CN111379175B - Preparation process of graphene oxide-based dyeing finishing agent - Google Patents
Preparation process of graphene oxide-based dyeing finishing agent Download PDFInfo
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- CN111379175B CN111379175B CN202010277259.6A CN202010277259A CN111379175B CN 111379175 B CN111379175 B CN 111379175B CN 202010277259 A CN202010277259 A CN 202010277259A CN 111379175 B CN111379175 B CN 111379175B
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
- D06P1/5285—Polyurethanes; Polyurea; Polyguanides
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/39—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using acid dyes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/6008—Natural or regenerated cellulose using acid dyes
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Abstract
The invention discloses a preparation process of a graphene oxide-based dyeing finishing agent, which comprises the steps of firstly treating graphene oxide at high temperature by potassium hydroxide, then uniformly dispersing the dispersed graphene oxide and polyurethane in a tetrahydrofuran solvent, carrying out ultrasonic treatment, and finally grafting chitosan on modified graphene oxide by utilizing the reaction between acyl chloride and active hydroxyl and amino, so that chitosan and graphene oxide can be uniformly combined, and the chitosan and the modified graphene oxide have good antibacterial effect on one hand, so that the antibacterial property of a treated fabric can be improved, and on the other hand, the chitosan and a dye and a fabric fiber can be combined by Van der Waals force, hydrogen bonds, ionic bonds and the like, so that the color fastness of the dye and the combination effect of the modified graphene oxide on the fabric fiber are improved.
Description
Technical Field
The invention belongs to the technical field of textiles, and particularly relates to a preparation process of a graphene oxide-based dyeing finishing agent.
Background
Fabric finishing is the application of a finishing agent to fabrics, which can change the surface properties of the fabrics, thereby endowing the fabrics with special functions, for example, hydrophobic and oleophobic finishing is the processing technology of treating the fabrics with a finishing agent with low surface tension, changing the surface characteristics of fibers, and making the fabric surface not easy to be wetted and spread by water or oil, thereby achieving the purposes of hydrophobic and oleophobic, antifouling finishing and easy decontamination finishing are the processing technologies of changing the surface properties or the surface state of the fibers, making the fabrics not easy to be stained under the wearing and using conditions, or making the stained stains easy to wash and not stain any more;
the dyeing finishing agent is a textile printing and dyeing auxiliary agent for treating a textile, enabling a dyeing agent to be tightly combined with the textile and improving the dyeing fastness of the textile, and has the main function of being combined with the textile fiber to form a finishing agent layer on the surface of the textile fiber, then combining the finishing agent with the dyeing agent in an electrostatic combination mode, a chemical bond combination mode and the like.
Disclosure of Invention
The invention aims to provide a preparation process of a graphene oxide-based dyeing finishing agent.
The technical problems to be solved by the invention are as follows:
the combination effect of the finishing agent to the dye and the combination effect between the finishing agent and the textile fiber in the prior art are not ideal, and the finishing agent can improve the dyeing effect of the dye after finishing before dyeing, but can be influenced by factors such as bacteria along with the prolonging of the service time, so that the fading and the discoloration can be caused by accelerated aging, and meanwhile, a plurality of dyeing finishing agents can cause the textile to be hardened and the hand feeling can be influenced due to the pursuit of the dyeing effect.
The purpose of the invention can be realized by the following technical scheme:
a preparation process of a graphene oxide-based dyeing finishing agent comprises the following steps:
preparing graphene oxide, wherein the graphene oxide is prepared by taking graphite as a raw material through oxidation intercalation, and the specific preparation method comprises a hummer method and a staudenmar method.
Step two, mixing the graphene oxide prepared in the step one and potassium hydroxide solid according to the weight ratio of 1:1-6, grinding uniformly, then heating the uniformly ground and mixed material in an inert gas atmosphere at the temperature of 600-1000 ℃ for 40-120min, washing the mixture with deionized water after heating until the washing water is neutral to remove potassium hydroxide components, and then drying the graphene oxide at the temperature of 40-80 ℃ to obtain pretreated graphene oxide;
in this step, through potassium hydroxide high temperature treatment oxidation graphite alkene, can promote oxidation graphite alkene's specific surface area to promote oxidation graphite alkene to the adsorption effect of dyestuff, thereby promote the colour fastness after the dyeing.
Step three, adding polyurethane and the pretreated graphene oxide obtained in the previous step into tetrahydrofuran respectively, performing ultrasonic treatment to uniformly disperse the pretreated graphene oxide in the tetrahydrofuran, adding the pretreated graphene oxide into a tetrahydrofuran solution of the polyurethane, performing ultrasonic treatment for 1-3h, performing vacuum bubble pumping, performing solid-liquid separation, flushing a solid-phase material through the tetrahydrofuran, removing unreacted polyurethane, and volatilizing the tetrahydrofuran to obtain high-dispersion graphene oxide;
2.5-10g of pretreated graphene oxide is added into every 1L of tetrahydrofuran, and the weight ratio of the pretreated graphene oxide to polyurethane is 1: 4-13;
in the step, dispersed graphene oxide and polyurethane are uniformly dispersed in a tetrahydrofuran solvent and subjected to ultrasonic treatment, in the process, a polyurethane molecular chain can be intercalated between graphene oxide lamella, so that the distance between graphene oxide lamella is increased, and the dispersion effect of the graphene oxide in subsequent treatment is improved.
Adding N, N-dimethylformamide into the high-dispersion graphene oxide obtained in the last step, performing ultrasonic dispersion to obtain a high-dispersion graphene oxide dispersion liquid, wherein the concentration mass of the high-dispersion graphene oxide is 2-10g/100mL, adding a thionyl chloride solution into the high-dispersion graphene oxide dispersion liquid, heating to 70-80 ℃, stirring for reaction for 24-72min, performing solid-liquid separation after the reaction is finished, washing a solid phase with tetrahydrofuran, and drying in vacuum at the temperature of 60-80 ℃ after washing to obtain acyl-chlorinated modified graphene oxide;
in the step, the surface of the graphene oxide is rich in carboxyl, and then the graphene oxide is subjected to acyl chlorination by thionyl chloride in the environment of N, N-dimethylformamide as a solvent;
preferably, in the fourth step, 1g of the highly dispersed graphene oxide is added to every 60-80mL of thionyl chloride.
Step five, adding chitosan into an organic solvent, heating and stirring until the chitosan is completely dissolved, then adding modified graphene oxide into the organic solvent, carrying out ultrasonic dispersion, carrying out heat preservation reaction at the temperature of 120 ℃ to 140 ℃ for 48-72h, after the reaction is finished, carrying out solid-liquid separation to remove the solvent, washing solid-phase substances with an organic acid solution to remove the unreacted chitosan, and then drying at the temperature of 60-80 ℃ to obtain the graphene oxide grafted with chitosan, namely a dyeing finishing agent;
in the step, the organic solvent is N, N-dimethylformamide, and the organic acid solution is an acetic acid solution with the volume concentration of 2% -6%; 1.5-3g of chitosan is added into each 100ml of organic solvent, and the mass ratio of the chitosan to the modified graphene oxide is 3-6: 1;
in the fourth step and the fifth step, firstly, chitosan is grafted on the modified graphene oxide by utilizing the reaction between acyl chloride, active hydroxyl and amino, so that chitosan and graphene oxide can be uniformly combined, and both the chitosan and the modified graphene oxide have good antibacterial effect, so that the antibacterial performance of the treated fabric can be improved, and on the other hand, the chitosan can be combined with the dye and the fabric fiber through van der waals force, hydrogen bonds, ionic bonds and the like, so that the color fastness of the dye and the combination effect of the modified graphene oxide on the fabric fiber are improved.
The invention also discloses a graphene oxide-based dyeing finishing agent prepared by the method;
the graphene oxide-based dyeing finishing agent is applied to textile dyeing, and the specific application steps are as follows:
preparing an acetic acid solution with the volume concentration of 2% -6%, adding a dyeing finishing agent, adding a cross-linking agent after uniform ultrasonic dispersion, in one embodiment of the invention, the cross-linking agent is epoxy chloropropane, adding a dye solution after continuous ultrasonic treatment, and after ultrasonic reaction for 20-60min, dropwise adding ammonia water into the dye solution until the mixed solution is neutral to obtain a dyeing finishing liquid;
the bleached fiber fabric is treated by the dyeing finishing liquor.
When the dyeing finishing liquid is prepared, the chitosan can be combined with dye and textile fiber through van der waals force, hydrogen bonds, ionic bonds and the like, so that the color fastness of the dye is improved, the fading can be avoided, and the chitosan and the graphene oxide both have good sterilization effects.
The invention has the beneficial effects that:
according to the preparation process of the dyeing finishing agent, the graphene oxide is treated at high temperature by the potassium hydroxide, so that the specific surface area of the graphene oxide can be increased, the adsorption effect of the graphene oxide on dye is improved, and the color fastness after dyeing is improved; then uniformly dispersing the dispersed graphene oxide and polyurethane in a tetrahydrofuran solvent and carrying out ultrasonic treatment, wherein in the process, a polyurethane molecular chain can be intercalated between graphene oxide lamella to improve the distance between graphene oxide lamella, so that the dispersion effect of the graphene oxide in subsequent treatment is improved, in addition, a hydrogen bond can be formed between-NH-bond of the polyurethane and C = O bond of the graphene oxide, so that the polyurethane can be wrapped on the graphene oxide lamella, on one hand, certain protection effect can be achieved on the graphene oxide in subsequent grinding treatment, on the other hand, the dispersion effect of the graphene oxide can be improved, and finally, the chitosan is grafted on the modified graphene oxide by utilizing the reaction between acyl chloride, active hydroxyl and amino, so that the chitosan and the graphene oxide can be uniformly combined, on one hand, the chitosan and the modified graphene oxide have good antibacterial effect, so that the antibacterial performance of the treated fabric can be improved, and on the other hand, the chitosan can be combined with the dye and the fabric fiber through van der Waals force, hydrogen bonds, ionic bonds and the like, so that the color fastness of the dye and the combination effect of the modified graphene oxide on the fabric fiber are improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation process of a graphene oxide-based dyeing finishing agent comprises the following steps:
preparing graphene oxide by a hummer method;
step two, mixing the graphene oxide prepared in the step one and potassium hydroxide solid according to a weight ratio of 1:5, grinding uniformly, heating the uniformly ground and mixed material in a nitrogen atmosphere at 800 ℃ for 80min, washing the mixture with deionized water until the washing water is neutral after heating is finished to remove potassium hydroxide components, and drying the graphene oxide at 60 ℃ to obtain pretreated graphene oxide;
step three, respectively adding polyurethane and the pretreated graphene oxide obtained in the previous step into tetrahydrofuran, adding 4g of the pretreated graphene oxide into each 1L of tetrahydrofuran, wherein the weight ratio of the pretreated graphene oxide to the polyurethane is 1:5, performing ultrasonic treatment to uniformly disperse the pretreated graphene oxide in the tetrahydrofuran, adding the mixture into a tetrahydrofuran solution of the polyurethane, performing ultrasonic treatment for 1.5h, performing vacuum bubble pumping, performing solid-liquid separation, flushing solid-phase materials through the tetrahydrofuran, removing unreacted polyurethane, and volatilizing the tetrahydrofuran to obtain high-dispersion graphene oxide;
adding N, N-dimethylformamide into the high-dispersion graphene oxide obtained in the previous step, and performing ultrasonic dispersion to obtain a high-dispersion graphene oxide dispersion liquid, wherein the concentration mass of the high-dispersion graphene oxide is 6g/100mL, adding a thionyl chloride solution into the high-dispersion graphene oxide dispersion liquid, and the mass-volume ratio of the high-dispersion graphene oxide to the thionyl chloride is 1: heating to 80 ℃ at a concentration of 60g/mL, stirring for reaction for 40min, after the reaction is finished, carrying out solid-liquid separation, washing a solid phase with tetrahydrofuran, and drying at 60 ℃ in vacuum to obtain acyl-chlorinated modified graphene oxide;
adding chitosan into N, N-dimethylformamide, adding 2g of chitosan into every 100ml of N, N-dimethylformamide, heating and stirring until the chitosan is completely dissolved, then adding modified graphene oxide into the N, N-dimethylformamide, keeping the mass ratio of the chitosan to the modified graphene oxide at 4:1, carrying out heat preservation reaction at 120 ℃ for 48 hours after ultrasonic dispersion is finished, carrying out solid-liquid separation to remove the solvent after the reaction is finished, washing the solid-phase substance by using an acetic acid solution with the volume concentration of 4%, removing the unreacted chitosan, and drying at the temperature of 60 ℃ to obtain the dyeing finishing agent.
Example 2
A preparation process of a graphene oxide-based dyeing finishing agent comprises the following steps:
preparing graphene oxide by a hummer method;
step two, mixing the graphene oxide prepared in the step one and potassium hydroxide solid according to the weight ratio of 1:6, grinding uniformly, heating the uniformly ground and mixed material in an inert gas atmosphere at the temperature of 800 ℃ for 80min, washing the mixture with deionized water until the washing water is neutral after heating is finished, removing potassium hydroxide components, and drying the graphene oxide at the temperature of 60 ℃ to obtain pretreated graphene oxide;
step three, respectively adding polyurethane and the pretreated graphene oxide obtained in the previous step into tetrahydrofuran, adding 6g of the pretreated graphene oxide into each 1L of tetrahydrofuran, wherein the weight ratio of the pretreated graphene oxide to the polyurethane is 1:8, performing ultrasonic treatment to uniformly disperse the pretreated graphene oxide in the tetrahydrofuran, adding the mixture into a tetrahydrofuran solution of the polyurethane, performing ultrasonic treatment for 2 hours, performing vacuum bubble pumping, performing solid-liquid separation, flushing a solid-phase material by the tetrahydrofuran, removing unreacted polyurethane, and volatilizing the tetrahydrofuran to obtain high-dispersion graphene oxide;
adding N, N-dimethylformamide into the high-dispersion graphene oxide obtained in the previous step, and performing ultrasonic dispersion to obtain a high-dispersion graphene oxide dispersion liquid, wherein the concentration mass of the high-dispersion graphene oxide is 2.5g/100mL, adding a thionyl chloride solution into the high-dispersion graphene oxide dispersion liquid, and the mass-volume ratio of the high-dispersion graphene oxide to the thionyl chloride is 1: heating to 80 ℃ at a concentration of 60g/mL, stirring for reaction for 60min, after the reaction is finished, carrying out solid-liquid separation, washing a solid phase with tetrahydrofuran, and drying at 60 ℃ in vacuum after washing to obtain acyl-chlorinated modified graphene oxide;
adding chitosan into N, N-dimethylformamide, adding 2g of chitosan into every 100ml of N, N-dimethylformamide, heating and stirring until the chitosan is completely dissolved, then adding modified graphene oxide into the N, N-dimethylformamide, keeping the mass ratio of the chitosan to the modified graphene oxide at 4:1, carrying out heat preservation reaction at 120 ℃ for 72 hours after ultrasonic dispersion is finished, carrying out solid-liquid separation to remove the solvent after the reaction is finished, washing the solid-phase substance by using an acetic acid solution with the volume concentration of 4%, removing the unreacted chitosan, and drying at the temperature of 60 ℃ to obtain the dyeing finishing agent.
Comparative example 1
A preparation process of a graphene oxide-based dyeing finishing agent comprises the following steps:
preparing graphene oxide by a hummer method;
step two, respectively adding polyurethane and the graphene oxide obtained in the previous step into tetrahydrofuran, adding 4g of graphene oxide into every 1L of tetrahydrofuran, wherein the weight ratio of the graphene oxide to the polyurethane is 1:5, performing ultrasonic treatment to uniformly disperse the graphene oxide in the tetrahydrofuran, adding the graphene oxide into a tetrahydrofuran solution of the polyurethane, performing ultrasonic treatment for 1.5h, performing vacuum bubble pumping, performing solid-liquid separation, flushing a solid-phase material by using the tetrahydrofuran, removing unreacted polyurethane, and volatilizing the tetrahydrofuran to obtain high-dispersion graphene oxide;
adding N, N-dimethylformamide into the high-dispersion graphene oxide obtained in the previous step, and performing ultrasonic dispersion to obtain a high-dispersion graphene oxide dispersion liquid, wherein the concentration mass of the high-dispersion graphene oxide is 6g/100mL, adding a thionyl chloride solution into the high-dispersion graphene oxide dispersion liquid, and the mass-volume ratio of the high-dispersion graphene oxide to the thionyl chloride is 1: heating to 80 ℃ at a concentration of 60g/mL, stirring for reaction for 40min, after the reaction is finished, carrying out solid-liquid separation, washing a solid phase with tetrahydrofuran, and drying at 60 ℃ in vacuum to obtain acyl-chlorinated modified graphene oxide;
adding chitosan into N, N-dimethylformamide, adding 2g of chitosan into every 100ml of N, N-dimethylformamide, heating and stirring until the chitosan is completely dissolved, then adding modified graphene oxide into the N, N-dimethylformamide, keeping the mass ratio of the chitosan to the modified graphene oxide at 4:1, carrying out heat preservation reaction at 120 ℃ for 48 hours after ultrasonic dispersion, carrying out solid-liquid separation after the reaction is finished, removing the solvent, washing the solid-phase substance by using an acetic acid solution with the volume concentration of 4%, removing the unreacted chitosan, and drying at the temperature of 60 ℃ to obtain the dyeing finishing agent.
Comparative example 2
A preparation process of a graphene oxide-based dyeing finishing agent comprises the following steps:
preparing graphene oxide by a hummer method;
step two, mixing the graphene oxide prepared in the step one and potassium hydroxide solid according to a weight ratio of 1:5, grinding uniformly, heating the uniformly ground and mixed material in a nitrogen atmosphere at 800 ℃ for 80min, washing the mixture with deionized water until the washing water is neutral after heating is finished to remove potassium hydroxide components, and drying the graphene oxide at 60 ℃ to obtain pretreated graphene oxide;
adding N, N-dimethylformamide into the pretreated graphene oxide obtained in the previous step, and performing ultrasonic dispersion to obtain a high-dispersion graphene oxide dispersion liquid, wherein the concentration mass of the high-dispersion graphene oxide is 6g/100mL, adding a thionyl chloride solution into the pretreated graphene oxide dispersion liquid, and the mass-volume ratio of the pretreated graphene oxide to the thionyl chloride is 1: heating to 80 ℃ at a concentration of 60g/mL, stirring for reaction for 40min, after the reaction is finished, carrying out solid-liquid separation, washing a solid phase with tetrahydrofuran, and drying at 60 ℃ in vacuum to obtain acyl-chlorinated modified graphene oxide;
adding chitosan into N, N-dimethylformamide, adding 2g of chitosan into every 100ml of N, N-dimethylformamide, heating and stirring until the chitosan is completely dissolved, then adding modified graphene oxide into the N, N-dimethylformamide, keeping the mass ratio of the chitosan to the modified graphene oxide at 4:1, carrying out heat preservation reaction at 120 ℃ for 48 hours after ultrasonic dispersion, carrying out solid-liquid separation after the reaction is finished, removing the solvent, washing the solid-phase substance by using an acetic acid solution with the volume concentration of 4%, removing the unreacted chitosan, and drying at the temperature of 60 ℃ to obtain the dyeing finishing agent.
Comparative example 3
A preparation process of a graphene oxide-based dyeing finishing agent comprises the following steps:
preparing graphene oxide by a hummer method;
adding N, N-dimethylformamide into the graphene oxide obtained in the previous step, and performing ultrasonic dispersion to obtain a graphene oxide dispersion liquid, wherein the concentration mass of the graphene oxide is 6g/100mL, adding a thionyl chloride solution into the graphene oxide dispersion liquid, and the mass-volume ratio of the graphene oxide to the thionyl chloride is 1: heating to 80 ℃ at a concentration of 60g/mL, stirring for reaction for 40min, after the reaction is finished, carrying out solid-liquid separation, washing a solid phase with tetrahydrofuran, and drying at 60 ℃ in vacuum to obtain acyl-chlorinated modified graphene oxide;
adding chitosan into N, N-dimethylformamide, adding 2g of chitosan into every 100ml of N, N-dimethylformamide, heating and stirring until the chitosan is completely dissolved, then adding modified graphene oxide into the N, N-dimethylformamide, keeping the mass ratio of the chitosan to the modified graphene oxide at 4:1, carrying out heat preservation reaction at 120 ℃ for 48 hours after ultrasonic dispersion, carrying out solid-liquid separation after the reaction is finished, removing the solvent, washing the solid-phase substance by using an acetic acid solution with the volume concentration of 4%, removing the unreacted chitosan, and drying at the temperature of 60 ℃ to obtain the dyeing finishing agent.
Experimental data and results analysis:
according to the embodiment and the comparative example, the graphene oxide-based dyeing finishing agent is prepared and applied to textile dyeing, and the specific application steps are as follows:
preparing an acetic acid solution with the volume concentration of 4%, adding a dyeing finishing agent, performing ultrasonic dispersion uniformly, adding epoxy chloropropane serving as a cross-linking agent, continuing ultrasonic treatment, adding a dye solution, performing ultrasonic reaction for 20-60min, and dropwise adding ammonia water until the mixed solution is neutral to obtain a dyeing finishing solution, wherein the concentration of the dyeing finishing agent in the dyeing finishing solution is 10g/L, the concentration of the epoxy chloropropane is 0.04mol/L, the dye is acid orange II, and the concentration of the dye is 2.5 g/L;
and soaking and rolling the cotton fabric twice with the finishing liquid for two times, wherein the rolling residual rate is 95%, and detecting after drying.
The detection items comprise hand feeling, dry rubbing fastness, wet rubbing fastness and antibacterial performance (according to GB/T20944.3-2008 standard), and specific results are shown in a table 1:
TABLE 1
| Test item | Hand feeling | Fastness to dry rubbing | Fastness to wet rubbing | Antibacterial properties (bacteriostasis rate%, Escherichia coli) |
| Example 1 | Softness | 4-5 | 4 | ＞92 |
| Example 2 | Softness | 4-5 | 4-5 | ＞96 |
| Comparative example 1 | Softness | 4 | 3-4 | ＞84 |
| Comparative example 2 | Is slightly hard | 4 | 3-4 | ＞90 |
| Comparative example 3 | Is slightly hard | 3-4 | 3 | ＞82 |
According to the results, the dyeing finishing agent prepared by the process has good hand feeling and color fastness and simultaneously has good bacteriostatic effect when used for treating cotton fiber fabrics.
The foregoing is merely exemplary and illustrative of the present invention and various modifications, additions and substitutions may be made by those skilled in the art to the specific embodiments described without departing from the scope of the invention as defined in the following claims.
Claims (8)
1. A preparation process of a graphene oxide-based dyeing finishing agent is characterized by comprising the following steps:
step one, preparing graphene oxide;
step two, mixing the graphene oxide prepared in the step one and potassium hydroxide solid according to the weight ratio of 1:1-6, grinding uniformly, then heating the uniformly ground and mixed material in an inert gas atmosphere at the temperature of 600-1000 ℃ for 40-120min, washing the mixture with deionized water after heating until the washing water is neutral, and then drying the graphene oxide at the temperature of 40-80 ℃ to obtain pretreated graphene oxide;
step three, respectively adding polyurethane and the pretreated graphene oxide obtained in the previous step into tetrahydrofuran, performing ultrasonic treatment to uniformly disperse the pretreated graphene oxide in the tetrahydrofuran, adding the pretreated graphene oxide into a tetrahydrofuran solution of the polyurethane, performing ultrasonic treatment for 1-3 hours, performing vacuum bubble pumping, performing solid-liquid separation, flushing solid-phase materials by using the tetrahydrofuran, and volatilizing the tetrahydrofuran to obtain high-dispersion graphene oxide;
adding N, N-dimethylformamide into the high-dispersion graphene oxide obtained in the last step, performing ultrasonic dispersion to obtain a high-dispersion graphene oxide dispersion liquid, wherein the concentration mass of the high-dispersion graphene oxide is 2-10g/100mL, adding a thionyl chloride solution into the high-dispersion graphene oxide dispersion liquid, heating to 70-80 ℃, stirring for reaction for 24-72min, performing solid-liquid separation after the reaction is finished, washing a solid phase with tetrahydrofuran, and drying in vacuum at the temperature of 60-80 ℃ after washing to obtain acyl-chlorinated modified graphene oxide;
and step five, adding chitosan into an organic solvent, heating and stirring until the chitosan is completely dissolved, then adding modified graphene oxide into the organic solvent, performing ultrasonic dispersion, performing heat preservation reaction at the temperature of 120-140 ℃ for 48-72 hours, performing solid-liquid separation to remove the solvent after the reaction is finished, washing solid-phase substances by using an organic acid solution to remove the unreacted chitosan, and then drying at the temperature of 60-80 ℃ to obtain the finished dyeing finishing agent.
2. The preparation process of the graphene oxide-based dyeing finishing agent according to claim 1, wherein in the first step, graphite is used as a raw material to prepare the graphene oxide through oxidation intercalation, and the specific preparation method comprises a hummer method and a staudenmar method.
3. The preparation process of the graphene oxide-based dyeing finishing agent according to claim 1, characterized in that 2.5-10g of pretreated graphene oxide is added to 1L of tetrahydrofuran in the third step, and the weight ratio of the pretreated graphene oxide to polyurethane is 1: 4-13.
4. The preparation process of the graphene oxide-based dyeing finishing agent according to claim 1, characterized in that the mass-to-volume ratio of the highly dispersed graphene oxide to thionyl chloride in step four is 1: 60-80 g/mL.
5. The process for preparing a graphene oxide-based dyeing finishing agent according to claim 1, wherein the organic solvent in the fifth step is N, N-dimethylformamide.
6. The process for preparing a graphene oxide-based dyeing finishing agent according to claim 1, wherein the organic acid solution in the fifth step is an acetic acid solution with a volume concentration of 2% -6%.
7. The preparation process of the graphene oxide-based dyeing finishing agent according to claim 1, wherein 1.5-3g of chitosan is added to every 100mL of organic solvent in the step five, and the mass ratio of chitosan to modified graphene oxide is 3-6: 1.
8. A graphene oxide-based dyeing finishing agent, characterized by being prepared according to the preparation process of any one of claims 1 to 7.
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| CN112501928A (en) * | 2020-11-25 | 2021-03-16 | 佛山市精度纺织有限公司 | Method for improving dyeing fastness by blending multiple dyes |
| CN114541156B (en) * | 2022-03-09 | 2024-07-09 | 台州东海翔染整有限公司 | High-water-washing garment fabric and high-water-washing dye thereof |
| CN115323577A (en) * | 2022-10-10 | 2022-11-11 | 南通缘棉家纺有限公司 | Wear-resistant antibacterial fabric and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102995394A (en) * | 2012-12-17 | 2013-03-27 | 常州大学 | Graphene oxide-based anti-bacterial finishing agent for dyeing, and preparation method and application thereof |
| CN104861643A (en) * | 2015-05-29 | 2015-08-26 | 安徽大学 | Preparation method of graphene/waterborne polyurethane composite material |
| CN109440499A (en) * | 2018-11-30 | 2019-03-08 | 河南健锋帽业有限公司 | A kind of reactive dyeing auxiliary agent of sodolin and application |
-
2020
- 2020-04-10 CN CN202010277259.6A patent/CN111379175B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102995394A (en) * | 2012-12-17 | 2013-03-27 | 常州大学 | Graphene oxide-based anti-bacterial finishing agent for dyeing, and preparation method and application thereof |
| CN104861643A (en) * | 2015-05-29 | 2015-08-26 | 安徽大学 | Preparation method of graphene/waterborne polyurethane composite material |
| CN109440499A (en) * | 2018-11-30 | 2019-03-08 | 河南健锋帽业有限公司 | A kind of reactive dyeing auxiliary agent of sodolin and application |
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