| 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. |
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