CN113122947B - Multi-base color-changing luminescent fiber with antibacterial property and preparation method thereof - Google Patents
Multi-base color-changing luminescent fiber with antibacterial property and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a multi-base color-changing luminescent fiber with antibacterial property and a preparation method thereof, wherein the preparation method comprises the following steps: introducing AIE chromophore into polystyrene chain end by atom transfer radical polymerization to obtain PS/AIE- (1,2), preparing PS/AIE- (1,2) into spinning solution, and performing electrostatic spinning to obtain multi-base color-changing luminescent fiber with antibacterial property; in the prepared fiber, a compound A and a compound B are covalently bonded to the fiber; the aggregation state of the compound A and the compound B is J aggregation; compound a and compound B each provide an AIE chromophore. The preparation method is simple and efficient by covalently bonding AIE monomer molecules into the nanofiber material, is suitable for industrial application, and the multi-primary color-changing luminescent fiber material with antibacterial property has the advantages of high stability and uniformity of AIE components, and good color-changing and color-fading durability of the material.
Description
Technical Field
The invention belongs to the technical field of composite materials, and relates to a multi-base color-changing luminescent fiber with antibacterial property and a preparation method thereof.
Background
The production of luminescent fibers can be categorized into two groups: composite luminescent fibers and structural luminescent fibers. The composite luminescent fiber is a relatively traditional synthetic fiber production process, namely a process of taking fiber-forming polymer as a matrix, adding luminescent substances (such as light-storing pigment, fluorescent powder or photoluminescence compounds), and then spinning or spraying. The luminescent fiber produced by the production method has the following characteristics: the wavelength range of the emitted light is wide, and the color of the light can be changed by the type of the added fluorescent powder; the operation is simple, and the process can be found according to the needs; the mechanical properties of the material are generally poor, which is linked to the compatibility between the raw materials. The structural luminescent fiber is characterized in that chromophoric groups are introduced on a fiber-forming polymer molecular chain (a main chain or a side chain) through covalent bond connection, so that the molecules of the polymer have color-changing characteristics, and the color-changing effect of the chromophoric groups is not influenced. The luminescent fiber has the advantages of constant wavelength, stable performance, wide application range and the like. In the field of future luminescent fibers, on one hand, it is expected that a new coloring approach can be developed, a plurality of novel structural luminescent fibers can be explored, the design of molecular structure and synthesis can be carried out according to the will of people under the guidance of chemical theory, and then experiments are carried out according to the design scheme with guidance, so as to manufacture luminescent fiber materials with specific structure and performance. On the other hand, feasible process technologies such as the combination of fluorescence technology and nanocrystallization technology are required to be deeply researched and applied to the manufacturing and production of fiber materials, so as to obtain fiber products with excellent performance; or the color-changing garment material processing technology can be completed by utilizing a microcapsule technology, a coating technology and the like by focusing on fabric weaving and after finishing. In the future, novel luminescent materials are developed to reduce the raw material cost of luminescent fibers and reduce the harm of the materials to human bodies and the pollution to the environment.
The luminescent fiber refers to a functional fiber capable of emitting light instantly or continuously under the condition of general illumination or special illumination. According to different properties of light irradiation, luminescent fibers can be divided into two categories, namely fluorescent fibers and long-afterglow luminescent fibers (also called light-storing fibers or noctilucent fibers). The fluorescent fiber can present specific color under the irradiation condition of special light (such as ultraviolet light), so the fluorescent fiber can be widely used in the anti-counterfeiting field; the long-afterglow luminescent fiber is a fiber which can continuously emit light for several hours in the dark after a light source is removed by accumulating sunlight or an indoor lighting source, and can be used for fire-fighting emergency, safety indication and the like.
In recent years, luminescent fiber materials have gained more and more importance in the research of textiles, printing, sensors and optoelectronic functional devices, but it is difficult to prepare nano materials with high fluorescence performance by the traditional method. Most of luminescent fiber materials are rigid planar molecules with a large pi conjugated system, have high fluorescence quantum yield in a dilute solution, but have reduced fluorescence or even no luminescence in an aggregation state, namely, fluorescence quenching is caused by aggregation. In practical applications, the fluorescent material is often made into a film or fiber filament form, so that the aggregation of fluorescent molecules and the resulting decrease of fluorescence are difficult to avoid, which greatly limits the practical application of the fluorescent fiber material.
In 2001, researchers found that silacyclopentadiene (silole) derivatives hardly emitted light in solution, and emitted light was greatly enhanced after forming a solid, and thus this phenomenon was defined as an "aggregation-induced emission (AIE)" phenomenon, abbreviated as AIE effect (chem. The compound with AIE effect fundamentally overcomes the problem of fluorescence quenching caused by aggregation, opens up a brand new angle for people to know organic luminescent materials, and attracts the interest of academics in AIE research. The molecules do not emit light or emit light very weakly in solution, and once in an aggregation state, such as nanoparticles or solid films, the luminous efficiency is greatly enhanced, which can reach thousands of times of the fluorescence quantum yield in a solution state. The aggregation-induced emission compound is an important source of a light-emitting and color-changing material, is an intelligent material, and has important potential application in the fields of stress sensing, trademark anti-counterfeiting, light-emitting devices and the like.
The electrostatic spinning is a convenient and efficient method for preparing continuous nano-micron fibers, and has the advantages of low cost, simple equipment and the like. With the development of electrostatic spinning technology and the requirements of different application fields on product structures, researchers are paying attention to how to prepare directionally arranged nanofibers by adding auxiliary electrodes or adjusting the shapes of receiving devices.
At present, photochromic luminescent materials are applied to fabrics, mainly by adding adhesives into paints for high-temperature baking or by adopting paint printing and coating, and have the defects of poor color fastness, poor weather resistance, poor durability and the like. In addition, a small part of photochromic fibers are produced and prepared by liquid crystal spinning, electrostatic spinning, grafting of spirooxazine groups or spiropyran groups, addition of fluorescent agents or surface adhesion of special microcapsules, but the preparation process is complex, has great harm to the environment and potential danger of damaging human health, and has the defects of easy damage of surface structure, poor fatigue resistance, short service life and the like. For example, the Chinese patent ZL200580011656 adopts electrostatic spinning to prepare photochromic fibers, and the method can only prepare ultrafine short fibers, and has low yield and complex production process. In the chinese patent CN101701052a, a chemical grafting method is adopted, in which an acrylate dye monomer containing a spirooxazine group is initiated to polymerize by benzoyl peroxide and grafted to a nitrocellulose macromolecular main chain for preparing a photochromic film and coating, the method has a complex process, uses a large amount of organic solvents, and cannot ensure the grafting rate. The method belongs to solution spinning, is complex in process and pollutes the environment, and in addition, the prepared fiber has low strength, so that the application of the prepared fiber is greatly limited. In the chinese patent CN104047069a, the photochromic dye and the low-melting nylon chips are melted, blended and granulated to prepare the master batch, and then the master batch is melted and blended with the low-melting cut particles to prepare the photochromic POY filament by drafting. Patent CN103556300A chooses fiber-grade polyethylene terephthalate as the core layer, polyethylene terephthalate added with phenoxy naphthoquinone photochromic material is used as the cortex, photochromic fiber is prepared, the method prepares thermal bonding fiber, which mainly plays a role in bonding other materials and supporting, can not be applied to the surface of products and the design of pattern textures, and has large limitation. In the chinese patent CN109402780a, a fiber-forming polymer is selected as a skin layer, a thermoplastic fiber-forming polymer is selected as a core layer, but photochromic dyes, antioxidants, spinning aids, thermal stabilizers, sensitizers and the like need to be added, the process is complex, and the microcapsule technical scheme has the problem of uneven distribution of the dyes.
A small molecule naphthalimide pyrazoline small molecule (TPP-NI) with AIE effect is added into a polyamide 6 (PA 6) solution to prepare the PA6/TPP-NI composite nano fluorescent fiber yarn with aggregation-induced emission effect, the mechanical property of the composite nano fiber bundle is slightly reduced compared with that of a pure PA6 fiber bundle, and the crystallinity is obviously reduced. The TPE-DBT-TPE conjugated compound is constructed by using tetraphenyl ethylene and dibenzothiophene, and is doped into polymethyl methacrylate (PMMA) to form a mixed system, and the TPE-DBT-TPE/PMMA nanofiber composite membrane is prepared by utilizing electrostatic spinning. There are methods of adding AIE molecules 2CNP2TPA and TPE-2N into polylactic acid (PLA) solution+Two AIE/PLA composite nano-fibers are prepared by an electrostatic spinning method, and the AIE photochromic luminescent fiber materials prepared by the methods have poor mechanical properties and durability.
The intermediate of the ring-opening process of the spiropyran allochroic material and the completed ring-opening body mostly exist in a zwitterion structure, so that the charge is relatively concentrated and is easily influenced by environmental factors to cause consumption, thereby having poor fatigue resistance. Oxygen in the air promotes its photodegradation by a radical process. Thus, there is no particularly significant effect of linking the spiropyran to the high polymer. For example, organic color-changing material nitro spiropyran is prepared as initiator, methyl methacrylate monomer is initiated to polymerize through the initiator to obtain polymer with spiropyran photochromic material at end, the polymer is doped with terbium rare earth complex to prepare spinning solution, and the nano-micron fiber capable of photochromism is prepared by utilizing electrostatic spinning technology. Some techniques adopt coaxial electrostatic spinning, and successfully prepare the room temperature vulcanized silicone rubber nano-fiber with the diameter ranging from 400 nm to 600nm by virtue of the protection and restriction effects of outer-layer rigid plastics. Meanwhile, the rare earth nano-fiber composite material is prepared by combining the excellent fluorescence property of the rare earth beta-diketone organic complex and applying the electrostatic spinning technology. The structural luminescent fibers prepared by the method need to be doped with rare earth metal complexes, and the dispersion degree and stability of the doped rare earth have great influence on the luminescent performance of the fibers; and the preparation method and the process flow are complex.
Nowadays, various chronic wounds are extremely easy to suffer from bacterial infection, and further cause septicemia, acute renal failure and other infection complications, and the wound infection in the world is a great problem threatening the health of future people. In addition, with the abuse of antibiotics, the mutation frequency of bacteria is remarkably accelerated, more and more drug-resistant variant strains appear, and super-drug-resistant bacteria continuously evolve, so that the research and development requirements of human on novel antibacterial drugs and antibacterial materials are particularly urgent.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a multi-primary color-changing luminescent fiber with antibacterial property and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following scheme:
the multi-base color-changing luminescent fiber with antibacterial property is characterized in that a compound A and a compound B are covalently bonded on the multi-base color-changing luminescent fiber; in the fiber, the aggregation state of the compound A and the compound B is J aggregation;
the structural formula of the compound A is as follows:
wherein X is O, S or Se;
the structural formula of the compound B is as follows:
the compound B is obtained by a one-step method through the reaction of monohydroxy tetraphenylethylene and 2-methacryloyl chloride.1H NMR(300MHz,(CD3)2CO, delta.) 7.30-7.46 (m, 19H), 6.43 (d, 2H), 2.01 (s, 3H) (this molecule has been reported and is part of the prior art).
As a preferable technical scheme:
in the multi-base color-changing luminescent fiber with antibacterial property, the molar ratio of the compound A to the compound B is 1:1-1.4 (the molar ratio is too low, the degree of action of two molecules is low, and too high, which can cause waste of high value-added raw materials), and the total content of the compound A and the compound B is 0.5-5.0% of the total mass of the multi-base color-changing luminescent fiber (when the content is too low, the antibacterial property of the fiber can be affected, and too high can cause waste of antibacterial components). The two molecules have intermolecular action at the microscopic level, and the J aggregation can be formed by pi accumulation, although the free movement of the covalent bond is limited to a certain extent by covalent bond insertion, the monomers are copolymerized, so that the J aggregation form still exists partially in theory.
The multi-primary color-changing luminescent fiber with antibacterial property has the average diameter of 20-200 nm, the Young modulus of 1000-2000 MPa and the tensile strength of 100-500 MPa.
The multi-primary color-changing luminescent fiber with antibacterial property, which is prepared from the raw materialsThe polybase color-changing luminescent fiber has higher ROS generation efficiency, and the maximum irradiation intensity is 10-100 mW/mm when the wavelength of near infrared light is 700-850 nm2(high near-infrared luminous intensity), the gram bacteria inhibition rate is more than or equal to 85 percent, and the staphylococcus aureus inhibition rate is more than or equal to 85 percent (has excellent photodynamic antibacterial curative effect).
The multi-primary color-changing luminescent fiber with antibacterial property has a smooth appearance, can change color for no more than 1s (can be quickly changed) under the illumination of excitation light with the wavelength of 350-370 nm or 550-570 nm, and can be completely faded within 1min after being moved away from a light source, namely, the color of the multi-primary color-changing luminescent fiber is recovered to the original color; the multi-primary color-changing luminescent fiber is repeatedly illuminated for 20 times, and the color-changing emission light intensity is more than 90% of the maximum intensity value.
The invention also provides a preparation method of the multi-primary color-changing luminescent fiber with antibacterial property, which comprises the following steps:
(1) The AIE chromophore is introduced into the end of polystyrene chain by atom transfer radical polymerization, which comprises the following steps: uniformly mixing styrene (PS), cuBr, a compound A, a compound B, PMDETA (pentamethyl diethylenetriamine) and refined cyclohexanone, polymerizing at 78-82 ℃ under the protection of inert gas, reacting for 6-10 h, quickly cooling, diluting with tetrahydrofuran, removing copper by using alkaline alumina to obtain a solution, dripping the solution into 50-100 mL of vigorously stirred methanol for chromatography, carrying out suction filtration and drying to obtain PS/AIE- (1,2);
the molar ratio of the styrene (PS), the CuBr, the compound A, the compound B and the PMDETA is as follows: 40, (0.04-0.08), (0.09-0.18); during chromatography, the volume ratio of the refined cyclohexanone to the tetrahydrofuran to the methanol is 1 (0.1-0.3) to 2.5-5; during polymerization, the molar volume ratio of the styrene to the refined cyclohexanone is 1mol (80-120) L;
the preparation process of the compound A comprises the following steps: adding a compound a and alkali into dry tetrahydrofuran at the temperature of-30 to-15 ℃, uniformly mixing, adding a compound b at room temperature, and continuously reacting for 10 to 15 hours to obtain a mixture; finally, filtering the mixture to obtain filtrate, concentrating the filtrate, and purifying by using a silica gel chromatography to obtain the compound A; (this molecule is newly designed and synthesized in the present invention)
The compound a is
The compound b is
(2) Dissolving PS/AIE- (1,2) in a solvent at room temperature, uniformly mixing (stirring for 5-7 h at room temperature) to obtain a spinning solution, and preparing the multi-primary color-changing luminescent fiber with antibacterial property by adopting a water bath electrostatic spinning method.
The preparation method of the multi-base color-changing luminescent fiber with antibacterial property is characterized in that the mass fraction of the spinning solution is 15-25%, the solvent is 1,3-dimethyl-2-imidazolidinone (DMI), dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or Diethoxymethane (DEM), and a DMF solution is preferred.
The preparation method of the multi-primary color-changing luminescent fiber with antibacterial property comprises the following steps of: placing the spinning solution into an injector, flying the spinning solution out of the tip of a spinning nozzle under the action of an electric field force generated by a high-voltage power supply and the thrust of a flow pump, flying the spinning solution for a certain distance, then falling the spinning solution into a fatty alcohol-polyoxyethylene ether bath tank filled with 4-6 per mill of mass fraction, drawing the obtained fiber out of the bath tank, then sequentially passing through a godet roller, a drying device and a tension device, and finally winding the fiber onto a rotating shaft coated with an aluminum foil to obtain continuous fiber (continuous fiber yarn);
the technological parameters of electrostatic spinning are as follows: the temperature is 22-28 ℃, the relative humidity of the environment is 42-48%, the spinning voltage is 20kV, the flow rate of the spinning solution is 1.0mL/h, the horizontal distance from the tip of the spinneret to the inner wall of the bath is 3.0-5.0 cm, and the vertical distance from the tip of the spinneret to the surface of the bath is 6.5-8.5 cm (the numerical range of the 'certain distance' in the previous section).
The mechanism of the invention is as follows:
the multi-primary color-changing luminescent fiber with antibacterial property contains AIE-1 type molecules and AIE-2 type molecules, on one hand, the introduction of the AIE-1 type molecules reduces the planarity of conjugated molecules, so that the skeleton structures of the two AIE molecules are aggregated in a solution, and the aggregation state is J aggregation; j aggregation can cause aggregation to induce fluorescence enhancement effect, the luminous intensity of the material obtained by adding two molecules together is higher than the sum of the luminous intensities of the material obtained by using a single molecule, namely the luminous intensity of AIE molecules can be enhanced to a certain degree, meanwhile, due to pi accumulation interaction and intermolecular energy transfer, a synergistic effect is generated, the luminous intensity of the AIE molecules can be enhanced to a certain degree by combining the surface effect and the interface effect of the nano-fiber, the material is endowed with higher active oxygen (ROS) generation efficiency, so that the fluorescence emission spectrum red shift of the AIE molecules is caused, higher-intensity near infrared luminescence is obtained, the material has excellent photodynamic antibacterial effect on gram bacteria, and infection caused by staphylococcus aureus and the like can be controlled. On the other hand, AIE molecules with multiple conjugated rigid-CN groups can insert their conjugated rigid groups into the bacterial cell wall, achieving beneficial antibacterial properties by inhibiting the synthesis of the bacterial cell wall by hindering transglycosylation and transpeptidation processes.
In addition, two molecules capable of photochromic luminescence are designed, two molecular frameworks with Aggregation Induced Emission (AIE) effects are introduced into the polymer block in a covalent bond mode to prepare the nanofiber, and the prepared nanofiber has the property of emitting fluorescence of different colors under the irradiation of ultraviolet light with different wavelengths. And the structural photochromic luminous molecule has rigid structure and good compatibility with materials, and is connected with the nanofiber through a covalent bond, so that the stability of AIE molecules in the fiber material is better than that of the conventional doping, the uniform dispersibility is better because reactants are fully stirred in the reaction process, and the defects of poor mechanical property, poor stability and uniformity and the like of the composite luminous fiber material can be overcome. The fiber material designed by the invention can rapidly change color within 1s under illumination and completely change color within 1min after being removed from a light source. The photochromic luminescent fiber changes color after being illuminated for 20 times, and the fading efficiency is not obviously changed, namely the durability is good.
Advantageous effects
(1) According to the preparation method of the multi-base color-changing luminescent fiber with the antibacterial property, the AIE monomer molecules are covalently combined into the nanofiber material, so that the preparation method is simple and efficient, and is suitable for industrial application;
(2) The multi-base color-changing luminescent fiber with antibacterial property has the advantages that the AIE component in the structural photochromic luminescent nanofiber material is high in stability, excellent in uniformity and good in color-changing and color-fading durability.
Drawings
Fig. 1 is a process flow diagram of electrospinning nanofiber bundles.
Detailed Description
The present invention will be further described with reference to the following embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The Young modulus test method comprises the following steps: FD-HY-1 Young modulus tester (Young modulus by bending method);
the tensile strength test method comprises the following steps: measured according to the national standard GB T14344-2008;
the structural formula of compound B in the examples is:
the preparation method is the prior art, and the compound B can be obtained by a one-step method through the reaction of monohydroxy tetraphenylethylene and 2-methacryloyl chloride.
Example 1
The preparation process of the compound A comprises the following steps: adding a compound a and alkali into dried tetrahydrofuran at the temperature of-30 ℃, uniformly mixing, adding a compound b at the temperature of 23 ℃, and continuously reacting for 10 hours to obtain a mixture; finally, filtering the mixture to obtain filtrate, concentrating the filtrate, and purifying by using a silica gel chromatography to obtain a compound A;
wherein, the compound a is
X is O, compound b is
The molar ratio of tetrahydrofuran, compound a, base, compound b is 80.
The structural formula of the prepared compound A is as follows:
wherein X is O.
Example 2
One compound is compound a, which is prepared by the process of: adding a compound a and alkali into dried tetrahydrofuran at the temperature of-22 ℃, uniformly mixing, adding a compound b at the temperature of 25 ℃, and continuously reacting for 13 hours to obtain a mixture; finally, filtering the mixture to obtain filtrate, concentrating the filtrate, and purifying by using a silica gel chromatography to obtain a compound A;
wherein, the compound a is
X is S, compound b is
The molar ratio of tetrahydrofuran, compound a, base, compound b is 120.
The structural formula of the prepared compound A is as follows:
wherein X is S.
Example 3
One compound is compound a, which is prepared by the process of: firstly adding a compound a and alkali into dry tetrahydrofuran at the temperature of-15 ℃, uniformly mixing, then adding a compound b at the temperature of 27 ℃, and continuously reacting for 15 hours to obtain a mixture; finally, filtering the mixture to obtain filtrate, concentrating the filtrate, and purifying by using a silica gel chromatography to obtain a compound A;
wherein, the compound a is
X is Se, compound b is
The molar ratio of tetrahydrofuran, compound a, base, and compound b is 110.
The structural formula of the prepared compound A is as follows:
wherein X is Se.
Example 4
A preparation method of multi-base color-changing luminescent fiber with antibacterial property comprises the following specific steps:
(1) Uniformly mixing styrene, cuBr, the compound A prepared in example 1, the compound B, PMDETA and refined cyclohexanone, polymerizing at 80 ℃ under the protection of inert gas, reacting for 6 hours, quickly cooling (the quick cooling time is 10s (ice bath)), diluting with tetrahydrofuran, removing copper by using alkaline alumina to obtain a solution, dripping the solution into 50mL of vigorously stirred methanol for chromatography, carrying out suction filtration and drying to obtain PS/AIE- (1,2);
wherein, the mol ratio of styrene to CuBr to the compound A to the compound B to the PMDETA is as follows: 40; during polymerization, the molar volume ratio of the compound A to the purified cyclohexanone is 1mol; during chromatography, the volume ratio of the purified cyclohexanone to the tetrahydrofuran to the methanol is 1;
(2) Dissolving the PS/AIE- (1,2) prepared in the step (1) in 1,3-dimethyl-2-imidazolidinone (DMI) at 23 ℃, and uniformly mixing (stirring for 5 hours at 23 ℃ and the stirring speed of 400 revolutions per minute (magnetic stirring)) to obtain a spinning solution with the mass fraction of 20%; adopting a water bath method for electrostatic spinning, as shown in figure 1, placing a spinning solution into an injector, flying the spinning solution out from the tip of a spinneret under the action of an electric field force generated by a high-voltage power supply and a thrust of a flow pump, flying the spinning solution for a certain distance, then falling into a fatty alcohol polyoxyethylene ether bath with 5 per mill of mass fraction, drawing the obtained fiber out of the bath, then sequentially passing through a godet roller, a drying device and a tension device, and finally winding the fiber onto a rotating shaft coated with an aluminum foil to prepare the multi-base color-changing luminescent fiber with antibacterial property;
wherein, the technological parameters of the water bath method electrostatic spinning are as follows: the spinning temperature is 22 ℃, the ambient relative humidity is 48%, the spinning voltage is 20kV, the flow rate of the spinning solution is 1.0mL/h, the horizontal distance from the tip of the spinning nozzle to the inner wall of the bath is 3cm, and the vertical distance (the flying distance of the spinning solution) from the surface of the bath is 6.5cm.
In the prepared multi-base color-changing luminescent fiber with antibacterial property, the compound A and the compound B are combined to the fiber through covalent bonds, and the aggregation state of the compound A and the compound B is J aggregation; the molar ratio of the compound A to the compound B is 1:1, and the total content of the compound A and the compound B is 0.5 percent of the total mass of the multi-primary color-changing luminescent fiber; the average diameter of the multi-primary color-changing luminescent fiber is 20nm, the Young modulus is 1000MPa, and the tensile strength is 100MPa; the maximum irradiation intensity of the multi-base color-changing luminescent fiber is 10mW/mm when the near infrared wavelength is 700nm2The bacteriostatic rate for gram bacteria is 85 percent, and the bacteriostatic rate for staphylococcus aureus is 85 percent; the time for the multi-primary color-changing luminescent fiber to change from white to blue under illumination (the wavelength of exciting light is 350-370 nm) is not more than 1s, and the multi-primary color-changing luminescent fiber is recovered to the primary color within 1min after being moved away from the light source; the multi-primary color-changing luminescent fiber changes color under the irradiation of exciting light after being illuminated for 20 times, namely after being repeatedly tested for 20 times, the intensity of the emitted light is 90 percent of the maximum intensity value, and the durability is good.
Example 5
A preparation method of multi-base color-changing luminescent fiber with antibacterial property comprises the following specific steps:
(1) Uniformly mixing styrene, cuBr, the compound A prepared in example 2, the compound B, PMDETA and refined cyclohexanone, polymerizing at 80 ℃ under the protection of inert gas, reacting for 7 hours, quickly cooling (the quick cooling time is 20s (ice bath)), diluting with tetrahydrofuran, removing copper by using alkaline alumina to obtain a solution, dripping the solution into 60mL of vigorously stirred methanol for chromatography, carrying out suction filtration and drying to obtain PS/AIE- (1,2);
the molar ratio of styrene to CuBr to compound A to compound B to PMDETA is as follows: 40; the molar volume ratio of the compound A to the purified cyclohexanone is 1mol; during chromatography, the volume ratio of the refined cyclohexanone to the tetrahydrofuran to the methanol is 1.1;
(2) Dissolving the PS/AIE- (1,2) prepared in the step (1) in Dimethylformamide (DMF) at 24 ℃, and uniformly mixing (stirring for 6 hours at 24 ℃ and the stirring speed of 450 revolutions per minute (magnetic stirring)) to obtain a spinning solution with the mass fraction of 20%; adopting a water bath method for electrostatic spinning, placing spinning solution into an injector, flying the spinning solution out from the tip of a spinneret under the action of an electric field force generated by a high-voltage power supply and a thrust force of a flow pump, flying the spinning solution for a certain distance, then falling into a fatty alcohol-polyoxyethylene ether bath with the full mass fraction of 5 per mill, drawing the obtained fiber out of the bath, then sequentially passing through a godet roller, a drying device and a tension device, and finally winding the fiber onto a rotating shaft coated with an aluminum foil to prepare the multi-base color-changing luminescent fiber with antibacterial property;
wherein, the technological parameters of the water bath electrostatic spinning are as follows: the temperature is 23 ℃, the ambient relative humidity is 47%, the spinning voltage is 20kV, the flow rate of the spinning solution is 1.0mL/h, the horizontal distance from the tip of the spinning nozzle to the inner wall of the bath is 3cm, and the vertical distance (the flying distance of the spinning solution) from the surface of the bath is 7cm.
In the prepared multi-base color-changing luminescent fiber with antibacterial property, the compound A and the compound B are combined to the fiber through covalent bonds, and the aggregation state of the compound A and the compound B is J aggregation; the molar ratio of the compound A to the compound B is 1.1, and the total content of the compound A and the compound B is 1 percent of the total mass of the multi-base color-changing luminescent fiber; the average diameter of the multi-primary color-changing luminescent fiber is 40nm, the Young modulus is 1200MPa, and the tensile strength is 150MPa; the maximum irradiation intensity of the polybase color-changing luminescent fiber is 50mW/mm when the wavelength of the near infrared light is 770nm2The bacteriostatic rate for gram bacteria is 87 percent, and the bacteriostatic rate for staphylococcus aureus is 86 percent; the time for the multi-primary color-changing luminescent fiber to change from white to blue under illumination (the wavelength of exciting light is 350-370 nm) is not more than 1s, and the multi-primary color-changing luminescent fiber is recovered to the primary color within 1min after being moved away from the light source; the multi-base color-changing luminescent fiber is illuminated 20 timesAfter the test is repeated for 20 times, the color is changed under the irradiation of exciting light, the intensity of the emitted light is 91 percent of the maximum intensity value, and the durability is good.
Example 6
A preparation method of multi-base color-changing luminescent fiber with antibacterial property comprises the following specific steps:
(1) Uniformly mixing styrene, cuBr, the compound A prepared in example 3, the compound B, PMDETA and refined cyclohexanone, polymerizing at 80 ℃ under the protection of inert gas, reacting for 8 hours, quickly cooling (the quick cooling time is 30s (ice bath)), diluting with tetrahydrofuran, removing copper by using alkaline alumina to obtain a solution, dripping the solution into 70mL of vigorously stirred methanol for chromatography, performing suction filtration and drying to obtain PS/AIE- (1,2);
the molar ratio of styrene to CuBr to compound A to compound B to PMDETA is as follows: 40, 0.05; during polymerization, the molar volume ratio of the compound A to the purified cyclohexanone is 1mol; during chromatography, the volume ratio of the purified cyclohexanone to the tetrahydrofuran to the methanol is 1;
(2) Dissolving PS/AIE- (1,2) prepared in the step (1) in dimethyl sulfoxide (DMSO) at 25 ℃, uniformly mixing (stirring for 7 hours at 25 ℃ and at a stirring speed of 500 revolutions per minute (magnetic stirring) to obtain a spinning solution with the mass fraction of 20 percent), adopting a water bath method for electrostatic spinning, putting the spinning solution into an injector, flying the spinning solution out from the tip of a spinneret under the action of electric field force generated by a high-voltage power supply and the thrust of a flow pump, flying for a certain distance, then falling into a fatty alcohol polyoxyethylene ether bath with the mass fraction of 5 per thousand, drawing the obtained fiber out of the bath, passing through a godet, a drying device and a tension device in sequence, and finally winding the fiber onto a rotating shaft coated with an aluminum foil to prepare the multi-photochromic luminescent fiber with antibacterial property;
wherein, the technological parameters of the water bath electrostatic spinning are as follows: the temperature is 24 ℃, the ambient relative humidity is 46%, the spinning voltage is 20kV, the flow rate of the spinning solution is 1.0mL/h, the horizontal distance from the tip of the spinning nozzle to the inner wall of the bath is 4cm, and the vertical distance (the flying distance of the spinning solution) from the surface of the bath is 7.5cm.
In the prepared multi-base color-changing luminescent fiber with antibacterial propertyCompound a and compound B are bound to the fiber by covalent bonds, and the aggregation state of compound a and compound B is J aggregation; the molar ratio of the compound A to the compound B is 1.2, and the total content of the compound A and the compound B is 1.5 percent of the total mass of the multi-base color-changing luminescent fiber; the average diameter of the multi-primary color-changing luminescent fiber is 70nm, the Young modulus is 1400MPa, and the tensile strength is 200MPa; the maximum irradiation intensity of the multi-base color-changing luminescent fiber is 80mW/mm when the near infrared wavelength is 830nm2The bacteriostatic rate for gram bacteria is 88 percent, and the bacteriostatic rate for staphylococcus aureus is 88 percent; the time for the multi-primary color-changing luminescent fiber to change from white to blue under illumination (the wavelength of exciting light is 350-370 nm) is not more than 1s, and the multi-primary color-changing luminescent fiber is recovered to the primary color within 1min after being moved away from the light source; the multi-primary color-changing luminescent fiber changes color under the irradiation of exciting light after being illuminated for 20 times, namely after being repeatedly tested for 20 times, the emitting light intensity is 92 percent of the maximum intensity value, and the durability is good.
Example 7
A preparation method of multi-base color-changing luminescent fiber with antibacterial property comprises the following specific steps:
(1) Uniformly mixing styrene, cuBr, the compound A prepared in example 1, the compound B, PMDETA and refined cyclohexanone, polymerizing at 80 ℃ under the protection of inert gas, reacting for 9 hours, quickly cooling (the quick cooling time is 10s (ice bath)), diluting with tetrahydrofuran, removing copper by using alkaline alumina to obtain a solution, dripping the solution into 80mL of vigorously stirred methanol for chromatography, carrying out suction filtration and drying to obtain PS/AIE- (1,2);
the molar ratio of styrene to CuBr to compound A to compound B to PMDETA is as follows: 40; the molar volume ratio of the compound A to the purified cyclohexanone is 1mol; during chromatography, the volume ratio of the purified cyclohexanone to the tetrahydrofuran to the methanol is 1.1;
(2) Dissolving the PS/AIE- (1,2) prepared in the step (1) in Diethoxymethane (DEM) at 26 ℃, uniformly mixing (stirring for 5 hours at 26 ℃ and at a stirring speed of 600 revolutions per minute (magnetic stirring) to obtain a spinning solution with the mass fraction of 20 percent), adopting a water bath method for electrostatic spinning, putting the spinning solution into an injector, flying the spinning solution out from the tip of a spinning nozzle under the action of electric field force generated by a high-voltage power supply and the thrust of a flow pump, flying for a certain distance, falling into a fatty alcohol polyoxyethylene ether bath with the mass fraction of 5 per thousand, drawing the obtained fiber out of the bath, passing through a godet roller, a drying device and a tension device in sequence, and finally winding the fiber onto a rotating shaft coated with aluminum foil to prepare the multi-photochromic luminescent fiber with antibacterial property;
wherein, the technological parameters of the water bath electrostatic spinning are as follows: the temperature is 25 ℃, the ambient relative humidity is 45%, the spinning voltage is 20kV, the flow rate of the spinning solution is 1.0mL/h, the horizontal distance from the tip of the spinning nozzle to the inner wall of the bath is 4cm, and the vertical distance (the flying distance of the spinning solution) from the surface of the bath is 8cm.
In the prepared multi-base color-changing luminescent fiber with antibacterial property, the compound A and the compound B are combined to the fiber through covalent bonds, and the aggregation state of the compound A and the compound B is J aggregation; the molar ratio of the compound A to the compound B is 1.3, and the total content of the compound A and the compound B is 2 percent of the total mass of the multi-primary color-changing luminescent fiber; the average diameter of the multi-primary color-changing luminescent fiber is 100nm, the Young modulus is 1600MPa, and the tensile strength is 300MPa; the maximum irradiation intensity of the polybase color-changing luminescent fiber is 30mW/mm when the near infrared wavelength is 720nm2The bacteriostatic rate for gram bacteria is 90 percent, and the bacteriostatic rate for staphylococcus aureus is 91 percent; the time for changing the multi-primary color-changing luminescent fiber from white to red under illumination (the wavelength of exciting light is 550-570 nm) is not more than 1s, and the multi-primary color-changing luminescent fiber is recovered to the primary color within 1min after being moved away from the light source; the multi-primary color-changing luminescent fiber changes color under the irradiation of exciting light after being illuminated for 20 times, namely after being repeatedly tested for 20 times, the emitting light intensity is 94 percent of the maximum intensity value, and the durability is good.
Example 8
A preparation method of multi-base color-changing luminescent fiber with antibacterial property comprises the following specific steps:
(1) Uniformly mixing styrene, cuBr, the compound A prepared in example 2, the compound B, PMDETA and refined cyclohexanone, polymerizing at 80 ℃ under the protection of inert gas, reacting for 10 hours, quickly cooling (the quick cooling time is 20s (ice bath)), diluting with tetrahydrofuran, removing copper by using alkaline alumina to obtain a solution, dripping the solution into 90mL of vigorously stirred methanol for chromatography, carrying out suction filtration and drying to obtain PS/AIE- (1,2);
the molar ratio of styrene to CuBr to compound A to compound B to PMDETA is as follows: 40; during polymerization, the molar volume ratio of the compound A to the purified cyclohexanone is 1mol; during chromatography, the volume ratio of the refined cyclohexanone to the tetrahydrofuran to the methanol is 1.2;
(2) Dissolving PS/AIE- (1,2) prepared in the step (1) in 1,3-dimethyl-2-imidazolidinone (DMI) at 27 ℃, uniformly mixing (stirring for 6 hours at 27 ℃ and the stirring speed of 700 revolutions per minute (magnetic stirring) to obtain a spinning solution with the mass fraction of 20 percent), adopting a water bath method for electrostatic spinning, putting the spinning solution into an injector, flying the spinning solution from the tip of a spinneret under the action of electric field force generated by a high-voltage power supply and the thrust of a flow pump, falling into a fatty alcohol polyoxyethylene ether bath with the mass fraction of 5 per thousand after flying for a certain distance, passing the obtained fiber out of the bath through a godet roller, a drying device and a tension device in turn, and finally winding the fiber onto a rotating shaft coated with an aluminum foil to prepare the multi-base color-changing luminescent fiber with antibacterial property;
wherein, the technological parameters of the water bath electrostatic spinning are as follows: the temperature is 26 ℃, the ambient relative humidity is 44%, the spinning voltage is 20kV, the flow rate of the spinning solution is 1.0mL/h, the horizontal distance from the tip of the spinning nozzle to the inner wall of the bath is 5cm, and the vertical distance (the flying distance of the spinning solution) to the surface of the bath is 8.5cm.
In the prepared multi-base color-changing luminescent fiber with antibacterial property, the compound A and the compound B are combined to the fiber through covalent bonds, and the aggregation state of the compound A and the compound B is J aggregation; the molar ratio of the compound A to the compound B is 1.4, and the total content of the compound A and the compound B is 3 percent of the total mass of the multi-base color-changing luminescent fiber; the average diameter of the multi-primary color-changing luminescent fiber is 150nm, the Young modulus is 1800MPa, and the tensile strength is 400MPa; the maximum irradiation intensity of the polybase color-changing luminescent fiber is 60mW/mm when the near-infrared wavelength is 790nm2The bacteriostatic rate for gram bacteria is 93 percent, and the bacteriostatic rate for staphylococcus aureus is 92 percent; multi-base color-changing luminescent fiber in illumination (the wavelength of exciting light is 550 to E)570 nm) for no more than 1s, and returns to the original color within 1min after the light source is removed; the multi-primary color-changing luminescent fiber changes color under the irradiation of exciting light after being illuminated for 20 times, namely after being repeatedly tested for 20 times, the intensity of the emitting light is 95 percent of the maximum intensity value, and the durability is good.
Example 9
A preparation method of multi-base color-changing luminescent fiber with antibacterial property comprises the following specific steps:
(1) Uniformly mixing styrene, cuBr, the compound A prepared in example 3, the compound B, PMDETA and refined cyclohexanone, polymerizing at 80 ℃ under the protection of inert gas, reacting for 10 hours, quickly cooling (the quick cooling time is 30s (ice bath)), diluting with tetrahydrofuran, removing copper by using alkaline alumina to obtain a solution, dripping the solution into 100mL of vigorously stirred methanol for chromatography, carrying out suction filtration and drying to obtain PS/AIE- (1,2);
the molar ratio of styrene to CuBr to compound A to compound B to PMDETA is as follows: 40; the molar volume ratio of the compound A to the purified cyclohexanone is 1mol; during chromatography, the volume ratio of the refined cyclohexanone to the tetrahydrofuran to the methanol is 1.2;
(2) Dissolving PS/AIE- (1,2) prepared in the step (1) in dimethyl formamide (DMF) at 26 ℃, uniformly mixing (stirring for 7 hours at 26 ℃ and at a stirring speed of 800 revolutions per minute (magnetic stirring) to obtain a spinning solution with the mass fraction of 20 percent), adopting a water bath method for electrostatic spinning, putting the spinning solution into an injector, flying the spinning solution out from the tip of a spinneret under the action of electric field force generated by a high-voltage power supply and the thrust of a flow pump, flying for a certain distance, then falling into a fatty alcohol polyoxyethylene ether bath with the mass fraction of 5 per thousand, drawing the obtained fiber out of the bath, passing through a godet roller, a drying device and a tension device in sequence, and finally winding the fiber onto a rotating shaft coated with an aluminum foil to prepare the multi-photochromic luminescent fiber with antibacterial property;
wherein, the technological parameters of the water bath method electrostatic spinning are as follows: the temperature is 28 ℃, the ambient relative humidity is 42%, the spinning voltage is 20kV, the flow rate of the spinning solution is 1.0mL/h, the horizontal distance from the tip of the spinning nozzle to the inner wall of the bath is 5cm, and the vertical distance (the flying distance of the spinning solution) from the surface of the bath is 8.5cm.
In the prepared multi-base color-changing luminescent fiber with antibacterial property, the compound A and the compound B are combined to the fiber through covalent bonds, and the aggregation state of the compound A and the compound B is J aggregation; the molar ratio of the compound A to the compound B is 1.4, and the total content of the compound A and the compound B is 5 percent of the total mass of the multi-primary color-changing luminescent fiber; the average diameter of the multi-primary color-changing luminescent fiber is 200nm, the Young modulus is 2000MPa, and the tensile strength is 500MPa; the maximum irradiation intensity of the multi-base color-changing luminescent fiber is 100mW/mm when the near infrared wavelength is 850nm2The gram bacteria inhibition rate is 95%, and the staphylococcus aureus inhibition rate is 96%; the time for changing the multi-primary color-changing luminescent fiber from white to red under illumination (the wavelength of exciting light is 550-570 nm) is not more than 1s, and the multi-primary color-changing luminescent fiber is recovered to the primary color within 1min after being moved away from the light source; the multi-primary color-changing luminescent fiber changes color under the irradiation of exciting light after being illuminated for 20 times, namely after being repeatedly tested for 20 times, the intensity of the emitted light is 98 percent of the maximum intensity value, and the durability is good.
Claims (10)
1. A multi-base color-changing luminescent fiber with antibacterial property is characterized in that: the compound A and the compound B are covalently bonded on the multi-primary color-changing luminescent fiber; in the fiber, the aggregation state of the compound A and the compound B is J aggregation;
the structural formula of the compound A is as follows:
wherein X is O, S or Se;
the structural formula of the compound B is as follows:
2. the multi-primary color-changing luminescent fiber having antibacterial properties according to claim 1, wherein the molar ratio of the compound a to the compound B is 1:1 to 1.4, and the total content of the compound a and the compound B is 0.5% to 5.0% of the total mass of the multi-primary color-changing luminescent fiber.
3. The multi-primary color-changing luminescent fiber having antibacterial properties according to claim 1, wherein the average diameter of the multi-primary color-changing luminescent fiber is 20 to 200nm, the Young's modulus is 1000 to 2000MPa, and the tensile strength is 100 to 500MPa.
4. The multi-primary color-changing luminescent fiber with antibacterial property of claim 1, wherein the maximum irradiation intensity of the multi-primary color-changing luminescent fiber is 10-100 mW/mm when the wavelength of the near infrared light is 700-850 nm2。
5. The multi-primary color-changing luminescent fiber with antibacterial property of claim 4, wherein the multi-primary color-changing luminescent fiber has a color-changing time of not more than 1s under the illumination of the excitation light with the wavelength of 350-370 nm or 550-570 nm, and returns to the original color within 1min after being removed from the light source; the multi-primary color-changing luminescent fiber has the emission light intensity of color change of more than 90% of the maximum intensity value after repeated illumination for 20 times.
6. The method for preparing multi-primary color-changing luminescent fiber with antibacterial property according to any one of claims 1 to 5, characterized by comprising the following steps:
(1) Uniformly mixing styrene, cuBr, a compound A, a compound B, PMDETA and refined cyclohexanone, polymerizing at 78-82 ℃ under the protection of inert gas, reacting for 6-10 h, cooling, diluting with tetrahydrofuran, removing copper by using alkaline alumina to obtain a solution, dripping the solution into 50-100 mL of vigorously stirred methanol for chromatography, carrying out suction filtration and drying to obtain PS/AIE- (1,2);
the mol ratio of the styrene to the CuBr to the compound A to the compound B to the PMDETA is as follows: 40, (0.04-0.08), (0.09-0.18); during chromatography, the volume ratio of the refined cyclohexanone to the tetrahydrofuran to the methanol is 1 (0.1-0.3) to 2.5-5; during polymerization, the molar volume ratio of the styrene to the refined cyclohexanone is 1mol (80-120) L;
the preparation process of the compound A comprises the following steps: adding a compound a and alkali into dry tetrahydrofuran at the temperature of-30 to-15 ℃, uniformly mixing, adding a compound b at room temperature, and continuously reacting for 10 to 15 hours to obtain a mixture; finally, filtering the mixture to obtain filtrate, concentrating the filtrate, and purifying by using a silica gel chromatography to obtain the compound A; the compound a is
The compound b is
(2) Dissolving PS/AIE- (1,2) in a solvent at room temperature, uniformly mixing to obtain a spinning solution, and preparing the multi-primary color-changing luminescent fiber with antibacterial property by adopting a water bath electrostatic spinning method.
7. The method for preparing multi-primary color-changing luminescent fibers with antibacterial property according to claim 6, characterized in that the mass fraction of the spinning solution is 15-25%.
8. The method of claim 6, wherein the solvent is 1,3-dimethyl-2-imidazolidinone, dimethylformamide, dimethylsulfoxide or diethoxymethane.
9. The method for preparing multi-primary color-changing luminescent fiber with antibacterial property according to claim 6, wherein the water bath electrostatic spinning process comprises the following steps: the spinning solution is placed in an injector, flies out from the tip of a spinning nozzle under the action of an electric field force generated by a high-voltage power supply and the thrust of a flow pump, flies for a certain distance, falls into a fatty alcohol-polyoxyethylene ether bath tank filled with 4-6 per mill of mass fraction, and the obtained fiber is drawn out from the bath tank, passes through a godet roller, a drying device and a tension device in sequence and is finally wound on a rotating shaft coated with an aluminum foil to obtain the continuous fiber.
10. The method for preparing multi-primary color-changing luminescent fiber with antibacterial property according to claim 9, wherein the technological parameters of the water bath electrostatic spinning method are as follows: the temperature is 22-28 ℃, the relative humidity of the environment is 42-48%, the spinning voltage is 20kV, the horizontal distance from the tip of the spinning nozzle to the inner wall of the bath is 3.0-5.0 cm, and the vertical distance from the tip of the spinning nozzle to the surface of the bath is 6.5-8.5 cm.
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