CN115521400A - Preparation method of poly N-isopropylacrylamide 3D self-deforming hydrogel - Google Patents
Preparation method of poly N-isopropylacrylamide 3D self-deforming hydrogel Download PDFInfo
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 137
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000011521 glass Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 11
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- 229910021389 graphene Inorganic materials 0.000 claims description 35
- 229920003213 poly(N-isopropyl acrylamide) Polymers 0.000 claims description 13
- 230000002457 bidirectional effect Effects 0.000 claims description 10
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 9
- 229940124543 ultraviolet light absorber Drugs 0.000 claims description 8
- 239000006096 absorbing agent Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 5
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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- C08F2/00—Processes of polymerisation
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- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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Abstract
A preparation method of poly N-isopropyl acrylamide 3D self-deforming hydrogel relates to a preparation method of hydrogel. The invention aims to solve the problems that the existing 3D printing technology cannot simultaneously process the complex macrostructure and the microscopic anisotropic structure of a hydrogel material and cannot construct the complex 3D self-deforming hydrogel. The method comprises the following steps: 1. preparing PNIPAM solution; 2. preparing a polymerized PNIPAM hydrogel; 3. the polymerized PNIPAM hydrogel was removed from the glass mold. The poly N-isopropylacrylamide 3D self-deforming hydrogel prepared by the invention can generate self-deforming behavior under external stimulation, and the work opens up a new way for constructing complex three-dimensional self-deforming hydrogel, and is beneficial to the development of complex biomedical implants and soft robots. The invention can obtain the poly N-isopropyl acrylamide 3D self-deforming hydrogel.
Description
Technical Field
The invention relates to a preparation method of hydrogel.
Background
Nature has been considered as the source of inspiration for the development of artificial intelligence materials. For example, biological organisms can adjust the shape of the organisms to adapt to various environmental requirements and external interference, such as the phototropic rotation of sunflowers and the predation behavior of fly-catching grass, because the anisotropic strain change of the anisotropic structure in the organisms is caused by external stimulus, so that the organisms deform, and under the inspired by the phenomenon, scientists develop various bionic hydrogel materials capable of spontaneously deforming under different external stimuli (such as light, heat, an electric field, a magnetic field and pH), so that the biological organisms have wide application prospects in the fields of soft robots, bionic actuators, biosensing, drug release and the like.
The existing design strategy is to introduce an anisotropic structure into a 2D hydrogel sheet through modes of ion printing, photoetching, electric field, magnetic field, pre-stored energy patterning and the like, and to induce anisotropic strain change through external stimulation, so that the gel sheet is spontaneously deformed into a complex 3D configuration, but the gel sheet can be restored to an initial 2D state after the stimulation is removed, and the two-dimensional geometrical structure prevents enrichment and complication of gel deformation, thereby greatly limiting the application range of the deformed hydrogel. To solve the above problems, scientists have utilized 3D printing techniques to prepare 3D hydrogel materials by controlling the orientation of nanofillers or by introducing different components in different layers. However, current 3D printing techniques cannot simultaneously process the complex macrostructure and the microscopic anisotropic structure of hydrogel materials, and can only be used for constructing relatively simple 3D deformed hydrogels.
Disclosure of Invention
The invention aims to solve the problems that the existing 3D printing technology cannot simultaneously process the complex macrostructure and the microscopic anisotropic structure of a hydrogel material and cannot construct a complex 3D self-deforming hydrogel, and provides a preparation method of a poly N-isopropylacrylamide 3D self-deforming hydrogel.
A preparation method of poly N-isopropyl acrylamide 3D self-deforming hydrogel is completed according to the following steps:
1. adding N-isopropyl acrylamide, N' -methylene bisacrylamide, an ultraviolet absorbent and 2-hydroxy-2-methyl propiophenone into deionized water, and performing ultrasonic treatment to obtain a PNIPAM solution;
2. injecting the PNIPAM solution into a glass mold, covering a cut photomask on the surface of the glass mold according to the requirement of a pre-designed 3D configuration, fixing the glass mold under a UV lamp, and performing unidirectional illumination or bidirectional illumination for 4-8 hours to obtain polymerized PNIPAM hydrogel;
3. and (3) taking the polymerized PNIPAM hydrogel out of the glass mold to obtain the pre-designed 3D configuration poly N-isopropylacrylamide 3D self-deformation hydrogel.
The principle of the invention is as follows:
1. in the polymerization process, due to the existence of the ultraviolet light absorber, during unidirectional illumination, the UV illumination intensity can be rapidly attenuated along the illumination direction, for the illumination side, the high illumination intensity can cause the side to have high polymerization and crosslinking speeds, so that the side forms a freely contractible polymer network at first, then the polymer network formed on the non-illumination side can be limited by the network of the illumination side and cannot be freely contracted, so that the non-illumination side generates contraction internal stress, meanwhile, the high polymerization speed of the illumination side can cause the concentration of unreacted monomers on the side to be lower, and under the drive of the concentration gradient, the monomers on the non-illumination side can automatically diffuse to the illumination side, so that the illumination side has high polymer network density, and the polymer network on the non-illumination side is looser, so that a vertical gradient structure and a non-uniform internal stress field are formed in hydrogel in the polymerization process. Taking out the hydrogel from the glass mold, releasing stress, and spontaneously deforming the hydrogel into a required 3D shape;
2. the poly N-isopropylacrylamide 3D self-deforming hydrogel prepared by the invention can generate self-deforming behavior under external stimulation, and the work opens up a new way for constructing complex three-dimensional self-deforming hydrogel, and is beneficial to the development of complex biomedical implants and soft robots.
The invention has the advantages that:
1. PNIPAM hydrogels shrink the polymeric network during polymerization due to limited osmotic pressure. In the first step, ultraviolet light absorbent (such as graphene oxide GO) is introduced into the solution, the polymerization rate of monomers in the solution is attenuated along the thickness direction by unidirectional ultraviolet light irradiation, and the gel sheet forms a vertical gradient structure and a non-uniform internal stress field due to the difference of the polymerization rate; taking out the hydrogel sample, releasing the internal stress, and spontaneously deforming the prepared gel film into an expected 3D shape;
2. in the first step, graphene Oxide (GO) is used as a light absorbent, the higher the content of the graphene oxide is, the larger the generated internal stress is, the higher the curling degree is, therefore, hydrogel samples with different graphene oxide contents are prepared, the bending angle is measured, and the proper concentration of GO is finally determined;
3. in the second step, a photomask is applied to the glass mold, the photomask is used for controlling local areas to carry out UV illumination in different directions and in different modes (unidirectional illumination and bidirectional illumination), so that the precise regulation and control of microscopic anisotropic structures and internal stress fields of different local areas in the polymerization process are realized, and 3D self-deforming hydrogel with different complex shapes is prepared according to actual needs;
4. the deformation behavior of the poly N-isopropylacrylamide 3D self-deforming hydrogel in water is characterized in that the hydrogel generates an anisotropic structure in the polymerization process, and the hydrogel is expanded and then contracted in a deformation process due to anisotropic strain change caused by high-temperature stimulation;
5. the invention designs a simple and universal photoetching forming strategy to construct the complex 3D self-deforming hydrogel in one step, the preparation method is simple, various complex 3D configurations can be constructed, theoretical guidance and technical reference are provided for the development of the 3D self-deforming hydrogel, and the practical application of the hydrogel in the fields of soft robots, tissue engineering, biosensing and the like is promoted.
The invention can obtain the poly N-isopropyl acrylamide 3D self-deforming hydrogel.
Drawings
FIG. 1 is an SEM image of the overall cross-section of a poly-N-isopropylacrylamide 3D self-deforming hydrogel prepared in example 1;
FIG. 2 shows the bending angle changes of poly-N-isopropylacrylamide 3D self-deforming hydrogel prepared with different graphene oxide concentrations as light absorbers;
FIG. 3 is a graph showing the variation of the bending angle of a poly (N-isopropylacrylamide) 3D self-deforming hydrogel with the width of a unidirectional irradiation region;
FIG. 4 is an optical photograph of the poly N-isopropylacrylamide 3D self-deformable hydrogel prepared in example 2, wherein 1 is a schematic view of a photomask covered on the upper surface of a glass mold, 2 is a schematic view of a photomask covered on the lower surface of a glass mold, 3 is the poly N-isopropylacrylamide 3D self-deformable hydrogel prepared in example 2, and 4 is a pre-designed 3D-configuration poly N-isopropylacrylamide 3D self-deformable hydrogel;
FIG. 5 is an optical photograph of the poly N-isopropylacrylamide 3D self-deformable hydrogel prepared in example 3, wherein 1 is a schematic view of a photomask covered on the upper surface of a glass mold, 2 is a schematic view of a photomask covered on the lower surface of a glass mold, 3 is the poly N-isopropylacrylamide 3D self-deformable hydrogel prepared in example 3, and 4 is a pre-designed 3D-configuration poly N-isopropylacrylamide 3D self-deformable hydrogel;
FIG. 6 is an optical photograph of the poly N-isopropylacrylamide 3D self-deformable hydrogel prepared in example 4, wherein 1 is a schematic view of a photomask covered by the upper surface of a glass mold, 2 is a schematic view of a photomask covered by the lower surface of a glass mold, 3 is the poly N-isopropylacrylamide 3D self-deformable hydrogel prepared in example 4, and 4 is a pre-designed 3D-configuration poly N-isopropylacrylamide 3D self-deformable hydrogel;
FIG. 7 is an optical photograph of the poly N-isopropylacrylamide 3D self-deformable hydrogel prepared in example 5, wherein 1 is a schematic view of a photomask covered on the upper surface of a glass mold, 2 is a schematic view of a photomask covered on the lower surface of a glass mold, 3 is the poly N-isopropylacrylamide 3D self-deformable hydrogel prepared in example 5, and 4 is a pre-designed 3D-configuration poly N-isopropylacrylamide 3D self-deformable hydrogel;
FIG. 8 is an optical photograph of the poly N-isopropylacrylamide 3D self-deformable hydrogel prepared in example 6, wherein 1 is a schematic view of a photomask covered by the upper surface of a glass mold, 2 is a schematic view of a photomask covered by the lower surface of a glass mold, 3 is the poly N-isopropylacrylamide 3D self-deformable hydrogel prepared in example 6, and 4 is a pre-designed 3D-configuration poly N-isopropylacrylamide 3D self-deformable hydrogel;
fig. 9 is a graph of ultraviolet-visible light transmission spectra of graphene oxide aqueous solutions with different concentrations, in which the concentration of the graphene oxide aqueous solution 1 is 0.0005%, the concentration of the graphene oxide aqueous solution 2 is 0.001%, and the concentration of the graphene oxide aqueous solution 3 is 0.01%;
fig. 10 is an intensity attenuation graph of graphene oxide aqueous solutions with different concentrations, in which the concentration of the graphene oxide aqueous solution of 1 is 0.0005%, the concentration of the graphene oxide aqueous solution of 2 is 0.001%, and the concentration of the graphene oxide aqueous solution of 3 is 0.01%;
FIG. 11 shows the deformation process of the poly N-isopropylacrylamide 3D self-deforming hydrogel prepared in example 2 in 45 ℃ water, wherein 1 is before placing in 45 ℃ water, 2 is when placing in 45 ℃ water for 10s, 3 is when placing in 45 ℃ water for 50s, and 4 is when placing in 45 ℃ water for 90 s;
FIG. 12 shows the deformation process in water at 35 ℃ of the poly (N-isopropylacrylamide) 3D self-deforming hydrogel prepared in example 3, wherein 1 is before placing in water at 45 ℃,2 is when placing in water at 45 ℃ for 10s, 3 is when placing in water at 45 ℃ for 50s, and 4 is when placing in water at 45 ℃ for 90 s;
FIG. 13 is an optical photograph of a poly N-isopropylacrylamide 3D self-deforming hydrogel prepared in example 7;
FIG. 14 is an optical photograph of a poly N-isopropylacrylamide 3D self-deforming hydrogel prepared in example 8;
FIG. 15 shows the deformation process of the poly N-isopropylacrylamide 3D self-deformable hydrogel prepared in example 7 in 45 ℃ water, wherein 1 is before placing in 45 ℃ water, 2 is when placing in 45 ℃ water for 15s, and 3 is when placing in 45 ℃ water for 55 s.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
The first embodiment is as follows: the preparation method of the poly-N-isopropylacrylamide 3D self-deforming hydrogel comprises the following steps:
1. adding N-isopropylacrylamide, N' -methylenebisacrylamide, an ultraviolet light absorber and 2-hydroxy-2-methyl propiophenone into the deionized water, and performing ultrasonic treatment to obtain a PNIPAM solution;
2. injecting the PNIPAM solution into a glass mold, covering a cut photomask on the surface of the glass mold according to the requirement of a pre-designed 3D configuration, fixing the glass mold under a UV lamp, and performing unidirectional illumination or bidirectional illumination for 4-8 hours to obtain polymerized PNIPAM hydrogel;
3. and (3) taking the polymerized PNIPAM hydrogel out of the glass mold to obtain the pre-designed 3D configuration poly N-isopropylacrylamide 3D self-deforming hydrogel.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the ultraviolet light absorber is graphene oxide, UVF-22 or UV-1130; the UVF-22 is purchased from Waila Hua En rubber and plastic new material company, and the UV-1130 is purchased from Qingdao Jiidejia new material technology company, inc. The other steps are the same as those in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the mass fraction of the N-isopropyl acrylamide in the PNIPAM solution in the step one is 12-20%. The other steps are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: the mass fraction of the N, N' -methylene bisacrylamide in the PNIPAM solution in the step one is 0.5-1.0%. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the mass fraction of the ultraviolet light absorber in the PNIPAM solution in the first step is 0.0005-0.15%. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode is as follows: the difference between this embodiment and one of the first to fifth embodiments is as follows: the mass fraction of the 2-hydroxy-2-methyl propiophenone in the PNIPAM solution in the step one is 0.2-0.3%. The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and the first to sixth embodiments is: the power of ultrasonic treatment in the step one is 100W-200W, and the time of ultrasonic treatment is 15 min-20 min. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: and in the second step, the upper surface and the lower surface of the glass mold are both made of light-transmitting glass, and the four side surfaces are provided with gaskets which are light-proof. The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: the mass fraction of the photoabsorber in the PNIPAM solution in the first step is 0.1%. The other steps are the same as those in the first to eighth embodiments.
The specific implementation mode is ten: the difference between this embodiment and one of the first to ninth embodiments is as follows: placing the pre-designed 3D configuration poly N-isopropylacrylamide 3D self-deformable hydrogel obtained in the third step in water with the temperature of more than 35 ℃, wherein the hydrogel can expand firstly and then contract into the pre-designed 3D configuration.
The other steps are the same as those in the first to ninth embodiments.
The present invention will be described in detail below with reference to the accompanying drawings and examples.
Example 1: a preparation method of poly N-isopropyl acrylamide 3D self-deforming hydrogel is completed according to the following steps:
1. adding N-isopropylacrylamide, N' -methylenebisacrylamide, graphene oxide and 2-hydroxy-2-methyl propiophenone into deionized water, and performing ultrasonic treatment at the ultrasonic power of 200W for 20min to obtain a PNIPAM solution;
the mass fraction of N-isopropyl acrylamide in the PNIPAM solution in the step one is 15%;
the mass fraction of N, N' -methylene bisacrylamide in the PNIPAM solution in the step one is 0.7%;
the mass fraction of graphene oxide in the PNIPAM solution in the step one is 0.1%;
the mass fraction of the 2-hydroxy-2-methyl propiophenone in the PNIPAM solution in the step one is 0.2%;
2. injecting the PNIPAM solution into a glass mold, covering a cut photomask on the upper surface of the glass mold according to the requirement of a pre-designed 3D configuration, fixing the glass mold under a UV lamp, and performing unidirectional illumination for 6h to obtain polymerized PNIPAM hydrogel;
the illumination width of the UV lamp in the second step is 10mm;
3. and (3) taking the polymerized PNIPAM hydrogel out of the glass mold to obtain the pre-designed 3D configuration poly N-isopropylacrylamide 3D self-deforming hydrogel.
FIG. 1 is an SEM image of the overall cross-section of a poly-N-isopropylacrylamide 3D self-deforming hydrogel prepared in example 1;
changing the mass fractions of graphene oxide in the PNIPAM solution of step one in example 1 to 0.025%, 0.05%, 0.125% and 0.15%, and keeping the other conditions unchanged, the bending angle changes of the respectively obtained poly N-isopropylacrylamide 3D self-deformable hydrogel are shown in fig. 2;
FIG. 2 shows the bending angle changes of poly-N-isopropylacrylamide 3D self-deforming hydrogel prepared with different graphene oxide concentrations as light absorbers;
as can be seen from fig. 2, the higher the content of the added graphene oxide, the larger the bending angle of the hydrogel under the same illumination width, the too high concentration may result in too narrow a photomask and not using a design with a small angle, and the too low concentration may result in too wide a photomask and not using a design with a large angle, so that the proper concentration of the graphene oxide is determined by comparing fig. 2, and a better width range is ensured when designing the photomask.
The change of the bending angle of the poly-N-isopropylacrylamide 3D self-deformable hydrogel obtained by changing the unidirectional illumination width of the UV lamp described in the first step and the second step of example 1 into 1mm, 1.5mm, 2mm, 2.5mm and 3mm under the same other conditions is shown in FIG. 3;
FIG. 3 is a graph showing the variation of the bending angle of a poly (N-isopropylacrylamide) 3D self-deforming hydrogel with the width of a unidirectional irradiation region;
as can be seen from FIG. 3, by the variation of the unidirectional illumination width and the bending angle of the hydrogel provided in FIG. 3, when designing a hydrogel with a complex 3D shape, the required width of the photomask in different regions can be determined according to the bending angle of each region of the pre-designed shape and the data given in FIG. 3.
Example 2: a preparation method of poly N-isopropyl acrylamide 3D self-deforming hydrogel is completed according to the following steps:
1. adding N-isopropylacrylamide, N' -methylenebisacrylamide, an ultraviolet light absorbent and 2-hydroxy-2-methyl propiophenone into the deionized water, and performing ultrasonic treatment for 20min at the ultrasonic power of 200W to obtain a PNIPAM solution;
the mass fraction of N-isopropyl acrylamide in the PNIPAM solution in the step one is 15%;
the mass fraction of N, N' -methylene bisacrylamide in the PNIPAM solution in the step one is 0.7%;
the ultraviolet absorber in the first step is graphene oxide, and the mass fraction of the graphene oxide in the PNIPAM solution is 0.1%;
the mass fraction of the 2-hydroxy-2-methyl propiophenone in the PNIPAM solution in the step one is 0.2%;
2. injecting the PNIPAM solution into a glass mold, covering the cut photomask on the upper surface and the lower surface of the glass mold according to the requirement of a pre-designed 3D configuration, fixing the glass mold under a UV lamp, and performing bidirectional illumination for 6h to obtain polymerized PNIPAM hydrogel;
the illumination width range of the UV lamp in the step two is as follows: the width of each line on the upper surface of the glass mold is 3mm, the width of the cross line on the lower surface of the glass mold is 2mm, and the widths of the other lines are 3mm;
3. and (3) taking the polymerized PNIPAM hydrogel out of the glass mold to obtain the pre-designed 3D configuration poly N-isopropylacrylamide 3D self-deforming hydrogel.
FIG. 4 is an optical photograph of the poly N-isopropylacrylamide 3D self-deformable hydrogel prepared in example 2, wherein 1 is a schematic view of a photomask covered on the upper surface of a glass mold, 2 is a schematic view of a photomask covered on the lower surface of a glass mold, 3 is the poly N-isopropylacrylamide 3D self-deformable hydrogel prepared in example 2, and 4 is a pre-designed 3D-configuration poly N-isopropylacrylamide 3D self-deformable hydrogel;
from fig. 4, through calculation of the bending angles of the different regions of the 3D mold shown in fig. 4, the upper and lower surface photomask structures of the mold shown in fig. 1 and 2 were designed, and after 6 hours of bidirectional illumination, the corresponding 3D self-deformable hydrogel shown in fig. 4 was obtained, which shows that this strategy can prepare complex 3D shapes.
Example 3: the difference between this example and example 2 is: the illumination width range of the UV lamp in the step two is as follows: the width of two diagonal lines in the upper surface of the glass mold is 2.4mm, the width of the other lines is 2mm, and each line in the lower surface of the glass mold is 2mm. The other steps and parameters were the same as in example 2.
FIG. 5 is an optical photograph of the poly N-isopropylacrylamide 3D self-deformable hydrogel prepared in example 3, wherein 1 is a schematic view of a photomask covered on the upper surface of a glass mold, 2 is a schematic view of a photomask covered on the lower surface of a glass mold, 3 is the poly N-isopropylacrylamide 3D self-deformable hydrogel prepared in example 3, and 4 is a pre-designed 3D-configuration poly N-isopropylacrylamide 3D self-deformable hydrogel;
from fig. 5, through calculation of the bending angles of the different regions of the 3D mold shown in fig. 4, the upper and lower surface photomask structures of the mold shown in fig. 1 and 2 are designed, and after 6 hours of bidirectional illumination, the corresponding 3D self-deformable hydrogel shown in fig. 5 is obtained, further showing that this strategy can prepare complex 3D shapes.
Example 4: the difference between this example and example 2 is: the illumination width range of the UV lamp in the step two is as follows: the width of each line of the photomask covered on the upper surface and the lower surface of the glass mold is 2mm. The other steps and parameters were the same as in example 2.
FIG. 6 is an optical photograph of the poly N-isopropylacrylamide 3D self-deformable hydrogel prepared in example 4, wherein 1 is a schematic view of a photomask covered by the upper surface of a glass mold, 2 is a schematic view of a photomask covered by the lower surface of a glass mold, 3 is the poly N-isopropylacrylamide 3D self-deformable hydrogel prepared in example 4, and 4 is a pre-designed 3D-configuration poly N-isopropylacrylamide 3D self-deformable hydrogel;
from fig. 6, through calculation of the bending angles of the different regions of the 3D mold shown in fig. 4, the upper and lower surface photomask structures of the mold shown in fig. 1 and 2 are designed, and after 6 hours of bidirectional illumination, the corresponding 3D self-deformable hydrogel shown in fig. 6 is obtained, further showing that this strategy can prepare complex 3D shapes.
Example 5: the difference between this example and example 2 is: the illumination width range of the UV lamp in the step two is as follows: the widths of the lines of the photomask covered on the upper surface and the lower surface of the glass mold are both 2mm. The other steps and parameters were the same as in example 2.
FIG. 7 is an optical photograph of the poly N-isopropylacrylamide 3D self-deformable hydrogel prepared in example 5, in which 1 is a schematic view of a photomask covered by the upper surface of a glass mold, 2 is a schematic view of a photomask covered by the lower surface of a glass mold, 3 is the poly N-isopropylacrylamide 3D self-deformable hydrogel prepared in example 5, and 4 is a pre-designed 3D-configuration poly N-isopropylacrylamide 3D self-deformable hydrogel;
from fig. 7, through calculation of the bending angles of the different regions of the 3D mold shown in fig. 4, the upper and lower surface photomask structures of the mold shown in fig. 1 and 2 are designed, and after 6 hours of bidirectional illumination, the corresponding 3D self-deformable hydrogel shown in fig. 7 is obtained, further showing that this strategy can prepare complex 3D shapes.
Example 6: the difference between this example and example 2 is: the illumination width range of the UV lamp in the second step is as follows: the widths of the lines of the photomask covered on the upper surface and the lower surface of the glass mold are both 2mm. The other steps and parameters were the same as in example 2.
FIG. 8 is an optical photograph of the poly N-isopropylacrylamide 3D self-deformable hydrogel prepared in example 6, wherein 1 is a schematic view of a photomask covered by the upper surface of a glass mold, 2 is a schematic view of a photomask covered by the lower surface of a glass mold, 3 is the poly N-isopropylacrylamide 3D self-deformable hydrogel prepared in example 6, and 4 is a pre-designed 3D-configuration poly N-isopropylacrylamide 3D self-deformable hydrogel;
from fig. 8, through calculation of the bending angles of the different regions of the 3D mold shown in fig. 4, the upper and lower surface photomask structures of the mold shown in fig. 1 and 2 are designed, and after 6 hours of bidirectional illumination, the corresponding 3D self-deformable hydrogel shown in fig. 8 is obtained, further showing that this strategy can prepare complex 3D shapes.
Fig. 9 is a graph of ultraviolet-visible light transmission spectra of graphene oxide aqueous solutions with different concentrations, in which the concentration of the graphene oxide aqueous solution 1 is 0.0005%, the concentration of the graphene oxide aqueous solution 2 is 0.001%, and the concentration of the graphene oxide aqueous solution 3 is 0.01%;
fig. 10 is an intensity attenuation graph of graphene oxide aqueous solutions with different concentrations, in which the concentration of the graphene oxide aqueous solution of 1 is 0.0005%, the concentration of the graphene oxide aqueous solution of 2 is 0.001%, and the concentration of the graphene oxide aqueous solution of 3 is 0.01%;
as can be seen from fig. 9 and 10, the rate of the decay of the light intensity increases with the increase of the graphene oxide concentration, and thus the bending angle of the hydrogel increases with the increase of the graphene oxide concentration.
FIG. 11 shows the deformation process of the poly N-isopropylacrylamide 3D self-deforming hydrogel prepared in example 2 in 45 ℃ water, wherein 1 is before placing in 45 ℃ water, 2 is when placing in 45 ℃ water for 10s, 3 is when placing in 45 ℃ water for 50s, and 4 is when placing in 45 ℃ water for 90 s;
as can be seen from FIG. 11, it is further verified that the gradient structure is formed inside the hydrogel, and the deformation process is caused because the polymer network on the illuminated side is dense, so that the deswelling rate is high, so that the hydrogel is contracted to the illuminated side first and then expands to the illuminated side, and the deswelling degree of the non-illuminated side is higher than that of the illuminated side, so that the hydrogel is bent to the non-illuminated side again.
FIG. 12 shows the deformation process of the poly N-isopropylacrylamide 3D self-deforming hydrogel prepared in example 3 in water at 45 ℃, wherein 1 is before placing in water at 45 ℃,2 is when placing in water at 45 ℃ for 10s, 3 is when placing in water at 45 ℃ for 50s, and 4 is when placing in water at 45 ℃ for 90 s;
as can be seen from FIG. 12, it is further verified that the gradient structure is formed inside the hydrogel, and the deformation process is caused because the polymer network on the illuminated side is dense, so that the deswelling rate is high, so that the hydrogel is contracted to the illuminated side first and then expands to the illuminated side, and the deswelling degree of the non-illuminated side is higher than that of the illuminated side, so that the hydrogel is bent to the non-illuminated side again.
Example 7: the difference between this example and example 1 is: the ultraviolet light absorber in the first step is UVF-22, which is purchased from Waiha Hua En rubber and plastic new material Co. The other steps and parameters were the same as in example 1.
Example 8: the difference between this example and example 1 is: the ultraviolet light absorber described in step one is UV-1130, available from Jiede Geidejia New materials science and technology, inc., qingdao. The other steps and parameters were the same as in example 1.
FIG. 13 is an optical photograph of a poly N-isopropylacrylamide 3D self-deforming hydrogel prepared in example 7;
as can be seen from fig. 13, when different light absorbers are used instead of graphene oxide, the unilaterally illuminated hydrogel sample is also bent, so that the poly N-isopropylacrylamide 3D self-deformation hydrogel can be prepared.
FIG. 14 is an optical photograph of a poly N-isopropylacrylamide 3D self-deformable hydrogel prepared in example 8.
As can be seen from fig. 14, when different light absorbers were used instead of graphene oxide, the unilaterally illuminated hydrogel sample was also bent, so that the poly N-isopropylacrylamide 3D self-deforming hydrogel could be prepared.
FIG. 15 shows the deformation process of the poly (N-isopropylacrylamide) 3D self-deforming hydrogel prepared in example 7 in 45 ℃ water, wherein 1 is before placing in 45 ℃ water, 2 is when placing in 45 ℃ water for 15s, and 3 is when placing in 45 ℃ water for 55 s;
as can be seen from FIG. 15, a gradient structure exists in the poly-N-isopropylacrylamide 3D self-deforming hydrogel prepared by using different light absorbers, and the deformation behavior can be generated under the external stimulation.
Claims (10)
1. A preparation method of poly N-isopropyl acrylamide 3D self-deforming hydrogel is characterized in that the preparation method of the poly N-isopropyl acrylamide 3D self-deforming hydrogel is completed according to the following steps:
1. adding N-isopropylacrylamide, N' -methylenebisacrylamide, an ultraviolet light absorber and 2-hydroxy-2-methyl propiophenone into the deionized water, and performing ultrasonic treatment to obtain a PNIPAM solution;
2. injecting the PNIPAM solution into a glass mold, covering the cut photomask on the surface of the glass mold according to the requirement of a pre-designed 3D configuration, fixing the glass mold under a UV lamp, and performing unidirectional illumination or bidirectional illumination for 4-8 hours to obtain polymerized PNIPAM hydrogel;
3. and (3) taking the polymerized PNIPAM hydrogel out of the glass mold to obtain the pre-designed 3D configuration poly N-isopropylacrylamide 3D self-deforming hydrogel.
2. The method for preparing the poly (N-isopropylacrylamide) 3D self-deforming hydrogel according to claim 1, wherein the ultraviolet light absorber is graphene oxide, UVF-22 or UV-1130; the UVF-22 is purchased from Waisha Hua En rubber and plastic new material company, and the UV-1130 is purchased from Qingdao Jiede new material technology company, inc.
3. The method for preparing a poly (N-isopropylacrylamide) 3D self-deforming hydrogel according to claim 1 or 2, wherein the mass fraction of N-isopropylacrylamide in the PNIPAM solution in the step one is 12% to 20%.
4. The method for preparing poly (N-isopropylacrylamide) 3D self-deforming hydrogel according to claim 1 or 2, wherein the mass fraction of N, N' -methylenebisacrylamide in the PNIPAM solution in the step one is from 0.5% to 1.0%.
5. The method of claim 1 or 2, wherein the mass fraction of the UV absorber in the PNIPAM solution in the first step is 0.0005% -0.15%.
6. The method for preparing a poly (N-isopropylacrylamide) 3D self-deforming hydrogel according to claim 1 or 2, wherein the mass fraction of 2-hydroxy-2-methylpropiophenone in the PNIPAM solution in the step one is 0.2% to 0.3%.
7. The method for preparing the poly (N-isopropylacrylamide) 3D self-deforming hydrogel according to claim 1, wherein the ultrasonic treatment power in the first step is 100W to 200W, and the ultrasonic treatment time is 15min to 20min.
8. The method for preparing poly (N-isopropylacrylamide) 3D self-deforming hydrogel according to claim 1, wherein in step two, the upper and lower surfaces of the glass mold are both made of light-transmitting glass, and the four side surfaces are provided with gaskets and are light-proof.
9. The method of claim 5, wherein the light absorber is present in the PNIPAM solution at a concentration of 0.1% by weight of the poly (N-isopropylacrylamide) 3D self-deforming hydrogel.
10. The method for preparing poly (N-isopropylacrylamide) 3D self-deforming hydrogel according to claim 1, wherein the pre-designed 3D-configuration poly (N-isopropylacrylamide) 3D self-deforming hydrogel obtained in step three is placed in water at a temperature of > 35 ℃ and undergoes expansion and then contraction to the pre-designed 3D configuration.
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