.
[12]周璐瑛.交联染色体系的染整一步法研究[J].染料工业,1989,5：33-37.
[13]Hensel H R, Lutzel G. New cotton dyes[J]. Angewandte Chemie International Edition, 1965,4(4):312-321.
[14]章杰.交链染料的色变现象分析[J].印染,1985,4：20-22.
[15]Lei X P, Lewis D M, Shen X M, et al. Crosslinking nucleophilic dyes on wool[J].Dyes and Pigments,1996,30(4):271-281.
[16]应燮元.新型交联染料的应用[J].上海染料,1987,4：17-22.
[17]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.
[18]李英玲.多胺型和多羧酸型大分子染料的合成及应用：(博士学位论文)[D].大连：大连理工大学,2007.
[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]黄健.聚乙烯胺型可交联高分子染料的合成与应用：(硕士学位论文)[D].大连：大连理工大 学,2005.
[21]刘峰.聚烯丙基胺型高分子染料的合成与应用：(硕士学位论文)[D].大连：大连理工大学,2001.
[22]Phillip E S, Rockville M. Method for dyeing human hair with cationic polymeric dyes. US4182612[P].1980.
[23]Larry B F, Spartanburg. Polymeric anthraquinone derived colorants. US4137243[P].1979.
[24]党喃燕.多胺型交联染料染色性能研究：(博士学位论文)[D].大连：大连理工大学,2010.
[25]David M. K., Thomas E. M. Inter-and intralayer energy transfer in zirconium phosphate-poly(allylamine hydrochloricde) multiplayers:an efficient photon antenna and a spectroscopic rule for self-assembled thin films[J]. Journal of the American Chemical Society,1996,118(17):4222-4223.
[26]Sochi 0.,Takahisa T. Naphthalenesulphonyl groups as fluorescence probs for examining the conformational behavior of polyallylamine[J]. Journal of Photochemistry and Photobiology A:Chemistry,1997,111(1-3):233-239.
[27]Dawson D J, Gless R D, Wingard R E. Poly(vinylamine hydrochloride). Synthesis and utilization for the preparation of water-soluble polymeric dyes[J]. Journal of the American Chemical Society,1976,98(19):5996-6000.
[28]Dawson D J, Otteson K M, Wang P C, et al. Soluble Functional Polymers.2. Utilization of Water-Insoluble Chromophores in Water-Soluble Polymeric Dyes[J]. Macromolecules, 1978,11(2):320-324.
[29]Varnavski 0, Ispasoiu R G, Narewal M, et al. Nonlinear Optical Properties of Water-Soluble Polymeric Dyes with Biological Applications[J]. Macromolecules, 2000,33(11):4061-4068.
[30]Roth I, Spange S. Kinetic studies on the nucleophilic aromatic substitution of fluoronitrobenzene derivatives with polyvinylamine in water mediated by 2,6-0-dimethyl-β-cyclodextrin[J]. Macromolecules,2005,38(24):10034-10041.
.[31] Roth I, Jbarah A A, Holze R, et al.2-Nitro-1,4-Diamino benzene-Functionalized Poly(vinyl amine)s as Water-Soluble UV-Vis-Sensitive pH Sensors[J]. Macromolecular Rapid Communications,2006,27(3):193-199.
[32]Pinschmidt R K. Polyvinylamine at last[J]. Journal of Polymer Science Part A:Polymer Chemistry,2010,48(11):2257-2283.
[33]刑其毅,裴伟伟,徐瑞秋,等.基础有机化学[M].北京：高等教育出版社,2005.
[34]Achari A E, Coqueret X, Lablache-Comb ier A, et al. Preparation of polyvinylamine from polyacrylamide:a reinvestigation of the hofmann reaction[J]. Die Makromolekulare Chemie,1993,194(7):1879-1891.
[35]Tanaka H, Senju R. Preparation of Polyvinylamine by the Hofmann Degration of Polyacrylamide[J]. Bulletin of the Chemical Society of Japan,1976,49(10):2821-2823.
[36]Yamamoto Y, Sefton M V. Surface grafting of poly (ethylene glycol) onto poly(acrylamide-co-vinyl amine) cross-linked films under mild conditions[J]. J Biomater Sci Polym Edn,1998,9(5):427-437.
[37]胡志勇,张淑芬,杨锦宗,等.聚乙烯胺Hofmann降级法合成及其热稳定性研究[J].大连理工大学学报,2002,42(6)：659-662
[38]Lowe A B, McCormick C L. Synthesis and Solution Properties of Zwitterionic Polyraers[J]. Chemical Reviews,2002,102(11):4177-4190.
[39]Zhang Q,Zhang Q F, Zhang S B, et al. Synthesis and characterization of sulfonated poly(aryl ether sulfone) containing pendent quaternary ammonium groups for proton exchange membranes[J]. Journal of Membrane Science,2010,354(1-2):23-31.
[40]An H, Lu C, Wang P, et al. A novel hydrophobically associating polyampholytes of poly(AM/AA/AMQC12):preparation, characterization, and solution properties[J]. Polymer Bulletin,2011,67(1):141-158.
[41]Ho B S,Tan B H, Tan J P K, et al. Inverse Microemulsion Polymerization of Sterically Stabilized Polyampholyte Microgels[J]. Langmuir,2008,24(15):7698-7703.
[42]Bhardwaj Y K, Kumar V, Sabharwal S. Swelling behavior of radiation-polymerized polyampholytic two-component gels:Dynamic and equilibrium swelling kinetics[J]. Journal of Applied Polymer Science,2003,88(3):730-742.
[43]Ji E, Whitten D G, Schanze K S. pH-Dependent Optical Properties of a Poly(phenylene ethynylene) Conjugated Polyampholyte[J]. Langmuir,2010,27(5):1565-1568.
[44]Chen W, Leung V, Kroener H, et al. Polyvinylamine-Phenylboronic Acid Adhesion to Cellulose Hydrogel[J]. Langmuir,2009,25 (12):6863-6868.
[45]Chen W, Chen L, Pelton R. Polyvinylamine Boronate Adhesion to Cellulose Hydrogel[J]. Biomacromolecules,2006,7(3):701-702.
[46]Xiao H, Tao R, Cui W, et al. Solution properties of a novel ampholytic polyphenylene sulfide[J]. Journal of Applied Polymer Science,2012:DOI:10.1002/APP.36809.
[47]Kudaibergenov S E, Ciferri A. Natural and synthetic polyampholytes,2a functions and applications[J]. Macromolecular Rapid Communications,2007,28(20):1969-1986.
[48]Dai S, Ravi P, Tam K C. pH-Responsive polymers:synthesis, properties and applications[J]. Soft Matter,2008,4(3):435-449.
[49]Braun 0, Selb J, Candau F. Synthesis in microemulsion and characterization of stimuli-responsive polyelectrolytes and polyampholytes based on N-isopropylacrylamide [J]. Polymer,2001,42(21):8499-8510.
[50]Iatridi Z.Mattheolabakis G, Avgoustakis K, et al. Self-assembly and drug delivery studies of pH/thermo-sensitive polyampholytic (A-co-B)-b-C-b-(A-co-B) segmented terpolymers[J]. Soft Matter,2011,7(23):11160-11168.
[51]Deng L, Zhai Y, Guo S, et al. Investigation on properties of P((MAA-co-DMAEMA)-g-EG) polyampholyte nanogels[J]. Journal of Nanoparticle Research,2009,11 (2):365-374.
[52]Zha L, Banik B, Alexis F. Stimulus responsive nanogels for drug delivery [J]. Soft Matter, 2011,7 (13):5908-5916.
[53]Du J Z, Sun T M, Song W J, et al. A Tumor-Acidity-Activated Charge-Conversional Nanogel as an Intelligent Vehicle for Promoted Tumoral-Cell Uptake and Drug Delivery[J]. Angewandte Chemie International Edition,2010,49(21):3621-3626.
[54]Xu S M,Zhang S F, Lu R W, et al. Study on adsorption behavior between Cr(VI) and crosslinked amphoteric starch[J]. Journal of Applied Polymer Science,2003,89(1): 263-267.
[55]Rivas B L, Villegas S, Ruf B. Water-insoluble polymers containing amine, sulfonic acid, and carboxylic acid groups:Synthesis, characterization, and metal-ion-retention properties[J]. Journal of Applied Polymer Science,2006,99(6):3266-3274.
[56]Bratskaya S Y, Pestov A V, Yatluk Y G, et al. Heavy metals removal by flocculation/precipitation using N-(2-carboxyethyl)chitosans[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects,2009,339(1-3):140-144.
[57]Copello G J, Diaz L E, Dall'Orto V C. Adsorption of Cd(Ⅱ) and Pb(Ⅱ) onto a one step-synthesized polyampholyte:Kinetics and equilibrium studies[J]. Journal of Hazardous Materials,2012,217-218:374-381.
[58]张凤英,杨光,刘延彪,等.高温高盐油藏用化学驱油剂的研究[J].精细石油化工进展,2005,6(5)：8-12.
[59]张黎明.具有反聚电解质溶液行为的两性聚合物[J].高分子通报,1998(4)：80-85.
[60]Li C, Adamcik J, Zhang A, et al. Twofold pH and temperature stimuli-responsive behaviour in block copolypeptide-decorated single wall carbon nanotubes[J]. Chemical Communications,2011,47(1):262-264.
[61]Lee Y, Geckeler K E. Polyampholyte-Wrapped Carbon Nanotubes:Preparation and Internalization by Embryonic Fibroblast Cells[J]. Macromolecular Rapid Communications, 2011,32(19):1518-1525.
[62]Chen G, Wu G, Wang L, et al. Layer-by-layer assembly of single-charged ions with a rigid polyampholyte[J]. Chemical Communications,2008,15:1741-1743.
[63]Wang X, Zhang L, Wang L, et al. Layer-by-Layer Assembled Polyampholyte Microgel Films for Simultaneous Release of Anionic and Cationic Molecules[J]. Langmuir,2010,26(11): 8187-8194.
[64]Osada Y, Gong J P. Soft and Wet Materials:Polymer Gels[J]. Advanced Materials,1998, 10(11):827-837.
[65]Ezell R G, McCormick C L. Electrolyte-and pH-responsive polyampholytes with potential as viscosity-control agents in enhanced petroleum recovery[J]. Journal of Applied Polymer Science,2007,104(5):2812-2821.
[66]Tan B H, Ravi P, Tan L N, et al. Synthesis and aqueous solution properties of sterically stabilized pH-responsive polyampholyte microgels[J]. Journal of Colloid and Interface Science,2007,309(2):453-463.
[67]Tan B H, Ravi P, Tam K C. Synthesis and Characterization of Novel pH-Responsive Polyampholyte Microgels[J]. Macromolecular Rapid Communications,2006,27(7):522-528.
[68]Xiong Z, Peng B, Han X, et al. Dual-stimuli responsive behaviors of diblock polyampholyte PDMAEMA-b-PAA in aqueous solution[J]. Journal of Colloid and Interface Science,2011,356(2):557-565.
[69]Chen W, Pelton R, Leung V. Solution Properties of Polyvinylamine Derivatized with Phenylboronic Acid[J]. Macromolecules,2009,42(4):1300-1305.
[70]Tanaka H. Hofmann reaction of polyacrylamide:Realtionship between reaction condition and degree of polymerization of polyvinylamine[J]. Journal of Polymer Science:Polymer Chemistry Edition,1979,17(4):1239-1245.
[71]Godbey W T, Wu K K, Mikos A G. Size matters:molecular weight affects the efficiency of poly(ethylenimine) as a gene delivery vehicle[J]. Journal of Biomedical Materials Research,1999,45(3):268-275.
[72]董卫国,徐静,黄俊鹏.氮气吸附法表征棉纤维的孔结构[J].纺织学报,2007,28(6)：5-7.
[73]Kim S H, Nam Y S, Lee T S, et al. Silk Fibroin Nanofiber. Electrospinning, Properties, and Structure[J]. Polymer Journal,2003,35(2):185-190.
[74]张行荣.聚马来酸型染料和羟甲基型大分子染料的设计合成及应用：(博士学位论文)[D].大连：大连理工大学,2011.
[75]候毓芬,程侣伯.活性染料[M].北京：化学工业出版社,1991.
[76]Holcapek M, Jandera P, Prikryl J. Analysis of sulphonated dyes and intermediates by electrospray mass spectrometry[J]. Dyes and Pigments,1999,43(2):127-137.
[77]Holcapek M, Jandera P, Zderadicka P. High performance liquid chromatography-mass spectrometric analysis of sulphonated dyes and intermediates[J]. Journal of Chromatography A,2001,926(1):175-186.
[78]Hu Z, Zhang S, Yang J, et al. Some properties of aqueous-solutions of poly(vinylamine chloride) [J]. Journal of Applied Polymer Science,2003,89(14):3889-3893.
[79]Sumaru K, Matsuoka H, Yamaoka H. Exact Evaluation of Characteristic Protonation of Poly(vinylamine) in Aqueous Solution[J]. The Journal of Physical Chemistry,1996, 100(21):9000-9005.
[80]Koetse M, Laschewsky A, Verbiest T. Films grown from polyamines and reactive dyes by alternating polyelectrolyte adsorption/surface activation (CoMPAS) [J]. Materials Science and Engineering:C,1999,10(1-2):107-113.
[81]Mao M, Truner R. Aggregation of Rod-Coil Block Copolymers Containing Rigid Polyampholyte Blocks in Aqueous Solution[J]. Journal of the American Chemical Society, 2007,129(13):3832-3822.
[82]Konstantinova T, Petrova P. On the synthesis of some bifunctional reactive triazine dyes[J]. Dyes and Pigments,2002,52(2):115-120.
[83]徐华.多羧酸及多羧酸酯型大分子染料的合成和应用：(博士学位论文)[D].大连：大连理工大学,2011.
[84]黄昊飞.含氟三嗪活性染料的研究：(博士学位论文)[D].大连：大连理工大学,2010.
[85]Li Y, Zhang S, Yang J, et al. Synthesis and application of novel crosslinking polyamine dyes with good dyeing performance[J]. Dyes and Pigments,2008,76(2):508-514.
[86]Dang N Y, Ma W, Zhang S F, et al. Studies on Anti-wrinkle Properties of Silk Fabrics Dyed with Reactive and Crosslinking Dyes[J]. Textile Research Journal,2010,80(4): 374-382.
[87]Tang B T, Zhang S F, Yang J Z, et al. Synthesis of a novel water-soluble crosslinking polymeric dye with good dyeing properties[J]. Dyes and Pigments,2006,68(1):69-73.
[88]Tang Y F, Li Y L, Zhang S F, et al. Fixation of a tetraethylene pentamine dye on cotton and silk by bifunctional crosslinkers[J]. Coloration Technology,2006,122(2):82-85.
[89]HamLin J D, Phillips D A S, Whiting A. UV/Visible spectroscopic studies of the effects of common salt and urea upon reactive dye solutions [J]. Dyes and Pigments,1999,41 (1-2): 137-142.
[90]汤艳峰,交联染色用交联剂的合成与应用性能研究：(博士学位论文)[D].大连：大连理工大学,2006.
[2]中国染料工业协会.中国染料工业“十二五”发展规划纲要(一)[J].印染,2011,18：47-50.
[3]Lewis D. M. Coloration in the next century[J]. Review of Progress in Coloration and Related Topics,1999,29:23-28.
[4]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[J].精细化工,2008,25(6)：595-599.
[5]Egger W B, Kissling B, Robison T. Economic durable cellulosics dyeings with reactant-fixable dyes[J]. American Dyestuff Reporter,1982,71(9):55-61.
[6]Lutzel G. Dye fixation by means of polyfunctional crosslinking agents[J]. Journal of the Society of Dyers and Colourists,1966,82 (8):293-299.
[7]侯文杰,蒋嵩,张淑芬,等.交联染料的研究进展[J].染料与染色,2004,41(3)：129-130.
[8]董志芳,陆琼.新型交联染料染色体系的研究[J].染料工业,1987,2：37-44.
[9]Lei X P, Lewis D M, Wang Y N. The production of level fast dyeings on wool with nucleophilic dyes and a crosslinking agent[J]. Journal of the society of dyers and colorist,1992,108(9):383-387.
[10]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[J]. Journal of the Society of Dyers and Colourists,1995,111(12):385-390.
[11]章杰.交链染料的研究-棉用染料的一种创新[J].染料工业,1987,6：1-9.
[12]周璐瑛.交联染色体系的染整一步法研究[J].染料工业,1989,5：33-37.
[13]Hensel H R, Lutzel G. New cotton dyes[J]. Angewandte Chemie International Edition, 1965,4(4):312-321.
[14]章杰.交链染料的色变现象分析[J].印染,1985,4：20-22.
[15]Lei X P, Lewis D M, Shen X M, et al. Crosslinking nucleophilic dyes on wool[J].Dyes and Pigments,1996,30(4):271-281.
[16]应燮元.新型交联染料的应用[J].上海染料,1987,4：17-22.
[17]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.
[18]李英玲.多胺型和多羧酸型大分子染料的合成及应用：(博士学位论文)[D].大连：大连理工大学,2007.
[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]黄健.聚乙烯胺型可交联高分子染料的合成与应用：(硕士学位论文)[D].大连：大连理工大 学,2005.
[21]刘峰.聚烯丙基胺型高分子染料的合成与应用：(硕士学位论文)[D].大连：大连理工大学,2001.
[22]Phillip E S, Rockville M. Method for dyeing human hair with cationic polymeric dyes. US4182612[P].1980.
[23]Larry B F, Spartanburg. Polymeric anthraquinone derived colorants. US4137243[P].1979.
[24]党喃燕.多胺型交联染料染色性能研究：(博士学位论文)[D].大连：大连理工大学,2010.
[25]David M. K., Thomas E. M. Inter-and intralayer energy transfer in zirconium phosphate-poly(allylamine hydrochloricde) multiplayers:an efficient photon antenna and a spectroscopic rule for self-assembled thin films[J]. Journal of the American Chemical Society,1996,118(17):4222-4223.
[26]Sochi 0.,Takahisa T. Naphthalenesulphonyl groups as fluorescence probs for examining the conformational behavior of polyallylamine[J]. Journal of Photochemistry and Photobiology A:Chemistry,1997,111(1-3):233-239.
[27]Dawson D J, Gless R D, Wingard R E. Poly(vinylamine hydrochloride). Synthesis and utilization for the preparation of water-soluble polymeric dyes[J]. Journal of the American Chemical Society,1976,98(19):5996-6000.
[28]Dawson D J, Otteson K M, Wang P C, et al. Soluble Functional Polymers.2. Utilization of Water-Insoluble Chromophores in Water-Soluble Polymeric Dyes[J]. Macromolecules, 1978,11(2):320-324.
[29]Varnavski 0, Ispasoiu R G, Narewal M, et al. Nonlinear Optical Properties of Water-Soluble Polymeric Dyes with Biological Applications[J]. Macromolecules, 2000,33(11):4061-4068.
[30]Roth I, Spange S. Kinetic studies on the nucleophilic aromatic substitution of fluoronitrobenzene derivatives with polyvinylamine in water mediated by 2,6-0-dimethyl-β-cyclodextrin[J]. Macromolecules,2005,38(24):10034-10041.
.[31] Roth I, Jbarah A A, Holze R, et al.2-Nitro-1,4-Diamino benzene-Functionalized Poly(vinyl amine)s as Water-Soluble UV-Vis-Sensitive pH Sensors[J]. Macromolecular Rapid Communications,2006,27(3):193-199.
[32]Pinschmidt R K. Polyvinylamine at last[J]. Journal of Polymer Science Part A:Polymer Chemistry,2010,48(11):2257-2283.
[33]刑其毅,裴伟伟,徐瑞秋,等.基础有机化学[M].北京：高等教育出版社,2005.
[34]Achari A E, Coqueret X, Lablache-Comb ier A, et al. Preparation of polyvinylamine from polyacrylamide:a reinvestigation of the hofmann reaction[J]. Die Makromolekulare Chemie,1993,194(7):1879-1891.
[35]Tanaka H, Senju R. Preparation of Polyvinylamine by the Hofmann Degration of Polyacrylamide[J]. Bulletin of the Chemical Society of Japan,1976,49(10):2821-2823.
[36]Yamamoto Y, Sefton M V. Surface grafting of poly (ethylene glycol) onto poly(acrylamide-co-vinyl amine) cross-linked films under mild conditions[J]. J Biomater Sci Polym Edn,1998,9(5):427-437.
[37]胡志勇,张淑芬,杨锦宗,等.聚乙烯胺Hofmann降级法合成及其热稳定性研究[J].大连理工大学学报,2002,42(6)：659-662
[38]Lowe A B, McCormick C L. Synthesis and Solution Properties of Zwitterionic Polyraers[J]. Chemical Reviews,2002,102(11):4177-4190.
[39]Zhang Q,Zhang Q F, Zhang S B, et al. Synthesis and characterization of sulfonated poly(aryl ether sulfone) containing pendent quaternary ammonium groups for proton exchange membranes[J]. Journal of Membrane Science,2010,354(1-2):23-31.
[40]An H, Lu C, Wang P, et al. A novel hydrophobically associating polyampholytes of poly(AM/AA/AMQC12):preparation, characterization, and solution properties[J]. Polymer Bulletin,2011,67(1):141-158.
[41]Ho B S,Tan B H, Tan J P K, et al. Inverse Microemulsion Polymerization of Sterically Stabilized Polyampholyte Microgels[J]. Langmuir,2008,24(15):7698-7703.
[42]Bhardwaj Y K, Kumar V, Sabharwal S. Swelling behavior of radiation-polymerized polyampholytic two-component gels:Dynamic and equilibrium swelling kinetics[J]. Journal of Applied Polymer Science,2003,88(3):730-742.
[43]Ji E, Whitten D G, Schanze K S. pH-Dependent Optical Properties of a Poly(phenylene ethynylene) Conjugated Polyampholyte[J]. Langmuir,2010,27(5):1565-1568.
[44]Chen W, Leung V, Kroener H, et al. Polyvinylamine-Phenylboronic Acid Adhesion to Cellulose Hydrogel[J]. Langmuir,2009,25 (12):6863-6868.
[45]Chen W, Chen L, Pelton R. Polyvinylamine Boronate Adhesion to Cellulose Hydrogel[J]. Biomacromolecules,2006,7(3):701-702.
[46]Xiao H, Tao R, Cui W, et al. Solution properties of a novel ampholytic polyphenylene sulfide[J]. Journal of Applied Polymer Science,2012:DOI:10.1002/APP.36809.
[47]Kudaibergenov S E, Ciferri A. Natural and synthetic polyampholytes,2a functions and applications[J]. Macromolecular Rapid Communications,2007,28(20):1969-1986.
[48]Dai S, Ravi P, Tam K C. pH-Responsive polymers:synthesis, properties and applications[J]. Soft Matter,2008,4(3):435-449.
[49]Braun 0, Selb J, Candau F. Synthesis in microemulsion and characterization of stimuli-responsive polyelectrolytes and polyampholytes based on N-isopropylacrylamide [J]. Polymer,2001,42(21):8499-8510.
[50]Iatridi Z.Mattheolabakis G, Avgoustakis K, et al. Self-assembly and drug delivery studies of pH/thermo-sensitive polyampholytic (A-co-B)-b-C-b-(A-co-B) segmented terpolymers[J]. Soft Matter,2011,7(23):11160-11168.
[51]Deng L, Zhai Y, Guo S, et al. Investigation on properties of P((MAA-co-DMAEMA)-g-EG) polyampholyte nanogels[J]. Journal of Nanoparticle Research,2009,11 (2):365-374.
[52]Zha L, Banik B, Alexis F. Stimulus responsive nanogels for drug delivery [J]. Soft Matter, 2011,7 (13):5908-5916.
[53]Du J Z, Sun T M, Song W J, et al. A Tumor-Acidity-Activated Charge-Conversional Nanogel as an Intelligent Vehicle for Promoted Tumoral-Cell Uptake and Drug Delivery[J]. Angewandte Chemie International Edition,2010,49(21):3621-3626.
[54]Xu S M,Zhang S F, Lu R W, et al. Study on adsorption behavior between Cr(VI) and crosslinked amphoteric starch[J]. Journal of Applied Polymer Science,2003,89(1): 263-267.
[55]Rivas B L, Villegas S, Ruf B. Water-insoluble polymers containing amine, sulfonic acid, and carboxylic acid groups:Synthesis, characterization, and metal-ion-retention properties[J]. Journal of Applied Polymer Science,2006,99(6):3266-3274.
[56]Bratskaya S Y, Pestov A V, Yatluk Y G, et al. Heavy metals removal by flocculation/precipitation using N-(2-carboxyethyl)chitosans[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects,2009,339(1-3):140-144.
[57]Copello G J, Diaz L E, Dall'Orto V C. Adsorption of Cd(Ⅱ) and Pb(Ⅱ) onto a one step-synthesized polyampholyte:Kinetics and equilibrium studies[J]. Journal of Hazardous Materials,2012,217-218:374-381.
[58]张凤英,杨光,刘延彪,等.高温高盐油藏用化学驱油剂的研究[J].精细石油化工进展,2005,6(5)：8-12.
[59]张黎明.具有反聚电解质溶液行为的两性聚合物[J].高分子通报,1998(4)：80-85.
[60]Li C, Adamcik J, Zhang A, et al. Twofold pH and temperature stimuli-responsive behaviour in block copolypeptide-decorated single wall carbon nanotubes[J]. Chemical Communications,2011,47(1):262-264.
[61]Lee Y, Geckeler K E. Polyampholyte-Wrapped Carbon Nanotubes:Preparation and Internalization by Embryonic Fibroblast Cells[J]. Macromolecular Rapid Communications, 2011,32(19):1518-1525.
[62]Chen G, Wu G, Wang L, et al. Layer-by-layer assembly of single-charged ions with a rigid polyampholyte[J]. Chemical Communications,2008,15:1741-1743.
[63]Wang X, Zhang L, Wang L, et al. Layer-by-Layer Assembled Polyampholyte Microgel Films for Simultaneous Release of Anionic and Cationic Molecules[J]. Langmuir,2010,26(11): 8187-8194.
[64]Osada Y, Gong J P. Soft and Wet Materials:Polymer Gels[J]. Advanced Materials,1998, 10(11):827-837.
[65]Ezell R G, McCormick C L. Electrolyte-and pH-responsive polyampholytes with potential as viscosity-control agents in enhanced petroleum recovery[J]. Journal of Applied Polymer Science,2007,104(5):2812-2821.
[66]Tan B H, Ravi P, Tan L N, et al. Synthesis and aqueous solution properties of sterically stabilized pH-responsive polyampholyte microgels[J]. Journal of Colloid and Interface Science,2007,309(2):453-463.
[67]Tan B H, Ravi P, Tam K C. Synthesis and Characterization of Novel pH-Responsive Polyampholyte Microgels[J]. Macromolecular Rapid Communications,2006,27(7):522-528.
[68]Xiong Z, Peng B, Han X, et al. Dual-stimuli responsive behaviors of diblock polyampholyte PDMAEMA-b-PAA in aqueous solution[J]. Journal of Colloid and Interface Science,2011,356(2):557-565.
[69]Chen W, Pelton R, Leung V. Solution Properties of Polyvinylamine Derivatized with Phenylboronic Acid[J]. Macromolecules,2009,42(4):1300-1305.
[70]Tanaka H. Hofmann reaction of polyacrylamide:Realtionship between reaction condition and degree of polymerization of polyvinylamine[J]. Journal of Polymer Science:Polymer Chemistry Edition,1979,17(4):1239-1245.
[71]Godbey W T, Wu K K, Mikos A G. Size matters:molecular weight affects the efficiency of poly(ethylenimine) as a gene delivery vehicle[J]. Journal of Biomedical Materials Research,1999,45(3):268-275.
[72]董卫国,徐静,黄俊鹏.氮气吸附法表征棉纤维的孔结构[J].纺织学报,2007,28(6)：5-7.
[73]Kim S H, Nam Y S, Lee T S, et al. Silk Fibroin Nanofiber. Electrospinning, Properties, and Structure[J]. Polymer Journal,2003,35(2):185-190.
[74]张行荣.聚马来酸型染料和羟甲基型大分子染料的设计合成及应用：(博士学位论文)[D].大连：大连理工大学,2011.
[75]候毓芬,程侣伯.活性染料[M].北京：化学工业出版社,1991.
[76]Holcapek M, Jandera P, Prikryl J. Analysis of sulphonated dyes and intermediates by electrospray mass spectrometry[J]. Dyes and Pigments,1999,43(2):127-137.
[77]Holcapek M, Jandera P, Zderadicka P. High performance liquid chromatography-mass spectrometric analysis of sulphonated dyes and intermediates[J]. Journal of Chromatography A,2001,926(1):175-186.
[78]Hu Z, Zhang S, Yang J, et al. Some properties of aqueous-solutions of poly(vinylamine chloride) [J]. Journal of Applied Polymer Science,2003,89(14):3889-3893.
[79]Sumaru K, Matsuoka H, Yamaoka H. Exact Evaluation of Characteristic Protonation of Poly(vinylamine) in Aqueous Solution[J]. The Journal of Physical Chemistry,1996, 100(21):9000-9005.
[80]Koetse M, Laschewsky A, Verbiest T. Films grown from polyamines and reactive dyes by alternating polyelectrolyte adsorption/surface activation (CoMPAS) [J]. Materials Science and Engineering:C,1999,10(1-2):107-113.
[81]Mao M, Truner R. Aggregation of Rod-Coil Block Copolymers Containing Rigid Polyampholyte Blocks in Aqueous Solution[J]. Journal of the American Chemical Society, 2007,129(13):3832-3822.
[82]Konstantinova T, Petrova P. On the synthesis of some bifunctional reactive triazine dyes[J]. Dyes and Pigments,2002,52(2):115-120.
[83]徐华.多羧酸及多羧酸酯型大分子染料的合成和应用：(博士学位论文)[D].大连：大连理工大学,2011.
[84]黄昊飞.含氟三嗪活性染料的研究：(博士学位论文)[D].大连：大连理工大学,2010.
[85]Li Y, Zhang S, Yang J, et al. Synthesis and application of novel crosslinking polyamine dyes with good dyeing performance[J]. Dyes and Pigments,2008,76(2):508-514.
[86]Dang N Y, Ma W, Zhang S F, et al. Studies on Anti-wrinkle Properties of Silk Fabrics Dyed with Reactive and Crosslinking Dyes[J]. Textile Research Journal,2010,80(4): 374-382.
[87]Tang B T, Zhang S F, Yang J Z, et al. Synthesis of a novel water-soluble crosslinking polymeric dye with good dyeing properties[J]. Dyes and Pigments,2006,68(1):69-73.
[88]Tang Y F, Li Y L, Zhang S F, et al. Fixation of a tetraethylene pentamine dye on cotton and silk by bifunctional crosslinkers[J]. Coloration Technology,2006,122(2):82-85.
[89]HamLin J D, Phillips D A S, Whiting A. UV/Visible spectroscopic studies of the effects of common salt and urea upon reactive dye solutions [J]. Dyes and Pigments,1999,41 (1-2): 137-142.
[90]汤艳峰,交联染色用交联剂的合成与应用性能研究：(博士学位论文)[D].大连：大连理工大学,2006.