CN102535198B - Dyeing method of acid dyes assisted by functionalized carbon nanotubes - Google Patents
Dyeing method of acid dyes assisted by functionalized carbon nanotubes Download PDFInfo
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- CN102535198B CN102535198B CN201110407637.9A CN201110407637A CN102535198B CN 102535198 B CN102535198 B CN 102535198B CN 201110407637 A CN201110407637 A CN 201110407637A CN 102535198 B CN102535198 B CN 102535198B
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Abstract
The invention provides a dyeing method of acid dyes assisted by functionalized carbon nanotubes for leather. The dyeing method comprises the steps of adding acid dyes in a dyed dye bath; and further adding carbon nanotubes processed by acidification or modified carbon nanotubes grafted with hexanediamine. The binding degree between the dyes and leather fibers can be enhanced based on the properties of physical adsorption, hydrogen bonding and so on of the functionalized carbon nanotubes and the acid dyes as well as the chemical action between the active groups on the functionalized carbon nanotubes and the active groups on a tanning agent or the leather fibers, thereby improving dye uptake of the dyes, improving the fastness of dyes to washing with water, soap, sweat and alkali and so on, significantly improving color fastness to solar light, and effectively improving the quality of the dyed products. In addition, the dye content in dyeing wastewater is reduced greatly, thereby lowering the treatment cost of dyeing wastewater.
Description
Technical field
The invention belongs to leather chemical industry field, a kind of method that particularly acid dyes assisted by functionalized carbon nanotubes dyes to leather.
Background technology
ACID DYES is the dyestuff that a class must dye in acid medium, its Application Areas is extensive, is mainly used in the dyeing of wool, silk and polyamide fibre, also a large amount of dyeing for leather, paper, ink, be the common dyes of leather coloring, in leather coloring, occupy an important position.
After ACID DYES ionizes in the aqueous solution, generate coloured anion and colourless metal cation, so be called again anionic dye, the hydrophilic group great majority in dyestuff are sulfonic group, and minority ACID DYES contains carboxylic acid group.
ACID DYES is because having a series of advantage, and as complete in chromatogram, bright in colour, good penetrability are easy to use, of many uses, and is subject to the favor of the industry such as leather, obtained developing rapidly.Yet ACID DYES is because its molecule is less, hydrophilic group is many, makes its WATER RESISTANCE poor, not water-fastness, and particularly the alkaline-resisting fastness of washing is poor, is also subject in the use certain limitation.In order to overcome these shortcomings, this patent is by adding nano material-CNT to improve, and receives certain effect.
CNT (Carbon nanotubes, CNTs) is as monodimension nanometer material, lightweight, and hexagonal structure connects perfect, has the features such as specific area is large, mechanical strength is high, electrical conductivity is high, good heat resistance.Thereby make it there is special machinery, physics, chemical property, in the numerous areas such as engineering material, catalysis, absorption-separation, energy storage device, electrode material, there is important application prospect, CNTs is applied to acid dyeing, can improve the dye-uptake of dyestuff, improve dyestuff water-fastness, soap, sweat is washed, the fastness of alkali cleaning etc., light fastness also obviously improves, and ABRASION RESISTANCE, Bearable dry and wet wipe performance improve, and can effectively improve the quality of pollutant product.The processing cost that dyes in dyeing waste water content obviously declines, can save dyeing waste-water.
Yet there are no report with carbon nano-tube modification acid dyeing aspect of performance, more there are no patent, deliver both at home and abroad.
This patent utilizes the high surface ratio of CNT, to the fabulous absorption property of composite and enhancing toughening effect, is applied in the dyeing of ACID DYES, belongs to pioneering both at home and abroad.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method that acid dyes assisted by functionalized carbon nanotubes dyes to leather, and after this colouring method, leather to be dyeed and the conjugation of dyestuff are stronger, and the leather resistance to water after dyeing is better.
For achieving the above object, the present invention is by the following technical solutions:
A kind of method that acid dyes assisted by functionalized carbon nanotubes dyes to leather, first the CNT after the acidifying of ACID DYES quality consumption 0.1～0.5% is joined in dye bath, rotate after 10～30 minutes, add wherein ACID DYES, treat that dyeing finishes, and uses formic acid fixation.
A kind of method that acid dyes assisted by functionalized carbon nanotubes dyes to leather, first head adds ACID DYES in dye bath, rotate 30～60 minutes, treat that ACID DYES permeates evenly in leather, then the carboxylated CNT that is 0.1%～0.5% by dyestuff quality consumption joins in dye bath, rotate 20-40 minute, finally use formic acid fixation.
A kind of method that acid dyes assisted by functionalized carbon nanotubes dyes to leather, first in dye bath, add ACID DYES, rotate 30-60 minute, permeate evenly in leather until dyestuff after, the modified carbon nano-tube of the hexamethylene diamine grafting of dyestuff quality consumption 0.1%-0.6% is joined in dye bath, rotate 10-30 minute, finally use formic acid fixation.
The preparation method of the modified carbon nano-tube of described hexamethylene diamine grafting is: the stirring and refluxing 34-36 hour at 60-70 ℃ by carboxylated CNT and thionyl chloride first, then 85-90 ℃ of distillation, obtain the CNT of chloride, then the CNT of hexamethylene diamine and chloride is dissolved with oxolane respectively, then, CNT and the hexamethylene diamine of the chloride after dissolving are joined respectively in there-necked flask and constant pressure funnel, temperature is controlled at 60-65 ℃, hexamethylene diamine in constant pressure funnel is slowly added drop-wise in there-necked flask, within 1-1.5 hour, drip off, and continue to react 24 hours, then, 85～90 ℃ of distillations 3～6 hours, finally by washing, centrifugation, after vacuumize, obtain the modified carbon nano-tube of hexamethylene diamine grafting.
The preparation method of described carboxylated CNT is: the mass ratio of first CNT being take with acid solution mixes as 0.025:1, then suspension is made in ultrasonic processing, standing immersion 24～48 hours, then at 110～120 ℃ of heating-condensing backflow 1-2 hour, finally repeatedly washing with separated until pH is neutral.
The method that acid dyes assisted by functionalized carbon nanotubes of the present invention dyes to leather at least has the following advantages: the present invention dyeing dye bath in except adding ACID DYES, further add CNT after acidification or the modified carbon nano-tube of hexamethylene diamine grafting, utilize the performances such as the physical absorption of functionalized carbon nano-tube and ACID DYES and Hydrogenbond, and the chemical action of the active group on the active group on functionalized carbon nano-tube and tanning agent and leather fiber improves the conjugation of dyestuff and leather fiber, thereby increase the dye-uptake of dyestuff, improve the water-fastness of dyestuff, soap, sweat is washed, the fastness of alkali cleaning etc., light fastness also obviously improves, can effectively improve the quality of pollutant product.The processing cost that dyes in dyeing waste water content obviously declines, can save dyeing waste-water.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in detail:
Embodiment 1
(1) according to mass ratio, be 0.025:1 mixes CNT with acid solution after, within ultrasonic 10～20 minutes, process and be mixed with suspension, standing immersion 24～48 hours, then at 110～120 ℃ of heating-condensing backflow 1-2 hour, finally washing is neutral with separated until pH repeatedly, to remove the impurity in CNT, and make carboxyl isoreactivity reactive group on its surface band, thereby obtain carboxylated CNT;
(2) dyestuff after modification is used for to leather coloring, first adjust liquor ratio and the temperature of dye bath in rotary drum, then the carboxylated CNT that is 0.1～0.5% by ACID DYES quality consumption joins in dye bath, rotate 10-30 minute, finally add ACID DYES, treat that dyeing finishes, and uses formic acid fixation.
Embodiment 2
(1) according to mass ratio, be 0.025:1 mixes CNT with acid solution after, within ultrasonic 10～20 minutes, process and be mixed with suspension, standing immersion 24～48 hours, then at 110 ℃～120 ℃ heating-condensing backflow 1-2 hour, finally washing is neutral with separated until pH repeatedly, to remove the impurity in CNT, and make carboxyl isoreactivity reactive group on its surface band, thereby obtain carboxylated CNT;
(2) dyestuff after modification is used for to leather coloring, adjust liquor ratio and the temperature of dye bath in rotary drum, then in dye bath, add ACID DYES, rotate 30～60 minutes, treat that dyestuff permeates evenly in skin, the carboxylic carbon nano-tube that is 0.1%～0.5% by dyestuff quality consumption joins in dye bath, rotates 20-40 minute, finally uses formic acid fixation.
Embodiment 3
(1) according to mass ratio, be 0.025:1 mixes CNT with acid solution after, within ultrasonic 10-20 minute, process and be mixed with suspension, standing immersion 24-48 hour, then at 110 ℃ of-120 ℃ of heating-condensing backflow 1-2 hour, finally washing is neutral with separated until pH repeatedly, to remove the impurity in CNT, and make carboxyl isoreactivity reactive group on its surface band, thereby obtain carboxylated CNT;
(2) carboxylated CNT step (1) being obtained and thionyl chloride be stirring and refluxing 24-36 hour at 60 ℃-70 ℃, then at 85 ℃-90 ℃, distills 3-6 hour, obtains the CNT of chloride; Use respectively organic solvent (as: oxolane) to dissolve the CNT of hexamethylene diamine and chloride, then the CNT of the chloride of dissolving and hexamethylene diamine are joined respectively in there-necked flask and constant pressure funnel, temperature is controlled at 60-65 ℃, the hexamethylene diamine in constant pressure funnel is slowly added drop-wise in there-necked flask, within 1-1.5 hour, drip off, and continue to react 24 hours, then at 85 ℃-90 ℃, distillation 3-6 hour, washing, centrifugation, vacuumize, obtains the modified carbon nano-tube of hexamethylene diamine grafting;
(3) adjust liquor ratio and the temperature of dye bath in rotary drum, then in dye bath, add ACID DYES, rotate 30-60 minute, treat that dyestuff permeates evenly in skin, the modified carbon nano-tube of the hexamethylene diamine grafting of dye dosage 0.1%-0.6% is joined in dye bath, rotate 10-30 minute.
The foregoing is only one embodiment of the present invention, it not whole or unique embodiment, the conversion of any equivalence that those of ordinary skills take technical solution of the present invention by reading description of the present invention, is claim of the present invention and contains.
Claims (7)
1. the method that acid dyes assisted by functionalized carbon nanotubes dyes to leather, it is characterized in that: first the CNT after acidifying is joined in dye bath, rotate after 10～30 minutes, add wherein ACID DYES, treat that dyeing finishes, and uses formic acid fixation, wherein, by mass, the consumption of described CNT is 0.1～0.5% of ACID DYES consumption.
2. the method that acid dyes assisted by functionalized carbon nanotubes as claimed in claim 1 dyes to leather, it is characterized in that: the preparation method of the CNT after described acidifying is: the mass ratio of first CNT being take with acid solution mixes as 0.025:1, then suspension is made in ultrasonic processing, standing immersion 24～48 hours, then at 110～120 ℃ of heating-condensing backflow 1-2 hour, finally repeatedly washing with separated until pH is neutral.
3. the method that acid dyes assisted by functionalized carbon nanotubes dyes to leather, it is characterized in that: first in dye bath, add ACID DYES, rotate 30～60 minutes, treat that ACID DYES permeates evenly in leather, then carboxylated CNT is joined in dye bath, rotate 20-40 minute, finally use formic acid fixation, wherein, by mass, the consumption of carboxylated CNT is ACID DYES 0.1～0.5%.
4. the method that acid dyes assisted by functionalized carbon nanotubes as claimed in claim 3 dyes to leather, it is characterized in that: the preparation method of described carboxylated CNT is: the mass ratio of first CNT being take with acid solution mixes as 0.025:1, then suspension is made in ultrasonic processing, standing immersion 24～48 hours, then at 110～120 ℃ of heating-condensing backflow 1-2 hour, finally repeatedly washing with separated until pH is neutral.
5. the method that acid dyes assisted by functionalized carbon nanotubes dyes to leather, it is characterized in that: first in dye bath, add ACID DYES, rotate 30-60 minute, permeate evenly in leather until dyestuff after, the modified carbon nano-tube of hexamethylene diamine grafting is joined in dye bath, rotate 10-30 minute, finally use formic acid fixation, wherein, by mass, the consumption of the modified carbon nano-tube of hexamethylene diamine grafting is ACID DYES 0.1～0.5%.
6. the method that acid dyes assisted by functionalized carbon nanotubes as claimed in claim 5 dyes to leather, it is characterized in that: the preparation method of the modified carbon nano-tube of described hexamethylene diamine grafting is: the stirring and refluxing 34-36 hour at 60-70 ℃ by carboxylated CNT and thionyl chloride first, then 85-90 ℃ of distillation, obtain the CNT of chloride, then the CNT of hexamethylene diamine and chloride is dissolved with oxolane respectively, then, CNT and the hexamethylene diamine of the chloride after dissolving are joined respectively in there-necked flask and constant pressure funnel, temperature is controlled at 60-65 ℃, hexamethylene diamine in constant pressure funnel is slowly added drop-wise in there-necked flask, within 1-1.5 hour, drip off, and continue to react 24 hours, then, 85～90 ℃ of distillations 3～6 hours, finally by washing, centrifugation, after vacuumize, obtain the modified carbon nano-tube of hexamethylene diamine grafting.
7. the method that acid dyes assisted by functionalized carbon nanotubes as claimed in claim 6 dyes to leather, it is characterized in that: the preparation method of described carboxylated CNT is: the mass ratio of first CNT being take with acid solution mixes as 0.025:1, then suspension is made in ultrasonic processing, standing immersion 24～48 hours, then at 110～120 ℃ of heating-condensing backflow 1-2 hour, finally repeatedly washing with separated until pH is neutral.
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| CN105671833A (en) * | 2015-10-30 | 2016-06-15 | 朱忠良 | Cold-pad batch dyeing process of loose fibers |
| CN108560292B (en) * | 2018-05-04 | 2021-06-25 | 河北科技大学 | Method for applying surface modified carbon nano tube to multifunctional dyed wool |
| CN110344267B (en) * | 2019-06-28 | 2021-08-31 | 苏州经贸职业技术学院 | Preparation method of easy-dyeing and color-fixing soaping-resistant fabric based on reactive dye dyeing |
| CN117364500B (en) * | 2023-10-10 | 2024-04-16 | 东莞市粤雄纺织品有限公司 | Anhydrous dyeing preparation process of color-changing yarn and yarn prepared by same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1436721A (en) * | 2002-02-08 | 2003-08-20 | 中国科学院化学研究所 | Prepn of water soluble carbon nanotube |
| CN1699155A (en) * | 2005-04-27 | 2005-11-23 | 武汉大学 | Preparation method for water soluble carbon nanotube |
| CN1978670A (en) * | 2006-11-24 | 2007-06-13 | 陕西科技大学 | Antistatic leather and its preparing method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007084393A (en) * | 2005-09-26 | 2007-04-05 | National Institute Of Advanced Industrial & Technology | Carotenoid including structure |
| US9123893B2 (en) * | 2009-11-25 | 2015-09-01 | Nissan Chemical Industries, Ltd. | Carbon nano-tube dispersant |
-
2011
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1436721A (en) * | 2002-02-08 | 2003-08-20 | 中国科学院化学研究所 | Prepn of water soluble carbon nanotube |
| CN1699155A (en) * | 2005-04-27 | 2005-11-23 | 武汉大学 | Preparation method for water soluble carbon nanotube |
| CN1978670A (en) * | 2006-11-24 | 2007-06-13 | 陕西科技大学 | Antistatic leather and its preparing method |
Non-Patent Citations (7)
| Title |
|---|
| JP特开2007-84393A 2007.04.05 |
| 孙友昌等.碳纳米管改性丙烯酸树脂涂饰材料的性能研究.《中国皮革》.2011,第40卷(第17期),第18-21页. |
| 孙友昌等.碳纳米管改性铬鞣剂鞣革性能的研究.《中国皮革》.2010,第39卷(第21期), |
| 徐静等.紫外吸收光谱法研究ZnO_碳纳米管复合材料催化降解偶氮染料.《光谱学与光谱分析》.2007,第27卷(第12期),2510-2513. |
| 碳纳米管改性丙烯酸树脂涂饰材料的性能研究;孙友昌等;《中国皮革》;20110930;第40卷(第17期);第18-21页 * |
| 碳纳米管改性铬鞣剂鞣革性能的研究;孙友昌等;《中国皮革》;20101130;第39卷(第21期);第18-20，29页 * |
| 紫外吸收光谱法研究ZnO_碳纳米管复合材料催化降解偶氮染料;徐静等;《光谱学与光谱分析》;20071231;第27卷(第12期);第2510-2513页 * |
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