CN112267168B - Preparation method of high-strength photoluminescent hydrogel fiber - Google Patents
Preparation method of high-strength photoluminescent hydrogel fiber Download PDFInfo
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Abstract
The invention relates to the field of high polymer materials, and discloses a preparation method of a high-strength photoluminescence hydrogel fiber. The invention takes poly N-hydroxyethyl acrylamide as a matrix, polyvinyl alcohol as a reinforcement and carbon-supported silver nanoparticles as a luminescent material, and adopts a two-step aqueous solution polymerization method to synthesize the poly N-hydroxyethyl acrylamide/polyvinyl alcohol interpenetrating network hydrogel. The photoluminescent hydrogel fiber prepared by the method disclosed by the invention has high mechanical strength, high toughness and flexibility, and a photoluminescent function, and has a huge application value in the fields of photoelectric devices, flexible wearable devices, sensors, photosensitive materials and the like.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a preparation method of a high-strength photoluminescence hydrogel fiber.
Background
Carbon quantum dots (CDs) have attracted much attention since their discovery in 2004 due to their excellent physicochemical properties. Compared with the traditional semiconductor quantum dots and organic dyes, the carbon quantum dots not only have the characteristics of low raw material source, simple preparation method and the like, but also have the unique advantages of low toxicity, good biocompatibility, stable optical property, adjustable excitation and emission wavelength, easy surface functionalization modification and the like, and have wide application in the fields of photocatalysis, biological imaging, lighting devices, fluorescent probes, biological sensing and the like.
The hydrogel generally has the disadvantages of low gel strength, poor toughness, slow water absorption speed and the like, so that the application of the hydrogel in fields with relatively high strength requirements, such as artificial muscles, memory switch elements, mechanical transmission devices, biosensors and the like, is greatly limited. The improvement of the mechanical strength of the hydrogel can be realized by means of increasing the crosslinking density, reducing the swelling degree of the gel, introducing a fibrous reinforcing agent, preparing an interpenetrating network (IPN) and the like. The polyvinyl alcohol (PVA) has the characteristics of good compatibility with other materials, high mechanical strength, capability of forming a three-dimensional network by self-crosslinking and the like, and the polyacrylamide and the PVA are organically combined together, so that the application range of the hydrogel can be widened, the mechanical strength of the hydrogel can be obviously improved, and the PVA hydrogel has a wider application range.
Luminescent materials have irreplaceable effects in the human development history, and it can be said that development of luminescent materials has pushed social progress to some extent. Currently, macromolecules with luminescent properties can be used directly, or photoluminescent hydrogels can be obtained by integrating various photoluminescent substances (such as organic dye molecules and rare earth metal complexes) into the polymer network of the hydrogel. However, the synthesized luminescent hydrogel has poor luminescence property, difficult spectrum regulation, brittle and fragile quality and poor mechanical property, and the application range of the luminescent hydrogel is severely limited.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a high-intensity photoluminescence hydrogel fiber. The invention adopts poly N-hydroxyethyl acrylamide as a matrix, polyvinyl alcohol as an enhancer and carbon-supported silver nanoparticles as a luminescent material, and adopts a two-step aqueous solution polymerization method to synthesize the poly N-hydroxyethyl acrylamide/polyvinyl alcohol interpenetrating network hydrogel. The cross-linking of the poly-N-hydroxyethyl acrylamide, the self-crosslinking of the polyvinyl alcohol and the mutual winding of the poly-N-hydroxyethyl acrylamide and the polyvinyl alcohol networks can greatly improve the mechanical strength of the hydrogel under the combined action of the poly-N-hydroxyethyl acrylamide, the self-crosslinking of the polyvinyl alcohol and the poly-N-hydroxyethyl acrylamide and the polyvinyl alcohol networks. Meanwhile, the invention adopts a repeated freezing and thawing method to ensure that a microcrystalline region appears in the hydrogel, thereby realizing physical crosslinking. The hydrogel fiber obtained by the method has good mechanical property and photoluminescence property.
The specific technical scheme of the invention is as follows: a preparation method of high-strength photoluminescence hydrogel fibers comprises the following preparation steps:
step 1) preparation of carbon nanodots: weighing heparin sodium, placing the heparin sodium into a container, adding deionized water, carrying out ultrasonic oscillation until the heparin sodium is completely dissolved, pouring the obtained mixed solution into a hydrothermal reaction kettle, and carrying out heating reaction; after the reaction, the mixed solution is cooled to room temperature, then is centrifuged, and the supernatant is taken and filtered repeatedly for a plurality of times by a 0.22 mu m microporous filtering membrane; putting the liquid obtained by filtering into a dialysis membrane for dialysis; and (4) drying the liquid obtained by dialysis in vacuum to obtain the solid carbon nanodots.
The carbon nano particles prepared by using the heparin sodium as a raw material and adopting a hydrothermal method have uniform particle size distribution, small average particle size, good particle size appearance and crystallization degree, contain a large amount of hydroxyl, amino, carbonyl and carboxyl groups on the surface, and have good water solubility and stability.
Step 2) preparation of the carbon-supported silver nanoparticles: placing 0.008-0.012 g of the carbon nanodots obtained in the step 1) into a container, adding 8-12mL of deionized water, performing water bath ultrasound to uniformly disperse the carbon nanodots, and then adding a silver nitrate solution; and (3) irradiating the obtained mixed solution under ultraviolet light, and obtaining the carbon-supported silver nanoparticle solution when the mixed solution is changed from yellow to dark brown.
The carbon nano-particle has abundant functional groups on the surface, and the electron transfer of the carbon nano-particle can lead Ag to be excited by ultraviolet light + Reducing into silver nano particles. And the prepared nano particles can be monodisperse in the solvent even if no addition of carbon nano dots is added due to the hydrophilicity of the carbon nano dotsAny other substance, dispersion in a solvent also has good stability.
Ag + The photoreduction process of (A) is influenced by the ultraviolet irradiation time, the longer the ultraviolet irradiation time is, the Ag + The larger the reduction amount of (A), the larger the particle size of the silver nanoparticles, and the fluorescence characteristics may be changed accordingly. The selection of an appropriate illumination time is therefore particularly important for the performance impact of the silver nanoparticles.
Step 3) preparation of polyvinyl alcohol saturated solution: adding excessive polyvinyl alcohol into deionized water, heating to 85-95 ℃ in a water bath, stirring for dissolving, and then standing until the polyvinyl alcohol is not dissolved any more, thereby obtaining a polyvinyl alcohol saturated solution.
Since polyvinyl alcohol has a certain degree of polymerization, it is necessary to promote the diffusion of solvent molecules into the polymer under certain conditions of temperature rise and stirring so that polyvinyl alcohol can be swollen and dissolved.
Step 4) preparation of the N-hydroxyethyl acrylamide prepolymer: weighing N-hydroxyethyl acrylamide monomer, placing in a container, adding distilled water, fully stirring and dissolving to prepare 45-55wt% of N-hydroxyethyl acrylamide monomer solution; and then placing the container in a constant-temperature water bath at 75-85 ℃ for heat preservation for 1-3min, adding a cross-linking agent N, N' -methylene bisacrylamide, stirring and dissolving, adding an initiator ammonium persulfate to initiate prepolymerization, and continuously stirring in the polymerization process to ensure that the polymerization is uniform, so as to obtain an N-hydroxyethyl acrylamide prepolymer solution.
Step 5): when the viscosity of the N-hydroxyethyl acrylamide prepolymer solution is increased, quickly introducing the polyvinyl alcohol saturated solution obtained in the step 3) and the carbon-supported silver nanoparticle solution obtained in the step 2), adding the same amount of the cross-linking agent N, N' -methylene bisacrylamide in the step 4), fully stirring to completely dissolve the cross-linking agent, and then introducing an initiator ammonium persulfate.
Under the action of an initiator, hydrogen atoms in hydroxyl groups are ionized to generate a large number of crosslinking points for self-crosslinking of the polyvinyl alcohol, and a three-dimensional network structure formed after the self-crosslinking of the polyvinyl alcohol has a decisive effect on the improvement of the mechanical strength of the hydrogel.
The interaction between the polyvinyl alcohol molecular chain and the poly N-hydroxyethyl acrylamide network mainly comprises physical winding and hydrogen bond interaction. In addition, when synthesizing the poly N-hydroxyethyl acrylamide/polyvinyl alcohol interpenetrating network hydrogel, a polyvinyl alcohol saturated solution with the temperature of 85-95 ℃ is adopted, so that part of snowflake polyvinyl alcohol is crystallized and separated out, and the separated polyvinyl alcohol and a poly N-hydroxyethyl acrylamide matrix are combined by virtue of a large amount of hydrogen bonding. When the dosage of the polyvinyl alcohol is increased, the precipitated polyvinyl alcohol is increased, and when the load action time is long enough to cause the gel to have cracks, the stress required for further propagation of the cracks is also increased continuously, so that the dissociation work between the precipitated polyvinyl alcohol and the poly-N-hydroxyethyl acrylamide is overcome to be gradually increased, and the toughness of the hydrogel is enhanced.
Step 6): and (3) after the reaction is finished, quickly transferring the reaction solution into an injector while the reaction solution is hot, injecting the reaction solution into a coagulating bath by using the injector to coagulate into fibers, standing for 4-8 h, taking out and naturally drying to obtain the hydrogel fibers.
And adding a cross-linking agent N, N' -methylene-bisacrylamide in the reaction, so that the obtained polymer has a certain chemical bond cross-linking degree and has certain strength. The reaction time is not suitable to be too long or too short, the polymerization degree is not high when the reaction time is too short, the strength cannot meet the condition of fiber application, the reaction time cannot be too long, the polymer has too high crosslinking degree when the reaction time is too long, a spinning solution cannot be formed for wet spinning, or the fiber is too hard and has no flexibility when the spinning is carried out in time, so that the fiber is hard, brittle and easy to break.
Step 7): freezing the hydrogel fiber at-80 deg.C to-60 deg.C for 3-5h, taking out, thawing at room temperature for 10-14h, freezing at-80 deg.C to-60 deg.C for 3-5h, thawing, and repeating for several times to form microcrystalline region physical crosslinking, and finally obtaining high-strength photoluminescent hydrogel fiber.
The polyvinyl alcohol enables a polyvinyl alcohol chain to generate certain orientation in repeated low-temperature freezing and thawing processes, and a physical cross-linking microcrystalline region is formed to form a cross-linking network, so that the mechanical property of the hydrogel is enhanced.
Preferably, in the step 1), the concentration of the sodium heparin aqueous solution in the mixed solution is 0.02-0.03 g/mL, the reaction temperature is 130-150 ℃, and the reaction time is 10-15h.
Preferably, in the step 1), the centrifugal rotating speed is 8000-12000 r/min, and the centrifugal time is 5-15min; the specification of the dialysis membrane is 1000 Da, and the dialysis time is 40-50 h; the vacuum drying temperature is 35-45 deg.C, and the vacuum drying time is 40-50 h.
Preferably, in the step 2), the ultrasonic time is 20-40 minutes, the concentration of the silver nitrate solution is 0.008-0.012 mol/L, the ultraviolet wavelength is 360-370 nm, and the illumination time is 70-90 minutes.
Preferably, in step 3), M of the polyvinyl alcohol n The alcoholysis rate is more than 99 percent for 89000-98000, and the stirring time is 1-3 h.
Preferably, in step 4), the crosslinking agent N, N' -methylenebisacrylamide is added in an amount of 1.5 to 2.5% by mass of the total mass of the N-hydroxyethylacrylamide monomer solution, and the ammonium persulfate is added in an amount of 600 to 700 mg/mL.
Preferably, in the step 5), the mass ratio of the N-hydroxyethyl acrylamide prepolymer solution to the polyvinyl alcohol saturated solution is (90) - (70).
Preferably, in step 6), the coagulation bath is a sodium hydroxide aqueous solution with a mass fraction of 1-3%.
Compared with the prior art, the invention has the beneficial effects that:
(1) The carbon nanodots with excellent performance are prepared by taking heparin sodium as a raw material and adopting a hydrothermal method, the cost is low, the synthesis is simple, and the raw material is very easy to obtain.
(2) The method takes the carbon nanodots as a reducing agent to synthesize the silver nanoparticles quickly, simply and greenly under the irradiation of ultraviolet light. The carbon-carried silver nano-particles obtained by the method have good optical performance and lower photoluminescence threshold. Meanwhile, due to the hydrophilicity of the carbon nano dots, the prepared nano particles can be monodisperse in the solvent, and the dispersion in the solvent has good stability even if no other substances are added.
(3) The two-step aqueous solution polymerization method is adopted to synthesize the poly-N-hydroxyethyl acrylamide/polyvinyl alcohol interpenetrating network hydrogel, and the poly-N-hydroxyethyl acrylamide and the polyvinyl alcohol are organically combined together, so that the application range of the hydrogel is widened, and the mechanical strength of the hydrogel is obviously improved. The crosslinking of the poly-N-hydroxyethyl acrylamide, the self-crosslinking of the polyvinyl alcohol and the mutual winding of the poly-N-hydroxyethyl acrylamide and the polyvinyl alcohol network greatly improve the mechanical strength of the hydrogel under the combined action of the poly-N-hydroxyethyl acrylamide, the polyvinyl alcohol and the polyvinyl alcohol network. Meanwhile, a repeated freezing and thawing method is adopted, so that a microcrystalline region appears in the hydrogel, and physical crosslinking is realized.
(4) The hydrogel fiber prepared by the method of the invention not only has stable photoluminescence performance, but also has good mechanical performance, which can not be realized by the traditional luminescent hydrogel material. The hydrogel achieves the condition of preparing fiber by the mode of coexisting chemical crosslinking and physical crosslinking.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
A preparation method of a high-intensity photoluminescence hydrogel fiber comprises the following preparation steps:
step 1): preparing carbon nanodots: 0.55 g of heparin sodium is weighed and placed in a beaker, 20 mL of deionized water is added, and the mixture is ultrasonically vibrated until the heparin sodium is completely dissolved. Pouring the mixed solution into a 50 mL hydrothermal reaction kettle with a polytetrafluoroethylene lining, and heating and reacting for 12h at 140 ℃. And cooling the reacted mixed solution to room temperature, and then placing the mixed solution in a centrifuge tube for centrifugation for 10 min at the rotation speed of 10000 r/min. The supernatant was collected and filtered repeatedly 3 times through a 0.22 μm microfiltration membrane. Putting the filtered liquid into a dialysis membrane of 1000 Da for dialysis, and dialyzing in ultrapure water for 48 h. And (3) placing the dialyzed liquid in a vacuum drying box, and drying for 48 hours at the temperature of 40 ℃ to obtain the carbon nanodot solid.
Step 2): preparing the carbon-supported silver nanoparticles: placing 0.01 g of the carbon nanodots prepared in the step 1) in a beaker, adding 10mL of deionized water, performing ultrasonic treatment in an ultrasonic water bath kettle for 30 min to uniformly disperse the carbon nanodots, and then adding 0.01 mol/L of silver nitrate solution; the mixed solution is placed under 365 nm ultraviolet light for irradiation for 80 min, and when the mixed solution changes from yellow to dark brown, silver ions are converted into silver nano particles.
Step 3): dissolving polyvinyl alcohol: will M n Adding polyvinyl alcohol with the alcoholysis rate being more than 99% into 10mL of deionized water according to the specification of 89000-98000, heating the mixture to 90 ℃ in a water bath, dissolving the polyvinyl alcohol by vigorous stirring, heating and stirring the mixture for 3 hours, and then standing the mixture until the polyvinyl alcohol cannot be completely dissolved to obtain a saturated polyvinyl alcohol solution for later use.
Step 4): n-hydroxyethyl acrylamide prepolymerization: weighing 3 g of N-hydroxyethyl acrylamide monomer, placing the N-hydroxyethyl acrylamide monomer in a beaker, adding a proper amount of distilled water, fully stirring and dissolving to prepare a 50% N-hydroxyethyl acrylamide monomer solution; and then placing the beaker in a constant-temperature water bath kettle at 80 ℃ for heat preservation for 2min, adding 60 mg of cross-linking agent N, N '-methylene bisacrylamide, stirring to dissolve the cross-linking agent N, N' -methylene bisacrylamide, adding 1.95 g of initiator ammonium persulfate to initiate prepolymerization, and continuously stirring in the polymerization process to ensure uniform polymerization.
And step 5): when the viscosity of the N-hydroxyethyl acrylamide prepolymer solution is increased, rapidly introducing 0.6 g of a 90 ℃ polyvinyl alcohol solution in step 3) and 0.3 ml of a silver-loaded nanoparticle solution in step 2), adding the same amount of a crosslinking agent N, N' -methylenebisacrylamide in step 4), sufficiently stirring to completely dissolve the crosslinking agent, and then introducing 1.55 g of initiator ammonium persulfate to react for 5 hours.
Step 6): and (3) after the reaction is finished, quickly transferring the reaction solution into an injector while the reaction solution is hot, injecting the reaction solution into a sodium hydroxide aqueous solution with the mass fraction of 2% by using the injector to solidify into fibers, standing for 6 hours, taking out and naturally drying to obtain the hydrogel fibers.
Step 7): and (3) freezing the hydrogel fiber at-70 ℃ for 4h, taking out, unfreezing at room temperature for 12h, freezing at-70 ℃ for 4h, unfreezing, and repeating for three times to form microcrystalline region physical crosslinking, thereby finally obtaining the high-strength photoluminescence hydrogel fiber.
The high-strength photoluminescent hydrogel fiber obtained in the embodiment has the tensile strength of 0.77 MPa and the elongation of 1475%, and the precipitation of the snowflake-shaped PVA plays a certain toughening role in the hydrogel.
Example 2
A preparation method of high-strength photoluminescence hydrogel fibers comprises the following preparation steps:
step 1): preparing carbon nanodots: 0.55 g of heparin sodium is weighed and placed in a beaker, 20 mL of deionized water is added, and the mixture is ultrasonically vibrated until the heparin sodium is completely dissolved. Pouring the mixed solution into a 50 mL hydrothermal reaction kettle with a polytetrafluoroethylene lining, and heating and reacting for 12h at 140 ℃. And cooling the reacted mixed solution to room temperature, and then placing the mixed solution in a centrifuge tube for centrifugation for 10 min at the rotation speed of 10000 r/min. The supernatant was collected and filtered repeatedly 3 times through a 0.22 μm microfiltration membrane. Putting the filtered liquid into a dialysis membrane of 1000 Da, and dialyzing in ultrapure water for 48 h. And (3) placing the dialyzed liquid in a vacuum drying box, and drying for 48 hours at the temperature of 40 ℃ to obtain the carbon nanodot solid.
Step 2): preparing carbon-supported silver nanoparticles: putting 0.01 g of the carbon nanodots prepared in the step 1) into a beaker, adding 10mL of deionized water, performing ultrasonic treatment in an ultrasonic water bath for 30 min to uniformly disperse the carbon nanodots, and then adding 0.01 mol/L of silver nitrate solution; the mixed solution is placed under 365 nm ultraviolet light for irradiation for 80 min, and when the mixed solution changes from yellow to dark brown, silver ions are converted into silver nano particles.
And step 3): dissolving polyvinyl alcohol: will M n According to the method, according to the technical scheme, polyvinyl alcohol with the alcoholysis rate being more than 99% is added into 10mL of deionized water, the mixture is heated to 90 ℃ in a water bath, the polyvinyl alcohol is dissolved by vigorous stirring, the mixture is heated and stirred for 3 hours, and then the mixture is kept stand until the polyvinyl alcohol cannot be completely dissolved, so that a polyvinyl alcohol saturated solution is obtained for later use.
And step 4): n-hydroxyethyl acrylamide prepolymerization: weighing 3 g of N-hydroxyethyl acrylamide monomer, placing the monomer in a beaker, adding a proper amount of distilled water, fully stirring and dissolving to prepare a 50% N-hydroxyethyl acrylamide monomer solution; then placing the beaker in a constant-temperature water bath kettle at 80 ℃ for heat preservation for 2min, adding 60 mg of cross-linking agent N, N' -methylene-bis-acrylamide, stirring for dissolving, adding 1.95 g of initiator ammonium persulfate to initiate prepolymerization, and continuously stirring in the polymerization process to ensure uniform polymerization.
And step 5): when the viscosity of the N-hydroxyethyl acrylamide prepolymer solution becomes high, quickly introducing 1.2 g of 90 ℃ polyvinyl alcohol solution in step 3) and 0.3 ml of silver-loaded nanoparticle solution in step 2), adding the same amount of cross-linking agent N, N' -methylene-bis-acrylamide as in step 4), fully stirring to completely dissolve the cross-linking agent, then introducing 1.55 g of initiator ammonium persulfate, and reacting for 5 hours.
Step 6): and (3) after the reaction is finished, quickly transferring the reaction solution into an injector while the reaction solution is hot, injecting the reaction solution into a sodium hydroxide aqueous solution with the mass fraction of 2% by using the injector to solidify into fibers, standing for 4-8 h, taking out and naturally drying to obtain the hydrogel fibers.
Step 7): and (3) freezing the hydrogel fiber at-80 ℃ for 3h, taking out, unfreezing at room temperature for 10h, freezing at-80 ℃ for 3h, unfreezing, and repeating for three times to form microcrystalline region physical crosslinking, thereby finally obtaining the high-strength photoluminescence hydrogel fiber.
The high-strength photoluminescence hydrogel fiber obtained in the embodiment has the tensile strength of 0.90 MPa and the elongation of 1657%, and the precipitation of the snowflake-shaped PVA plays a certain toughening role on the hydrogel.
Example 3
A preparation method of a high-intensity photoluminescence hydrogel fiber comprises the following preparation steps:
step 1): preparing carbon nanodots: 0.55 g of heparin sodium is weighed and placed in a beaker, 20 mL of deionized water is added, and the mixture is ultrasonically vibrated until the heparin sodium is completely dissolved. The mixed solution is poured into a 50 mL hydrothermal reaction kettle with a polytetrafluoroethylene lining, and the mixture is heated and reacted for 12 hours at the temperature of 140 ℃. And cooling the reacted mixed solution to room temperature, and then placing the mixed solution in a centrifuge tube for centrifugation for 10 min at the rotation speed of 10000 r/min. The supernatant was collected and filtered 3 times with a 0.22 μm microfiltration membrane. The filtered liquid was put into dialysis membrane for dialysis (MWCO = 3500/8000) and dialyzed in ultrapure water for 48 h. And (3) placing the dialyzed liquid in a vacuum drying box, and drying for 48 hours at the temperature of 40 ℃ to obtain the carbon nanodot solid.
Step 2): preparing the carbon-supported silver nanoparticles: placing 0.01 g of the carbon nanodots prepared in the step 1) in a beaker, adding 10mL of deionized water, performing ultrasonic treatment in an ultrasonic water bath kettle for 30 min to uniformly disperse the carbon nanodots, and then adding 0.01 mol/L of silver nitrate solution; the mixed solution is placed under 365 nm ultraviolet light for irradiation for 80 min, and when the mixed solution changes from yellow to dark brown, silver ions are converted into silver nano particles.
And step 3): dissolving polyvinyl alcohol: will M n According to the method, according to the technical scheme, polyvinyl alcohol with the alcoholysis rate being more than 99% is added into 10mL of deionized water, the mixture is heated to 90 ℃ in a water bath, the polyvinyl alcohol is dissolved by vigorous stirring, the mixture is heated and stirred for 3 hours, and then the mixture is kept stand until the polyvinyl alcohol cannot be completely dissolved, so that a polyvinyl alcohol saturated solution is obtained for later use.
And step 4): n-hydroxyethyl acrylamide prepolymerization: weighing 3 g of N-hydroxyethyl acrylamide monomer, placing the monomer in a beaker, adding a proper amount of distilled water, fully stirring and dissolving to prepare a 50% N-hydroxyethyl acrylamide monomer solution; then placing the beaker in a constant-temperature water bath kettle at 80 ℃ for heat preservation for 2min, adding 60 mg of cross-linking agent N, N' -methylene-bis-acrylamide, stirring for dissolving, adding 1.95 g of initiator ammonium persulfate to initiate prepolymerization, and continuously stirring in the polymerization process to ensure uniform polymerization.
Step 5): when the viscosity of the N-hydroxyethyl acrylamide prepolymer solution is increased, rapidly introducing 1.8 g of the polyvinyl alcohol solution at 90 ℃ in step 3) and 0.3 ml of the silver-loaded nanoparticle solution in step 2), adding the same amount of the cross-linking agent N, N' -methylenebisacrylamide in step 4), sufficiently stirring to completely dissolve the cross-linking agent, and then introducing 1.55 g of initiator ammonium persulfate to react for 5 hours.
Step 6): and (3) after the reaction is finished, quickly transferring the reaction solution into an injector while the reaction solution is hot, injecting the reaction solution into a sodium hydroxide aqueous solution with the mass fraction of 2% by using the injector to solidify into fibers, standing for 4-8 h, taking out and naturally drying to obtain the hydrogel fibers.
Step 7): and (3) freezing the hydrogel fiber at-60 ℃ for 5h, taking out, unfreezing at room temperature for 14h, freezing at-60 ℃ for 5h, unfreezing, and repeating for three times to form a microcrystal region physical crosslinking, thereby finally obtaining the high-strength photoluminescence hydrogel fiber.
The high-strength photoluminescent hydrogel fiber obtained in the embodiment has the tensile strength of 1.24 MPa and the elongation of 1843%, and the precipitation of the snowflake-shaped PVA plays a certain toughening role in the hydrogel.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modifications, alterations and equivalent changes made to the above embodiment according to the technical spirit of the present invention still belong to the protection scope of the technical solution of the present invention.
Claims (5)
1. A preparation method of high-strength photoluminescence hydrogel fibers is characterized by comprising the following preparation steps:
step 1) preparation of carbon nanodots: weighing heparin sodium, placing the heparin sodium into a container, adding deionized water, carrying out ultrasonic oscillation until the heparin sodium is completely dissolved, pouring the obtained mixed solution into a hydrothermal reaction kettle, and carrying out heating reaction; after the reaction, the mixed solution is cooled to room temperature, then is centrifuged, and the supernatant is taken and filtered repeatedly for a plurality of times by a 0.22 mu m microporous filtering membrane; putting the filtered liquid into a dialysis membrane for dialysis; drying the liquid obtained by dialysis in vacuum to obtain solid carbon nanodots;
step 2) preparation of the carbon-supported silver nanoparticles: placing 0.008-0.012 g of the carbon nanodots obtained in the step 1) in a container, adding 8-12mL of deionized water, performing water bath ultrasound to uniformly disperse the carbon nanodots, and then adding a silver nitrate solution; irradiating the obtained mixed solution under ultraviolet light, and obtaining a carbon-supported silver nanoparticle solution when the mixed solution is changed from yellow to dark brown; wherein: the ultrasonic time is 20-40 minutes, the concentration of silver nitrate solution is 0.008-0.012 mol/L, the ultraviolet wavelength is 360-370 nm, and the illumination time is 70-90 minutes;
step 3) preparation of polyvinyl alcohol saturated solution: adding excessive polyvinyl alcohol into deionized water, heating to 85-95 ℃ in a water bath, stirring for dissolving, and then standing until the polyvinyl alcohol is not dissolved any more, so as to obtain a polyvinyl alcohol saturated solution;
step 4) preparation of N-hydroxyethyl acrylamide prepolymer: weighing N-hydroxyethyl acrylamide monomer, placing in a container, adding distilled water, fully stirring and dissolving to prepare 45-55wt% of N-hydroxyethyl acrylamide monomer solution; then placing the container in a constant-temperature water bath at 75-85 ℃ for heat preservation for 1-3min, adding a cross-linking agent N, N' -methylene bisacrylamide, stirring and dissolving, adding an initiator ammonium persulfate to initiate prepolymerization, and continuously stirring in the polymerization process to ensure that the polymerization is uniform, so as to obtain an N-hydroxyethyl acrylamide prepolymer solution; the addition amount of the cross-linking agent N, N' -methylene-bisacrylamide is 1.5-2.5% of the total mass of the N-hydroxyethyl acrylamide monomer solution, and the addition amount of the ammonium persulfate is 600-700 mg/mL;
step 5): when the viscosity of the N-hydroxyethyl acrylamide prepolymer solution is increased, quickly introducing the polyvinyl alcohol saturated solution obtained in the step 3) and the carbon-supported silver nanoparticle solution obtained in the step 2), adding the same amount of the cross-linking agent N, N' -methylene bisacrylamide in the step 4), fully stirring to completely dissolve the cross-linking agent, and then introducing an initiator ammonium persulfate; the mass ratio of the N-hydroxyethyl acrylamide prepolymer solution to the polyvinyl alcohol saturated solution is (90) - (70);
step 6): after the reaction is finished, quickly transferring the reaction solution into an injector while the reaction solution is hot, injecting the reaction solution into a coagulating bath by using the injector for coagulating into fibers, standing for 4-8 h, taking out the fibers, and naturally drying to obtain hydrogel fibers;
step 7): freezing the hydrogel fiber at-80 deg.C to-60 deg.C for 3-5h, taking out, thawing at room temperature for 10-14h, freezing at-80 deg.C to-60 deg.C for 3-5h, thawing, and repeating for several times to form microcrystalline region physical crosslinking to obtain high-strength photoluminescent hydrogel fiber.
2. The method of claim 1, wherein: in the step 1), the concentration of the sodium heparin aqueous solution in the mixed solution is 0.02-0.03 g/mL, the reaction temperature is 130-150 ℃, and the reaction time is 10-15h.
3. The method of claim 1, wherein: in the step 1), the centrifugal rotating speed is 8000-12000 r/min, and the centrifugal time is 5-15min; the specification of the dialysis membrane is 1000 Da, and the dialysis time is 40-50 h; the vacuum drying temperature is 35-45 ℃, and the vacuum drying time is 40-50 h.
4. The method of claim 1, wherein: m of polyvinyl alcohol in step 3) n =89000-98000, the alcoholysis rate is more than 99%, and the stirring time is 1-3 h.
5. The method of claim 1, wherein: in the step 6), the coagulating bath is a sodium hydroxide aqueous solution with the mass fraction of 1-3%.
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