3D printing hydrogel precursor solution, cured product and preparation method and application thereof

Abstract

The invention relates to the technical field of materials, and provides a 3D printing hydrogel precursor solution, a cured product and a preparation method and application thereof. The hydrogel precursor solution for 3D printing comprises the following components in percentage by mass: 5%-35% of a surfactant, 5%-30% of acrylamide, 0.5%-5% of a hydrophobic monomer, 0.05%-5% of a water-soluble polymer, 1%-5% of a photoinitiator and the balance of a sodium sulfate solution. The 3D printing hydrogel precursor solution is suitable for photocuring 3D printing and can be cured under the action of light to form 3D printing hydrogel, and the formed 3D printing hydrogel has good mechanical properties and self-repairing characteristics at the same time, has good adaptability in some application scenarios with high requirements for strength and durability, and has good application prospects. Wide popularization and application prospects are realized.

Description

Technical Field

[0001] The present application relates to the field of material technology, and in particular to a 3D printing hydrogel precursor solution, a cured product, and a preparation method and application thereof. Background Art

[0002] Hydrogels are polymer materials with three-dimensional network structures that can absorb large amounts of water while maintaining their unique physical properties. Due to their excellent biocompatibility and structural properties similar to those of the natural extracellular matrix, they have shown broad application prospects in fields such as biomedicine, flexible electronics, and soft robotics.

[0003] In recent years, with the development of 3D printing technology, the rapid and efficient preparation of functional, high-resolution, customized hydrogels has become possible.

[0004] However, current 3D printed hydrogels are difficult to combine good mechanical properties and self-healing properties, which limits their adaptability in some application scenarios with high requirements for strength and durability. Summary of the Invention

[0005] In response to the above-mentioned deficiencies in the prior art, the present application provides a 3D printing hydrogel precursor solution, a cured product, and a preparation method and application thereof, aiming to solve the problem that the current 3D printing hydrogel is difficult to have both good mechanical properties and self-healing properties, which limits its adaptability in some application scenarios with high requirements for strength and durability.

[0006] To achieve the above-mentioned invention objectives, the technical solutions adopted in this application are as follows:

[0007] In a first aspect, an embodiment of the present application provides a 3D printing hydrogel precursor solution, which includes the following components, calculated by mass percentage: 5% to 35% surfactant, 5% to 30% acrylamide, 0.5% to 5% hydrophobic monomer, 0.05% to 5% water-soluble polymer, 1% to 5% photoinitiator, and the balance is sodium sulfate solution.

[0008] In a second aspect, the present application also provides a method for preparing the 3D printing hydrogel precursor solution of the first aspect, comprising the following steps:

[0009] The surfactant is dissolved in a sodium sulfate solution to prepare a micellar solution;

[0010] Acrylamide, hydrophobic monomer, water-soluble polymer and photoinitiator are added to the micelle solution and mixed evenly to obtain a 3D printing hydrogel precursor solution.

[0011] In a third aspect, the present invention also provides a method for preparing a solidified product, comprising the following steps:

[0012] The 3D printing hydrogel precursor solution of the first aspect is placed in a 3D printer, and its cured product is formed layer by layer. The parameter conditions of 3D printing are set as follows: the initial exposure time parameter is 5s to 60s, the single layer exposure time parameter is 1s to 30s, and the printing layer thickness parameter is 0.01mm to 0.5mm.

[0013] In a fourth aspect, an embodiment of the present application further provides a cured product, which is prepared by the method for preparing the cured product of the third aspect.

[0014] In a fifth aspect, the embodiments of the present application further provide another 3D printing hydrogel precursor solution, comprising a mixed solution and a photoinitiator; the mass ratio of the mixed solution to the photoinitiator is 20 to 100:1;

[0015] The mixed solution comprises the following components by mass percentage: 5% to 35% of surfactant, 5% to 30% of acrylamide, 0.5% to 5% of hydrophobic monomer, 0.05% to 5% of water-soluble polymer, and the balance is sodium sulfate solution.

[0016] In a sixth aspect, embodiments of the present application further provide the use of the 3D printing hydrogel precursor solution of the first aspect, or the cured product of the fourth aspect, or the 3D printing hydrogel precursor solution of the fifth aspect in the preparation of tissue engineering scaffold materials or organ tissue substitutes.

[0017] The beneficial effects of the present application include at least: the 3D printing hydrogel precursor solution provided in the embodiments of the present application is suitable for photocuring 3D printing, and can be cured under the action of light to form a cured product (i.e., 3D printed hydrogel). The formed 3D printed hydrogel has both good mechanical properties and self-healing properties, has good adaptability in some application scenarios with high requirements for strength and durability, and has broad prospects for promotion and application. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following briefly introduces the drawings required for use in the embodiments or descriptions of the prior art. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0019] Figure 1 3D printed hydrogels prepared in Examples 1 to 3 of the present application are stress-strain curves;

[0020] Figure 2 is the stress-strain curve of the 3D printed hydrogel prepared in Examples 4 to 6 of the present application;

[0021] Figure 3 This is the tensile stress-strain curve of the self-repair of the 3D printed hydrogel prepared in Example 5 of the present application after being cut;

[0022] Figure 4 This is a physical picture of the 3D printed artificial hydrogel ear prepared in Example 7 of the present application;

[0023] Figure 5 These are the stress-strain curves of the 3D printed hydrogels prepared in Examples 1 and 18 to 20 of the present application. DETAILED DESCRIPTION

[0024] In order to make the technical problems, technical solutions and beneficial effects to be solved by this application more clearly understood, the following is a further detailed description of this application in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain this application, but the implementation methods of this application are not limited thereto.

[0025] Unless otherwise defined, the technical terms used in the following examples have the same meanings as commonly understood by those skilled in the art. The experimental reagents used in the following examples, unless otherwise specified, are conventional biochemical reagents; the amounts of the experimental reagents used, unless otherwise specified, are the amounts used in routine experimental procedures; and the experimental methods, unless otherwise specified, are conventional methods.

[0026] In a first aspect, an embodiment of the present application provides a 3D printing hydrogel precursor solution, which includes the following components, calculated by mass percentage: 5% to 35% surfactant, 5% to 30% acrylamide, 0.5% to 5% hydrophobic monomer, 0.05% to 5% water-soluble polymer, 1% to 5% photoinitiator, and the balance is sodium sulfate solution.

[0027] In some embodiments, the surfactant is at least one of cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS), 3-[(3-cholamidopropyl)dimethylamino]-1-propanesulfonic acid (CHAPS) or polysorbate.

[0028] In some embodiments, the hydrophobic monomer is at least one of lauryl methacrylate (LMA), stearyl methacrylate (SMA), octadecyl acrylate (SA), tridecafluorooctyl acrylate (TFOA), or N-octadecyl acrylamide (ODAm).

[0029] In some embodiments, the water-soluble polymer is at least one of polymethacrylic acid (PMMA), polyethylene glycol (PEG), polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), polyethyleneimine (PEI) or hyaluronic acid (HA).

[0030] In some embodiments, the photoinitiator is at least one of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (ie, TPO photoinitiator) and lithium phenyl-2,4,6-trimethylbenzoylphosphinate.

[0031] In some embodiments, the molecular weight of the water-soluble polymer is 1000-100000 Da. For example, the molecular weight of the water-soluble polymer can be 1000 Da, 2000 Da, 3000 Da, 4000 Da, 5000 Da, 10000 Da or 100000 Da.

[0032] In some embodiments, the molar concentration of the sodium sulfate solution is 0.05 to 0.5 mol / L. For example, the molar concentration of the sodium sulfate solution can be 0.05 mol / L, 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, or 0.5 mol / L.

[0033] In a second aspect, the present application also provides a method for preparing the 3D printing hydrogel precursor solution of the first aspect, comprising the following steps:

[0034] S1, dissolving the surfactant in a sodium sulfate solution to prepare a micellar solution;

[0035] S2. Add acrylamide, hydrophobic monomer, water-soluble polymer and photoinitiator to the micelle solution, mix them evenly, and obtain a 3D printing hydrogel precursor solution.

[0036] The preparation method of the 3D printing hydrogel precursor solution of the embodiment of the present application is as follows: first, a surfactant is dissolved in a sodium sulfate solution to form a micellar solution; then, acrylamide, a hydrophobic monomer, a water-soluble polymer and a photoinitiator are added to the micellar solution; in the micellar solution, the hydrophobic monomer and acrylamide are copolymerized to form a copolymer (as a molecular chain constituting a first cross-linked network), and the surfactant and the hydrophobic monomer form a hydrophobic region (as a physical cross-linking site, which can promote 3D printing molding), so that the copolymer is cross-linked to form a first cross-linked network with a three-dimensional network structure; the water-soluble polymer serves as a second cross-linked network, which interpenetrates with the first cross-linked network to form a double-network three-dimensional structure, which can further improve the printability of the precursor solution, disperse the stress of the prepared 3D printing hydrogel, and improve the mechanical properties of the material.

[0037] By forming the first cross-linked network, it not only provides initial mechanical strength for the subsequently prepared 3D printed hydrogel, but also can greatly enhance the hydrophobic force within the precursor solution system, so that the precursor solution has a better solid-liquid separation effect during 3D printing, avoiding unclear separation between the solidified part and the liquid, and improving the printing resolution.

[0038] The first cross-linked network and the second cross-linked network interpenetrate to form a double-network three-dimensional structure, which can increase the viscosity of the precursor solution and make it easier to be carried by the platform during the 3D printing process, which is beneficial to improving the efficiency of preparing 3D printed hydrogels.

[0039] Acrylamide, hydrophobic monomers, and surfactants interact to form various non-covalent bonds (such as electrostatic interactions, hydrophobic interactions, and hydrogen bonds), resulting in a reversible, dynamic first crosslinked network. This first crosslinked network interpenetrates with the second crosslinked network (a water-soluble polymer), forming a dual network structure. This dual network dissipates energy through bond breakage and recombination under external forces, and spontaneously repairs itself after breakage.

[0040] In some embodiments, in the above step S1, a surfactant may be added to the sodium sulfate solution, and stirred or ultrasonically treated to prepare a micellar solution.

[0041] In some embodiments, in the above step S2, acrylamide, hydrophobic monomer, water-soluble polymer and photoinitiator can be added to the micelle solution and ultrasonically dissolved in a water bath at a temperature of 15°C to 45°C to obtain a 3D printing hydrogel precursor solution.

[0042] In a third aspect, the present invention also provides a method for preparing a solidified product, comprising the following steps:

[0043] The 3D printing hydrogel precursor solution of the first aspect is placed in a 3D printer to form a 3D printed hydrogel layer by layer, wherein the 3D printing parameters are set as follows: initial exposure time of 5s to 60s, single layer exposure time of 1s to 30s, and printing layer thickness of 0.01mm to 0.5mm.

[0044] In some embodiments, the step of placing the 3D printing hydrogel precursor solution of the first aspect into a 3D printer includes:

[0045] Using a pH regulator, adjusting the pH value of the 3D printing hydrogel precursor solution to 6 to 10 to obtain a prepolymer solution;

[0046] The prepolymer solution is placed into a 3D printer.

[0047] In some embodiments, the pH adjuster may be an acid solution or an alkaline solution. Specifically, the acid solution may be a dilute sulfuric acid solution having a mass percentage concentration of 0.5% to 20% (e.g., a dilute sulfuric acid solution having a mass percentage concentration of 0.5%, 1%, 2%, 5%, 10%, 15%, or 20%); and the alkaline solution may be a sodium hydroxide solution having a mass percentage concentration of 4% to 20% (e.g., a sodium hydroxide solution having a mass percentage concentration of 4%, 5%, 8%, 10%, 15%, or 20%).

[0048] By using a pH regulator to adjust the pH value of the 3D printed hydrogel precursor solution, the mechanical strength of the prepared 3D printed hydrogel can be flexibly adjusted to meet the actual application requirements of different application scenarios, thereby further expanding the scope of application of 3D printed hydrogels.

[0049] In a fourth aspect, an embodiment of the present application further provides a cured product, which is prepared by the method for preparing the cured product of the third aspect.

[0050] First, the solidified product (i.e., 3D printed hydrogel) has excellent mechanical properties (including strength and toughness), and its mechanical properties can be precisely controlled according to the actual needs of different application scenarios. The mechanical properties of the 3D printed hydrogel are similar to those of various tissues in the human body and are suitable for biomedical applications such as organ model construction and tissue engineering scaffolds. For example, it can be used to prepare tissue engineering scaffolds or organ tissue substitutes. Second, the 3D printed hydrogel has good self-repairing properties and is durable and reusable. Third, 3D printing technology can precisely control the shape and size of 3D printed hydrogels, enabling precise molding and personalized design customization of complex three-dimensional structures.

[0051] In a fifth aspect, an embodiment of the present application further provides a 3D printing hydrogel precursor solution, comprising a mixed solution and a photoinitiator; the mass ratio of the mixed solution to the photoinitiator is 20 to 100:1; the mixed solution comprises the following components in mass percentage: 5% to 35% surfactant, 5% to 30% acrylamide, 0.5% to 5% hydrophobic monomer, 0.05% to 5% water-soluble polymer, and the balance is sodium sulfate solution; the photoinitiator comprises a photoinitiator.

[0052] In some embodiments, the surfactant is at least one of cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS), 3-[(3-cholamidopropyl)dimethylamino]-1-propanesulfonic acid (CHAPS), or polysorbate. The hydrophobic monomer is at least one of lauryl methacrylate (LMA), stearyl methacrylate (SMA), octadecyl acrylate (SA), tridecafluorooctyl acrylate (TFOA), or N-octadecyl acrylamide (ODAm). The water-soluble polymer is at least one of polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, polyethyleneimine, polymethacrylic acid, or hyaluronic acid. The photoinitiator is 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (i.e., TPO photoinitiator).

[0053] In some embodiments, the molecular weight of the water-soluble polymer is 1,000 to 100,000 Da.

[0054] In some embodiments, the concentration of the sodium sulfate solution is 0.05 to 0.5 mol / L.

[0055] In some embodiments, the mixed solution in the fifth aspect and the photoinitiator can be mixed in a mass ratio of 20 to 100:1 to obtain a 3D printing hydrogel precursor solution, and then the 3D printing hydrogel precursor solution is placed in a 3D printer to form a 3D printed hydrogel layer by layer, wherein the 3D printing parameters are set as follows: initial exposure time is 5s to 60s, single layer exposure time is 1s to 30s, and printing layer thickness is 0.01mm to 0.5mm.

[0056] In a sixth aspect, embodiments of the present application further provide the use of the 3D printing hydrogel precursor solution of the first aspect, or the cured product of the fourth aspect, or the 3D printing hydrogel precursor solution of the fifth aspect in the preparation of tissue engineering scaffold materials or organ tissue substitutes.

[0057] Tissue engineering scaffold materials can be urethra scaffold materials, vascular scaffold materials, bile duct materials, cartilage materials, etc.

[0058] Organ tissue substitutes may be cartilage substitutes (such as ear cartilage substitutes, nasal cartilage substitutes, etc.), meniscus substitutes, etc.

[0059] The 3D printing hydrogel precursor solution and its cured product (3D printing hydrogel) provided in the embodiments of the present application have good biocompatibility and are not likely to cause immune rejection reactions when used inside the human body. They can be used to prepare implantable stents in the body, etc.

[0060] The present application has been subjected to multiple tests, and part of the test results are cited as a reference to further describe the invention in detail, which will be described in detail in conjunction with specific embodiments.

[0061] Example 1

[0062] This embodiment provides a 3D printed hydrogel, and the preparation steps are as follows:

[0063] (1) Preparation of 3D printing hydrogel precursor solution:

[0064] Weigh 3.0g of hexadecyltrimethylammonium bromide and dissolve it in 6.5ml of sodium sulfate solution (molar concentration, 0.1mol / L). Magnetic stirring or ultrasonic heating until completely dissolved is used to prepare a micellar solution. Weigh 0.1g of lauryl methacrylate and add it to the micellar solution. Once completely dissolved, add 1.5g of acrylamide and 44mg of polymethacrylic acid (molecular weight, 50,000Da). Mix thoroughly, then add 250mg of photoinitiator TPO. Ultrasonication is performed for 20 minutes to obtain a 3D printing hydrogel precursor solution.

[0065] (2) Preparation of cured product (3D printed hydrogel):

[0066] The 3D printing hydrogel precursor solution prepared in step (1) was placed in a 3D printer, and the 3D printing parameters were set as follows: initial exposure time was 10 s, single layer exposure time was 2 s, printing layer thickness was 0.05 mm, and the wavelength of ultraviolet light for initiating photopolymerization reaction was 405 nm. The hydrogel was printed layer by layer to form a rectangular parallelepiped with a size of 50 mm × 4 mm × 2 mm.

[0067] Example 2

[0068] This embodiment provides a 3D printed hydrogel, and the preparation steps are as follows:

[0069] (1) Preparation of 3D printing hydrogel precursor solution:

[0070] Weigh 3.0g of hexadecyltrimethylammonium bromide and dissolve it in 6.5ml of sodium sulfate solution (molar concentration, 0.1mol / L). Magnetic stirring or ultrasonic heating until completely dissolved is used to prepare a micellar solution. Weigh 0.1g of lauryl methacrylate and add it to the micellar solution. Once completely dissolved, add 1.5g of acrylamide and 44mg of polymethacrylic acid (molecular weight, 50,000Da). Mix thoroughly, then add 250mg of photoinitiator TPO. Ultrasonication is performed for 20 minutes to obtain a 3D printing hydrogel precursor solution.

[0071] (2) Preparation of cured product (3D printed hydrogel):

[0072] Sodium hydroxide solution was added dropwise to the 3D printing hydrogel precursor solution prepared in step (1) to adjust the pH value of the 3D printing hydrogel precursor solution to 8, thereby obtaining a prepolymer solution. The prepolymer solution was placed in a 3D printer, and the 3D printing parameters were set as follows: initial exposure time of 10 seconds, single layer exposure time of 2 seconds, printing layer thickness of 0.05 mm, and ultraviolet light wavelength of 405 nm for initiating photopolymerization reaction. The prepolymer solution was printed layer by layer to form a rectangular hydrogel with a size of 50 mm × 4 mm × 2 mm.

[0073] Example 3

[0074] This embodiment provides a 3D printed hydrogel, and the preparation steps are as follows:

[0075] (1) Preparation of 3D printing hydrogel precursor solution:

[0076] Weigh 3.0g of hexadecyltrimethylammonium bromide and dissolve it in 6.5ml of sodium sulfate solution (molar concentration, 0.1mol / L). Magnetic stirring or ultrasonic heating until completely dissolved is used to prepare a micellar solution. Weigh 0.1g of N-lauryl methacrylate and add it to the micellar solution. Once completely dissolved, add 1.5g of acrylamide and 44mg of polymethacrylic acid (molecular weight, 50,000Da). Mix thoroughly, then add 250mg of photoinitiator TPO. Ultrasonication is performed for 20 minutes to obtain a 3D printing hydrogel precursor solution.

[0077] (2) Preparation of cured product (3D printed hydrogel):

[0078] Sodium hydroxide solution was added dropwise to the 3D printing hydrogel precursor solution prepared in step (1) to adjust the pH value of the 3D printing hydrogel precursor solution to 10, thereby obtaining a prepolymer solution. The prepolymer solution was placed in a 3D printer, and the 3D printing parameters were set as follows: initial exposure time of 10 seconds, single layer exposure time of 2 seconds, printing layer thickness of 0.05 mm, and ultraviolet light wavelength of 405 nm for initiating photopolymerization reaction. The hydrogel was printed layer by layer to form a rectangular parallelepiped with a size of 50 mm × 4 mm × 2 mm.

[0079] Example 4

[0080] This embodiment provides a 3D printed hydrogel, and the preparation steps are as follows:

[0081] (1) Preparation of 3D printing hydrogel precursor solution:

[0082] Weigh 2.0g of sodium dodecyl sulfate and dissolve it in 6.5ml of sodium sulfate solution (molar concentration, 0.1mol / L). Magnetic stirring or ultrasonic heating until completely dissolved is used to prepare a micellar solution. Weigh 0.3g of N-octadecyl acrylamide and add it to the micellar solution. Once completely dissolved, add 1.5g of acrylamide and 21mg of polyethyleneimine (molecular weight, 50,000Da). Mix thoroughly, then add 250mg of photoinitiator TPO. Ultrasonication is performed for 20 minutes to obtain a 3D printing hydrogel precursor solution.

[0083] (2) Preparation of cured product (3D printed hydrogel):

[0084] A dilute sulfuric acid solution was added dropwise to the 3D printing hydrogel precursor solution prepared in step (1) to adjust the pH value of the 3D printing hydrogel precursor solution to 7, thereby obtaining a prepolymer solution. The prepolymer solution was placed in a 3D printer, and the 3D printing parameters were set as follows: initial exposure time of 10 seconds, single layer exposure time of 2 seconds, printing layer thickness of 0.05 mm, and ultraviolet light wavelength of 405 nm for initiating photopolymerization reaction. The prepolymer solution was printed layer by layer to form a rectangular hydrogel with a size of 50 mm × 4 mm × 2 mm.

[0085] Example 5

[0086] This embodiment provides a 3D printed hydrogel, and the preparation steps are as follows:

[0087] (1) Preparation of 3D printing hydrogel precursor solution:

[0088] Weigh 2.0g of sodium dodecyl sulfate and dissolve it in 6.5ml of sodium sulfate solution (molar concentration, 0.1mol / L). Magnetic stirring or ultrasonic heating until completely dissolved is used to prepare a micellar solution. Weigh 0.3g of N-octadecyl acrylamide and add it to the micellar solution. Once completely dissolved, add 1.5g of acrylamide and 41mg of polyethyleneimine (molecular weight, 50,000Da). Mix thoroughly, then add 250mg of photoinitiator TPO. Ultrasonication is performed for 20 minutes to obtain a 3D printing hydrogel precursor solution.

[0089] (2) Preparation of cured product (3D printed hydrogel):

[0090] A dilute sulfuric acid solution was added dropwise to the 3D printing hydrogel precursor solution prepared in step (1) to adjust the pH value of the 3D printing hydrogel precursor solution to 7, thereby obtaining a prepolymer solution. The prepolymer solution was placed in a 3D printer, and the 3D printing parameters were set as follows: initial exposure time of 10 seconds, single layer exposure time of 2 seconds, printing layer thickness of 0.05 mm, and ultraviolet light wavelength of 405 nm for initiating photopolymerization reaction. The prepolymer solution was printed layer by layer to form a rectangular hydrogel with a size of 50 mm × 4 mm × 2 mm.

[0091] Example 6

[0092] This embodiment provides a 3D printed hydrogel, and the preparation steps are as follows:

[0093] (1) Preparation of 3D printing hydrogel precursor solution:

[0094] Weigh 2.0g of sodium dodecyl sulfate and dissolve it in 6.5ml of sodium sulfate solution (molar concentration, 0.1mol / L). Magnetic stirring or ultrasonic heating until completely dissolved is used to prepare a micellar solution. Weigh 0.3g of N-octadecyl acrylamide and add it to the micellar solution. Once completely dissolved, add 1.5g of acrylamide and 62mg of polyethyleneimine (molecular weight, 50,000Da). Mix thoroughly, then add 250mg of photoinitiator TPO. Ultrasonication is performed for 20 minutes to obtain a 3D printing hydrogel precursor solution.

[0095] (2) Preparation of cured product (3D printed hydrogel):

[0096] A dilute sulfuric acid solution was added dropwise to the 3D printing hydrogel precursor solution prepared in step (1) to adjust the pH value of the 3D printing hydrogel precursor solution to 7, thereby obtaining a prepolymer solution. The prepolymer solution was placed in a 3D printer, and the 3D printing parameters were set as follows: initial exposure time of 10 seconds, single layer exposure time of 2 seconds, printing layer thickness of 0.05 mm, and ultraviolet light wavelength of 405 nm for initiating photopolymerization reaction. The prepolymer solution was printed layer by layer to form a rectangular hydrogel with a size of 50 mm × 4 mm × 2 mm.

[0097] Example 7

[0098] This embodiment provides a 3D printed hydrogel, and the preparation steps are as follows:

[0099] (1) Preparation of 3D printing hydrogel precursor solution:

[0100] Weigh 2.0g of sodium dodecyl sulfate and dissolve it in 6.5ml of sodium sulfate solution (molar concentration, 0.1mol / L). Magnetic stirring or ultrasonic heating until completely dissolved is used to prepare a micellar solution. Weigh 0.3g of N-octadecyl acrylamide and add it to the micellar solution. Once completely dissolved, add 1.5g of acrylamide and 41mg of polyethyleneimine (molecular weight, 50,000Da). Mix thoroughly, then add 250mg of photoinitiator TPO. Ultrasonication is performed for 20 minutes to obtain a 3D printing hydrogel precursor solution.

[0101] (2) Preparation of cured product (3D printed hydrogel):

[0102] A dilute sulfuric acid solution was added dropwise to the 3D printing hydrogel precursor solution prepared in step (1) to adjust the pH value of the 3D printing hydrogel precursor solution to 7, thereby obtaining a prepolymer solution. The prepolymer solution was placed in a 3D printer, and the 3D printing parameters were set as follows: an initial exposure time of 30 seconds, a single layer exposure time of 5 seconds, a printing layer thickness of 0.05 mm, and a UV wavelength of 405 nm for initiating the photopolymerization reaction. The artificial ear model (artificial hydrogel ear) was printed layer by layer.

[0103] Example 8

[0104] This embodiment provides a 3D printed hydrogel, and the preparation steps are as follows:

[0105] (1) Preparation of 3D printing hydrogel precursor solution:

[0106] Weigh 3.0g of hexadecyltrimethylammonium bromide and dissolve it in 6.5ml of sodium sulfate solution (molar concentration, 0.1mol / L). Magnetic stirring or ultrasonic heating until completely dissolved is used to prepare a micellar solution. Weigh 0.1g of lauryl methacrylate and add it to the micellar solution. Once completely dissolved, add 1.5g of acrylamide and 44mg of polymethacrylic acid (molecular weight, 50,000Da). Mix thoroughly, then add 250mg of photoinitiator TPO. Ultrasonication is performed for 20 minutes to obtain a 3D printing hydrogel precursor solution.

[0107] (2) Preparation of cured product (3D printed hydrogel):

[0108] Sodium hydroxide solution was added dropwise to the 3D printing hydrogel precursor solution prepared in step (1) to adjust the pH value of the 3D printing hydrogel precursor solution to 8, thereby obtaining a prepolymer solution. The prepolymer solution was placed in a 3D printer, and the 3D printing parameters were set as follows: initial exposure time of 10 seconds, single layer exposure time of 2 seconds, printing layer thickness of 0.05 mm, and ultraviolet light wavelength of 405 nm for initiating photopolymerization reaction. The artificial urethra model was formed by printing layer by layer.

[0109] Example 9

[0110] This embodiment provides a 3D printed hydrogel, and the preparation steps are as follows:

[0111] (1) Preparation of 3D printing hydrogel precursor solution:

[0112] Weigh 3.0 g of 3-[(3-cholamidopropyl)dimethylamino]-1-propanesulfonic acid and dissolve it in 6.5 ml of sodium sulfate solution (molar concentration, 0.1 mol / L). Stir magnetically or ultrasonically heat until completely dissolved to prepare a micellar solution. Weigh 0.1 g of lauryl methacrylate and add it to the micellar solution. Once completely dissolved, add 1.5 g of acrylamide and 44 mg of polyvinyl alcohol (molecular weight, 50,000 Da). Mix thoroughly, then add 250 mg of TPO (photoinitiator). Ultrasonicate for 20 minutes to obtain a 3D printing hydrogel precursor solution.

[0113] (2) Preparation of cured product (3D printed hydrogel):

[0114] The 3D printing hydrogel precursor solution prepared in step (1) was placed in a 3D printer, and the 3D printing parameters were set as follows: initial exposure time was 10 s, single layer exposure time was 2 s, printing layer thickness was 0.05 mm, and the wavelength of ultraviolet light for initiating photopolymerization reaction was 405 nm. The hydrogel was printed layer by layer to form a rectangular parallelepiped with a size of 50 mm × 4 mm × 2 mm.

[0115] Example 10

[0116] This embodiment provides a 3D printed hydrogel, and the preparation steps are as follows:

[0117] (1) Preparation of 3D printing hydrogel precursor solution:

[0118] Weigh 3.0g of polysorbate and dissolve it in 6.5ml of sodium sulfate solution (molar concentration, 0.1mol / L). Magnetic stirring or ultrasonic heating until completely dissolved is used to prepare a micellar solution. Weigh 0.1g of lauryl methacrylate and add it to the micellar solution. Once completely dissolved, add 1.5g of acrylamide and 44mg of polyvinyl alcohol (molecular weight, 50,000Da). Mix thoroughly, then add 250mg of photoinitiator TPO and ultrasonicate for 20 minutes to obtain a 3D printing hydrogel precursor solution.

[0119] (2) Preparation of cured product (3D printed hydrogel):

[0120] The 3D printing hydrogel precursor solution prepared in step (1) was placed in a 3D printer, and the 3D printing parameters were set as follows: initial exposure time was 10 s, single layer exposure time was 2 s, printing layer thickness was 0.05 mm, and the wavelength of ultraviolet light for initiating photopolymerization reaction was 405 nm. The hydrogel was printed layer by layer to form a rectangular parallelepiped with a size of 50 mm × 4 mm × 2 mm.

[0121] Example 11

[0122] This embodiment provides a 3D printed hydrogel, and the preparation steps are as follows:

[0123] (1) Preparation of 3D printing hydrogel precursor solution:

[0124] Weigh 3.0g of hexadecyltrimethylammonium bromide and dissolve it in 6.5ml of sodium sulfate solution (molar concentration, 0.1mol / L). Magnetic stirring or ultrasonic heating until completely dissolved is used to prepare a micellar solution. Weigh 0.1g of stearic methacrylate and add it to the micellar solution. Once completely dissolved, add 1.5g of acrylamide and 44mg of polyvinyl alcohol (molecular weight, 50,000Da). Mix thoroughly, then add 250mg of photoinitiator TPO and ultrasonicate for 20 minutes to obtain a 3D printing hydrogel precursor solution.

[0125] (2) Preparation of cured product (3D printed hydrogel):

[0126] The 3D printing hydrogel precursor solution prepared in step (1) was placed in a 3D printer, and the 3D printing parameters were set as follows: initial exposure time was 10 s, single layer exposure time was 2 s, printing layer thickness was 0.05 mm, and the wavelength of ultraviolet light for initiating photopolymerization reaction was 405 nm. The hydrogel was printed layer by layer to form a rectangular parallelepiped with a size of 50 mm × 4 mm × 2 mm.

[0127] Example 12

[0128] This embodiment provides a 3D printed hydrogel, and the preparation steps are as follows:

[0129] (1) Preparation of 3D printing hydrogel precursor solution:

[0130] Weigh 3.0g of hexadecyltrimethylammonium bromide and dissolve it in 6.5ml of sodium sulfate solution (molar concentration, 0.1mol / L). Magnetic stirring or ultrasonic heating until completely dissolved is used to prepare a micellar solution. Weigh 0.1g of tridecafluorooctyl acrylate and add it to the micellar solution. Once completely dissolved, add 1.5g of acrylamide and 44mg of polyvinyl alcohol (molecular weight, 50,000Da). Mix thoroughly, then add 250mg of photoinitiator TPO. Ultrasonication is performed for 20 minutes to obtain a 3D printing hydrogel precursor solution.

[0131] (2) Preparation of cured product (3D printed hydrogel):

[0132] The 3D printing hydrogel precursor solution prepared in step (1) was placed in a 3D printer, and the 3D printing parameters were set as follows: initial exposure time was 10 s, single layer exposure time was 2 s, printing layer thickness was 0.05 mm, and the wavelength of ultraviolet light for initiating photopolymerization reaction was 405 nm. The hydrogel was printed layer by layer to form a rectangular parallelepiped with a size of 50 mm × 4 mm × 2 mm.

[0133] Example 13

[0134] This embodiment provides a 3D printed hydrogel, and the preparation steps are as follows:

[0135] (1) Preparation of 3D printing hydrogel precursor solution:

[0136] Weigh 3.0g of hexadecyltrimethylammonium bromide and dissolve it in 6.5ml of sodium sulfate solution (molar concentration, 0.1mol / L). Magnetic stirring or ultrasonic heating until completely dissolved is used to prepare a micellar solution. Weigh 0.1g of lauryl methacrylate and add it to the micellar solution. Once completely dissolved, add 1.5g of acrylamide and 44mg of polyethylene glycol (molecular weight, 50,000Da). Mix thoroughly, then add 250mg of the photoinitiator TPO. Ultrasonication is performed for 20 minutes to obtain a 3D printing hydrogel precursor solution.

[0137] (2) Preparation of cured product (3D printed hydrogel):

[0138] The 3D printing hydrogel precursor solution prepared in step (1) was placed in a 3D printer, and the 3D printing parameters were set as follows: initial exposure time was 10 s, single layer exposure time was 2 s, printing layer thickness was 0.05 mm, and the wavelength of ultraviolet light for initiating photopolymerization reaction was 405 nm. The hydrogel was printed layer by layer to form a rectangular parallelepiped with a size of 50 mm × 4 mm × 2 mm.

[0139] Example 14

[0140] This embodiment provides a 3D printed hydrogel, and the preparation steps are as follows:

[0141] (1) Preparation of 3D printing hydrogel precursor solution:

[0142] Weigh 3.0g of hexadecyltrimethylammonium bromide and dissolve it in 6.5ml of sodium sulfate solution (molar concentration, 0.1mol / L). Magnetic stirring or ultrasonic heating until completely dissolved is used to prepare a micellar solution. Weigh 0.1g of lauryl methacrylate and add it to the micellar solution. Once completely dissolved, add 1.5g of acrylamide and 44mg of polyvinylpyrrolidone (molecular weight, 50,000Da). Mix thoroughly, then add 250mg of photoinitiator TPO. Ultrasonication is performed for 20 minutes to obtain a 3D printing hydrogel precursor solution.

[0143] (2) Preparation of cured product (3D printed hydrogel):

[0144] The 3D printing hydrogel precursor solution prepared in step (1) was placed in a 3D printer, and the 3D printing parameters were set as follows: initial exposure time was 10 s, single layer exposure time was 2 s, printing layer thickness was 0.05 mm, and the wavelength of ultraviolet light for initiating photopolymerization reaction was 405 nm. The hydrogel was printed layer by layer to form a rectangular parallelepiped with a size of 50 mm × 4 mm × 2 mm.

[0145] Example 15

[0146] This embodiment provides a 3D printed hydrogel, and the preparation steps are as follows:

[0147] (1) Preparation of 3D printing hydrogel precursor solution:

[0148] Weigh 3.0g of hexadecyltrimethylammonium bromide and dissolve it in 6.5ml of sodium sulfate solution (molar concentration, 0.1mol / L). Magnetic stirring or ultrasonic heating until completely dissolved is used to prepare a micellar solution. Weigh 0.1g of lauryl methacrylate and add it to the micellar solution. Once completely dissolved, add 1.5g of acrylamide and 44mg of hyaluronic acid (molecular weight, 50,000Da). Mix thoroughly, then add 250mg of photoinitiator TPO. Ultrasonication is performed for 20 minutes to obtain a 3D printing hydrogel precursor solution.

[0149] (2) Preparation of cured product (3D printed hydrogel):

[0150] The 3D printing hydrogel precursor solution prepared in step (1) was placed in a 3D printer, and the 3D printing parameters were set as follows: initial exposure time was 10 s, single layer exposure time was 2 s, printing layer thickness was 0.05 mm, and the wavelength of ultraviolet light for initiating photopolymerization reaction was 405 nm. The hydrogel was printed layer by layer to form a rectangular parallelepiped with a size of 50 mm × 4 mm × 2 mm.

[0151] Example 16

[0152] This embodiment provides a 3D printed hydrogel, and the preparation steps are as follows:

[0153] (1) Preparation of 3D printing hydrogel precursor solution:

[0154] Weigh 3.0g of hexadecyltrimethylammonium bromide and dissolve it in 6.5ml of sodium sulfate solution (molar concentration, 0.1mol / L). Magnetic stirring or ultrasonic heating until completely dissolved is used to prepare a micellar solution. Weigh 0.1g of lauryl methacrylate and add it to the micellar solution. Once completely dissolved, add 1.5g of acrylamide and 44mg of polyvinyl alcohol (molecular weight, 50,000Da). Mix thoroughly, then add 250mg of photoinitiator TPO. Ultrasonication is performed for 20 minutes to obtain a 3D printing hydrogel precursor solution.

[0155] (2) Preparation of cured product (3D printed hydrogel):

[0156] The 3D printing hydrogel precursor solution prepared in step (1) was placed in a 3D printer, and the 3D printing parameters were set as follows: initial exposure time was 10 s, single layer exposure time was 2 s, printing layer thickness was 0.05 mm, and the wavelength of ultraviolet light for initiating photopolymerization reaction was 405 nm. The hydrogel was printed layer by layer to form a rectangular parallelepiped with a size of 50 mm × 4 mm × 2 mm.

[0157] Example 17

[0158] (1) Preparation of mixed solution:

[0159] Weigh 3.0 g of hexadecyltrimethylammonium bromide and dissolve it in 6.5 ml of sodium sulfate solution (molar concentration, 0.1 mol / L). Stir magnetically or ultrasonically heat until completely dissolved to prepare a micellar solution. Weigh 0.1 g of lauryl methacrylate and add it to the micellar solution. Once completely dissolved, add 1.5 g of acrylamide and 44 mg of polymethacrylic acid (molecular weight, 50,000 Da). Mix thoroughly to obtain a mixed solution.

[0160] (2) Preparation of cured product (3D printed hydrogel):

[0161] 250 mg of photoinitiator TPO was added to the mixed solution prepared in step (1), and ultrasonication was performed for 20 min to obtain a 3D printing hydrogel precursor solution. The 3D printing hydrogel precursor solution was placed in a 3D printer, and the 3D printing parameters were set as follows: initial exposure time was 10 s, single layer exposure time was 2 s, printing layer thickness was 0.05 mm, and the wavelength of ultraviolet light for initiating photopolymerization reaction was 405 nm. The hydrogel was printed layer by layer to form a rectangular hydrogel with a size of 50 mm × 4 mm × 2 mm.

[0162] Example 18

[0163] This embodiment provides a 3D printed hydrogel, and the preparation steps are as follows:

[0164] (1) Preparation of 3D printing hydrogel precursor solution:

[0165] Weigh 3.0g of hexadecyltrimethylammonium bromide and dissolve it in 6.5ml of sodium sulfate solution (molar concentration, 0.1mol / L). Magnetic stirring or ultrasonic heating until completely dissolved is used to prepare a micellar solution. Weigh 0.1g of octadecyl acrylate and add it to the micellar solution. Once completely dissolved, add 1.5g of acrylamide and 44mg of polymethacrylic acid (molecular weight, 50,000Da). After mixing thoroughly, add 250mg of photoinitiator TPO and ultrasonicate for 20 minutes to obtain a 3D printing hydrogel precursor solution.

[0166] (2) Preparation of cured product (3D printed hydrogel):

[0167] The 3D printing hydrogel precursor solution prepared in step (1) was placed in a 3D printer, and the 3D printing parameters were set as follows: initial exposure time was 10 s, single layer exposure time was 2 s, printing layer thickness was 0.05 mm, and the wavelength of ultraviolet light for initiating photopolymerization reaction was 405 nm. The hydrogel was printed layer by layer to form a rectangular parallelepiped with a size of 50 mm × 4 mm × 2 mm.

[0168] Example 19

[0169] This embodiment provides a 3D printed hydrogel, and the preparation steps are as follows:

[0170] (1) Preparation of 3D printing hydrogel precursor solution:

[0171] Weigh 3.0g of hexadecyltrimethylammonium bromide and dissolve it in 6.5ml of sodium sulfate solution (molar concentration, 0.1mol / L). Magnetic stirring or ultrasonic heating until completely dissolved is used to prepare a micellar solution. Weigh 0.1g of N-tert-butylacrylamide and add it to the micellar solution. Once completely dissolved, add 1.5g of acrylamide and 44mg of polymethacrylic acid (molecular weight, 50,000Da). Mix thoroughly, then add 250mg of photoinitiator TPO. Ultrasonication is performed for 20 minutes to obtain a 3D printing hydrogel precursor solution.

[0172] (2) Preparation of cured product (3D printed hydrogel):

[0173] The 3D printing hydrogel precursor solution prepared in step (1) was placed in a 3D printer, and the 3D printing parameters were set as follows: initial exposure time was 10 s, single layer exposure time was 2 s, printing layer thickness was 0.05 mm, and the wavelength of ultraviolet light for initiating photopolymerization reaction was 405 nm. The hydrogel was printed layer by layer to form a rectangular parallelepiped with a size of 50 mm × 4 mm × 2 mm.

[0174] Example 20

[0175] This embodiment provides a 3D printed hydrogel, and the preparation steps are as follows:

[0176] (1) Preparation of 3D printing hydrogel precursor solution:

[0177] Weigh 3.0g of hexadecyltrimethylammonium bromide and dissolve it in 6.5ml of sodium sulfate solution (molar concentration, 0.1mol / L). Magnetic stirring or ultrasonic heating until completely dissolved is used to prepare a micellar solution. Weigh 0.1g of behenyl methacrylate and add it to the micellar solution. Once completely dissolved, add 1.5g of acrylamide and 44mg of polymethacrylic acid (molecular weight, 50,000Da). Mix thoroughly, then add 250mg of photoinitiator TPO. Ultrasonication is performed for 20 minutes to obtain a 3D printing hydrogel precursor solution.

[0178] (2) Preparation of cured product (3D printed hydrogel):

[0179] The 3D printing hydrogel precursor solution prepared in step (1) was placed in a 3D printer, and the 3D printing parameters were set as follows: initial exposure time was 10 s, single layer exposure time was 2 s, printing layer thickness was 0.05 mm, and the wavelength of ultraviolet light for initiating photopolymerization reaction was 405 nm. The hydrogel was printed layer by layer to form a rectangular parallelepiped with a size of 50 mm × 4 mm × 2 mm.

[0180] The 3D printed hydrogels prepared in Examples 1 to 3 were placed in the middle of the clamp of a universal mechanical testing machine (Model AGS-J, Shimadzu Instruments (Suzhou) Co., Ltd.), and the stretching speed was set to 50 mm / min. The hydrogels were stretched until they broke, and their stress-strain curves were measured. The test results are shown in Figure 2. Figure 1 shown.

[0181] like Figure 1 As shown in the figure, as the pH value of the 3D printed hydrogel precursor solution increases, the mechanical strength of the 3D printed hydrogel increases significantly.

[0182] The 3D printed hydrogels prepared in Examples 9 to 17 above were placed in the middle of the clamp of a universal mechanical testing machine (model AGS-J, Shimadzu Instruments (Suzhou) Co., Ltd.), the tensile speed was set to 50 mm / min, the hydrogels were stretched until they broke, and their stress-strain curves were measured. The test results were no significantly different from those in Example 1.

[0183] The 3D printed hydrogels prepared in Examples 4 to 6 were placed in the middle of the clamp of a universal mechanical testing machine (Model AGS-J, Shimadzu Instruments (Suzhou) Co., Ltd.), and the stretching speed was set to 50 mm / min. The hydrogels were stretched until they broke, and their stress-strain curves were measured. The test results are shown in Figure 2. Figure 2 shown.

[0184] like Figure 2 As shown in the figure, when the mass percentage of polyethyleneimine in the total mass of the 3D printing hydrogel precursor solution is 0.2% to 0.4%, the mechanical strength of the 3D printed hydrogel increases significantly with the increase of polyethyleneimine content. When the mass percentage of polyethyleneimine in the total mass of the 3D printing hydrogel precursor solution exceeds 0.4%, the mechanical strength of the 3D printed hydrogel decreases significantly.

[0185] The 3D printed hydrogel prepared in Example 5 was cut, and then the cross-section was re-contacted and placed in a constant temperature and humidity chamber at 37°C and 50% humidity for self-repair. After 2 hours of repair, it was taken out and a tensile stress-strain curve test was performed using a universal testing machine (model AGS-J, Shimadzu Instruments (Suzhou) Co., Ltd.). The test results are shown in Figure 2. Figure 3shown.

[0186] like Figure 3 As shown, under this repair condition, the repair rate of the 3D printed hydrogel can reach 75% (the ratio of the integrated area under the stress-strain curve), which indicates that the 3D printed hydrogel of the embodiment of the present application has good self-repair properties.

[0187] The 3D printed artificial hydrogel ear prepared in Example 7 was wiped with dust-free paper to dry the excess water on the surface of the 3D printed hydrogel. Then, a camera was used to magnify and observe and record the structure of the 3D printed hydrogel microarray. The results are as follows: Figure 4 shown.

[0188] The 3D printed hydrogels prepared in Examples 1 and 18 to 20 were placed in the middle of the clamp of a universal mechanical testing machine (Model AGS-J, Shimadzu Instruments (Suzhou) Co., Ltd.), and the stretching speed was set to 50 mm / min. The hydrogels were stretched until they broke, and their stress-strain curves were measured. The test results are shown in Figure 2. Figure 5 shown.

[0189] from Figure 5 It can be seen that when lauryl methacrylate and octadecyl acrylate are used as hydrophobic monomers, the resulting 3D printed hydrogels have good mechanical strength. When N-tert-butyl acrylamide is used as the hydrophobic monomer, its hydrophobicity mainly comes from the tert-butyl group. The tert-butyl side chains hinder the orderly arrangement of the monomers in the micellar solution, forming a loose network after polymerization. The resulting hydrogel has uneven pore size and poor mechanical strength. When behenyl methacrylate is used as the hydrophobic monomer, its hydrophobicity mainly comes from the long behenyl chain, which is too hydrophobic and easily forms excessive cross-links.

[0190] The above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. These modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present application, and should all be included in the scope of protection of the present application.

Claims

1. A 3D printing hydrogel precursor solution, characterized in that: The composition comprises the following components by mass percentage: 5% to 35% of surfactant, 5% to 30% of acrylamide, 0.5% to 5% of hydrophobic monomer, 0.05% to 5% of water-soluble polymer, 1% to 5% of photoinitiator, and the balance is sodium sulfate solution.

2. The 3D printing hydrogel precursor solution according to claim 1, characterized in that The surfactant is at least one of cetyltrimethylammonium bromide, sodium lauryl sulfate, 3-[(3-cholamidopropyl)dimethylamino]-1-propanesulfonic acid or polysorbate; and / or, the hydrophobic monomer is at least one of lauryl methacrylate, stearyl methacrylate, octadecyl acrylate, tridecafluorooctyl acrylate, or N-octadecyl acrylamide; and / or, the water-soluble polymer is at least one of polymethacrylic acid, polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, polyethyleneimine or hyaluronic acid; And / or, the photoinitiator is at least one of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and lithium phenyl-2,4,6-trimethylbenzoylphosphinate.

3. The 3D printing hydrogel precursor solution according to claim 1, characterized in that The molecular weight of the water-soluble polymer is 1000 to 100000 Da.

4. The 3D printing hydrogel precursor solution according to claim 1, characterized in that The molar concentration of the sodium sulfate solution is 0.05-0.5 mol / L.

5. The method for preparing a 3D printing hydrogel precursor solution according to any one of claims 1 to 4, wherein: The steps include: The surfactant is dissolved in a sodium sulfate solution to prepare a micellar solution; Acrylamide, hydrophobic monomer, water-soluble polymer and photoinitiator are added to the micelle solution and mixed evenly to obtain a 3D printing hydrogel precursor solution.

6. A method for preparing a solidified product, characterized in that: The steps include: The 3D printing hydrogel precursor solution according to any one of claims 1 to 4 is placed in a 3D printer, and its cured product is formed layer by layer, wherein the 3D printing parameters are set as follows: initial exposure time is 5s to 60s, single layer exposure time is 1s to 30s, and printing layer thickness is 0.01mm to 0.5mm.

7. The method for preparing a cured product according to claim 6, wherein: The 3D printing hydrogel precursor solution according to any one of claims 1 to 4 is placed into a 3D printer, comprising: Using a pH regulator, adjusting the pH value of the 3D printing hydrogel precursor solution to 6 to 10 to obtain a prepolymer solution; The prepolymer solution is placed into a 3D printer.

8. A cured product, characterized in that The cured product is obtained by the method for preparing a cured product according to claim 6 or 7.

9. A 3D printing hydrogel precursor solution, characterized in that: Comprising a mixed solution and a photoinitiator; the mass ratio of the mixed solution to the photoinitiator is 20 to 100:1; The mixed solution comprises the following components by mass percentage: 5% to 35% of surfactant, 5% to 30% of acrylamide, 0.5% to 5% of hydrophobic monomer, 0.05% to 5% of water-soluble polymer, and the balance is sodium sulfate solution.

10. Use of the 3D printing hydrogel precursor solution according to any one of claims 1 to 4, or the cured product according to claim 8, or the 3D printing hydrogel precursor solution according to claim 9 in the preparation of tissue engineering scaffold materials or organ tissue substitutes.

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