Antibacterial disperse dye and preparation method thereof
Antibacterial disperse dyes were prepared by covalently grafting betaine with disperse dyes through homogeneous reaction for fabric dyeing. This solved the problems of high production cost and easy performance degradation of antibacterial textiles, and achieved long-lasting antibacterial effect and cost savings in the dyeing process.
Patent Information
- Application Number
- CN202511023097.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-24
- Publication Date
- 2026-02-03
AI Technical Summary
Existing antibacterial textiles are expensive to produce and their antibacterial properties are prone to degradation. Current technologies are also unable to effectively impart long-lasting antibacterial properties to fabrics during the dyeing process.
An antibacterial disperse dye was prepared by covalently grafting the natural small-molecule antibacterial agent betaine with the self-made disperse dye 1-(6-aminohexanoamino)anthraquinone using a homogeneous reaction. This dye was then used for fabric dyeing, avoiding the need for additional finishing or modification treatments.
It achieves lasting antibacterial properties on fabrics during the dyeing process, reduces production costs, and ensures good fabric durability.
Smart Images
Figure CN121450123A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the fields of chemical engineering and materials technology, and in particular to an antibacterial disperse dye and its preparation method. Background Technology
[0002] As is well known, under suitable temperature and humidity, porous textiles can provide a suitable environment for the growth and reproduction of bacteria. The growth and rapid reproduction of bacteria on textiles not only releases unpleasant odors but also reduces the strength of the fabric.
[0003] With the increasing emphasis on public health by national policies and the growing awareness and improvement of people's health and environmental consciousness, the research and development of antibacterial materials, especially antibacterial textiles, has received widespread attention. Currently, the methods for producing antibacterial textiles can be broadly categorized into five types: First, direct spinning, which involves directly weaving natural fibers with good antibacterial properties into antibacterial textiles; second, blending spinning, which involves blending antibacterial materials with spinning polymers, spinning them into antibacterial fibers, and then processing the resulting fibers into textiles; third, composite spinning, which involves using composite spinning components to create antibacterial fibers with structures such as core-sheath type, parallel type, inlaid type, and hollow multi-core type; fourth, surface modification, which involves chemically or physically treating fibers or fabrics to activate them, and then introducing antibacterial components onto the surface of the fibers or fabrics; and fifth, finishing, which involves finishing textiles with antibacterial materials to obtain antibacterial textiles. However, whether it is direct spinning, blend spinning or composite spinning, it will inevitably increase the production cost of interior materials; antibacterial textiles prepared by finishing methods will inevitably lead to a decline in antibacterial performance during long-term use due to the limited affinity between antibacterial agents and fabrics; surface modification will damage the performance of fabrics during the modification process and the modification process will also increase production costs. Summary of the Invention
[0004] The purpose of this invention is to provide an antibacterial disperse dye and its preparation method, which improves the durability of dyed fabrics and imparts antibacterial properties to fabrics during the dyeing process without additional finishing, thereby saving costs.
[0005] In a first aspect, the present invention provides an antibacterial disperse dye, the general structural formula of which is:
[0006]
[0007] Secondly, the present invention provides a method for preparing the aforementioned antibacterial disperse dye, comprising the following steps:
[0008] (1) Betaine was treated with dilute hydrochloric acid to obtain protonated betaine;
[0009] (2) Protonated betaine is dissolved in anhydrous ethanol solution to form betaine-anhydrous ethanol solution, then an activator is added and stirred to generate an active ester intermediate;
[0010] (3) Dissolve 1-(6-aminohexylamino)anthraquinone in N,N-dimethylformamide solution, and then slowly add it dropwise to the active ester intermediate prepared in step (2) to carry out covalent grafting reaction;
[0011] (4) After the covalent grafting reaction is completed, the reaction solution is washed once with dilute hydrochloric acid to remove unreacted amines, then the acidic byproducts are neutralized with saturated NaHCO3, and finally washed with salt water and distilled water to obtain the antibacterial disperse dye.
[0012] In the method for preparing an antibacterial disperse dye as described above, preferably, the amount of betaine used in step (1) is 1.2-1.5M.
[0013] In the method for preparing an antibacterial disperse dye as described above, preferably, the amount of anhydrous ethanol used in step (2) is 10-20 M.
[0014] In the method for preparing an antibacterial disperse dye as described above, preferably, the activator in step (1) is a carbodiimide reagent and a hydroxybenzotriazole.
[0015] In the method for preparing an antibacterial disperse dye as described above, preferably, the amount of carbodiimide reagent used in the step is 1.1-1.3M, and the amount of hydroxybenzotriazole used is 1.1-1.3M.
[0016] In the method for preparing an antibacterial disperse dye as described above, preferably, the reaction temperature of the active ester intermediate in step (2) is 0–5°C and the stirring time is 30–60 min.
[0017] In the method for preparing an antibacterial disperse dye as described above, preferably, the amount of 1-6-(aminohexylamino)anthraquinone in step (3) is 1.0 M, and the amount of N,N-dimethylformamide is 0.1-0.2 M.
[0018] In the method for preparing an antibacterial disperse dye as described above, preferably, the covalent grafting reaction temperature in step (3) is 60–100℃ and the stirring time is 90–150 min.
[0019] Compared with existing technologies, this invention prepares an antibacterial disperse dye by homogeneously reacting the natural small-molecule antibacterial agent betaine with a self-made disperse dye 1-(6-aminohexylamino)anthraquinone, and then directly applies it to the dyeing of automotive interior fabrics. The covalent grafting of the dye and antibacterial agent results in better durability of the fabric dyed with the antibacterial disperse dye; the dyeing process imparts antibacterial properties to the fabric, eliminating the need for additional finishing or modification processes, thus effectively saving production costs. Attached Figure Description
[0020] Figure 1 These are the infrared spectra of the antibacterial disperse dyes prepared in Examples 1 and 2 of this invention;
[0021] Figure 2 This is the NMR spectrum of the antibacterial disperse dye prepared in Example 1 of the present invention;
[0022] Figure 3 This is a diagram illustrating the antibacterial performance of polyester fabric dyed with antibacterial disperse dye against Escherichia coli (a) and Staphylococcus aureus (b) in Example 1 of the present invention.
[0023] Figure 4 This is a schematic diagram illustrating the antibacterial durability of polyester fabric dyed with antibacterial disperse dye against Escherichia coli and Staphylococcus aureus in Embodiment 1 of the present invention.
[0024] Figure 5 This is a diagram showing the antibacterial performance of dyed polyester fabric against Escherichia coli (a) and Staphylococcus aureus (b) in Example 2 of the present invention.
[0025] Figure 6 This is a diagram illustrating the antibacterial performance of polyester fabric dyed with antibacterial disperse dye against Escherichia coli (a) and Staphylococcus aureus (b) in Comparative Example 1 of the present invention. Detailed Implementation
[0026] The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present invention, and should not be construed as limiting the present invention.
[0027] In a first aspect, the present invention provides an antibacterial disperse dye with the following general structural formula:
[0028]
[0029] Secondly, the present invention provides a method for preparing an antibacterial disperse dye, comprising the following steps:
[0030] (1) Betaine was treated with dilute hydrochloric acid to obtain protonated betaine;
[0031] (2) Protonated betaine is dissolved in anhydrous ethanol solution to form betaine-anhydrous ethanol solution, then an activator is added and stirred to generate an active ester intermediate;
[0032] (3) Dissolve 1-(6-aminohexylamino)anthraquinone in N,N-dimethylformamide solution, and then slowly add it dropwise to the active ester intermediate prepared in step (2) to carry out covalent grafting reaction;
[0033] (4) After the covalent grafting reaction is completed, the reaction solution is washed once with dilute hydrochloric acid to remove unreacted amines, then the acidic byproducts are neutralized with saturated NaHCO3, and finally washed with salt water and distilled water to obtain the antibacterial disperse dye.
[0034] In the embodiments provided by the present invention, the amount of betaine in step (1) is 1.2-1.5M; the amount of anhydrous ethanol in step (2) is 10-20M; the activator in step (1) is carbodiimide reagent and hydroxybenzotriazole; the amount of carbodiimide reagent in step (2) is 1.1-1.3M, and the amount of hydroxybenzotriazole is 1.1-1.3M; the reaction temperature of the active ester intermediate in step (2) is 0-5℃, and the stirring time is 30-60min; the amount of 1-6-(aminohexylamino)anthraquinone in step (3) is 1.0M, and the amount of N,N-dimethylformamide is 0.1-0.2M; the covalent grafting reaction temperature in step (3) is 60-100℃, and the stirring time is 90-150min.
[0035] This invention prepares a disperse dye with antibacterial properties by reacting the natural small molecule antibacterial agent betaine with a self-made disperse dye 1-(6-aminohexylamino)anthraquinone in a homogeneous manner, and then directly applies it to the dyeing of automotive interior fabrics. The carboxylic acid group of betaine exists in zwitterionic form and needs to be protonated to free carboxylic acid (-COOH) under acidic conditions. It is then activated by a carbodiimide reagent (1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride) and hydroxybenzotriazole, undergoing an amidation reaction with the primary amino group of 1-6-(aminohexylamino)anthraquinone. However, in this reaction, betaine is soluble in solvents such as anhydrous ethanol, while 1-(6-aminohexylamino)anthraquinone is insoluble in ethanol, preventing the reaction from proceeding. This invention first dissolves 1-(6-aminohexylamino)anthraquinone in a small amount of N,N-dimethylformamide solution, then slowly adds it dropwise to a betaine-anhydrous ethanol solution, using N,N-dimethylformamide as a co-solvent to dissolve 1-(6-aminohexylamino)anthraquinone in the reaction system. A covalent grafting reaction then occurs, ultimately yielding an antibacterial disperse dye.
[0036] It should be noted that if other solvents are used, protonated betaine and 1-(6-aminohexylamino)anthraquinone cannot be dissolved in a homogeneous phase, thus preventing the covalent grafting reaction from proceeding. However, by dissolving protonated betaine in ethanol and then using N,N-dimethylformamide as a co-solvent, 1-(6-aminohexylamino)anthraquinone can be dissolved in the reaction system to form a homogeneous phase with the protonated betaine, allowing the reaction to proceed.
[0037] Example 1
[0038] First, 1.2 M betaine was treated with 0.1 M dilute hydrochloric acid to obtain protonated betaine, which was then dissolved in 15 M anhydrous ethanol to form a betaine-anhydrous ethanol solution. Subsequently, 1.1 M each of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and hydroxybenzotriazole were added, and the mixture was stirred at 0-5 °C for 30 minutes to generate an active ester intermediate. Finally, 1.2 M 1-(6-aminohexylamino)anthraquinone was dissolved in 0... In a 0.1M N,N-dimethylformamide solution, the solution is slowly added dropwise to the above anhydrous ethanol mixture. N,N-dimethylformamide acts as a dye co-solvent to dissolve 1-(6-aminohexylamino)anthraquinone in the reaction system. The mixture is then reacted at 80°C for 120 minutes. The reaction solution is washed once with 0.1M dilute hydrochloric acid to remove unreacted amines. It is then washed five times with saturated NaHCO3 and acidic byproducts, followed by washing with brine and distilled water to obtain an antibacterial disperse dye. The antibacterial disperse dye obtained above is used to dye polyester fabrics using conventional polyester fabric dyeing methods to obtain antibacterial dyed polyester fabrics.
[0039] Reference Figure 1 As shown, the infrared spectrum of the dye prepared by the method in this embodiment changed, indicating that the betaine small molecules were grafted onto the dye surface after the reaction, resulting in an antibacterial disperse dye.
[0040] Example 2
[0041] The procedure is the same as in Example 1, except that the amount of betaine is changed to 0M. The obtained disperse dye is used to dye the polyester fabric using a conventional polyester fabric dyeing method to obtain dyed polyester fabric.
[0042] Comparative Example 1
[0043] The steps are the same as in Example 1, except that the cosolvent N,N-dimethylformamide is replaced with chloroform, and finally the obtained disperse dye is used to dye the polyester fabric using a conventional polyester fabric dyeing method to obtain dyed polyester fabric.
[0044] Antibacterial disperse dyes were obtained using the preparation method in Example 1. To demonstrate the antibacterial properties of the prepared dye molecules, no betaine antibacterial agent was added in Example 2. The molecular structures (infrared spectra) and antibacterial properties of the dyes obtained in the two examples were compared. Figure 1 It can be observed that the dye prepared in Example 1 has a high viscosity at 1620 cm⁻¹. -1 A distinct characteristic peak appears at 1710 cm⁻¹, which is a characteristic peak of amide bonds. The dye prepared in Example 2, however, shows a peak at 1710 cm⁻¹. -1 The characteristic peak at the specified location did not shift. This indicates that, after the amidation reaction, betaine was grafted onto the surface of 1-(6-aminohexylamino)anthraquinone to form an antibacterial disperse dye. To further determine the structure of the antibacterial disperse dye prepared in this invention and the prepared antibacterial dye, the dye prepared in Example 1 was subjected to 1H NMR spectroscopy, as shown below. Figure 2 As shown, the structure of the prepared antibacterial disperse dye was finally determined.
[0045] Polyester fabrics were dyed using conventional polyester fabric dyeing methods with the antibacterial disperse dyes obtained in Examples 1 and 2 above, resulting in antibacterial dyed polyester fabrics. Antibacterial tests against Escherichia coli and Staphylococcus aureus were then conducted on the dyed polyester fabrics. The results showed... Figure 3 and Figure 5 Among them Figure 3 (a) and Figure 5 (a) Antibacterial activity tests against Escherichia coli were conducted on polyester fabrics dyed with antibacterial disperse dyes prepared in Examples 1 and 2, respectively. Figure 3 (b) and Figure 5 (b) Antimicrobial activity tests against Staphylococcus aureus were conducted on polyester fabrics dyed with the antimicrobial disperse dyes prepared in Examples 1 and 2, respectively. The experiments revealed that they possessed excellent antimicrobial properties. This is because the betaine molecule contains a quaternary ammonium salt structure, which can destroy cells and inhibit bacterial growth upon contact with bacteria, thereby achieving excellent antimicrobial effects. After grafting betaine into the dye molecule structure, the fabric surface is covered with a large number of quaternary ammonium salt groups during the dyeing process, resulting in excellent antimicrobial properties.
[0046] Another feature of this invention is the use of N,N-dimethylformamide as a solvent for 1-(6-aminohexylamino)anthraquinone, forming a homogeneous system with ethanol to further induce a covalent grafting reaction. In Comparative Example 1, the cosolvent N,N-dimethylformamide was replaced with chloroform, and then a dye was prepared and dyed to obtain dyed fabric. Figure 6The antibacterial properties of the fabric prepared in Comparative Example 1 were demonstrated. The results showed that it did not exhibit antibacterial properties against *Escherichia coli* or *Staphylococcus aureus*. This is because chloroform and ethanol, in which 1-(6-aminohexylamino)anthraquinone is dissolved, are immiscible and cannot form a homogeneous system. Therefore, the covalent grafting reaction between betaine and 1-(6-aminohexylamino)anthraquinone cannot proceed, and no effective antibacterial disperse dye is obtained. Consequently, the fabric prepared in Comparative Example 1 does not possess antibacterial properties.
[0047] In addition, another advantage of the present invention is that when polyester fabric is dyed with the antibacterial disperse dye prepared by the present invention, the molecular chain segment movement of polyester is intensified when it is above the glass transition temperature, and larger gaps are formed. At this time, the dye enters the fiber and completes the dyeing process, resulting in a highly durable antibacterial functional fabric. Figure 4 The results demonstrate the antibacterial properties of the antibacterial functional fabric prepared in Example 1 against Escherichia coli and Staphylococcus aureus after 5000 washes. The results show that the fabric dyed with antibacterial disperse dyes exhibits good durability; the dyeing process itself imparts antibacterial properties to the fabric, eliminating the need for additional finishing or modification processes, thus effectively saving production costs.
[0048] The above description, based on the embodiments shown in the figures, details the structure, features, and effects of the present invention. The above description is only a preferred embodiment of the present invention, but the present invention is not limited to the scope of implementation shown in the figures. Any changes made in accordance with the concept of the present invention, or equivalent embodiments modified to have equivalent changes, that do not exceed the spirit covered by the specification and figures, should be within the protection scope of the present invention.
Claims
1. An antibacterial disperse dye, characterized in that, The structural general formula of the antibacterial disperse dye is:
2. A process for the preparation of the antibacterial disperse dye according to claim 1, characterized in that, The method comprises the following steps: (1) treating betaine with dilute hydrochloric acid to obtain protonated betaine; (2) dissolving the protonated betaine in anhydrous ethanol solution to form a betaine-anhydrous ethanol solution, then adding an activating agent, and stirring to generate a labile ester intermediate; (3) dissolving 1-(6-aminohexylamino)anthraquinone in N,N-dimethylformamide solution, slowly adding the solution into the labile ester intermediate prepared in step (2), and performing covalent grafting reaction; (4) after the covalent grafting reaction is completed, washing the reaction solution with dilute hydrochloric acid once to remove unreacted amine, neutralizing the acidic byproduct with saturated NaHCO3, and finally washing with brine and distilled water to obtain the antibacterial disperse dye.
3. The method of preparing an antibacterial disperse dye according to claim 2, characterized in that, The amount of betaine used in step (1) is 1.2-1.5M.
4. The method of preparing an antibacterial disperse dye according to claim 2, characterized in that, The amount of anhydrous ethanol used in step (2) is 10-20M.
5. The method of preparing an antibacterial disperse dye according to claim 2, characterized in that, The activating agent used in step (1) is a carbodiimide reagent and a hydroxybenzotriazole.
6. The process for the preparation of an antibacterial disperse dye according to claim 5, characterized in that, The amount of the carbodiimide reagent used in step (1) is 1.1-1.3M, and the amount of the hydroxybenzotriazole used is 1.1-1.3M.
7. The method of preparing an antimicrobial disperse dye according to claim 2, wherein The reaction temperature of the labile ester intermediate in step (2) is 0-5℃, and the stirring time is 30-60min.
8. The method for preparing the antibacterial disperse dye according to claim 2, characterized in that, The amount of 1-6-(aminohexylamino)anthraquinone used in step (3) is 1.0M, and the amount of N,N-dimethylformamide used is 0.1-0.2M.
9. The method for preparing the antibacterial disperse dye according to claim 2, characterized in that, The covalent grafting reaction temperature in step (3) is 60-100℃, and the stirring time is 90-150min.