CN107973876B - Preparation method of magnetic nano hydrogel photonic crystal with multi-responsiveness core-shell structure - Google Patents
Preparation method of magnetic nano hydrogel photonic crystal with multi-responsiveness core-shell structure Download PDFInfo
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Abstract
The invention relates to a preparation method of a magnetic nano hydrogel photonic crystal with a multi-responsiveness core-shell structure, which comprises the following steps: mixing NIPAM, a cross-linking agent, an emulsifier and an initiator for reaction to obtain PNIPAM; diluting with deionized water, sequentially adding a cross-linking agent, AA, an initiator and a catalyst, and continuously stirring for reaction to obtain PNIPAM/PAA with an IPN structure; 1/2 concentrated to the original mass concentration, and Fe2+、NaNO2Reacting with ammonia water to obtain IPN/Fe3O4(ii) a Adding NIPAM, cross-linking agent and initiator to react to obtain PNIPAM @ (IPN/Fe)3O4) (ii) a Concentrating to 2-8 wt%, and self-assembling to obtain the multi-responsiveness core-shell structure magnetic nano hydrogel photonic crystal. The method has simple process, easily obtained raw materials and environmental protection; the prepared product has a core-shell structure and temperature/pH/magnetism triple responsiveness, and has great application prospects in optics and biomedicine.
Description
Technical Field
The invention belongs to the technical field of nano hydrogel photonic crystals, and particularly relates to a preparation method of a magnetic nano hydrogel photonic crystal with a multi-responsiveness core-shell structure.
Background
The photonic crystal is a material with a periodic structure formed by orderly arranging two or more materials with different refractive indexes in a certain space. The unique periodic structure can generate 'Bragg scattering' of the electromagnetic wave, when the refractive index of the material is large enough, light is blocked when the light is transmitted, so that a 'photon forbidden band' is formed, and when the frequency of the light wave falls in the forbidden band, the light cannot be transmitted.
The three-dimensional photonic crystal material constructed by the polymer colloid particles with the stimulus response property can sensitively and quickly sense the change of the external environment. By adjusting the spatial arrangement of the lattice period of the photonic crystal, the propagation path of the electromagnetic wave can be adjusted and controlled and the change of the bright structural color can be realized.
Currently, colloidal particles that can prepare photonic crystals of three-dimensional close-packed structures are classified into hard spheres and soft spheres. Most of the hard spherical photonic crystals are constructed by silica particles and polystyrene microspheres, and most of the soft spherical photonic crystals are constructed by poly (N-isopropylacrylamide) PNIPAM polymer microspheres. The polymer microsphere can generate an obvious volume transformation process near the critical phase transformation temperature, so that the lattice period of the polymer microsphere is spatially expanded or reduced, and the position of a photon forbidden band is changed. The magnetic photonic crystal is based on the photonic crystal, and magnetic material components are introduced to make the photonic crystal have magnetism, so that a plurality of new properties are derived: the forbidden band magneto-optical response is enhanced, the magneto-chromic effect is achieved, the electromagnetic wave non-reciprocal propagation effect is achieved, and the like. Therefore, the photonic crystal material with the stimulus response property can be applied to the fields of communication technology, photoswitches, display equipment, biological monitoring, chemical sensing and the like. For example: MnFe with good magneto-optical performance is prepared by J.M.Caicedo and the like by using a microwave heating method2O4-SiO2Composite magnetic photonic crystals (Pascu O, Caicedo J M, Lou Pazgarca a M, et al]Nanoscale, 2011.); preparation of PVP @ Fe by Luo et al3O4Magnetic photonic crystals and investigated their magneto-chromic effects at different pH conditions (Luo W, Ma H, Mou F, et al. Steric-repulsion-based magnetic reactive photonic crystals [ J.)]Advanced Materials, 2014). However, these preparations are too complicated and are basically limited to hard-sphere photonic crystals, and magnetic nano-hydrogel photonic crystals based on soft spheres have not been reported.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a magnetic nano hydrogel photonic crystal with a multi-responsiveness core-shell structure, and the synthesis process adopted by the invention is simple and feasible, and is environment-friendly. The prepared nano hydrogel has a core-shell structure, has pH/temperature/magnetic triple responsiveness, can stably exist in water, can be rapidly self-assembled at room temperature within the concentration range of 2-8 wt% to form a three-dimensional photonic crystal, and shows a bright structural color.
The invention relates to a preparation method of a magnetic nano photonic crystal with a multi-responsiveness core-shell structure, which comprises the following steps:
(1) adding a monomer N-isopropylacrylamide NIPAM, a cross-linking agent and an emulsifier into deionized water, filling nitrogen and removing oxygen at room temperature, stirring for dissolving, reacting in a nitrogen atmosphere, adding an initiator for continuous reaction, and dialyzing to obtain the temperature-sensitive nano hydrogel PNIPAM; wherein the mass ratio of the monomer NIPAM to the cross-linking agent to the emulsifier to the initiator is 100: 1-3: 2-5: 3-6;
(2) diluting the nano hydrogel PNIPAM obtained in the step (1) with deionized water, adding a cross-linking agent, stirring in a nitrogen atmosphere, sequentially adding monomer acrylic acid AA, an initiator and a catalyst at room temperature, continuously stirring, and dialyzing to obtain the interpenetrating network IPN structure nano hydrogel PNIPAM/PAA; wherein the mass ratio of PNIPAM, monomer AA, cross-linking agent, initiator and catalyst is 100: 5-20: 5-30: 3-6: 3-6;
(3) concentrating the IPN structure nano hydrogel PNIPAM/PAA obtained in the step (2) to 1/2 of the original mass concentration, filling nitrogen to remove oxygen, and sequentially adding Fe at room temperature2+、NaNO2Stirring and reacting the mixture with ammonia water and nitrogen atmosphere, and dialyzing the mixture to obtain the magnetic IPN structure nano hydrogel IPN/Fe3O4(ii) a Wherein PNIPAM/PAA, Fe2+、NaNO2The dosage ratio of ammonia water is 100 g: 0.007-0.07 g: 0.0007-0.014 g: 0.01-1 mL;
(4) adding the nanometer hydrogel IPN/Fe obtained in the step (3)3O4Adding NIPAM monomer and cross-linking agent, charging nitrogen at room temperature to remove oxygen, stirring under nitrogen atmosphere, heating to react, adding initiator to continue reaction, dialyzing to obtain the product with coreMulti-responsiveness magnetic nano hydrogel PNIPAM @ (IPN/Fe) with shell structure3O4) (ii) a Wherein IPN/Fe3O4The dosage ratio of the NIPAM, the cross-linking agent and the initiator is 50 mL: 0.05-0.3 g: 0.0025-0.075 g: 0.005-0.09 g;
(5) the nano hydrogel PNIPAM @ (IPN/Fe) obtained in the step (4)3O4) Concentrating to 2-8 wt%, standing at room temperature, and self-assembling to obtain the multi-responsiveness core-shell structure magnetic nano photonic crystal.
The cross-linking agent in the step (1) is N, N' -methylene Bisacrylamide (BIS), the emulsifier is Sodium Dodecyl Sulfate (SDS), and the initiator is Ammonium Persulfate (APS).
And (2) stirring in the step (1) is magnetic stirring, and the stirring time is 25-35 min.
The technological parameters of the reaction in the step (1) are as follows: the reaction temperature is 60-80 ℃, and the reaction time is 30-50 min; the continuous reaction time is 1-4 h.
The cross-linking agent in the step (2) is N, N' -methylene Bisacrylamide (BIS), the initiator is Ammonium Persulfate (APS), and the catalyst is sodium metabisulfite (Na)2S2O5。
And (3) diluting by 5-8 times in the step (2).
The stirring in the step (2) is magnetic stirring, and the stirring time is 15-40 min; the continuous stirring time is 15-60 min.
The concentration of the ammonia water in the step (3) is 25-30 wt%.
And (4) filling nitrogen in the step (3) for 20-40 min.
The stirring in the step (3) is mechanical stirring, and Fe is added2+The stirring time is 20-60 min; adding NaNO2The later stirring time is 5-20 min; the stirring time after adding ammonia water is 1-3 h.
The cross-linking agent in the step (4) is N, N' -methylene Bisacrylamide (BIS), and the initiator is Ammonium Persulfate (APS).
And (4) filling nitrogen for 30-50 min.
And (4) stirring in the step (4) is magnetic stirring, and the stirring time is 20-40 min.
The process parameters of the temperature rise reaction in the step (4) are as follows: the reaction temperature is 50-70 ℃, and the reaction time is 30-40 min; adding an initiator and continuing the reaction for 1-4 h.
The dialysis process conditions in the steps (1), (2), (3) and (4) are as follows: soaking the membrane in deionized water of a dialysis bag with the molecular weight cutoff of 8000-14000 for 3-7 days, and changing water 3 times every day.
The concentration temperature in the step (5) is 40-60 ℃.
The invention uses monomer isopropyl acrylamide NIPAM of temperature sensitive high molecular poly isopropyl acrylamide PNIPAM as monomer, uses pH/temperature dual responsiveness interpenetrating nano hydrogel prepared by hydrophilic acrylic acid AA as functional monomer as template, and uses PAA to ionize COO under alkaline condition-The method is characterized in that ferrous ions are introduced into the IPN structure nano hydrogel through electrostatic adsorption and complexation, and Fe is generated through the action of iron ions and ammonia water through in-situ polymerization3O4Successfully prepare Fe-loaded material with core-shell structure3O4The nano hydrogel PNIPAM @ (IPN/Fe) with temperature/pH/magnetic triple response3O4) The hydrogel can be rapidly self-assembled to form photonic crystals in a certain concentration range.
Advantageous effects
(1) The method has the advantages of simple process, easily obtained raw materials and environmental protection.
(2) The IPN-structured nano hydrogel PNIPAM/PAA prepared by the invention has better biocompatibility than the traditional PNIPAM, and meanwhile, the pH sensitivity of the nano hydrogel is endowed by the addition of the hydrophilic monomer AA; mixing Fe3O4Loading the nanometer hydrogel into interpenetrating polymer network structure through in-situ polymerization to obtain the magnetic IPN structure nanometer hydrogel IPN/Fe3O4And the nano hydrogel is endowed with magnetic performance, so that the nano hydrogel has temperature/pH/magnetic triple responsivity.
(3) The invention uses temperature sensitive macromolecule PNIPAM to coat magnetic nano hydrogel to prepare multi-responsiveness magnetic nano hydrogel PNIPAM @ (IPN/Fe) with a core-shell structure3O4) Is capable of reacting with Fe3O4Better coating and avoiding Fe3O4Self-aggregation, improved biocompatibility, good monodispersity, and fast self-assembly to form photonic crystal under certain concentration, and has wide application foreground in optics and biomedicine, especially in cancer treatment and medicine transmission.
(4) The introduction of the magnetic particles leads to the red shift of the Bragg diffraction peak, so that the signal intensity of the Bragg diffraction peak of the gel is increased, and the photonic forbidden band region can be adjusted by adjusting the introduction amount of the magnetic particles.
Drawings
Fig. 1 is an optical picture of a multi-responsive magnetic nano hydrogel three-dimensional photonic crystal prepared in embodiments 1 to 3 of the present invention, wherein the optical picture corresponds to embodiment 1, embodiment 2, and embodiment 3 from left to right;
FIG. 2 shows the core-shell structure nano-hydrogel PNIPAM @ (IPN/Fe) prepared in example 2 of the present invention3O4) A spectrum of the crystal growth rate;
FIG. 3 is a comparison graph of optical images of the IPN-structured nano hydrogel PNIPAM/PAA prepared in example 3 of the present invention concentrated to a concentration of 3.5 wt% (left) and the multiple-responsive core-shell-structured magnetic nano hydrogel photonic crystal (right);
FIG. 4 shows the IPN-structured nano-hydrogel PNIPAM/PAA and the core-shell-structured magnetic nano-hydrogel PNIPAM @ (IPN/Fe) prepared in example 3 of the present invention3O4) A hydrated particle size map of (a);
FIG. 5 shows the IPN-structured nano-hydrogel PNIPAM/PAA and the core-shell-structured magnetic nano-hydrogel PNIPAM @ (IPN/Fe) prepared in example 3 of the present invention3O4) A spectrum when concentrated to a concentration of 3.5 wt%;
FIG. 6 shows PNIPAM @ (IPN/Fe) of magnetic nano-hydrogel with core-shell structure prepared in example 3 of the present invention3O4) A VSM map of.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. 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.
Example 1
(1) 3.7681g of monomeric N-isopropylacrylamide NIPAM, 0.0677g of crosslinker BIS and 0.1508g of emulsifier SDS were dissolved in 250mL of deionized water, and N was bubbled in at room temperature2Deoxidizing, magnetically stirring for 30min, reacting for 30min at 70 ℃ in a nitrogen atmosphere, dissolving 0.1687g of initiator APS in 10mL of deionized water, adding the solution, keeping the nitrogen atmosphere, continuing to react for 4h, soaking in deionized water for dialysis for 7 days by using a dialysis bag with the cut-off molecular weight of 8000-14000, changing water three times every day, removing residual reaction raw materials and electrolyte in a reaction system, and obtaining the temperature-sensitive nano hydrogel PNIPAM.
(2) Diluting 90mL of PNIPAM obtained in step (1) by 6 times with deionized water, adding 1.8752g of cross-linking agent BIS, magnetically stirring for 30min under nitrogen atmosphere, adding 9.0658g of monomer acrylic acid AA under ice bath, magnetically stirring for 20min, adding 0.6102g of initiator APS, and 0.6102g of catalyst Na2S2O5Respectively dissolving the raw materials in 5mL of deionized water, sequentially adding the solutions, keeping the nitrogen atmosphere, continuously reacting for 20min, soaking the raw materials in deionized water for dialysis for 7 days by using a dialysis bag with the molecular weight cutoff of 8000-14000, changing water for three times every day, removing residual reaction raw materials and electrolyte in a reaction system, and obtaining the interpenetrating network IPN structure nano hydrogel PNIPAM/PAA.
(3) Concentrating the IPN structure nano hydrogel PNIPAM/PAA obtained in the step (2) to 1/2 of the original mass concentration, and taking 150g, N of the concentrated hydrogel2Oxygen is discharged for 30min, and 0.0288g of Fe is added at room temperature2+，N2Mechanically stirring for 40min under protection, and adding 0.0035g NaNO2Adding 0.03mL of 25 wt% ammonia water after 5min, keeping the nitrogen atmosphere for continuous reaction for 1h, then soaking a dialysis bag with the molecular weight cutoff of 8000-14000 in deionized water for dialysis for 7 days, changing water three times every day, removing residual reaction raw materials and electrolyte in a reaction system, and obtaining the iron-loaded magnetic interpenetrating network structure nanogel IPN/Fe3O4。
(4) Taking 50mL of the nano hydrogel IPN/Fe obtained in the step (3)3O4Adding 0.1056g of monomer NIPAM and 0.0114g of cross-linking agent BIS, charging nitrogen at room temperature for 40min to remove oxygen, magnetically stirring for 30min, heating to 60 ℃ for reaction for 30min, dissolving 0.0252g of initiator APS in 2mL of deionized water, adding the solution, maintaining the nitrogen atmosphere, continuously reacting for 4h, soaking the solution in deionized water by using a dialysis bag with the molecular weight cutoff of 8000-14000 for dialysis for 7 days, changing water three times every day, removing residual reaction raw materials and electrolyte in a reaction system, and obtaining the multi-responsive magnetic nano hydrogel PNIPAM @ with the core-shell structure (IPN/Fe)3O4)。
(5) The nano hydrogel PNIPAM @ (IPN/Fe) obtained in the step (4)3O4) And (3) placing the mixture in an oven, concentrating the mixture to 3.5 wt% at 50 ℃, taking the mixture out, standing the mixture at room temperature, and performing self-assembly to obtain the magnetic nano hydrogel photonic crystal with the multi-responsiveness core-shell structure.
The multi-response core-shell structure magnetic nano-hydrogel photonic crystal prepared in the embodiment shows an attractive color, as shown in FIG. 1.
Example 2
(1) 3.7954g of monomeric N-isopropylacrylamide NIPAM, 0.0672g of crosslinker BIS, 0.1521g of emulsifier SDS are dissolved in 250mL of deionized water, and N is bubbled at room temperature2Deoxidizing, magnetically stirring for 30min, reacting for 30min at 70 ℃ in a nitrogen atmosphere, dissolving 0.1668g of initiator APS in 10mL of deionized water, adding the solution, keeping the nitrogen atmosphere, continuing to react for 4h, soaking in deionized water for dialysis for 7 days by using a dialysis bag with the cut-off molecular weight of 8000-14000, changing water three times every day, removing residual reaction raw materials and electrolyte in a reaction system, and obtaining the temperature-sensitive nano hydrogel PNIPAM.
(2) Diluting 90mL of PNIPAM obtained in step (1) by 6 times with deionized water, adding 1.8321g of crosslinking agent BIS, magnetically stirring for 30min under nitrogen atmosphere, adding 8.9958g of monomer acrylic acid AA under ice bath, magnetically stirring for 20min, then adding 0.6023g of initiator APS and 0.6023g of catalyst Na2S2O5Respectively dissolved in 5mL of deionized water, and sequentiallyAdding the solution, keeping the nitrogen atmosphere, continuously reacting for 20min, soaking the solution in a dialysis bag with the molecular weight cutoff of 8000-14000 in deionized water for dialysis for 7 days, changing water three times every day, and removing residual reaction raw materials and electrolyte in a reaction system to obtain the interpenetrating network IPN structure nano hydrogel PNIPAM/PAA.
(3) Concentrating the IPN structure nano hydrogel PNIPAM/PAA obtained in the step (2) to 1/2 of the original mass concentration, and taking 150g, N of the concentrated hydrogel2Discharging oxygen for 30min, adding 0.0831g Fe at room temperature2+，N2Mechanically stirring for 40min under protection, and adding 0.0103g NaNO2Adding 0.08mL of 25 wt% ammonia water after 5min, keeping the nitrogen atmosphere for continuous reaction for 2.5h, then soaking a dialysis bag with the molecular weight cutoff of 8000-14000 in deionized water for dialysis for 7 days, changing water three times every day, removing residual reaction raw materials and electrolyte in a reaction system, and obtaining the iron-loaded magnetic interpenetrating network structure nanogel IPN/Fe3O4。
(4) Taking 50mL of the nano hydrogel IPN/Fe obtained in the step (3)3O4Adding 0.1129g of NIPAM monomer and 0.0121g of BIS cross-linking agent, charging nitrogen at room temperature for 40min to remove oxygen, magnetically stirring for 30min, increasing the temperature to 60 ℃ for reaction for 30min, dissolving 0.0254g of initiator APS in 2mL of deionized water, adding the solution, keeping the nitrogen atmosphere, continuing the reaction for 4h, soaking a dialysis bag with the molecular weight cutoff of 8000-14000 in the deionized water for dialysis for 7 days, changing water three times every day, removing residual reaction raw materials and electrolyte in the reaction system, and obtaining the multi-responsiveness magnetic nano hydrogel PNIPAM @ (IPN/Fe) with the core-shell structure3O4)。
(5) The nano hydrogel PNIPAM @ (IPN/Fe) obtained in the step (4)3O4) And (3) placing the mixture in an oven, concentrating the mixture to 3.5 wt% at 50 ℃, taking the mixture out, standing the mixture at room temperature, and performing self-assembly to obtain the magnetic nano hydrogel photonic crystal with the multi-responsiveness core-shell structure.
The multi-response core-shell structure magnetic nano-hydrogel photonic crystal prepared in the embodiment shows an attractive color, as shown in FIG. 1.
The multiple responsivity obtained in this exampleMagnetic nano hydrogel PNIPAM @ (IPN/Fe) with core-shell structure3O4) The spectrogram of the crystal growth speed is shown in fig. 2, and the magnetic nano hydrogel with the core-shell structure can perform colloidal particle self-assembly within 1min and has quick response.
Example 3
(1) 3.8156g of monomeric N-isopropylacrylamide NIPAM, 0.0654g of crosslinker BIS, 0.1498g of emulsifier SDS are dissolved in 250mL of deionized water, and N is bubbled at room temperature2Deoxidizing, magnetically stirring for 30min, reacting for 30min at 70 ℃ in a nitrogen atmosphere, dissolving 0.1654g of initiator APS in 10mL of deionized water, adding the solution, keeping the nitrogen atmosphere, continuing to react for 4h, soaking in deionized water for dialysis for 7 days by using a dialysis bag with the cut-off molecular weight of 8000-14000, changing water three times every day, removing residual reaction raw materials and electrolyte in a reaction system, and obtaining the temperature-sensitive nano hydrogel PNIPAM.
(2) Diluting 90mL of PNIPAM obtained in step (1) by 6 times with deionized water, adding 1.8547g of cross-linking agent BIS, magnetically stirring for 30min under nitrogen atmosphere, adding 9.1246g of monomer acrylic acid AA under ice bath, magnetically stirring for 20min, adding 0.6054g of initiator APS, and 0.6054g of catalyst Na2S2O5Respectively dissolving the raw materials in 5mL of deionized water, sequentially adding the solutions, keeping the nitrogen atmosphere, continuously reacting for 20min, soaking the raw materials in deionized water for dialysis for 7 days by using a dialysis bag with the molecular weight cutoff of 8000-14000, changing water for three times every day, removing residual reaction raw materials and electrolyte in a reaction system, and obtaining the interpenetrating network IPN structure nano hydrogel PNIPAM/PAA.
(3) Concentrating the IPN structure nano hydrogel PNIPAM/PAA obtained in the step (2) to 1/2 of the original mass concentration, and taking 150g, N of the concentrated hydrogel2Oxygen was removed for 30min and 0.0421g Fe were added at room temperature2+，N2Stirring mechanically for 40min under protection, and adding 0.0052g NaNO2Adding 0.04mL of 25 wt% ammonia water after 5min, keeping the nitrogen atmosphere for continuous reaction for 1.5h, then soaking a dialysis bag with the molecular weight cutoff of 8000-14000 in deionized water for dialysis for 7 days, changing water three times every day, removing residual reaction raw materials and electrolytes in a reaction system to obtain the iron carrierMagnetic interpenetrating network structure nanogel IPN/Fe3O4。
(4) Taking 50mL of the nano hydrogel IPN/Fe obtained in the step (3)3O4Adding 0.1012g of monomer NIPAM and 0.0105g of cross-linking agent BIS, charging nitrogen at room temperature for 40min to remove oxygen, magnetically stirring for 30min, increasing the temperature to 60 ℃ for reaction for 30min, dissolving 0.0248g of initiator APS in 2mL of deionized water, adding the solution, maintaining the nitrogen atmosphere, continuously reacting for 4h, soaking the solution in deionized water by using a dialysis bag with the molecular weight cutoff of 8000-14000 for dialysis for 7 days, changing water three times every day, removing residual reaction raw materials and electrolyte in the reaction system, and obtaining the multi-responsive magnetic nano hydrogel PNIPAM @ with the core-shell structure (IPN/Fe)3O4)。
(5) The nano hydrogel PNIPAM @ (IPN/Fe) obtained in the step (4)3O4) And (3) placing the mixture in an oven, concentrating the mixture to 3.5 wt% at 50 ℃, taking the mixture out, standing the mixture at room temperature, and performing self-assembly to obtain the magnetic nano hydrogel photonic crystal with the multi-responsiveness core-shell structure.
The multi-response core-shell structure magnetic nano-hydrogel photonic crystal prepared in the embodiment shows an attractive color, as shown in FIG. 1.
The IPN structured nano hydrogel PNIPAM/PAA obtained in step (2) of this example was also placed in an oven, concentrated to 3.5 wt% at 50 ℃, taken out and left to stand at room temperature, as a comparison, the results are shown in fig. 3. Due to Fe3O4The introduction of the particles improves the refractive index of the IPN structure nano hydrogel, so that the IPN structure nano hydrogel displays bright structural color, the hydrated particle size graph and the spectrogram of the IPN structure nano hydrogel are shown in figures 4 and 5, and the high refractive index Fe can be known3O4The introduction of the particles and the coating of the PNIPAM macromolecule layer do not change the particle size greatly, the particle size is only increased by 63nm, but the Bragg diffraction peak is red-shifted by 200nm, so that the particle size can be reduced to Fe3O4The introduction of the particles increases the effective refractive index of the IPN nano hydrogel and shifts the Bragg diffraction peak of the IPN nano hydrogel to the long wave direction.
Magnetic nano hydrogel PNIPAM @ (IPN/Fe) with core-shell structure prepared by the embodiment3O4) VSM test results ofAs shown in FIG. 6, a small amount of Fe was observed3O4The introduction of the nano-hydrogel not only improves the effective refractive index of the nano-hydrogel, but also endows the nano-hydrogel with certain magnetic responsiveness.
Claims (10)
1. A preparation method of a magnetic nano photonic crystal with a multi-responsiveness core-shell structure comprises the following steps:
(1) adding a monomer N-isopropylacrylamide NIPAM, a cross-linking agent and an emulsifier into deionized water, filling nitrogen and removing oxygen at room temperature, stirring for dissolving, reacting in a nitrogen atmosphere, adding an initiator for continuous reaction, and dialyzing to obtain the temperature-sensitive nano hydrogel PNIPAM; wherein the mass ratio of the monomer NIPAM to the cross-linking agent to the emulsifier to the initiator is 100: 1-3: 2-5: 3-6;
(2) diluting the nano hydrogel PNIPAM obtained in the step (1) with deionized water, adding a cross-linking agent, stirring in a nitrogen atmosphere, sequentially adding monomer acrylic acid AA, an initiator and a catalyst at room temperature, continuously stirring, and dialyzing to obtain the interpenetrating network IPN structure nano hydrogel PNIPAM/PAA; wherein the mass ratio of PNIPAM, monomer AA, cross-linking agent, initiator and catalyst is 100: 5-20: 5-30: 3-6: 3-6;
(3) concentrating the IPN structure nano hydrogel PNIPAM/PAA obtained in the step (2) to 1/2 of the original mass concentration, filling nitrogen to remove oxygen, and sequentially adding Fe at room temperature2+、NaNO2Stirring and reacting the mixture with ammonia water and nitrogen atmosphere, and dialyzing the mixture to obtain the magnetic IPN structure nano hydrogel IPN/Fe3O4(ii) a Wherein PNIPAM/PAA, Fe2+、NaNO2The dosage ratio of ammonia water is 100 g: 0.007-0.07 g: 0.0007-0.014 g: 0.01-1 mL;
(4) adding the nanometer hydrogel IPN/Fe obtained in the step (3)3O4Adding NIPAM monomer and cross-linking agent, charging nitrogen at room temperature to remove oxygen, stirring under nitrogen atmosphere, heating for reaction, adding initiator for continuous reaction, and dialyzing to obtain multiple-responsiveness magnetic nano-hydrogel PNIPAM @ (IPN/Fe) with core-shell structure3O4) (ii) a Wherein IPN/Fe3O4The dosage ratio of the NIPAM, the cross-linking agent and the initiator is 50 mL: 0.05-0.3 g: 0.0025-0.075 g: 0.005-0.09 g;
(5) the nano hydrogel PNIPAM @ (IPN/Fe) obtained in the step (4)3O4) Concentrating to 2-8 wt%, standing at room temperature, and self-assembling to obtain the multi-responsiveness core-shell structure magnetic nano photonic crystal.
2. The preparation method of the multiple-responsiveness core-shell structure magnetic nanophotonic crystal according to claim 1, wherein: the cross-linking agent in the step (1) is N, N' -methylene Bisacrylamide (BIS), the emulsifier is Sodium Dodecyl Sulfate (SDS), and the initiator is Ammonium Persulfate (APS).
3. The preparation method of the multiple-responsiveness core-shell structure magnetic nanophotonic crystal according to claim 1, wherein: the stirring in the step (1) is magnetic stirring, and the stirring time is 25-35 min; the technological parameters of the reaction are as follows: the reaction temperature is 60-80 ℃, and the reaction time is 30-50 min; the continuous reaction time is 1-4 h.
4. The preparation method of the multiple-responsiveness core-shell structure magnetic nanophotonic crystal according to claim 1, wherein: the cross-linking agent in the step (2) is N, N' -methylene Bisacrylamide (BIS), the initiator is Ammonium Persulfate (APS), and the catalyst is sodium metabisulfite (Na)2S2O5。
5. The preparation method of the multiple-responsiveness core-shell structure magnetic nanophotonic crystal according to claim 1, wherein: the dilution multiple in the step (2) is 5-8 times; stirring is carried out by magnetic stirring for 15-40 min; the continuous stirring time is 15-60 min.
6. The preparation method of the multiple-responsiveness core-shell structure magnetic nanophotonic crystal according to claim 1, wherein: the concentration of the ammonia water in the step (3) is 25-30 wt%; the nitrogen charging time is 20-40 min; the stirring is mechanical stirring, and Fe is added2+The stirring time is 20-60 min; addingInto NaNO2The later stirring time is 5-20 min; the stirring time after adding ammonia water is 1-3 h.
7. The preparation method of the multiple-responsiveness core-shell structure magnetic nanophotonic crystal according to claim 1, wherein: the cross-linking agent in the step (4) is N, N' -methylene Bisacrylamide (BIS), and the initiator is Ammonium Persulfate (APS).
8. The preparation method of the multiple-responsiveness core-shell structure magnetic nanophotonic crystal according to claim 1, wherein: the nitrogen charging time in the step (4) is 30-50 min; stirring is magnetic stirring, and the stirring time is 20-40 min; the technological parameters of the temperature rise reaction are as follows: the reaction temperature is 50-70 ℃, and the reaction time is 30-40 min; adding an initiator and continuing the reaction for 1-4 h.
9. The preparation method of the multiple-responsiveness core-shell structure magnetic nanophotonic crystal according to claim 1, wherein: the dialysis process conditions in the steps (1), (2), (3) and (4) are as follows: soaking the membrane in deionized water of a dialysis bag with the molecular weight cutoff of 8000-14000 for 3-7 days, and changing water 3 times every day.
10. The preparation method of the multiple-responsiveness core-shell structure magnetic nanophotonic crystal according to claim 1, wherein: the concentration temperature in the step (5) is 40-60 ℃.
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