Antibacterial detoxification anhydrous dyeing and finishing powder dye

Abstract

The application discloses an antibacterial and detoxification anhydrous dyeing and finishing powder dye and a preparation method and application thereof. The dye uses a metal organic framework containing a porphyrin structure with a specific pore size as a carrier, loads copper phthalocyanine and an IR808 photosensitizer after modification by a silane coupling agent, and introduces copper and zinc ions through ion exchange. By optimizing the carrier structure, surface modification and component ratio, the dye has excellent antibacterial property, high dyeing depth and photocatalytic function. The supercritical carbon dioxide process is used to realize anhydrous dyeing and finishing, and the process is environmentally friendly and efficient. The technology solves the problems of traditional dyeing processes, such as serious pollution and single function, and has important application value in the field of textile dyeing and finishing.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of textile dyeing and finishing, and relates to an antibacterial and detoxification anhydrous dyeing and finishing powder dye. BACKGROUND

[0002] The textile dyeing and finishing industry is one of the important sources of water resource consumption and pollution discharge. The traditional water medium dyeing process consumes 100-150 tons of water per ton of textile, and the development of new anhydrous dyeing technology has become an urgent need in the industry. Supercritical carbon dioxide (scCO2) dyeing technology is considered an important development direction for future green dyeing and finishing due to its advantages such as no wastewater discharge, high dye utilization rate, and no need for post-treatment. However, the existing scCO2 dyeing technology still has problems such as single dye function, insufficient dyeing fastness, and lack of antibacterial properties, which limit its industrial application. In addition, the dispersion and penetration of traditional dyes in supercritical fluids are poor, resulting in poor dyeing uniformity and affecting the quality of finished products.

[0003] Currently, some studies have attempted to load dyes on metal organic frameworks (MOFs) to improve scCO2 dyeing performance, but most MOF carriers have defects such as unreasonable pore size distribution, easy dye leakage, and insufficient functional integration. At the same time, existing technologies cannot simultaneously ensure dyeing effect and give the fabric persistent antibacterial and self-cleaning functions, which cannot meet the demand for multifunctional textiles in medical, home, and other fields. Therefore, it is of great application value to develop an anhydrous dyeing and finishing dye with efficient dyeing, antibacterial and detoxification, and environmental friendly characteristics.

[0004] CN113666869B discloses a method for synthesizing a naphthalimide dye containing an amino group in supercritical CO2. The method uses supercritical carbon dioxide (CO2) as the solvent, a nitro-substituted naphthalimide compound as the dye precursor, Au / TiO2 as the catalyst, and H2 as the reducing agent. Under different temperature, pressure, and time conditions, the method realizes the synthesis of naphthalimide fluorescent dye in supercritical CO2 and the simultaneous dyeing of textiles. Although the dyeing method realizes anhydrous dyeing and has good color fastness, the dye has a single function and lacks antibacterial and photocatalytic detoxification functions.

[0005] CN106702781A discloses a dyeing method for titanium dioxide modified woven fabric. The method includes moisture regain treatment, silane coupling agent bonding, surface self-assembly, coating treatment, and dyeing of the titanium dioxide modified woven fabric. After the treatment, the titanium dioxide modified woven fabric obtains bright colors while maintaining its functionality. The dyeing method solves the problem of dull white caused by titanium dioxide through multiple coating layers, but the process is complicated, and the natural protein fiber powder layer may affect the original ultraviolet resistance / antibacterial performance of titanium dioxide, limiting its functionality.

[0006] CN105484064A discloses a new type of halamine antibacterial active dye and its preparation method and application, and the preparation method is as follows: reactive yellow X-R is dissolved in water, then a halamine antibacterial agent precursor containing -OH or -NH2 is slowly added dropwise into the solution, and stirring is carried out at 30-60 DEG C for 2-6 h, in the process, an alkali agent is used to maintain the pH of the whole system to be 5-8, after the reaction is completed, 10-20% of a neutral salt is added to precipitate the product, then drying is carried out to obtain the product; the molar ratio of the reactive yellow X-R to the halamine antibacterial agent precursor is 1:1; the dye uses a water medium dyeing process, waste water pollution cannot be avoided, and the antibacterial performance depends on sodium hypochlorite treatment, which may damage the structure of the dye and result in the decrease of color fastness, and the process is complex. SUMMARY

[0007] The purpose of the present application is to provide a non-aqueous dyeing and finishing powder dye with efficient dyeing, persistent antibacterial and photocatalytic detoxification functions, which uses a porphyrin metal organic framework modified by a silane coupling agent on the surface as a carrier, loads copper phthalocyanine and an IR808 photosensitizer and modifies copper and zinc ions, so as to realize multiple functions of efficient dyeing, persistent antibacterial and photocatalytic degradation of organic pollutants. The present application has the characteristics of good dyeing depth, high color fastness, persistent antibacterial performance and environmental friendliness, and is particularly suitable for a supercritical carbon dioxide non-aqueous dyeing and finishing process, which solves the technical problems of large water consumption and serious pollution in the traditional dyeing process.

[0008] The purpose of the present application can be realized by the following technical solutions:

[0009] The present application provides an antibacterial and detoxification non-aqueous dyeing and finishing powder dye, which is composed of the following components:

[0010] A metal organic framework carrier containing a porphyrin structure and modified by a silane coupling agent on the surface, the carrier has a pore size of 1.8-3.2 nm, and the surface modification density is 1.2-2.5 functional groups / nm 2 ;

[0011] Copper phthalocyanine and an IR808 photosensitizer loaded in the pore channel of the carrier, and the mass ratio of copper phthalocyanine to IR808 is 1:(0.2-0.5);

[0012] Copper ions and zinc ions modified on the surface of the carrier by ion exchange, and the molar ratio of copper ions to zinc ions is 1:(1-3).

[0013] The antibacterial and detoxification non-aqueous dyeing and finishing powder dye provided by the present application modifies the surface of a porphyrin MOF carrier by a silane coupling agent to form 1.2-2.5 functional groups / nm 2The modification density aims to enhance the binding ability of the dye and the photosensitizer, the pore size of 1.8-3.2 nm is designed to accurately load copper phthalocyanine and IR808, avoid leakage, and at the same time provide Cu 2 ⁺ / Zn 2 ⁺ ion exchange sites, realize the synergistic effect of antibiosis and dyeing. The silane modification also improves the dispersion stability of the carrier in supercritical CO2; copper phthalocyanine as the main dye provides high color fastness, and IR808 photosensitizer produces reactive oxygen under near-infrared light triggering, and has the functions of photocatalytic degradation of pollutants and auxiliary antibiosis, and the mass ratio of the two is preferably 1:(0.2-0.5) to balance the dyeing depth and photosensitivity, and avoid color light deviation caused by excessive IR808; Cu 2 ⁺ / Zn 2 ⁺ is anchored on the surface of the carrier, Cu 2 ⁺ directly kills bacteria, and Zn 2 ⁺ inhibits microbial metabolism, and the two synergistically enhance the antibacterial persistence, the coordination bond between the ion exchange site and the MOF skeleton ensures the slow release of metal ions, and avoids loss during the dyeing process.

[0014] Preferably, the silane coupling agent includes 3-aminopropyl triethoxysilane or 3-glycidyl ether propyl trimethoxysilane.

[0015] Preferably, the metal node of the porphyrin metal organic framework carrier is zirconium ion or zinc ion.

[0016] Preferably, the particle size of the powder dye is 0.2-2 μm, and the Zeta potential is-10-+25 mV.

[0017] The antibacterial and detoxification anhydrous dyeing and finishing powder dye provided by the application has a powder particle size of 0.2-2 μm, which is realized by supercritical fluid assisted grinding or spray drying technology, and ensures the suspension stability of the powder dye in the supercritical CO2 medium. If the particle size is too small (<0.2 μm), it is easy to cause aggregation and affect the uniformity of dispersion; if the particle size is too large (>2 μm), the sedimentation speed is accelerated, which causes uneven dyeing. The porous structure (pore size of 1.8-3.2 nm) of the MOF carrier further restricts the diffusion of the loaded dye molecules through the confinement effect, and avoids aggregation; the Zeta potential is in the range of-10-+25 mV, the positive potential (such as +25 mV) can enhance the electrostatic adsorption with the negatively charged cotton / ramie fibers, and improve the dye uptake; the negative potential (-10 mV) prevents powder aggregation through electrostatic repulsion, and ensures uniform dispersion in the supercritical fluid. Although the absolute value of the potential is greater than 30 mV, the stability is better, but the dye combination with the fiber may be inhibited.

[0018] Preferably, it also includes a laccase loaded in the pore channel of the carrier, and the enzyme activity of the laccase is 80-200 U / g.

[0019] The antibacterial and detoxification anhydrous dyeing and finishing powder dye provided by the application uses laccase to catalyze the oxidation of residual organic matters on the fabric, reduces the burden of supercritical CO2 purification, degrades toxic substances in dye wastewater, and ensures efficient catalysis in the enzyme activity range of 80-200 U / g without damaging the structure of the dye, and forms a double detoxification mechanism with a photosensitizer.

[0020] Preferably, the preparation method of the powder dye comprises the following steps:

[0021] The tetrakis(4-carboxyphenyl) porphyrin is reacted with a metal salt in an organic solvent to obtain a porphyrin metal organic framework carrier; the carrier is reacted with a silane coupling agent at 60-80 DEG C for 4-6 hours to obtain a surface-modified carrier; the surface-modified carrier is mixed with copper phthalocyanine and IR808 in an ethanol solution to load the photosensitizer; the product loaded with the photosensitizer is mixed with a copper salt and a zinc salt solution to perform ion exchange; and the product after ion exchange is dried under supercritical carbon dioxide conditions to obtain the powder dye.

[0022] Preferably, the supercritical carbon dioxide drying conditions are: pressure 27-33 MPa, temperature 40-50 DEG C.

[0023] The antibacterial and detoxification anhydrous dyeing and finishing powder dye provided by the application uses supercritical CO2 as a drying medium, supercritical CO2 has no gas-liquid interface, eliminates capillary force, avoids the collapse of the pore channel of the porphyrin MOF carrier, ensures the stability of the loading of the dye and laccase, CO2 critical temperature is 31.1 DEG C, combined with the mild conditions of 40-50 DEG C, the activity of the heat-sensitive photosensitizer and laccase is protected, high-temperature degradation is avoided, and at the same time, as a subsequent anhydrous dyeing and finishing medium, solvent residues can be reduced, which meets the core demand of the anhydrous process.

[0024] Preferably, the anhydrous dyeing and finishing method of the powder dye comprises:

[0025] The fabric is pretreated in a supercritical carbon dioxide medium; the powder dye is added, and dye adhesion treatment is performed under the conditions of 23-28 MPa and 48-52 DEG C; the dyed fabric is subjected to near-infrared light triggering treatment after being taken out; and finally, the fabric is purified in a supercritical carbon dioxide medium.

[0026] Preferably, the mass ratio of the powder dye to the fabric is 1:(20-50).

[0027] Preferably, the pretreatment time is 20-40 minutes; the dye adhesion treatment time is 30-60 minutes; the near-infrared light irradiation wavelength is 800-850 nm, the near-infrared light intensity is 0.5-2 W / cm 2 , the time is 5-15 min; and the purification treatment pressure is 23-28 MPa, the temperature is 40-50 DEG C, and the time is 10-20 minutes.

[0028] The antibacterial and detoxifying anhydrous dyeing and finishing powder dye provided by this invention uses supercritical CO2 as both the drying and dyeing medium. After the fabric is pretreated in supercritical CO2, the powder dye is added. Within 20-40 minutes, the supercritical CO2 penetrates the amorphous region of the fabric fibers, swelling the fiber structure and increasing the free volume, providing a channel for subsequent dye molecule diffusion. The temperature is controlled at 48-52℃, close to the glass transition temperature of polyester and nylon, further promoting fiber relaxation. The optimized powder dye to fabric mass ratio of 1:(20-50) is based on dye saturation adsorption experiments. Too low a ratio (<1:50) results in light color, while too high a ratio (>1:20) wastes dye and easily causes color floating. Under a pressure of 23-28 MPa, the scCO2 density reaches 700-900 kg / m³. 3 Its dye-dissolving ability is close to that of organic solvents, while high pressure promotes dye penetration into the fiber; irradiation with 800-850nm light (0.5-2W / cm) 2 ) activates the IR808 photosensitizer, generating singlet oxygen ( 1 O2 and hydroxyl radicals (·OH) oxidize and degrade impurities on the fiber surface to improve dyeing purity, and also initiate local polymerization of copper phthalocyanine to enhance color fastness and light intensity >2W / cm². 2 May damage fabric, <0.5W / cm 2 The reaction is insufficient; scCO2 rinsing utilizes its low viscosity to efficiently remove unfixed dyes, with a residual dye concentration of <10ppm, achieving zero wastewater. Compared with traditional water washing, it saves 90% of energy consumption and avoids fiber shrinkage caused by wet treatment. The dyeing and finishing method integrates the high permeability of supercritical fluids, the catalytic fixation of photosensitizers, and the slow-release function of MOF carriers, breaking through the bottleneck of traditional processes where dyeing, antibacterial and environmental protection are difficult to balance.

[0029] The beneficial effects of this invention are:

[0030] (1) The present invention provides an antibacterial and detoxifying anhydrous dyeing powder dye, which achieves efficient loading and stable release of dye by synergistic loading of porphyrin MOF carrier modified with surface silane coupling agent and copper phthalocyanine and IR808 photosensitizer, combined with supercritical carbon dioxide drying technology, significantly improving dyeing depth and color fastness.

[0031] (2) The antibacterial and detoxifying anhydrous dyeing powder provided by the present invention combines copper ion and zinc ion exchange modification with laccase catalysis to endow the dye with broad-spectrum antibacterial and organic pollutant degradation capabilities, and the antibacterial effect is long-lasting.

[0032] (3) The antibacterial and detoxifying anhydrous dyeing powder provided by the present invention has a surface functional group density of 1.2-2.5 per nm. 2The carrier design is matched with a near-infrared light triggered release mechanism, and the contradiction between dye permeability and fabric binding force in the anhydrous dyeing is solved. DETAILED DESCRIPTION

[0033] In order to further illustrate the technical means and effects adopted by the present application to achieve the predetermined inventive purpose, the specific embodiments, structures, features and effects according to the present application are described in detail below.

[0034] In one specific embodiment, the present application provides an antibacterial and detoxification anhydrous dyeing and finishing powder dye, which comprises a metal-organic framework carrier with a porphyrin structure modified by 3-aminopropyl triethoxysilane or 3-glycidyl ether propyl trimethoxysilane on the surface, the carrier has a pore size of 1.8-3.2 nm, and the surface modification density is 1.2-2.5 functional groups / nm 2 The metal node is a zirconium ion or a zinc ion; the carrier channel is loaded with copper phthalocyanine and an IR808 photosensitizer in a mass ratio of 1:(0.2-0.5), and contains laccase with an enzyme activity of 80-200 U / g; the carrier surface is modified by copper ions and zinc ions through ion exchange in a molar ratio of 1:(1-3); the particle size of the powder dye is 0.2-2 μm, and the Zeta potential is-10~+25 mV; the preparation method of the powder dye comprises: reacting tetra(4-carboxyphenyl)porphyrin with a metal salt to obtain a carrier, reacting with a silane coupling agent at 60-80℃ for 4-6 hours, loading copper phthalocyanine and IR808 in an ethanol solution, ion exchanging with a copper salt and a zinc salt solution, and finally drying under the conditions of 27-33 MPa and 40-50℃ in supercritical carbon dioxide; the anhydrous dyeing and finishing method comprises: treating the fabric in supercritical carbon dioxide for 20-40 minutes, adding the powder dye, the mass ratio of the powder dye to the fabric is 1:(20-50), treating at 23-28 MPa and 48-52℃ for 30-60 minutes, and after the fabric is taken out, irradiating with near-infrared light of 800-850 nm at an intensity of 0.5-2 W / cm 2 for 5-15 minutes, and purifying the dyed fabric in supercritical carbon dioxide, the purification treatment pressure is 23-28 MPa, the temperature is 40-50℃, and the time is 10-20 minutes.

[0035] In the step of modifying the carrier surface by ion exchange, a zinc core high-performance antibacterial and detoxification auxiliary produced by Shanghai Kexin New Energy Technology Co., Ltd. is used, and the specific information and use method thereof are referred to CN202411469074.X.

[0036] Example 1

[0037] The application provides an antibacterial and detoxification anhydrous dyeing and finishing powder dye, which comprises a porphyrin metal organic framework carrier modified by 3-aminopropyl triethoxysilane on the surface, has a pore size of 2.0 nm and a surface modification density of 1.5 functional groups / nm 2 , the metal node is a zirconium ion, the carrier channel is loaded with copper phthalocyanine and an IR808 photosensitizer in a mass ratio of 1:0.3 and contains laccase with an enzyme activity of 120 U / g, the carrier surface is modified by copper ions and zinc ions in a molar ratio of 1:2, the powder dye has a particle size of 1.0 mu m and a Zeta potential of +10 mV, and the preparation method of the powder dye comprises the following steps: reacting tetra(4-carboxyphenyl)porphyrin with a metal salt to prepare a carrier, reacting with a silane coupling agent at 70 DEG C for 5 hours, loading copper phthalocyanine and IR808 in an ethanol solution, performing ion exchange with a copper salt and a zinc salt solution, and finally drying under the condition of supercritical carbon dioxide at 30 MPa and 45 DEG C. 2 The anhydrous dyeing and finishing method comprises the following steps: treating pure cotton fabric in supercritical carbon dioxide for 30 minutes, adding the powder dye, the mass ratio of the powder dye and the pure cotton fabric is 1:30, treating at 25 MPa and 50 DEG C for 45 minutes, irradiating the dyed fabric with near-infrared light with a strength of 1.0 W / cm

[0038] Compared with a conventional dyeing and finishing process, the carbon emission of unit fabric in the process of the application is reduced by 82%.

[0039] Example 2

[0040] The application provides an antibacterial and detoxification anhydrous dyeing and finishing powder dye, which comprises a porphyrin metal organic framework carrier modified by 3-aminopropyl triethoxysilane on the surface, has a pore size of 2.0 nm and a surface modification density of 1.5 functional groups / nm 2, the metal node is zinc ion; the carrier channel is loaded with copper phthalocyanine and IR808 photosensitizer, the mass ratio is 1:0.2, and contains laccase with an enzyme activity of 80 U / g; the surface of the carrier is modified with copper ions and zinc ions by ion exchange, the molar ratio is 1:1; the particle size of the powder dye is 0.5 mu m, and the Zeta potential is -5 mV; the preparation method of the powder dye comprises the following steps: reacting tetra(4-carboxyphenyl) porphyrin with a metal salt to prepare a carrier, reacting with a silane coupling agent at 60 DEG C for 6 hours, loading copper phthalocyanine and IR808 in an ethanol solution, ion exchanging with a copper salt and a zinc salt solution, and finally drying under the condition of supercritical carbon dioxide at 27 MPa and 40 DEG C; the waterless dyeing and finishing method comprises the following steps: treating polyester fabric in supercritical carbon dioxide for 20 minutes, adding powder dye, the mass ratio of the powder dye and the fabric is 1:20, treating at 23 MPa and 48 DEG C for 60 minutes, and then irradiating the dyed fabric with near-infrared light with a strength of 0.5 W / cm 2 , 800 nm for 15 minutes, and then purifying the dyed fabric in supercritical carbon dioxide, the purification pressure is 23 MPa, the temperature is 40 DEG C, and the time is 10 minutes.

[0041] Example 3

[0042] The application provides an antibacterial and detoxification waterless dyeing and finishing powder dye, which comprises a porphyrin metal organic framework carrier modified by 3-aminopropyl triethoxysilane on the surface, the carrier has a pore size of 3.2 nm, and the surface modification density is 1.2 functional groups / nm 2 , the metal node is zirconium ion; the carrier channel is loaded with copper phthalocyanine and IR808 photosensitizer, the mass ratio is 1:0.5, and contains laccase with an enzyme activity of 200 U / g; the surface of the carrier is modified with copper ions and zinc ions by ion exchange, the molar ratio is 1:3; the particle size of the powder dye is 2.0 mu m, and the Zeta potential is +20 mV; the preparation method of the powder dye comprises the following steps: reacting tetra(4-carboxyphenyl) porphyrin with a metal salt to prepare a carrier, reacting with a silane coupling agent at 80 DEG C for 4 hours, loading copper phthalocyanine and IR808 in an ethanol solution, ion exchanging with a copper salt and a zinc salt solution, and finally drying under the condition of supercritical carbon dioxide at 33 MPa and 50 DEG C; the waterless dyeing and finishing method comprises the following steps: treating pure cotton fabric in supercritical carbon dioxide for 40 minutes, adding powder dye, the mass ratio of the powder dye and the pure cotton fabric is 1:50, treating at 28 MPa and 52 DEG C for 30 minutes, and then irradiating the dyed fabric with near-infrared light with a strength of 2.0 W / cm 2 , 850 nm for 5 minutes, and then purifying the dyed fabric in supercritical carbon dioxide, the purification pressure is 28 MPa, the temperature is 50 DEG C, and the time is 20 minutes.

[0043] Example 4

[0044] The embodiment differs from example 1 only in that the mass ratio of copper phthalocyanine to IR808 is 1:0.4, and the rest of the parameters are exactly the same as example 1.

[0045] Example 5

[0046] The embodiment differs from example 1 only in that the molar ratio of copper to zinc ions is 1:1.5, and the rest of the parameters are exactly the same as example 1.

[0047] Example 6

[0048] The embodiment differs from example 1 only in that 3-glycidyloxypropyl trimethoxysilane is used instead of 3-aminopropyl triethoxysilane for surface modification of the carrier, and the rest of the parameters are exactly the same as example 1.

[0049] Example 7

[0050] The embodiment differs from example 1 only in that the laccase enzyme activity loaded in the pores of the carrier is 220 U / g, and the rest of the parameters are exactly the same as example 1.

[0051] Example 8

[0052] The embodiment differs from example 1 only in that the particle size of the powder dye is 0.5 μm, and the Zeta potential is -5 mV, and the rest of the parameters are exactly the same as example 1.

[0053] Comparative example 1

[0054] The comparative example differs from example 1 only in that a common antibacterial detoxification aid is used for ion exchange, and the rest of the parameters are exactly the same as example 1.

[0055] Comparative example 2

[0056] The comparative example differs from example 1 only in that the pore size of the carrier is 4.0 nm, and the rest of the parameters are exactly the same as example 1.

[0057] Comparative example 3

[0058] The comparative example differs from example 1 only in that the pore size of the carrier is 1.5 nm, and the rest of the parameters are exactly the same as example 1.

[0059] Comparative example 4

[0060] The comparative example differs from example 1 only in that the molar ratio of copper ions to zinc ions on the surface of the carrier is 1:4 (which exceeds the range of 1:(1-3) in claim 1), and the rest of the parameters are exactly the same as example 1.

[0061] Comparative example 5

[0062] The difference between the present comparative example and Example 1 is only that the supercritical carbon dioxide drying condition is 20 MPa, 35℃, and the rest of the parameters are exactly the same as those in Example 1.

[0063] The test data of the examples and comparative examples are shown in Table 1. Among them, the antibacterial rate is tested according to GB / T 20944.3-2008 (Staphylococcus aureus, contact time 30 min), the K / S value is tested using a Datacolor 650 colorimeter (determined at λmax, 8 layers), the color fastness is tested according to the ISO 105-C06 standard water washing (5 levels optimal), the photocatalytic degradation rate is the degradation rate of methylene blue solution (10 mg / L) under 500W xenon lamp irradiation for 2h, the dye loading rate is determined by thermogravimetric analysis (TGA) to measure the weight loss of the carrier, and the process stability is the relative standard deviation value of K / S value of 5 consecutive batches of production.

[0064] Table 1

[0065] Antibacterial rate (%) K / S value Color fastness (grade) Photocatalytic degradation rate (%) Dye loading rate (mg / g) Batch difference (%) Example 1 99.8±0.1 18.3±0.5 4-5 92.5±1.2 185±3 2.1 Example 2 98.7±0.3 16.8±0.7 4 89.3±1.5 172±5 3.5 Example 3 99.5±0.2 19.1±0.4 4-5 95.2±0.8 178±4 2.8 Example 4 99.7±0.2 17.9±0.6 4-5 93.7±1.0 183±2 3.2 Example 5 99.4±0.3 17.6±0.4 4-5 93.1±1.2 180±4 2.7 Example 6 98.9±0.2 18.5±0.6 4 91.7±1.3 183±3 2.3 Example 7 99.9±0.1 18.7±0.3 5 94.8±0.9 188±2 3.2 Example 8 97.5±0.4 15.2±0.8 3-4 87.6±1.8 165±6 4.1 Comparative Example 1 85.3±1.2 12.4±1.0 3 68.4±2.5 142±8 7.6

[0066] Through the comparative analysis of the above test data, the following conclusions can be drawn:

[0067] (1) The key performance indicators such as antibacterial rate, K / S value, color fastness and photocatalytic degradation rate in Examples 1-8 are significantly better than those in the comparative examples, indicating that the application significantly improves the antibacterial performance, dyeing effect and photocatalytic efficiency of the powder dye by using a specific pore size of porphyrin metal organic framework carrier, optimizing the modification of silane coupling agent and precisely controlling the ion exchange ratio;

[0068] (2) Comparing Example 1 and Example 6, although the dye loading rate is equivalent, the antibacterial rate decreases by 0.9 percentage points, indicating that amino silane coupling agent has more advantages in antibacterial performance;

[0069] (3) Comparing Example 1 and Example 7, the laccase enzyme activity of Example 7 is increased to 220 U / g, although the antibacterial rate reaches the highest value of 99.9%, but the process stability decreases slightly, indicating that the laccase activity in the range of 80-200 U / g can achieve the best balance;

[0070] (4) Comparing Example 1 and Example 8, the particle size of Example 8 is reduced to 0.5 μm and the Zeta potential is changed to -5 mV, resulting in a decrease of 17.0% in K / S value and a decrease of 10.8% in dye loading rate, which verifies the preferred range of 0.2-2 μm particle size and -10~+25 mV Zeta potential;

[0071] (5) Comparative Example 1 and Comparative Example 1 can be known, Comparative Example 1 adopts ordinary antibacterial detoxification auxiliary instead of patent zinc core auxiliary, and the antibacterial rate suddenly decreases by 14.5 percentage points, and the photocatalytic degradation rate decreases by 24.1 percentage points, which fully proves the key role of the zinc core high-performance antibacterial detoxification auxiliary;

[0072] The application successfully develops the antibacterial and detoxification anhydrous dyeing and finishing powder dye with excellent comprehensive performance by innovatively using the porphyrin metal organic framework carrier with a specific pore size, combining the optimized silane coupling agent surface modification technology and the precisely regulated metal ion exchange ratio. The technical scheme significantly improves the antibacterial effect, dyeing depth and photocatalytic degradation capacity of the dye, and ensures good process stability and reproducibility. Experimental data fully prove that the key technical parameter range of the application can realize the best balance among the antibacterial performance, dyeing effect and process stability, and provides a new type of efficient and environmentally-friendly solution for the textile dyeing and finishing industry.

[0073] The above is only a preferred embodiment of the application, and does not limit the application in any form. Although the application has been disclosed as above with a preferred embodiment, it is not intended to limit the application. Any person skilled in the art can make some changes or modifications to the above disclosed technical content to obtain equivalent embodiments with equivalent changes, without departing from the technical solution range of the application. Any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the application are still within the technical solution range of the application.

Claims

1. An antibacterial and detoxifying anhydrous dyeing powder, characterized in that, It consists of the following components: A metal-organic framework support containing a porphyrin structure, modified with a silane coupling agent, having a pore size of 1.8-3.2 nm and a surface modification density of 1.2-2.5 functional groups / nm. 2 ; Copper phthalocyanine and IR808 photosensitizer are loaded in the pores of the carrier, wherein the mass ratio of copper phthalocyanine to IR808 is 1:(0.2-0.5); Copper and zinc ions are ion-exchange modified onto the surface of the support, with a molar ratio of copper to zinc ions of 1:(1-3).

2. The powder dye according to claim 1, characterized in that, The silane coupling agent includes 3-aminopropyltriethoxysilane or 3-glycidyl etheroxypropyltrimethoxysilane.

3. The powder dye according to claim 1, characterized in that, The metal nodes of the metal-organic framework carrier containing porphyrin structure are zirconium ions or zinc ions.

4. The powder dye according to claim 1, characterized in that, The powder dye has a particle size of 0.2~2μm and a zeta potential of -10~+25mV.

5. The powder dye according to claim 4, characterized in that, It also includes laccase loaded within the pores of the carrier, the laccase having an enzyme activity of 80-200 U / g.

6. The powder dye according to claim 1, characterized in that, The preparation method of the powder dye includes the following steps: A metal-organic framework carrier containing a porphyrin structure was prepared by reacting tetra(4-carboxyphenyl)porphyrin with a metal salt in an organic solvent. The carrier was then reacted with a silane coupling agent at 60–80 °C for 4–6 hours to obtain a surface-modified carrier. The surface-modified carrier was then mixed with copper phthalocyanine and IR808 in an ethanol solution to load a photosensitizer. The photosensitizer-loaded product was then mixed with copper and zinc salt solutions for ion exchange. The ion-exchange product was dried under supercritical carbon dioxide conditions to obtain the powder dye.

7. The powder dye according to claim 6, characterized in that, The conditions for supercritical carbon dioxide drying are: pressure 27-33 MPa, temperature 40-50℃.

8. A supercritical carbon dioxide anhydrous dyeing and finishing method based on the powder dyes according to any one of claims 1 to 7, characterized in that, The anhydrous dyeing and finishing method includes: The fabric is pretreated in a supercritical carbon dioxide medium; powdered dye is added and dye adhesion treatment is carried out at 23-28 MPa and 48-52℃; after removal, the dyed fabric is subjected to near-infrared light triggering treatment; finally, the fabric is purified in a supercritical carbon dioxide medium.

9. The anhydrous dyeing and finishing method according to claim 8, characterized in that, The mass ratio of the powder dye to the fabric is 1:(20-50).

10. The anhydrous dyeing and finishing method according to claim 8, characterized in that, The pretreatment time is 20-40 minutes; the dye adhesion treatment time is 30-60 minutes; the near-infrared light irradiation wavelength is 800-850 nm, and the near-infrared light intensity is 0.5-2 W / cm². 2 The purification process takes 5-15 minutes; the pressure is 23-28 MPa, the temperature is 40-50℃, and the time is 10-20 minutes.