CN119684639A - A method for preparing a 3D printed double-layer magnetically responsive hydrogel - Google Patents
A method for preparing a 3D printed double-layer magnetically responsive hydrogel Download PDFInfo
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Abstract
一种3D打印的双层磁响应水凝胶的制备方法，它涉及3D打印磁响应水凝胶的方法，它是要解决现有的磁响应水凝胶机械性能差、磁性颗粒分布不均匀、3D打印成品率低的技术问题。本方法：利用N,N'‑亚甲基双丙烯酰胺、光引发剂、水、硅酸钠镁锂、重结晶N‑异丙基丙烯酰胺与二甲氨基丙基甲基丙酰胺制备凝胶液，经3D打印后得到温敏水凝胶型体；将温敏水凝胶型体放在铁盐溶液中浸泡后再转移到NaOH溶液中浸泡，得到磁响应水凝胶型体；将磁响应水凝胶与温敏水凝胶粘接，得到双层磁响应水凝胶，其剩余磁化强度3.92～4.98emu/g，杨氏模量3.82～5.34kPa，断裂伸长率230％～280％，可用于功能性水凝胶领域。
A preparation method of a 3D-printed double-layer magnetic responsive hydrogel, which relates to a method for 3D printing a magnetic responsive hydrogel, and is intended to solve the technical problems of poor mechanical properties, uneven distribution of magnetic particles, and low 3D printing yield of existing magnetic responsive hydrogels. The method comprises the following steps: preparing a gel solution using N,N'-methylenebisacrylamide, a photoinitiator, water, sodium magnesium lithium silicate, recrystallized N-isopropylacrylamide, and dimethylaminopropylmethylpropionamide, and obtaining a thermosensitive hydrogel body after 3D printing; soaking the thermosensitive hydrogel body in an iron salt solution and then transferring it to a NaOH solution for soaking to obtain a magnetic responsive hydrogel body; bonding the magnetic responsive hydrogel to the thermosensitive hydrogel to obtain a double-layer magnetic responsive hydrogel, which has a residual magnetization of 3.92 to 4.98emu/g, a Young's modulus of 3.82 to 5.34kPa, and an elongation at break of 230% to 280%, and can be used in the field of functional hydrogels.
Description
Technical Field
The invention relates to a method for 3D printing of magnetically-responsive hydrogel, and belongs to the technical field of 3D printing materials.
Background
Gels are used as a special dispersion system, wherein molecules are connected under certain conditions to form a network structure filled with a dispersion medium, and due to unique properties and internal structures, the gels are receiving more and more attention in the fields of drug delivery, biomedicine and the like. The gel material is combined with other materials with unique properties, and new functions such as temperature response hydrogel and magnetic hydrogel are endowed on the premise of keeping the characteristics of the gel material. Whereas the shape deformation of existing temperature-responsive hydrogels must be triggered in a liquid environment, which greatly limits their application, magnetic hydrogels generally incorporate Fe 3O4 magnetic nanoparticles directly into the hydrogel matrix, the aggregation of the magnetic particles in the hydrogel matrix is always a problem, while the distribution of the magnetic particles will significantly affect the mechanical properties of the magnetically-responsive hydrogels, which limits their practical application with low yields when using 3D printing.
Disclosure of Invention
The invention aims to solve the technical problems of poor mechanical property, uneven magnetic particle distribution and low 3D printing yield of the traditional magnetic response hydrogel, and provides a preparation method of the double-layer magnetic response hydrogel for 3D printing.
The preparation method of the 3D printed double-layer magnetically-responsive hydrogel comprises the following steps:
1. Weighing 0.1-1 part of N, N' -methylenebisacrylamide, 0.1-1 part of photoinitiator, 10-30 parts of water, 5-10 parts of sodium magnesium lithium silicate, 5-10 parts of recrystallized N-isopropyl acrylamide and 1-5 parts of dimethylaminopropyl methylpropionamide according to the weight part ratio;
2. Sequentially adding N, N' -methylene bisacrylamide and a photoinitiator into water, stirring for 5-15 min, adding sodium magnesium lithium silicate into an aqueous solution in batches under stirring, and continuing stirring until the mixed solution shows a gel state after the addition is completed within 10-30 seconds;
3. Adding the temperature-sensitive deformation gel solution into a 3D printer, performing 3D extrusion printing, and keeping the printing shape of the printing solution under the self-supporting function after printing and molding to obtain a gel body, transferring the gel body to an ultraviolet irradiation curing lamp for photo-curing for 2-3 min to obtain a cured body, transferring the cured body to room-temperature deionized water for full swelling, and removing unreacted monomers to obtain the temperature-sensitive hydrogel body;
4. Weighing ferric chloride hexahydrate and ferrous chloride tetrahydrate, adding the ferric chloride hexahydrate and the ferrous chloride tetrahydrate into deionized water, and magnetically stirring to completely dissolve solid particles to obtain an iron salt ion aqueous solution, wherein the molar ratio of Fe 2+ to Fe 3+ in the iron salt ion aqueous solution is 1:1;
5. Immersing the temperature-sensitive hydrogel body after the swelling is eliminated in an iron salt ion aqueous solution for 36-48 hours to enable the temperature-sensitive hydrogel body to be fully swollen, and obtaining a swollen temperature-sensitive hydrogel body, wherein ferrous ions Fe 2+ and ferric ions Fe 3+ in the iron salt ion aqueous solution enter gaps of a gel polymer network through the diffusion action of water molecules;
6. In the process, the swelling temperature sensitive hydrogel body is quickly changed into black after being contacted with NaOH solution, because divalent and trivalent iron ions are transferred into a gel network before being contacted with NaOH solution, hydroxide ions and iron ions form Fe 3O4 magnetic particles in situ in the gel network in the migration process of following water molecules, and the Fe 3O4 magnetic particles are formed in situ in the gel through full absorption and reaction;
7. And (3) bonding the temperature-sensitive hydrogel body obtained in the step (III) with the magnetic response hydrogel body obtained in the step (six), wherein the lower layer is the temperature-sensitive hydrogel, and the upper layer is the magnetic response hydrogel, so as to prepare the double-layer magnetic response hydrogel for 3D printing. The double-layer magnetically-responsive hydrogel can be subjected to a 4D deformation process under the magnetic field condition generated by current.
Further, the photoinitiator in the first step is (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide (TPO);
Further, in the first step, 0.5-1 part of N, N '-methylene bisacrylamide, 0.2-0.5 part of (2, 4, 6-trimethyl benzoyl) diphenyl phosphine oxide, 10-30 parts of water, 5-10 parts of sodium magnesium lithium silicate, 5-10 parts of recrystallized N-isopropyl acrylamide and 1-5 parts of dimethylaminopropyl methacrylamide are weighed according to the weight parts, sodium magnesium lithium silicate is used as a rheology modifier, N' -methylene bisacrylamide is used as a chemical crosslinking agent, N-isopropyl acrylamide and dimethylaminopropyl methacrylamide are used as temperature-sensitive monomers, so that a temperature-sensitive deformation gel liquid is prepared, and the temperature-sensitive deformation gel 3D printing liquid synthesized under the condition shows better 3D printing forming stability and yield, and the yield reaches 100%. Different lithium magnesium silicate contents can lead to temperature-sensitive deformation gel 3D printing fluid fluidity to be different, when lithium magnesium silicate weight portions are less than 5 portions, the contained angle between the liquid level of the printing fluid precursor and the container wall becomes smaller after the printing fluid precursor is inclined and stands for ten minutes, and the printing fluid precursor still has certain autonomous fluidity, is poor in shape retention and cannot be rapidly shaped, so that the printing fluid precursor cannot be self-supported during printing, and accurate 3D printing cannot be realized. When the content of lithium magnesium silicate is 5-10 parts, the included angle between the liquid level of the printing liquid precursor and the container wall is still 90 degrees after the printing liquid precursor is inclined and stood, and the inclined and stood state is still unchanged for ten minutes, so that the rapid forming and self-supporting can be realized when the content of lithium magnesium silicate is 5-10 parts, in addition, when the adding amount of lithium magnesium silicate is more than 10 parts, the printing liquid can become more viscous, the fluidity of the printing liquid is poor, and the accurate printing and forming cannot be realized.
Furthermore, the rotation speed of the centrifugal machine in the second step is 6000rpm, and the centrifugal time is 5min, so that the temperature-sensitive deformed gel 3D printing liquid is obtained.
The preparation method of the recrystallized N-isopropyl acrylamide comprises the steps of weighing 10gNIPAM, dissolving in toluene, heating to 60 ℃ to be completely dissolved in a magnetic stirring water bath kettle under stirring at a speed of 400rpm, adding 40mL of N-hexane into the solution, keeping the temperature of 60 ℃ and stirring for 20min, adding toluene and N-hexane again respectively, repeating the steps for two times, removing insoluble polymerization inhibitors by suction filtration of the mixed solution, standing the filtrate in a refrigerator at the temperature of-20 ℃ for 12h, suction filtering to remove the filtrate, obtaining white flocculent crystals, and freeze-drying to obtain 7g of NIPAM crystals with the yield of 70%;
The 3D extrusion printing method comprises the specific steps of storing a built model body as a file with a suffix name of-stl format, guiding the model into RepetierHost software to adjust proper printing positions and sizes, slicing the model, setting printer parameters, and then using a double-head direct-writing printer to perform 3D extrusion printing, wherein the printer parameters are that the printing speed of the used extrusion 3D printing equipment is 10-30 mm/s, a Teflon needle with the diameter of 0.4-1.2 mm is adopted as a 3D printing needle, the height of the printing needle is set to be 0.7-1.2 mm, and the extrusion speed of printing liquid is 10mm/s.
Further, the cured body in the third step is transferred to room temperature deionized water for full swelling, and the cured body is soaked in the room temperature deionized water for 24 hours for full swelling.
Further, the wavelength of the ultraviolet light curing lamp in the third step is 365nm.
Further, the magnetic stirring in the fourth step is performed at a stirring rate of 500-800 rpm for 20-30 min.
Further, the concentration of ferric chloride hexahydrate in the ferric salt ion aqueous solution in the fourth step is 0.05-0.2 mol/L.
Further, the method for swelling elimination of the temperature-sensitive hydrogel body in the fifth step comprises the steps of fully soaking the temperature-sensitive hydrogel body in deionized water at normal temperature for 40-48 hours to remove unreacted impurities, and then transferring the temperature-sensitive hydrogel body to 80 ℃ hot water to keep for 1-2 hours for shrinkage and swelling elimination.
Furthermore, the concentration of the NaOH solution in the step five is 1-5 mol/L respectively, and the mechanical properties of the magnetic hydrogel can be adjusted by changing the concentration of the alkaline solution.
The bonding method in the seventh step comprises the steps of uniformly mixing the strong glue Loctite 406 and ethyl acetate according to the volume ratio of 1:10 to obtain a glue water mixture, and bonding the temperature-sensitive hydrogel body and the magnetic response hydrogel body glue water mixture to prepare the double-layer magnetic response hydrogel.
The invention improves the performance of high-toughness and uniform-structure double-layer magnetic response hydrogel and 4D printing which can be used for 3D printing from the following aspects.
(1) The high-toughness and uniform-structure bilayer magnetically-responsive hydrogel for 3D printing, disclosed by the invention, has the advantages that the poly (N-isopropyl acrylamide) hydrogel matrix is crosslinked through sodium magnesium lithium silicate, fe 3O4 magnetic particles are deposited on a hydrogel polymer network in situ, and the magnetically-responsive hydrogel shows high toughness due to phase separation of the hydrogel in a high-concentration alkaline solution. The original liquid environment triggering hydrogel is changed into the magnetic response hydrogel, and the shape deformation method using the magnetic field opens up a new method for programming the complex 3D structure of the hydrogel, so that remote control can be realized and the hydrogel structure is far away from the liquid environment.
(2) According to the invention, the temperature-sensitive hydrogel is printed by adopting extrusion type 3D, a double layer consisting of the magnetically responsive hydrogel and the temperature-sensitive hydrogel is designed, and the double layer with a 2D structure can be changed into a 3D shape in an Alternating Magnetic Field (AMF) controlled by a magnetocaloric effect, so that the perfect realization of 4D printing is ensured.
(3) Preparing DMAPMA composite hydrogel, wherein sodium magnesium lithium silicate is uniformly dispersed in a hydrogel matrix. DMAPMA chain is crosslinked with sodium magnesium lithium silicate through non-covalent interaction, and due to hydrogen bond or ion or coordination interaction, magnetic particles can be uniformly distributed in hydrogel, and the fluidity of the temperature-sensitive deformation gel 3D printing liquid is regulated through the content of lithium magnesium silicate, so that accurate printing and forming are realized.
The 3D printable high-toughness magnetic response hydrogel with uniform structure has the residual magnetization intensity of 3.92-4.98 emu/g, the Young modulus of 3.82-5.34 kPa and the elongation at break of 230-280%, and can be used in the field of functional hydrogel preparation.
Drawings
FIG. 1 is a schematic diagram of the synthesis process of the temperature-sensitive magnetic gel in example 1, (a) temperature-sensitive gel printing, (b) iron ion solution soaking, (c) magnetic gel synthesis;
FIG. 2 is a cross-shaped magnetically responsive temperature sensitive gel sample prepared in example 1;
FIG. 3 is a graph showing the self-folding process of flowers in an alternating magnetic field of the flower-shaped double-layer magnetically-responsive hydrogel prepared in example 1;
FIG. 4 is a magnetic representation of the bilayer magnetically-responsive hydrogel prepared in example 1;
FIG. 5 is an XRD spectrum of the double-layer magnetically-responsive hydrogel prepared in examples 1 to 3;
FIG. 6 is a thermogravimetric analysis graph of the bilayer magnetically responsive hydrogels prepared in examples 1-3;
FIG. 7 is a hysteresis loop diagram of the bilayer magnetically responsive hydrogels prepared in examples 1-3.
Detailed Description
The present invention will be specifically described below by way of examples. All materials are commercially available, unless otherwise indicated.
Example 1 the preparation method of the bilayer magnetically-responsive hydrogel of this example was performed as follows:
1. Weighing 0.015g of N, N' -methylene bisacrylamide, 0.015g of photoinitiator (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide, 10mL of deionized water, 0.5g of sodium magnesium lithium silicate, 0.8g of recrystallized N-isopropyl acrylamide and 0.2g of dimethylaminopropyl methyl propionamide, wherein the preparation method of the recrystallized N-isopropyl acrylamide comprises the steps of weighing 10g of N-isopropyl acrylamide (NIPAM), dissolving in toluene, heating to 60 ℃ to complete dissolution in a magnetic stirring water bath kettle under stirring at a speed of 400rpm, adding 40mL of normal hexane into the solution, keeping constant temperature stirring at 60 ℃ for 20min, adding toluene and normal hexane again, repeating twice, removing insoluble polymerization inhibitor by suction filtration of the mixed solution, standing the filtrate in a refrigerator at-20 ℃ for 12h, suction filtering to remove filtrate, obtaining white flocculent crystals, and obtaining NIPAM crystals, wherein the yield is 70;
2. Sequentially adding N, N' -methylene bisacrylamide and a photoinitiator (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide into deionized water, stirring for 10min, adding sodium magnesium lithium silicate into an aqueous solution in batches under stirring, continuously stirring for 60min after the addition is completed within 30 seconds, and after the solution shows a gel state, respectively adding recrystallized N-isopropyl acrylamide and dimethylaminopropyl methylpropionamide into the mixed solution under the protection of nitrogen, stirring for 2h, transferring to a centrifuge, and centrifuging for 5min under the condition of the rotating speed of 6000rpm to remove bubbles in the gel solution, thereby obtaining a temperature-sensitive deformation gel solution;
3. Storing the built model body model as a file with a suffix of-stl format, guiding the model into RepetierHost software to adjust proper printing position and size, slicing the model, and setting printer parameters, wherein the printer parameters are that a Teflon needle with the diameter of 0.8mm is adopted as a 3D printing needle, the height of the printing needle is set to be 0.9mm, the extrusion speed of printing liquid is 10mm/s, adding a temperature-sensitive deformation gel solution into a 3D printer, and then performing 3D extrusion printing by using a double-head direct-writing printer to obtain a gel body, keeping the printing shape of the gel body by virtue of self-supporting function, transferring the gel body to an ultraviolet irradiation curing lamp for photo-curing for 2min to obtain a cured body, and transferring the cured body into deionized water at room temperature to enable the gel to be fully swelled to remove unreacted monomers to obtain the temperature-sensitive hydrogel body;
4. Weighing 4g of ferric chloride hexahydrate and 1.5g of ferrous chloride tetrahydrate, adding the ferric chloride hexahydrate and the ferrous chloride tetrahydrate into 100mL of deionized water, and stirring the mixture for 20min at a stirring rate of 500rpm by using a magnetic stirrer to completely dissolve solid particles to obtain an iron salt ion aqueous solution, wherein the molar ratio of Fe 2+ to Fe 3+ in the iron salt ion aqueous solution is 1:1;
5. Immersing the temperature-sensitive hydrogel body in deionized water at normal temperature for 48 hours to remove unreacted impurities, and transferring to 80 ℃ hot water to keep for 2 hours for shrinkage and swelling, immersing the swelled temperature-sensitive hydrogel body in ferric ion aqueous solution for 36 hours to enable the temperature-sensitive hydrogel body to be fully swelled, and obtaining a swelled temperature-sensitive hydrogel body, wherein ferrous ions Fe 2+ and ferric ions Fe 3+ in the ferric ion aqueous solution enter gaps of a gel polymer network through the diffusion action of water molecules;
6. In the process, the swelling temperature sensitive hydrogel body is quickly changed into black after being contacted with NaOH solution, because divalent and trivalent iron ions are transferred into a gel network before being contacted with sodium hydroxide solution, hydroxide ions and iron ions form Fe 3O4 magnetic particles in situ in the gel network in the migration process of following water molecules, and the Fe 3O4 magnetic particles are formed in situ in the gel through full absorption and reaction;
7. Uniformly mixing the strong glue Loctite 406 and ethyl acetate according to the volume ratio of 1:10 to obtain a glue water mixture, taking the temperature-sensitive hydrogel body obtained in the third step as a lower layer, taking the magnetic response hydrogel body obtained in the sixth step as an upper layer, and coating the glue water mixture between the upper layer and the lower layer for bonding to prepare the double-layer magnetic response hydrogel for 3D printing. The double-layer magnetically-responsive hydrogel can be subjected to a 4D deformation process under the magnetic field condition generated by current.
Fig. 1 is a schematic diagram of a process of obtaining a step six magnetic response hydrogel body from a step three temperature sensitive hydrogel body and a step five swelling temperature sensitive hydrogel body in example 1, wherein a is a step three temperature sensitive hydrogel body, b is a step five swelling temperature sensitive hydrogel body, and c is a step six magnetic response hydrogel body.
Fig. 2 is a photograph of a cross-shaped double-layer magnetic response hydrogel sample prepared in step six of example 1, a is a temperature-sensitive hydrogel printed in 3D, b is a magnetic response hydrogel generated by an in-situ precipitation method, c is a magnetic force test chart of the magnetic response hydrogel, and from c, it can be seen that the magnetic response hydrogel can be attracted by a magnet.
FIG. 3 is a petal-shaped double-layer magnetically-responsive hydrogel sample of example 1, which is placed in a coil, the coil is electrified to form a magnetic field, and the petal-shaped double-layer magnetically-responsive hydrogel sample is deformed under the magnetic field condition, as shown in FIG. 3, the whole deformation process requires 4.5min, and the temperature-sensitive hydrogel body of the lower layer can keep the gel steady state under the condition without fluidity.
FIG. 4 is a magnetic representation of the bilayer magnetically-responsive hydrogel prepared in example 1, as can be seen in FIG. 4, the bilayer magnetically-responsive hydrogel can be moved by an external magnetic field.
Example 2 the preparation method of the bilayer magnetically-responsive hydrogel of this example was performed as follows:
1. Weighing 0.03g of N, N' -methylenebisacrylamide, 0.03g of photoinitiator (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide, 10mL of deionized water, 1g of sodium magnesium lithium silicate, 0.7g of recrystallized N-isopropyl acrylamide and 0.3g of dimethylaminopropyl methylpropionamide, wherein the preparation method of the recrystallized N-isopropyl acrylamide is the same as that of example 1;
2. Sequentially adding N, N' -methylene bisacrylamide and a photoinitiator (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide into deionized water, stirring for 10min, adding sodium magnesium lithium silicate into an aqueous solution in batches under stirring, continuously stirring for 60min after the addition is completed within 30 seconds, and after the solution shows a gel state, respectively adding recrystallized N-isopropyl acrylamide and dimethylaminopropyl methylpropionamide into the mixed solution under the protection of nitrogen, stirring for 2h, transferring to a centrifuge, and centrifuging for 5min under the condition of the rotating speed of 6000rpm to remove bubbles in the gel solution, thereby obtaining a temperature-sensitive deformation gel solution;
3. Storing the built model body model as a file with a suffix name of-stl format, guiding the model into RepetierHost software to adjust proper printing position and size, slicing the model, and setting printer parameters, wherein the printer parameters are that a Teflon needle with the diameter of 0.8mm is adopted as a 3D printing needle, the height of the printing needle is set to be 1.1mm, the extrusion speed of printing liquid is 20mm/s, adding a temperature-sensitive deformation gel liquid into a 3D printer, and then performing 3D extrusion printing by using a double-head direct-writing printer to obtain a gel body, keeping the printing shape of the gel body by virtue of self-supporting function, transferring the gel body to an ultraviolet irradiation curing lamp for photo-curing for 2min to obtain a cured body, and transferring the cured body into deionized water at room temperature to enable the gel to be fully swelled to remove unreacted monomers to obtain the temperature-sensitive hydrogel body;
4. Weighing 4g of ferric chloride hexahydrate and 1.5g of ferrous chloride tetrahydrate, adding the ferric chloride hexahydrate and the ferrous chloride tetrahydrate into 100mL of deionized water, and stirring the mixture for 20min at a stirring rate of 500rpm by using a magnetic stirrer to completely dissolve solid particles to obtain an iron salt ion aqueous solution, wherein the molar ratio of Fe 2+ to Fe 3+ in the iron salt ion aqueous solution is 1:1;
5. Immersing the temperature-sensitive hydrogel body in deionized water at normal temperature for 48 hours to remove unreacted impurities, and transferring to 80 ℃ hot water to keep for 2 hours for shrinkage and swelling, immersing the swelled temperature-sensitive hydrogel body in ferric ion aqueous solution for 36 hours to enable the temperature-sensitive hydrogel body to be fully swelled, and obtaining a swelled temperature-sensitive hydrogel body, wherein ferrous ions Fe 2+ and ferric ions Fe 3+ in the ferric ion aqueous solution enter gaps of a gel polymer network through the diffusion action of water molecules;
6. In the process, the swelling temperature sensitive hydrogel body is quickly changed into black after being contacted with the NaOH solution, because divalent and trivalent iron ions are transferred into a gel network before being contacted with a sodium hydroxide solution, hydroxide ions and iron ions form Fe 3O4 magnetic particles in situ in the gel network in the migration process of following water molecules, and the Fe 3O4 magnetic particles are formed in situ in the gel through full absorption and reaction;
7. Uniformly mixing the strong glue Loctite 406 and ethyl acetate according to the volume ratio of 1:10 to obtain a glue water mixture, taking the temperature-sensitive hydrogel body obtained in the third step as a lower layer, taking the magnetic response hydrogel body obtained in the sixth step as an upper layer, and coating the glue water mixture between the upper layer and the lower layer for bonding to prepare the double-layer magnetic response hydrogel for 3D printing. The double-layer magnetically-responsive hydrogel can be subjected to a 4D deformation process under the magnetic field condition generated by current.
The bilayer magnetically responsive hydrogel prepared in example 2 was deformable under magnetic field conditions, which required 5 minutes for the entire deformation process, and the underlying temperature sensitive hydrogel maintained gel steady state without fluidity under the conditions.
Example 3 the preparation method of the bilayer magnetically-responsive hydrogel of this example was performed as follows:
1. Weighing 0.015g of N, N' -methylenebisacrylamide, 0.015g of photoinitiator (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide, 10mL of deionized water, 1g of sodium magnesium lithium silicate, 0.7g of recrystallized N-isopropyl acrylamide and 0.3g of dimethylaminopropyl methylpropionamide, wherein the preparation method of the recrystallized N-isopropyl acrylamide is the same as that of example 1;
2. Sequentially adding N, N' -methylene bisacrylamide and a photoinitiator (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide into deionized water, stirring for 10min, adding sodium magnesium lithium silicate into an aqueous solution in batches under stirring, continuously stirring for 60min after the addition is completed within 30 seconds, and after the solution shows a gel state, respectively adding recrystallized N-isopropyl acrylamide and dimethylaminopropyl methylpropionamide into the mixed solution under the protection of nitrogen, stirring for 2h, transferring to a centrifuge, and centrifuging for 5min under the condition of the rotating speed of 6000rpm to remove bubbles in the gel solution, thereby obtaining a temperature-sensitive deformation gel solution;
3. Storing the built model body model as a file with a suffix name of-stl format, guiding the model into RepetierHost software to adjust proper printing position and size, slicing the model, setting printer parameters, wherein the printer parameters are that the printing speed is 20mm/s, a Teflon pinhead with the diameter of 1.2mm is used as a 3D printing pinhead, the height of the printing pinhead is set to be 0.9mm, the extrusion speed of printing liquid is 20mm/s, adding a temperature-sensitive deformation gel liquid into a 3D printer, then using a double-head direct writing printer to perform 3D extrusion printing to obtain a gel body, keeping the printing shape of the gel body under self-supporting function, transferring the gel body under an ultraviolet irradiation curing lamp to obtain a cured body, and transferring the cured body into room temperature deionized water to soak for 48h, so that gel is fully swelled to remove unreacted monomers, thus obtaining the temperature-sensitive hydrogel body;
4. 3.5g of ferric chloride hexahydrate and 2g of ferrous chloride tetrahydrate are weighed and added into 100mL of deionized water, and the mixture is stirred for 20 minutes by a magnetic stirrer at a stirring rate of 500rpm to completely dissolve solid particles, so as to obtain an iron salt ion aqueous solution, wherein the molar ratio of Fe 2+ to Fe 3+ in the iron salt ion aqueous solution is 1:1;
5. Immersing the temperature-sensitive hydrogel body in deionized water at normal temperature for 48 hours to remove unreacted impurities, and transferring to 80 ℃ hot water to keep for 2 hours for shrinkage and swelling, immersing the swelled temperature-sensitive hydrogel body in ferric ion aqueous solution for 36 hours to enable the temperature-sensitive hydrogel body to be fully swelled, and obtaining a swelled temperature-sensitive hydrogel body, wherein ferrous ions Fe 2+ and ferric ions Fe 3+ in the ferric ion aqueous solution enter gaps of a gel polymer network through the diffusion action of water molecules;
6. in the process, the swelling temperature sensitive hydrogel body is quickly changed into black after being contacted with NaOH solution, because divalent and trivalent iron ions are transferred into a gel network before being contacted with sodium hydroxide solution, hydroxide ions and iron ions form Fe 3O4 magnetic particles in situ in the gel network in the migration process of following water molecules, and the Fe 3O4 magnetic particles are formed in situ in the gel through full absorption and reaction;
7. Uniformly mixing the strong glue Loctite 406 and ethyl acetate according to the volume ratio of 1:10 to obtain a glue water mixture, taking the temperature-sensitive hydrogel body obtained in the third step as a lower layer, taking the magnetic response hydrogel body obtained in the sixth step as an upper layer, and coating the glue water mixture between the upper layer and the lower layer for bonding to prepare the double-layer magnetic response hydrogel for 3D printing. The double-layer magnetically-responsive hydrogel can be subjected to a 4D deformation process under the magnetic field condition generated by current.
The double-layer magnetically-responsive hydrogel sample of the embodiment can deform under the magnetic field condition, the whole deformation process needs 5.2min, and the temperature-sensitive hydrogel at the lower layer can keep the gel steady state under the condition without fluidity.
XRD test is carried out on the double-layer magnetic response hydrogel prepared in the examples 1-3, the obtained XRD spectrogram is shown in figure 5, and as can be seen from figure 5, characteristic peaks in the spectrogram are matched with peaks of Fe 3O4, so that the double-layer magnetic response hydrogel contains Fe 3O4 particles, and meanwhile, the sizes of Fe 3O4 particles in the double-layer magnetic response hydrogel prepared in the examples 1-3 are not greatly different.
The thermal gravimetric analysis was performed on the double-layer magnetically-responsive hydrogels prepared in examples 1 to 3, and the thermal gravimetric curve obtained is shown in fig. 6, and it can be seen from fig. 6 that in the heat treatment process of the double-layer magnetically-responsive hydrogels, as the temperature increases, water is gasified, and most of the polymer materials are ablated, and the remainder is mainly inorganic matters, such as iron oxide. Compared with the double-layer magnetic response hydrogel prepared in examples 1-3, the double-layer magnetic response hydrogel in example 1 has the highest residual weight, which shows that the double-layer magnetic response hydrogel has the highest content of iron oxide, and the basis of the double-layer magnetic response hydrogel is magnetic Fe 3O4, so that the double-layer magnetic response hydrogel has the highest content of iron and has the optimal magnetic response.
Hysteresis loop tests are carried out on the double-layer magnetic response hydrogels prepared in examples 1-3, and the obtained hysteresis loop diagrams are shown in fig. 7, and as can be seen from fig. 7, the double-layer magnetic response hydrogels prepared in examples 1-3 all show obvious superparamagnetic behaviors, wherein the residual magnetization of the double-layer magnetic response hydrogels prepared in example 1 is maximum and is 4.98emu/g. The double layer magnetically-responsive hydrogel prepared in example 2 had a remanent magnetization of 4.14emu/g and the double layer magnetically-responsive hydrogel prepared in example 3 had a remanent magnetization of 3.92emu/g.
Mechanical property tests are carried out on the double-layer magnetic response hydrogel prepared in the examples 1-3, and the obtained mechanical properties are shown in Table 1.
Table 1 mechanical Properties of double-layer magnetic-response hydrogels prepared in examples 1 to3
| Sample of | Young's modulus (kPa) | Elongation at break (%) |
| Example 1 | 4.54 | 280 |
| Example 2 | 5.34 | 260 |
| Example 3 | 3.82 | 230 |
Example 4 the preparation method of the bilayer magnetically-responsive hydrogel of this example was performed as follows:
1. Weighing 0.015g of N, N' -methylenebisacrylamide, 0.015g of photoinitiator (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide, 10mL of deionized water, 1.5g of sodium magnesium lithium silicate, 0.8g of recrystallized N-isopropylacrylamide and 0.2g of dimethylaminopropyl methylpropionamide, wherein the preparation method of the recrystallized N-isopropylacrylamide is the same as that of example 1;
2. Sequentially adding N, N' -methylene bisacrylamide and a photoinitiator (2, 4, 6-trimethyl benzoyl) diphenyl phosphine oxide into deionized water, stirring for 10min, adding sodium magnesium lithium silicate into an aqueous solution in batches under stirring, continuously stirring for 60min after the addition is completed within 30 seconds, and after the solution shows a gel state, respectively adding recrystallized N-isopropyl acrylamide and dimethylaminopropyl methylpropionamide into the mixed solution under the protection of nitrogen, stirring for 2h, transferring to a centrifuge, and centrifuging for 5min under the condition of the rotating speed of 6000rpm to remove bubbles in the gel solution, thereby obtaining a temperature-sensitive deformation gel solution;
3. Storing the built model body model as a file with a suffix of-stl format, guiding the model into RepetierHost software to adjust proper printing position and size, slicing the model, and setting printer parameters, wherein the printer parameters are that a Teflon needle with the diameter of 0.8mm is adopted as a 3D printing needle, the height of the printing needle is set to be 0.9mm, the extrusion speed of printing liquid is 10mm/s, adding a temperature-sensitive deformation gel solution into a 3D printer, and then performing 3D extrusion printing by using a double-head direct-writing printer to obtain a gel body, keeping the printing shape of the gel body by virtue of self-supporting function, transferring the gel body to an ultraviolet irradiation curing lamp for photo-curing for 2min to obtain a cured body, and transferring the cured body into deionized water at room temperature to enable the gel to be fully swelled to remove unreacted monomers to obtain the temperature-sensitive hydrogel body;
4. Adding 4.0g of ferric chloride hexahydrate and 1.5g of ferrous chloride tetrahydrate into 100mL of deionized water, and stirring for 20min at a stirring rate of 500rpm by using a magnetic stirrer to completely dissolve solid particles to obtain an iron salt ion aqueous solution, wherein the molar ratio of Fe 2+ to Fe 3+ in the iron salt ion aqueous solution is 1:1;
5. Immersing the temperature-sensitive hydrogel body in deionized water at normal temperature for 48 hours to remove unreacted impurities, and transferring to 80 ℃ hot water to keep for 2 hours for shrinkage and swelling, immersing the swelled temperature-sensitive hydrogel body in ferric ion aqueous solution for 36 hours to enable the temperature-sensitive hydrogel body to be fully swelled, and obtaining a swelled temperature-sensitive hydrogel body, wherein ferrous ions Fe 2+ and ferric ions Fe 3+ in the ferric ion aqueous solution enter gaps of a gel polymer network through the diffusion action of water molecules;
6. In the process, the swelling temperature sensitive hydrogel body is quickly changed into black after being contacted with NaOH solution, because divalent and trivalent iron ions are transferred into a gel network before being contacted with sodium hydroxide solution, hydroxide ions and iron ions form Fe 3O4 magnetic particles in situ in the gel network in the migration process of following water molecules, and the Fe 3O4 magnetic particles are formed in situ in the gel through full absorption and reaction;
7. Uniformly mixing the strong glue Loctite 406 and ethyl acetate according to the volume ratio of 1:10 to obtain a glue water mixture, taking the temperature-sensitive hydrogel body obtained in the third step as a lower layer, taking the magnetic response hydrogel body obtained in the sixth step as an upper layer, and coating the glue water mixture between the upper layer and the lower layer for bonding to prepare the double-layer magnetic response hydrogel for 3D printing. The double-layer magnetically-responsive hydrogel can be subjected to a 4D deformation process under the magnetic field condition generated by current.
The double-layer magnetically-responsive hydrogel sample prepared in the embodiment can deform under the magnetic field condition, the whole deformation process needs 4.9min, and the temperature-sensitive gel at the lower layer keeps the gel steady state under the condition without fluidity.
The bilayer magnetically-responsive hydrogel prepared in this example had a residual magnetization of 4.53emu/g, a Young's modulus of 5.13kPa, and an elongation at break of 270%.
Claims (10)
1. The preparation method of the 3D printed double-layer magnetically-responsive hydrogel is characterized by comprising the following steps of:
1. Weighing 0.1-1 part of N, N' -methylenebisacrylamide, 0.1-1 part of photoinitiator, 10-30 parts of water, 5-10 parts of sodium magnesium lithium silicate, 5-10 parts of recrystallized N-isopropyl acrylamide and 1-5 parts of dimethylaminopropyl methylpropionamide according to the weight part ratio;
2. Sequentially adding N, N' -methylene bisacrylamide and a photoinitiator into water, stirring for 5-15 min, adding sodium magnesium lithium silicate into an aqueous solution in batches under stirring, and continuing stirring until the mixed solution shows a gel state after the addition is completed within 10-30 seconds;
3. Adding the temperature-sensitive deformation gel solution into a 3D printer, performing 3D extrusion printing, and keeping the printing shape of the printing solution under the self-supporting function after printing and molding to obtain a gel body, transferring the gel body to an ultraviolet irradiation curing lamp for photo-curing for 2-3 min to obtain a cured body, transferring the cured body to room-temperature deionized water for full swelling, and removing unreacted monomers to obtain the temperature-sensitive hydrogel body;
4. Weighing ferric chloride hexahydrate and ferrous chloride tetrahydrate, adding the ferric chloride hexahydrate and the ferrous chloride tetrahydrate into deionized water, and magnetically stirring to completely dissolve solid particles to obtain an iron salt ion aqueous solution, wherein the molar ratio of Fe 2+ to Fe 3+ in the iron salt ion aqueous solution is 1:1;
5. Immersing the temperature-sensitive hydrogel body after the swelling is eliminated in an iron salt ion aqueous solution for 36-48 hours to fully swell the temperature-sensitive hydrogel body, so as to obtain a swollen temperature-sensitive hydrogel body;
6. transferring the swollen temperature-sensitive hydrogel body into a NaOH solution and keeping for 20-24 hours to obtain a magnetically-responsive hydrogel body;
7. and (3) bonding the temperature-sensitive hydrogel body obtained in the step (III) with the magnetic response hydrogel body obtained in the step (six), wherein the lower layer is the temperature-sensitive hydrogel, and the upper layer is the magnetic response hydrogel, so as to prepare the double-layer magnetic response hydrogel for 3D printing.
2. The method of claim 1, wherein the photoinitiator in the first step is (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide.
3. The preparation method of the 3D printed double-layer magnetic response hydrogel according to claim 1 or 2, wherein in the first step, 0.5-1 part of N, N' -methylenebisacrylamide, 0.2-0.5 part of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide, 10-30 parts of water, 5-10 parts of sodium magnesium lithium silicate, 5-10 parts of recrystallized N-isopropyl acrylamide and 1-5 parts of dimethylaminopropyl methylpropionamide are weighed according to the weight part ratio.
4. The preparation method of the 3D printed double-layer magnetically-responsive hydrogel is characterized in that 10g of NIPAM is weighed and dissolved in toluene, heating is carried out in a magnetic stirring water bath kettle at a speed of 400rpm until the NIPAM is completely dissolved, 40mL of N-hexane is added into the solution, stirring is carried out for 20min at a constant temperature of 60 ℃, toluene and N-hexane are respectively added again, the process is repeated for two times, the mixed solution is subjected to suction filtration to remove insoluble polymerization inhibitor, filtrate is subjected to suction filtration to obtain white flocculent crystals, and NIPAM crystals are obtained through freeze drying.
5. The preparation method of the 3D printing double-layer magnetic response hydrogel is characterized by comprising the specific steps of storing a built model body as a file with a suffix of-stl format, guiding the model into RepetierHost software to adjust printing positions and sizes, slicing the model, setting printer parameters, and then using a double-head direct-writing printer to perform 3D extrusion printing, wherein the printer parameters are that the printing speed of an extrusion 3D printing device is 10-30 mm/s, a Teflon needle with the diameter of 0.4-1.2 mm is adopted as a 3D printing needle, the height of the printing needle is set to be 0.7-1.2 mm, and the extrusion speed of printing liquid is 10mm/s.
6. The method for preparing a 3D printed bilayer magnetically responsive hydrogel according to claim 1 or 2, wherein the transferring the cured body in step three into room temperature deionized water is to fully swell the cured body by soaking the cured body in room temperature deionized water for 24 hours.
7. The method for preparing a 3D printed bilayer magnetically-responsive hydrogel according to claim 1 or 2, wherein the wavelength of the uv light curing lamp in the third step is 365nm.
8. The preparation method of the 3D printed double-layer magnetically-responsive hydrogel is characterized in that the temperature-sensitive hydrogel body is fully soaked in normal-temperature deionized water for 40-48 hours to remove unreacted impurities, and then transferred to 80 ℃ hot water to be kept for 1-2 hours for shrinkage and swelling.
9. The method for preparing a 3D printed bilayer magnetically-responsive hydrogel according to claim 1 or 2, wherein the concentration of NaOH solution in the fifth step is 1-5 mol/L.
10. The preparation method of the 3D printed double-layer magnetically-responsive hydrogel is characterized by comprising the steps of uniformly mixing a strong adhesive Loctite 406 and ethyl acetate according to a volume ratio of 1:10 to obtain an adhesive-water mixture, and then bonding a temperature-sensitive hydrogel body and the magnetically-responsive hydrogel body adhesive-water mixture to prepare the double-layer magnetically-responsive hydrogel.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20170151733A1 (en) * | 2015-11-30 | 2017-06-01 | President And Fellows Of Harvard College | Method of 4d printing a hydrogel composite structure |
| CN111434698A (en) * | 2019-01-14 | 2020-07-21 | 中国科学院宁波材料技术与工程研究所 | Preparation method of 3D printing hydrogel and application of prepared hydrogel |
| CN115141320A (en) * | 2022-06-20 | 2022-10-04 | 湖北工业大学 | 4D-printable hydrophilic and hydrophobic hydrogel elastomer material and preparation method and application thereof |
| CN118667061A (en) * | 2024-06-28 | 2024-09-20 | 金陵科技学院 | Magnetic temperature-sensitive double-layer hydrogel and preparation method and application thereof |
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|---|---|---|---|---|
| US20170151733A1 (en) * | 2015-11-30 | 2017-06-01 | President And Fellows Of Harvard College | Method of 4d printing a hydrogel composite structure |
| CN111434698A (en) * | 2019-01-14 | 2020-07-21 | 中国科学院宁波材料技术与工程研究所 | Preparation method of 3D printing hydrogel and application of prepared hydrogel |
| CN115141320A (en) * | 2022-06-20 | 2022-10-04 | 湖北工业大学 | 4D-printable hydrophilic and hydrophobic hydrogel elastomer material and preparation method and application thereof |
| CN118667061A (en) * | 2024-06-28 | 2024-09-20 | 金陵科技学院 | Magnetic temperature-sensitive double-layer hydrogel and preparation method and application thereof |
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